text:
Death Toll in China Mining Blast Rises to 106
Posted: 11/24/2009 - The number of dead in China's worst mining accident in two years rose to 106 Wednesday after two more bodies were pulled out of the coal mine, state media said.
Posted: 11/24/2009 - The number of dead in China's worst mining accident in two years rose to 106 Wednesday after two more bodies were pulled out of the coal mine, state media said.
Posted: 11/24/2009 - A few miles (kilometers) off the main highway, on a remote hilltop covered with waist-high grass, bodies lay with twisted hands reaching in the air. They had been shot point-blank.
Posted: 11/23/2009 - Rescuers plucked a woman from choppy waters Monday, some 25 hours after she jumped from a crowded ferry that sank in a storm off Indonesia's Sumatra island. At least 29 people drowned, and 20 others were missing.
Updated: 11/24/2009 - A mother says her son has emerged from what doctors thought was a vegetative state to say he was fully conscious for 23 years but could not respond because he was paralyzed.
Posted: 11/23/2009 - Britain's authority on etiquette says it's more hygienic to exchange kisses on the cheek than to shake hands - so the swine flu pandemic should not make people afraid of kissing under the mistletoe this holiday season.
Posted: 11/22/2009 - Two exit polls indicate that Romania's resident has received more votes than any other candidate in the country's presidential election, but not enough to avoid a runoff.
Posted: 11/21/2009 - Rescuers working in frigid cold and darkness tried to reach 66 people believed trapped a third of a mile (half a kilometer) underground after a huge gas explosion Saturday ripped through a coal mine in northern China, killing at least 42 people.
Posted: 11/21/2009 - Prosecutors requested life sentences Saturday for an American student and her former Italian boyfriend accused of killing a young British woman in Italy.
Posted: 11/18/2009 - A couple suspected of helping spread some of the Internet's most aggressive computer viruses has been arrested in the English city of Manchester, police said Wednesday.
Posted: 11/18/2009 - A man appealing his conviction for murdering a British student testified Wednesday that he heard her arguing with her American roommate Amanda Knox minutes before she was slain.
Updated: 11/18/2009 - Thousands of stargazers stayed awake overnight for what was forecast as an intense Leonid meteor shower over Asia this year, but the show fizzled rather than sizzled for many viewers - partly due to cloud cover.
Posted: 11/17/2009 - Two top leaders of a mostly ethnic Hutu militia were arrested in Germany Wednesday on suspicion of committing crimes against humanity in Congo in what experts in the region called a major blow to one of the most brutal rebel groups in Africa.
Posted: 11/17/2009 - A former SS sergeant who worked unnoticed for decades as a train-station manager was charged with 58 counts of murder Tuesday after a student doing undergraduate research uncovered his alleged involvement in a massacre of Jewish forced laborers.
Posted: 11/17/2009 - Small groups of Mapuche Indians have so rattled Chile by seizing forests, burning buses and attacking police to demand land and autonomy that the leftist government has turned to dictatorship-era measures to quell the violence.
Posted: 11/17/2009 - A 13-year-old French boy stole his father's hunting rifle and took it to school with the intention of shooting his teachers, but his family and police intervened before anyone was hurt, police said.
Posted: 11/17/2009 - A prominent Western investor who has clashed with Russian authorities said Tuesday that a lawyer who advised his fund died in a Moscow jail after being denied medical care.
Posted: 11/17/2009 - Thousands marched through the Czech capital Tuesday in commemoration of a student protest 20 years ago that grew into the human tidal wave sweeping away the communist regime in what was then Czechoslovakia.
Posted: 11/17/2009 - A dispute between an Austrian Holocaust research center and an organization representing Vienna's Jewish committee over access to a vast archive has prompted a group of academics to withdraw support for the center, saying independent research is no longer possible, according to a letter obtained Tuesday by The Associated Press.
Posted: 11/17/2009 - Peruvian officials said Tuesday that an air force officer has confessed to passing national security secrets to Chile, where President Michelle Bachelet denied the espionage allegations, calling them offensive.
Posted: 11/17/2009 - Brushing back freshly dyed blond hair as she posed for pictures, the Brazilian woman whose short pink dress got her kicked out of college said Tuesday she's enjoying her newfound fame, but wants to go back to school - with a security guard.
Posted: 11/16/2009 - Britain's first convicted war criminal said Monday that some of his fellow soldiers frequently beat Iraqi detainees.
Posted: 11/16/2009 - Two men were granted a marriage license in Argentina's capital on Monday, breaking ground in a country and region where laws ban gay marriage.
Posted: 11/16/2009 - Six Jesuit priests killed by the army during El Salvador's civil war two decades ago were decorated with the country's highest honor Monday.
Posted: 11/16/2009 - Peruvian President Alan Garcia accused Chile of assaulting Peru's sovereignty, throwing his weight behind allegations that Chile paid a Peruvian military officer to spy.
Posted: 11/16/2009 - News blackouts unjustifiably prevented the public from learning why charges were dropped or suspended for some terror suspects, media lawyers told Canada's Supreme Court on Monday.


text: ""; ?> Guitar Tabs, Guitar Chords and Lyrics - Chordie guitar tabs, guitar chords and lyrics Artists Songs Public booksPublic My songbookSongbook ResourcesDiv Forum Browse artists: A B C D E F G H I J K L M N O P Q R S T U V W X Y Z # -first letter-A B C D E F G H I J K L M N O P Q R S T U V W X Y Z # Showing all songs - change Patti Smith - Blue Poles1 Blue Poles Currently 3/5 Stars. Currently 3/5 Stars. 1 2 3 4 5 CHORDS Am, B, C, D, Em, F, G, 224442Difficulty: hard return to normal F x03211 D xx0232 Am x02210 -Verse- -Chorus- Intro - Em C G B Verse Chorus Verse Chorus Harmonica solo (play chorus chords) Verse Chorus ...I write (guitaretab.com) play their songs - buy their music - support the artists copyright © 2011 chordie guitar chords 5 popular songs Hit The Road, Jack Traditional Let It Be Beatles Take Me Home Country Roads John Denver Perfect Day Lou Reed Let Her Cry Hootie & The Blowfish

subset: commoncrawl


text:
Maj. Gen. Mark S. BowmanDirector of Architecture, Operations, Networks and SpaceU.S. Army
Maj. Gen. Mark Bowman would have won the Federal 100 award if he had done nothing beyond leading the redesign of the Army's Signal Regiment.
But he also played a key role in data-center consolidation efforts that will save the Army an estimated 75 percent on data-center spending. And he led an initiative to bring voice-over-IP technology to the Army's three four-star headquarters in the continental United States.
Still, there's no denying the importance of the work he did in communications. "His redesign of the Signal Regiment concept has been instrumental in how the Army provides communications to warfighters on the ground," said Robert Carey, deputy CIO at the Defense Department. Bowman is "modernizing how the Army approaches IT from the ground up."
Read more about the 2011 Federal 100 award winners.
About the Author
Amber Corrin is a former staff writer for FCW and Defense Systems.
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Meet 100 women and men who are doing great things in federal IT.
Click here for the full list
Unisys Federal Systems' Venkatapathi Puvvada, this year's Eagle award winner for industry, stresses the importance of community.
Experts tell committee that business models, not technology, are the main obstacle to better sharing across systems.
Protests have delayed SEWP V, but industry experts say the contract vehicle offers agencies service and value that are hard to find.
The power of the individual informs FCW's coverage each and every day, but with the Federal 100, we take time to really spotlight and celebrate it. Get to know each of this year's winners.
The latest version of the Cybersecurity Information Sharing Act purportedly protects companies from liability and individuals from government intrusion.
Popular CIO is headed for the private sector.
The Census Bureau hasn't established a time frame for its cloud computing plans, including testing for scalability, security, and privacy protection, as well as determining a budget for cloud services.
President Obama's proposal to boost government coordination with the private sector got a warm welcome in the House Homeland Security Committee.
The spy agency wants to better integrate cybersecurity into its traditional human intelligence operations.
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text:
Chianti Region Wine Tasting Half-Day Trip from Florence
Read what other Viator.com travelers think about the Chianti Region Wine Tasting Half-Day Trip from Florence. What they loved, what they liked and what they think could be improved, it's all here to help you make the most of your next trip.
Click here for tour details, schedule and pricing
This tour was my favorite part of our trip to Italy. It was informative, relaxed, full of food, wine and fun. At the winery, we sat at large tables and were able to meet other people and enjoy the experience with old and new friends. The trip was well-timed and we even had some time after the winery to stop at a local village square and sample more wine! My only suggestion would be to improve the speaker system on the tour bus. It was difficult to hear the tour guide over the speakers.
Woo Hoo Fun trip. Good wine and snacks. Very good winery host and guide
The best tour guide ever! Had much more than expected, loved the castle, wine tour was fabulous, lots of interesting stories and information! Great food and wine and beautiful country side!
This tour was amazing!
This tour is a must. Not only was it a wonderful tour in the countryside and a tour of an ancient castle/winery but as a bonus we were educated about the production of olive oil.
This tour is all you would dream off. The view driving up to the vineyard was perfect. We had some incredible wine. The tour guide on bus and at the vineyard were awesome. You won regret a moment of it.
Decided to do a wine tasting tour last minute and found this one! Absolutely amazed!!! It was a wonderful experience and totally worth the money. We learned so much! The story behind the castle and winery is great too!
This is a great way to spend an afternoon if you are staying in Florence. The countryside was astonishingly beautiful and the castle tour was excellent.
I loved this trip! I believe our guide was named Irene and she was amazing. She knew her stuff and was very friendly. I enjoyed our stop in Greve in Chianti and the winery itself was very fun and informative. No negatives to this wonderful wine tasting trip!
A really great experience. Good food, wine and safe transportation.
This tour was amazing!
Do this tour! Bus ride to the vineyard isn't too long and the coach bus makes it an easy jaunt. You get a nice overview of the vineyard and winemaking process. However, it is by no means an in-depth tour of the vineyard. This tour really is a lot more about the wine tasting than it is about learning about the vineyard or winemaking. That being said, the wine tasting was awesome, as was the food! We're talking bottles on the table and giant plates full of really good snacks, all paired perfectly by the lovely guide/employee of the vineyard! By the time the bus leaves the vineyard, you will be full, you will be tipsy and you will have made some great new friends. The majority of the group on our tour decided to forego any exploration of the capital town of the Chianti region that they bring you to after the vineyard, instead preferring to visit the local wine shop for more wine tasting. This was quite enjoyable and recommended, unless you're a big history buff, to whom I might recommend wandering the town instead. We met so many awesome people on this tour, some of whom we spent the rest of the night eating dinner and gelato and drinking with. It really was one of the utmost highlights of our time in Florence and I am so glad we chose to do this tour!
AMAZING TOUR! Amazing scenery, just simply awesome! Don't even think twice, just book it you will not regret it!
It is always good to be back here in Chianti.
I took this tour twice and I still love it and would go for a third time
You should not miss this one at all.
Great guide
One of the highlights of the trip. Fun, informative--a perfect half day excursion out of Florence.


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In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.
1. A method of forming a film, the method comprising:
obtaining a layer of oriented seed crystals; and
growing the oriented seed crystals to form a film defining a surface, wherein the seed crystals growth rate parallel to the surface is substantially the same as their growth rate normal to the surface,
wherein growing the seed crystals comprises exposing the layer of oriented seed crystals to a solution that comprises a first structure directing agent.
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16. A method of forming a film, the method comprising:
disposing anisotropic seed crystals on a surface of a substrate, wherein each seed crystal has a short axis; and
exposing the seed crystals to a solution to grow the seed crystals, the solution comprising a structure directly agent,
wherein the growth rate of each seed crystal along its short axis is substantially the same as the growth rate along another axis.
17. The method of
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20. An article comprising:
a porous substrate having a surface; and
a layer of a framework material bound to the surface,
wherein the framework material layer is substantially continuous, and comprises a plurality of crystal grains that extend through the depth of the layer such that a lateral dimension of adjacent crystal grains is substantially the same at different depths through the layer and grain boundaries between adjacent crystal grains are oriented substantially perpendicular with respect to the surface.
21. The article of
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31. An article comprising:
a substrate having a surface; and
a layer of a framework material disposed on the surface,
wherein the article has a para-xylene permeance of at least about 1,000�10−10 mol/m2sPa and a para-xylene to ortho-xylene separation factor of at least about 100:1.
This application claims priority from Provisional Patent Application No. 60/452,375, entitled �CRYSTALLINE MEMBRANES,� filed on Mar. 6, 2003, the entire contents of which is hereby incorporated by reference.
This invention was made with Government support under grant numbers CTS-0091406 and CTS-0103010 awarded by the National Science Foundation, and grant number NAG8-1697 awarded by NASA. The Government has certain rights in the invention.
The invention relates to crystalline membranes, methods for making crystalline membranes, and applications of crystalline membranes.
Inorganic crystalline membranes are of interest in many industries as functional layers in, for example, porous or protective films. Zeolites are a class of inorganic crystalline materials with desirable characteristics for such membranes. Zeolites are crystalline aluminosilicates, containing molecular sized pores. For example, ZSM-5 zeolites have an MFI framework with intersecting pores having a diameter of 5 to 6 Angstroms. Zeolites are an important material for catalyzing reactions, and are commonly used in the catalytic cracking of petroleum and other reactions of hydrocarbons. They are commonly provided in a powder form and are used to selectively crack straight chain molecules over branched chain molecules. Furthermore, zeolite particles have been used to selectively form para-xylene, which is used to make terephthalic acid for various polymerization reactions and in the synthesis or rearrangement of xylenes.
Zeolites are formed with a three-dimensional structure in which tetrahedra of primarily SiO4 and AlO4 are crosslinked by sharing oxygen atoms, whereby the ratio of Si to O atoms is 1:2. Depending on the manner of bonding, the crystal structures can have various ring sizes containing 8, 10, 12, or 14 metal/semi-metal atoms. These rings define pores and chambers that are of molecular size. The presence of these chambers promotes the separation of molecules according to their size and their affinity to the zeolitic surface. Because zeolites are commonly available in the form of fine powders, catalytic systems including zeolites frequently use packed or fluidized beds made of zeolite crystal powders or small pellets made up of multiple zeolite crystals.
In general, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.
In one aspect, the invention features methods of forming a film that includes obtaining a layer of oriented seed crystals and growing the oriented seed crystals to form a film defining a surface, wherein the seed crystals' growth rate parallel to the surface is substantially the same as their growth rate normal to the surface.
Embodiments of the methods can include one or more of the following features and/or features of other aspects. For example, growing the seed crystals can include exposing the oriented seed crystal layer to a solution (e.g., an aqueous solution). The solution can include a first structure directing agent, and/or a mineralizing agent (e.g., potassium hydroxide or sodium hydroxide). During growth, the solution can be heated to between about 50� C. and 200� C. The method can also include forming the seed crystals using a seed structure directing agent, which can be the same or different than the first structure directing agent. Either structure directing agent can include an organic cation (e.g., tetrapropylammonium hydroxide (TPA)). They can be an oligomer (e.g., a dimer or trimer). In some embodiments, the first and/or seed structure directing agent is trimer TPA.
The layer of oriented seed crystals can be obtained by disposing seed crystals on a surface of a substrate. The seed crystals can include a framework material (e.g,. a zeolite such as silicalite-1). The framework material can have an MFI structure. The methods can include applying a coupling agent (e.g., a silane) to the surface of the substrate before disposing the seed crystals wherein the coupling agent bonds (e.g., covalently bonds) to the substrate surface and to the seed crystals.
The seed crystals can be disc-shaped (e.g., shaped as oval or round discs). Alternatively, the seed crystals can be box-like, coffin-shaped, or plate-like. Each seed crystal has a first crystallographic axis (e.g., a-, b-, or c-axis) and the first crystallographic axis of a majority (e.g., more than 50 percent of the seed crystals, such as more than 75, 85, 95 percent) of the seed crystals can be substantially parallel to each other. The first crystallographic axis of the seed crystals can be substantially normal or parallel to a plane of the substrate surface (e.g., at least 50 percent of the seed crystals crystallographic axes can be within 10 degrees of normal, such as within five degrees of normal). The oriented seed crystal layer can be a monolayer (i.e., the layer can be substantially only one seed crystal thick, e.g., about 10 percent or less of the seed crystals can overlap with other seed crystals).
During growth of the oriented seed crystal layer, the seed crystals growth rate parallel to the surface can be between about 0.5 and two times the growth rate normal to the surface.
In some embodiments, during growth of the layer, substantially no crystal nucleation occurs in the solution or on a surface of the seed crystals.
In general, in another aspect, the invention features methods of forming a film including disposing anisotropic seed crystals on a surface of a substrate, wherein each seed crystal has a short axis, and exposing the seed crystals to a solution to grow the seed crystals, wherein the growth rate of each seed crystal along its short axis is substantially the same as the growth rate along another axis.
Embodiments of the methods can include one or more of the following features and/or features of other aspects. For example, the seed crystals can form an oriented seed crystal layer on the substrate surface. For a majority (i.e., more than about 50 percent of the seed crystals, such as more than about 75, 85, 95 percent) of the seed crystals in the oriented seed crystal layer, the short axis can be oriented substantially orthogonal to the substrate surface. The seed crystals can include a framework material (e.g., a zeolite). In embodiments where the framework material is a zeolite, it can include channels running substantially parallel to the short axis.
The solution can include a structure directing agent. The seed crystals can be exposed to the solution for sufficiently long to form a substantially continuous layer of the seed crystal material (e.g., discontinuities can form about 5%, 3%, 2%, 1% or less of the layer).
In general, in a further aspect, the invention features articles including a porous substrate having a surface and a substantially continuous layer of a framework material bound to the surface, wherein the layer of framework material comprises a plurality of crystal grains that extend through the depth of the layer. In a substantially continuous layer, discontinuities can form about 5%, 3%, 2% or less of the layer.
Embodiments of the articles can include one or more of the following features and/or features of other aspects. For example, the framework material can be a zeolite (e.g., silicalite-1). The framework material can be a porous framework material. For example, the porous framework material can include channels that run through the depth of the layer. The framework material can have an MFI structure. The layer can include a plurality of crystalline grains. The crystalline grains can extend through the depth of the layer. The crystalline grains can have an oriented crystallographic axis, which can be, for example, orthogonal or parallel to the substrate surface. In some embodiments, the oriented crystallographic axis is the b-axis or a-axis of an MFI structure. An average ratio of the layer thickness to the crystalline grains' maximum size parallel to the substrate surface can be less than about two (e.g., about 1.5, 1.0, 0.5, or less). The average of the crystalline grains' maximum size parallel to the substrate surface can be at least 200 nanometers. The layer can be substantially intergrown (i.e., discontinuities in the framework material can include about 5%, 3%, 2% or less of the layer). The layer can be less than 50 microns thick, e.g., 10 microns, 5 microns, one micron thick, or less.
The porous substrate can include a metal oxide (e.g., α-alumina). The porous substrate can include mesoporous silica. The framework material can be covalently bonded to the substrate surface. For example, the article can include a coupling agent that covalently bonds the framework material to the substrate surface.
The articles can be prepared using methods described herein.
In another aspect, the invention features methods of separating a first compound from a second compound different from the first compound including filtering a mixture of the first and second compounds through the article to produce a filtrate, wherein a relative concentration of the first compound compared to the second compound in the filtrate is at least 10 times a relative concentration of the first compound compared to the second compound in the mixture. The first compound can be an isomer of the second compound. The relative concentration of the first compound compared to the second compound in the filtrate can be about 100 or more (e.g., more than 200, 300, 500, 1,000, 2,500) times the relative concentration of the first compound compared to the second compound in the mixture. The article can have a first compound permeance of about 1,000�10−10 mol/m2sPa or more (e.g., 2,000�10−10, 5,000�10−10, 10,000�10−10 mol/m2sPa or more).
In another aspect, the invention features a reactor including a reaction chamber and an article disposed relative to the reaction chamber, wherein during operation the reactor produces a compound which exits the reaction chamber through the article. The article can be substantially impermeable to reagents used in the reactor (e.g., can have a permeance less than about 10�10−10 mol/m2sPa for the reagents). The article can be substantially impermeable to reaction products other than the compound produced during operation of the reactor (e.g., can have a permeance less than about 10�10−10 mol/m2sPa for the reaction products).
In another aspect, the invention features a method of forming a reaction product, including providing the reactor, placing reaction reagents in the reaction chamber, reacting the reaction reagents in the reaction chamber to form the compound, and removing the compound through the article, wherein the removed compound is the reaction product.
In other aspects, the invention features molecular sieves including the article, and methods of making molecular sieves by obtaining the article and attaching the article to a fluid conduit to obtain the molecular sieve. The invention also features protective coatings including the article, and methods of making protective coatings by obtaining the article and applying the article to a surface of an object to form a protective coating for the object.
In general, in another aspect, the invention features articles including a substrate having a surface and a layer of a framework material disposed on the surface, wherein the article has a para-xylene permeance of about 1,000�10−10 mol/m2sPa or more (e.g., 2,000�10−10, 5,000�10−10, 10,000�10−10 mol/m2sPa or more) and a para-xylene to ortho-xylene separation factor of about 100:1 or more (e.g., 200:1, 300:1,500:1, 800:1, 1,000:1 or more).
In a further aspect, the invention features articles including a substrate having a surface and a layer of a framework material disposed on the surface, wherein the article has a benzene permeance of about 100�10−10 mol/m2sPa or more (e.g., 200�10−10, 500�10−10, 1000�10−10 mol/m2sPa or more) and a benzene to cyclohexane separation factor of about 15:1 or more (e.g., 20:1, 30:1, 50:1, 100:1 or more) at temperatures of about 150� C. or more (e.g., 155, 160, 200� C., or more).
Embodiments of the articles can include one or more of the features of other aspects. The articles can be prepared using methods described herein.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
Like reference symbols in the various drawings indicate like elements.
Referring to
Preferably, there are no discontinuities in layer 20. Discontinuities refer to voids in the framework material layer extending through the depth of the layer and having a maximum dimension parallel to the substrate surface greater than the size of channels in the framework material. In some embodiments, discontinuities refer to voids having a maximum dimension parallel to the substrate surface greater than about one nanometer (e.g., two nanometers, three nanometers, five nanometers, 10 nanometers or more). In general, discontinuities occupy less than about five percent of crystalline layer 20 (e.g., less than about three percent, two percent, one percent, one-half percent, or less). Crystalline layers that have relatively few discontinuities are said to be well-intergrown layers.
In certain embodiments, the framework material is a b-oriented MFI zeolite (e.g., silicalite-1). �b-oriented� refers to the crystalline axis oriented normal to the plane of the substrate. MFI structure is well known and generally described, for example, by Ch Baerlocher, W. M. Meier and D. H. Olson in, �Atlas of Zeolite Structure Types,� Fifth Revised Edition, Elsevier, 2001. More generally, the chemical makeup, framework structure, and orientation of the framework structure of layer 20 can vary depending on the specific application for which article 10 is to be used. Other examples of framework structures include LTA, LTL, FAU, BEA, MEL, MOR, MTW. These and other framework structures are described in the above-cited �Atlas of Zeolite Framework Types.�
The framework material can be preferentially oriented with respect to the substrate surface. For example, the framework material can be a-, b- or c-oriented or it can be hoh-oriented or otherwise oriented with a certain crystallographic zone axis mostly perpendicular to the substrate.
In certain embodiments, the framework material is a zeolite, however, in general the invention is not so limited. For example, the framework material can be composed of AlO4 and PO4 tetrahedra. In other examples, the framework material can be composed of SiO4 and AlO4 tetrahedra and TiO6 octahedra and/or TiO5 semi-octahedra. In a further example, the framework material can be composed of CeO6 octahedra and SiO4 terahedra.
The thickness of layer 20 can vary depending on the end use application of the multilayer article. Typically, the thickness of layer 20 is on the order of a few microns (e.g., about two microns, three microns, or five microns). In some embodiments, layer 20 can be relatively thin, e.g., one micron or less. Alternatively, layer 20 can have a thickness of about 10 microns or more, e.g., about 50 microns or more.
In some embodiments, the framework material of layer 20 can be porous. The framework material can have channels running through the depth of layer 20 (e.g., substantially orthogonal to the plane of substrate 30). Because the crystal grains are continuous through the depth of the layer, the channels can be substantially continuous through the layer. For example, a b-oriented MFI layer has channels with an approximate free diameter of 5.5 Angstrom running through the depth of the layer. Alternatively, or additionally, the framework material can have pores running substantially parallel to the plane of surface 32. For example, for a c-oriented MFI layer the channels run substantially parallel to the plane of the substrate. Typically, channels are formed from six, eight, ten, twelve, or fourteen or eighteen-membered rings (MR), although larger channels are possible. This corresponds to a channel diameter range of approximately 3-15 Angstroms (e.g., about 5, 6, 8, 10, or 12 Angstroms). In general, the diameter of the channels depends on the type of framework structure and the chemistry of the framework material. In titanosilicate microporous framework oxides and aluminosilicate zeolites, for example, the framework is anionic and the charge is balanced by extra-framework cations that can be positioned (e.g., by ion exchange) to alter the effective pore openings. In another example, substitution (e.g., isomorphous substitution) of Si or Al at the tetrahedral sites with other elements like B or Ti can alter the pore opening. Furthermore, in certain zeolites, isomorphous substitution of Si with B leads to pore size reduction.
In some embodiments, the substrate can be formed from an inorganic material, such as a metal, an alloy, a ceramic, or a metal oxide. Examples of metal substrate materials include aluminum or stainless steel. Examples of alloy substrate materials include Pd/Ag alloys.
Examples of ceramics include SiC. Examples of metal oxide substrate materials include alumina, zirconia, silica. In some embodiments, the substrate material can be a semiconductor material, such as silicon.
Alternatively, or additionally, the substrate can include an organic material, such as a polymer. Examples of polymers that can be used as substrate materials include polyethylene, poly methylmethacrylate, polyimide, polybenzimidazole, and teflon.
In some embodiments, the substrate is formed from a composite material (e.g., having both organic and inorganic components). One type of composite material includes a continuous phase polymer surrounding a dispersed phase inorganic material, such as a polymer/exfoliated clay, polymer/exfoliated or delaminated layered aluminosphosphate or layered silicate nanocomposite. Another type of composite includes a polymer substrate with a continuous or patterned metal, oxide, or alloy overlayer.
Substrate 30 can be formed from a porous material. For example, the substrate can include pores that run through its depth (e.g., orthogonal to the plane of the substrate). Examples of porous substrate materials include alumina, stainless steel, silicon carbide, anodized alumina, porous polymers, silica, titania, zirconia. The size of the pores can vary depending on the specific end use application. In some embodiments, the pores can be small, e.g., have diameters on the scale of nanometers, such as less than about five nanometers. In other embodiments, the pores may be relatively large, such as tens, hundreds, or even thousands of nanometers wide (e.g., more than about 10 nanometers, 50 nanometers, 100 nanometers, 200 nanometers, 500 nanometers, or 5000 nanometers).
Substrate 30 can include additional layers or coatings. These layers or coatings can be used to provide a smoother surface on which to form the framework material layer. For example, a coating of mesoporous silica can provide a smooth surface on an alpha-alumina substrate. In embodiments where the substrate material has fairly large pores (e.g., several hundred nanometers in diameter) at the surface, a layer of a material with smaller pores can be used to prevent the framework material forming within the substrate material pores. Alternatively, or additionally, materials can be deposited on the substrate surface to promote the adhesion of the framework material to the substrate. For example, the substrate surface can be functionalized using a coupling agent, which covalently bonds to the substrate surface and to the framework material. Examples of coupling agents that can be used to bond zeolite framework materials to a silica substrate surface are silane coupling agents, such as 3-chloropropyltrimethoxysilane (3CP-TMS). 3CP-TMS has two functional groups, one of which reacts with the support surface and the other reacts with crystals of the framework material deposited on the substrate surface. Other examples of coupling agents include diisocyanates, DNA, cationic and anionic polymers, polyamines, and halopropylsilyl agents.
General Two-Step Method
Layer 20 is formed in a two-step method. First, an oriented layer of seed crystals are deposited on the surface of the substrate. The seed crystals are usually anisotropic in shape. The seed crystal layer is oriented because at least one crystalline axis of the seed crystals is substantially aligned. For example, disc-shaped seed crystals can preferentially lie flat against the substrate surface. Once the seed crystals are deposited on the surface, the crystalline layer is formed by inducing secondary growth in the seed crystal layer. During the secondary growth, the rate at which the seed crystals grow in the substrate plane is controlled to be comparable to the out-of-plane growth rate. Accordingly, the ratio of the out-of-plane to in-plane growth rates is within a range where surface and bulk nucleation close to the seed layer is suppressed, but secondary growth is not columnar and the resulting layer is well-intergrown.
Thus, due to undesirable nucleation, the result of growth when the out-of-plane growth rate is very small is typically a film where the grains 216 do not generally extend through the depth of the crystalline layer. In other words, the crystallographic orientation of the framework material varies through the depth of the layer.
On the other hand, if the out-of-plane growth is much faster than the in-plane growth (e.g., νσ>>νπ), the result is usually a columnar film 225. A columnar film includes column-like grains 220, which are usually narrower in diameter closer to the seed crystals and expand as they grow away from the seed crystals. Because growth out-of-plane is so much more rapid than in-plane growth, columnar films can include discontinuities 222 and and/or enclosed voids 224.
Where the in-plane growth rate is comparable to the out-of-plane growth rate (e.g., νσ�νπ), resulting layer 230 includes grains that have uniform crystallographic orientation through their depth, and have minimal discontinuities or enclosed voids (e.g., no discontinuities or enclosed voids).
Although the exact ratio of out-of-plane to in-plane growth rates will vary as a function of the seed crystal chemistry, framework structure, orientation and the growth conditions (e.g., reagent chemistry and temperature), framework layers with desirable properties can be usually obtained where νσ/νπ is between about 2 and 0.5 (e.g., about 2, 1.5, 1, 0.8, 0.6, 0.5).
Seed crystals are formed in the presence of a structure directing agent (SDA), which, in essence, acts as a template for the particular crystalline structure to be formed. The charge distribution, size, and the geometric shape of an SDA can provide its structure directing properties. Thus, the ratio of seed crystal growth rates along different crystalline axes can be manipulated by varying the composition of the SDA. For example, the number of repeating units in an oligomeric SDA as well as the distance between the structure directing moieties can affect the relative growth rates of the resulting seed crystals. Variations in the chemistry of an SDA can also affect the seed crystal growth rate ratio.
One example of controlling the ratios of growth rates using specific SDAs is to use tetrapropylammonium hydroxide (TPA) based SDAs to form silicalite-1 seed crystals. One can vary the number of TPA units as well as the distance between the nitrogen atoms as shown in
Referring to
Without wishing to be bound by theory, the Lc/La ratio increase may be attributed to a better fit of the trimer in the straight versus the sinusoidal channel for the dimer TPA. In this particular example, examination of the (010) faces of TPA-, dimer-TPA- and trimer-TPA-grown silicalite-1 crystals by Atomic Force Microscopy (AFM) reveals an increased roughness and density of steps for the latter, suggesting increased 2-D nucleation on this face with increasing SDA length. That can be attributed to trimer-TPA depositing on (010) with its long axis perpendicular to this face. This arrangement is consistent with a better fit in the straight channels and similar to the one proposed for the dimer-TPA by E. de Vos Burchart and co-workers in Zeolites, 13:216 (1993). Variation of the carbon chain length that connects the N atoms in the TPA oligomers can further alter the fit in the various crystal directions. Accordingly, variation of carbon chain length may affect ratios of crystal growth rates along these directions by favoring one growth direction versus the other. Examples of variations of dimer TPAs include molecules that have a C5 carbon chain between the N atoms (formal name: Bis1,5(tripropylammonium) pentamethylene dihydroxide) and one that has a C7 carbon chain between the N atoms (formal name: Bis-1,7-(tripropylammonium) heptamethylene dihydroxide).
Although the effect of manipulating the relative growth rate of seed crystals using oligomeric SDAs is illustrated for a zeolite MFI crystal using TPA-based SDA's, the concept of manipulating the relative growth rate of framework structure seed crystals using oligomeric SDAs can be applied to other structures. For example, numerous high silica zeolites with structure types, such as BEA, ITE, CFI, and DON, can be formed using organic cation SDAs. It is believed that the charge to carbon atom ratio is a characteristic that can determine the structure directing ability of the cation. Thus, growth rate ratios for zeolites having the aforementioned structures can be manipulated by varying the charge to carbon atom ratio of the SDA. Furthermore, the size and shape of the cation can affect the dimensionality and size of the pore structure. Therefore, linking the original SDA in an oligomeric repeat motif retains the basic SDA characteristics, but can achieve two important outcomes: it can affect relative growth rates and thus modifying crystal shape and in-plane versus out-of-plane growth of seed layers; and/or it can reduce nucleation rates during synthesis. Both of these outcomes can allow formation of desirable microstructures.
Examples of organic structure directing agents that lead to various zeolite structures is provided by M. E. Davis and R. F. Lobo in �Zeolite and molecular-sieve synthesis,� Chem. Mat., 4(4):756-768 (1992) and Lobo and co-workers in �Structure-direction in zeolite synthesis,� Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, 21 (1-4):47-78 (1995).
Forming Seed Crystal Layers
Seed crystals can be formed using methods known in the art. For example, zeolite seed crystals can be formed by hydrothermal growth in a solution containing a structure directing agent, a base, an aluminum source, a silicon source, and a solvent. One example of a zeolite seed crystal formation method is disclosed by B. J. Schoeman and co-workers in J. Chem. Soc. Chem. Comm., 994 (1993). In this method, the crystals are of colloidal size (e.g., about one micron in diameter) and nearly spherical in shape. In another example, seed crystals are synthesized so that they have a well-developed coffin shape (See, e.g., S. Mintova et al., Microporous Mater., 11 (3-4): 149, 1997).
The composition, size, and shape of the seed crystals can vary depending on the desired composition of the framework layer to be formed. Typically, seed crystals are anisotropic in shape. For example, the seed crystals can be disc-like, ellipsoidal, leaf-like, plate-like, rectangular, or coffin-like. As discussed previously, seed crystals are typically formed in the presence of SDAs, which influence the seed crystal shape. For example, TPA yields a coffin-shaped MFI structure with the shortest dimension of the crystal along the b-axis, while dimer TPA with a C5 carbon chain between the N atoms yields cylindrical crystals with the largest dimension of the crystal along the b-axis, dimer TPA with C6 carbon chain between the N atoms yields leaf shaped crystals with the shortest dimension of the crystal along the a-axis and trimer-TPA yields an elongated leaf-shaped or plate-like MFI structure with the shortest dimension of the crystal along the a-axis. In another example, hexamethyleneimine as SDA yields plate-like layered silicate MCM-22(P) a precursor to microporous framework MCM-22.
In addition to TPA, other compounds that can be used as SDAs for zeolite seed crystal formation include tetraethylammonium hydroxide; diethylarnine; dimethylethylpropyl-ammonium hydroxide; tripropylamine; triethylpropylammonium hydroxide; 1,6 hexanediol; hexane 1,6-diamine; hexamethyleneimine; and pyrrolidine.
The size of the seed crystals can be selected based on the nature of the substrate surface and the method used to deposit them on the surface. Where the substrate surface is porous, for example, seed crystals are typically large enough to span the substrate pores in their preferred orientation. This minimizes seed crystals resting at an undesirable angle with respect to the substrate surface due to the pores. In some embodiments, the seed crystals can, on average, have a minimum dimension of less than about 500 nanometers (e.g., less than about 200 nanometers, such as 100 nanometers or less). Alternatively, or additionally, the seed crystals can have an average maximum dimension of more than about 200 nanometers (e.g., more than about 500 nanometers, such as 800 nanometers or more).
Optionally, the seed crystals can be calcined to remove the structure directing agent prior to being deposited on the substrate. Organic SDAs can be calcined by exposing them to temperatures of about 500� C. or more, for several hours (e.g., about 10 or more hours).
Several different strategies can be used to prepare oriented zeolite seed layers. These include slow dip coating, deposition after cationic polymer adsorption, and covalent bonding on functionalized surfaces. Slow dip coating methods are disclosed, for example, by L. C. Boudreau and M. Tsapatsis in Chem. Mater., 9:1705 (1997). J. Hedlund and co-workers have disclosed methods of deposition after cationic polymer adsorption in Microporous Mesoporous Mater., 28:185 (1999). Methods of covalent bonding on functionalized surfaces are described, for example, by K. Ha, and co-workers in Adv. Mater., 12:1614 (2000).
For seed crystals that do not easily form suspensions in an appropriate medium (e.g., water) due to, for example, their size, the method disclosed by Ha can provide good surface coverage and uniformity of the seed crystal monolayer. For example, referring to
Secondary Growth
Secondary growth of the seed crystal layer can be performed hydro-thermally by exposing the seed crystal layer to a synthesis solution under conditions at which the seed crystals can be grown into a continuous layer. A solution can be prepared for example, by following the steps described by G. Xomeritakis and co-workers in Ind. Eng. Chem. Res., 40:544 (2001). The composition of the synthesis solution can vary depending upon the particular framework material desired. In general, for zeolites the synthesis solution includes a structure directing agent, a base, an aluminum source, a silicon source, and a solvent. The solution components are usually the same as components used to form the seed crystals, although relative component concentrations can vary. The solution can contain elements other than aluminum and silicon, such as boron, phosphorous, titanium, iron.
In a particular embodiment where a layer of zeolite is to be formed, the synthesis solution preferably includes a mixture of trimer tetrapropylammonium hydroxide (trimer TPA), sodium hydroxide (NaOH), aluminum oxide (Al2O3), silica (SiO2), tetraethylorthosilicate (TEOS), and water (H2O). The trimer TPA serves as the structure directing agent, the NaOH serves as the base, the TEOS and silica serves as the silicon source, the aluminum oxide serves as the aluminum source, and the water serves as the solvent. However, various substitute components can be used for the above. As an example, instead of using trimer TPA, substitutes can include tetraethylammonium hydroxide; diethylamine; dimethylethylpropylammonium hydroxide; tripropylamine; triethylpropylammonium hydroxide; 1,6 hexanediol; hexane 1,6-diamine; and pyrrolidine; or oligomers of the above. The SDA can be the same as or different from the SDA used to form the seed crystals. Useful substitutes for the silicon source include sodium silicate, fumed silica (such as Cab-O-Sil� manufactured by Cabot Corporation, Boston, Mass.), and colloidal silica (such as Ludox� manufactured by du Pont, Wilmington, Del.). Instead of aluminum oxide, sodium aluminate or aluminum alkoxide can be used. Instead of using NaOH as the base, mineralizing agents such as potassium hydroxide (KOH), can be used, for example.
In another example, where a silicalite layer is to be formed, the solution includes SiO2, trimer TPA, KOH, H2O, and EtOH. While the relative amounts of the constituents can vary, the constituents are preferably used in the approximate molar ratios of about (20-80) SiO2, (1-10) trimer TPA, (5,000-20,000) H2O, (1-16) KOH, and (100-200) EtOH. More preferably, the molar ratios are about (40) SiO2, (5) trimer TPA, (9,500) H2O, and (160) EtOH. With a molar ratio for trimer TPA above or below about 20-80, the crystalline layer can be rough, uneven or discontinuous. Absence of KOH may lead to a rough, poorly intergrown deposit. For molar ratios above or below about 5,000-20,000 for water, the layer can become discontinuous or uneven.
Alternatively, when an a-oriented film of silicalite is desired, the secondary growth of the a-oriented seed layer may be performed using TPA or dimer TPA with C7 carbon chain between the N atoms.
For a synthesis solution without an aluminum source, such as the one described in the previous example, measured amounts of TPA and EtOH are first added to measured amounts of deionized water, and then stirred. A measured amount of SiO2 is then added dropwise while stirring. Initially, the solution may appear turbid. However, with continued stirring and addition of KOH, the solution becomes clear. The resulting synthesis solution is characterized by being substantially clear with low viscosity. It is substantially not in the form of a gel or slurry.
The seed layer on the substrate is exposed to the synthesis solution at an elevated temperature (e.g., between about 50� C. and 200� C., such as about 90� C.) by heating with a heat stage. The seed layer is exposed to the solution under at elevated temperature for a time sufficient to grow the layer of framework material to desired thickness and continuity. Although this time may vary depending on the particular chemistry, the seed layer is usually exposed to the synthesis solution for several hours (e.g., more than about five hours, eight hours, 10 hours). Alternatively, heating can be provided by microwaves. Heating by microwaves can reduce the time required to achieve the same amount of growth.
Undesirable reaction products can be removed by the addition of further reagents or other methods, such as by evaporation.
Optionally, SDA that is included in the layer of framework material during the secondary growth may be removed, e.g., by calcination. As for calcination of the seed crystals, the framework material can be heated to a temperature at which the SDA decomposes, while the framework material remains intact. For example, TPA can be calcined from a zeolite layer at temperatures of about 500� C. or more. Usually, the material is calcined in applications where a porous material is desired because the sites where the SDA molecules were incorporated typically correspond to channels in the structure.
Membranes of framework materials in accordance with the invention can be used as catalysts as well as for separating materials by contacting fluid against the membrane. Examples of mixtures that can be separated with zeolite membranes include oxygen/nitrogen, nitrogen/methane, carbon dioxide/methane, hydrogen/carbon monoxide, ethanol/water, branched hydrocarbons/straight hydrocarbons, specific types of xylene isomers/other xylene isomers, saturated/unsaturated hydrocarbons, benzene/cyclohexane, benzene/xylene isomers, concentrated biomolecules/fermentation liquors and for the purification of natural gas or flue stack effluents.
Xylene isomer separation by framework material membranes is one test for benchmarking the molecular sieving ability of these membranes. Although other separations (e.g., butane isomers) can be performed satisfactorily by defective membranes, xylene isomer separation relies on intracrystalline molecular sieving and therefore is an ideal probe of nanometer scale defects and intracrystalline transport pathways.
In some embodiments, the membranes can exhibit high para/ortho xylene selectivity and high para-xylene flux. For example, membranes made according to the methods described herein can exhibit para-xylene permeance of more than about 500�10−10 mol/m2sPa (e.g., about 800, 900, 1,000, 1,100, 1,200, 1,500�10−10 mol/m2 sPa or more) with a para/ortho separation factor of more than about 50 (e.g., about 75, 90, 100, 110, 120, 150 or more), as measured using the permeation conditions, set-up, and analysis procedure described by G. Xomeritakis and co-workers in Ind. Eng. Chem. Res., 40:544 (2001), and references cited therein.
Accordingly, in some embodiments, membranes of framework materials can be used to separate reaction products in a reactor. For example, referring to
Zeolitic membranes, for example, can also be useful in electrochemical systems, as described by D. R. Rolison, Chem. Rev., 90:867 (1990). Composite membranes containing zeolites and pressed zeolite pellets can be used in both batteries and electrodes. True continuous zeolite membrane thin films or membranes of interlocking crystals provide benefits and superior properties, compared to discontinuous zeolite membranes.
The zeolitic membranes formed by the methods disclosed herein can also be used in catalytic systems. The aluminum centers in zeolites can serve as a catalytic site. The aluminum has a net negative charge and therefore must have an associated cation. If the cation is a hydrogen ion, then the zeolite is referred to as being in the acidic form. This acidic form has been found to be very valuable in catalytic cracking as well as other hydrocarbon conversions. These include dehydrogenation, the conversion of olefins and paraffins to aromatics, the conversion of alcohols and ethers to hydrocarbons, the alkylation of aromatics, the disproportionation of toluene and the isomerization of xylenes.
The cation associated with the aluminum in the zeolite can also be a metal ion, such as sodium. Zeolites containing metal ions can carry out base catalyzed reactions. For example, such zeolites can be used to catalyze dehydrohalogenation reactions at temperatures as low as 40� C. to 50� C.
For some applications, transition metal ions such as platinum can be incorporated into the zeolite in place of hydrogen or sodium, by carrying out an ion exchange reaction. The platinum ions can be reduced to the metal form and can provide platinum agglomerates in the pores and channels of the zeolite. These metal agglomerates can serve as catalytic centers for the oxidation or reduction of organic materials. In each of these applications, acid, base and noble metal catalysis, the zeolitic membranes present a promising alternative to current technologies that use powdered zeolites in fluidized and fixed beds.
Framework membranes can also be used as protective layers. As a protective layer, it may be desirable to select a framework structure and orientation that does not provide channels that extend through the depth of the crystalline layer. Alternatively, or additionally, instead of removing the SDA from the membrane, the SDA molecules can be left in the crystal, effectively plugging the channels. As protective layers, the high degree of continuity of the framework material layer can provide films with lower permeability to undesirable materials than columnar membranes. Moreover, due to the large grain size, membranes can be more mechanically robust than those membranes where the grains do not extend through the membranes depth.
The invention is further described in the following examples, which do not limit the scope of the invention described in the claims.
Preparation of Supports
α-alumina discs of �2 millimeters in thickness and 22 millimeters in diameter were used as supports. The discs were made by pressing commercial α-alumina powders (Baikalox, CR-6, available from Baikowski Intl. Corp., Charlotte, N.C.) in a custom-made mold with the aid of a hydraulic press (Carver Model #3912, available from Carver, Inc., Wabash, Ind.) and sintered at 800� C. for about 30 hours and further at 1180� C. for about 2 hours. One side of the disc was polished by SiC sandpaper (Buehler, Grit size 600, available from Buehler, Ltd., Lake Bluff, Ill.) until no obvious scratches were observed by visual inspection under a light microscope. A scanning electron microscope (SEM) micrograph of a surface of an α-alumina support is shown in
Coating with a Mesoporous Silica Layer
The support surface was further smoothed by disposing a smooth mesoporous silica layer on top of the support by a sol-gel technique. This technique was based on the methods disclosed by Brinker and co-workers in �Continuous formation of supported cubic and hexagonal mesoporous films by sol-gel dip-coating,� Nature, 389:364 (1997). The procedure was slightly modified in the current study to apply the coating onto a porous support surface. The coating sol was prepared through a two-step hydrolysis procedure.
In the first step, 63 ml anhydrous ethanol (Fluka, 99.5%, available from Aldrich, Milwaukee, Wis.), 60 milliliters tetraethyl orthosilicate (TEOS, 98%, available from Aldrich, Milwaukee, Wis.) and 4.87 grams deionized water (DI water) were first mixed together. The pH of the mixture was adjusted to 4 by adding 0.2 milliliters 1M HCl. Then, the mixture was hydrolyzed by refluxing at 60� C. for 1.5 hours. A clear sol was obtained after hydrolysis and could be stored in the refrigerator for later use.
In the second step, 4 grams cetyltrimethylammonium bromide (CTAB surfactant, available from Aldrich, Milwaukee, Wis.) were added to 40 milliliters sol that was prepared according to the first step. The pH of the sol was adjusted to 2 by adding 7 milliliters 1M HCl under stirring. The solution was kept stirring until all surfactant was dissolved.
The sol was further aged at 50� C. for 2.5 days to increase the gelation rate so that the sol formed a continuous film on the substrate surface instead of penetrating into substrate pores. During the aging procedure, the sol polymerized and became progressively easier to gel. After the aging process was finished, the sol was diluted 256 times using anhydrous ethanol in order to decrease film thickness. The diluted sol was applied to the support surface by half immersing the support into the diluted sol with the polished side downward. After about 20 seconds, the support was horizontally slipped away and stopped in a vertical position. It was held at this position for about 40 seconds to let the solvent evaporate. Then the support was collected into a petri-dish, and immediately covered to avoid any dust contamination from the air. Finally, all silica films were calcined at 480� C. for about 4 hours with the heating and cooling rate of 1� C./min.
An SEM micrograph of a surface of an α-alumina support coated with a mesoporous silica layer is shown in
Preparation of b-oriented Seed Monolayer
Seed crystals were synthesized and a b-oriented seed crystal monolayer was deposited on top of the silica film. The seed crystals had a flat shape with approximate dimensions of 500 nanometers along the c-axis, 200 nanometers along the a-axis and 100 nanometers along the b-axis.
The seed crystals were synthesized from the mixture of DI water, tetrapropylammonium hydroxide (TPA, 1.0 M solution in water, available from Aldrich, Milwaukee, Wis.) and tetraethyl orthosilicate (TEOS, 98%, available from Aldrich, Milwaukee, Wis.). The synthesis solution was prepared by adding 30.5 grams TPA aqueous solution (1.0 M solution in water, available from Aldrich, Milwaukee, Wis.) into 240 grams deionized water (DI water). The solution was stirred for about one minute while 30 grams of TEOS (98%, Aldrich, Milwaukee, Wis.) was added to the mixture. Accordingly, the final molar composition of the synthesis solution was 5SiO2:1TPAOH:500H2O:20EtOH. The mixture was stirred at room temperature for about a day (approximately 24 hours), and was then evenly transferred to 7 TEFLON�-lined autoclaves. These autoclaves were then placed inside a rotation frame in an oven and heated to 130� C. for about 12 hours under rotation. Thereafter, the seed crystals were washed by repeated centrifugation and decanting until the pH of the seed suspension became neutral. Finally, the seed crystals were dried first at 90� C. overnight and further calcined at 525� C. for about 10 hours prior to seed layer deposition.
To covalently link seed crystals to the mesoporous silica layer surface, a silane-coupling agent, 3-chloropropyltrimethoxysilane (3CP-TMS, 97+%, available from Aldrich, Milwaukee, Wis.), was used as bridging agent. 3CP-TMS has two functional groups. One of the functional groups reacted with the support surface and the other reacted with seed crystals. Preparation of the seed crystal layer was performed in a humidity-free environment due to the water sensitivity of the bridging agent reactions. The following measures were taken to maintain humidity-free conditions: (a) all apparatus were thoroughly dried; (b) most operations were operated in a glove box filled with dry argon; (c) reactions were carried out in dry toluene; and (d) dry argon was kept flowing through the whole setup during the reactions.
To deposit seed crystals on a support surface, the support (coated with mesoporous silica layer) was first placed vertically inside a specially designed reactor using a TEFLON� holder. 40 milliliters of dry toluene (Mallinckrodt, 100%, commercially available from VWR International, Bristol, Conn.) was poured into the reactor under the flow of argon. Immediately after the toluene, 4 milliliters of 3CP-TMS were added to the toluene solution. The reactor was then closed and the mixture was heated to the boiling point of toluene (i.e., 110� C. at atmospheric pressure) under reflux. The reaction was allowed to proceed for about 3 hours. After this reaction, the silica layer surface was effectively functionalized with the silane-coupling agent, 3CP-TMS. The support was then taken out of the reactor, washed with fresh toluene, and dried at 130� C. in an oven for 20 minutes. The washing and drying procedure was done in the open air. 0.05 grams of flat seed crystals were placed in a dry reactor along with 40 milliliters of dry toluene. The reactor was sealed and sonicated using an ultrasound sonicator for 10 minutes. After sonication, the functionalized support was placed inside the reactor under the flow of argon, along with a small magnetic stir bar. During this step, the support was placed horizontally inside the reactor with the functionalized silica layer side facing up. The reactor was closed and heated to the boiling point of toluene under reflux. During the reaction, the magnetic stirring bar was rotated at 250 rpm to keep the seed suspension mixed. The reaction lasted for about 5 hours. The seeded support was then sonicated in fresh toluene for 30 seconds to remove any physically adsorbed seeds from the surface. Finally, the seeded support was dried at 90� C. first and then calcined at 450� C. for 4 hours with the heating and cooling rate of 1� C./min.
An SEM micrograph of a b-oriented seed layer is shown in
Secondary Growth
The synthesis solution for secondary growth was prepared by first dissolving 0.44 grams of potassium hydroxide (EM Science, 85%, available from VWR International, Bristol, Conn.) in 122 grams of DI water, followed by addition of 30.65 grams of trimer TPA (0.1525M in DI water). The solution was stirred for about one minute while 7.36 grams of TEOS (98%, Aldrich, Milwaukee, Wis.) was added to the mixture. Accordingly, the final molar composition of the synthesis solution was 40 SiO2:5 Trimer TPA:9500 H2O:8 KOH:160 EtOH. The mixture was stirred for another 5 hours at room temperature for hydrolysis. The mixture was then filtered into teflon-lined stainless steel autoclaves, each containing about 35 grams of the synthesis solution.
A seeded support was placed vertically inside the solution with the aid of a TEFLON� holder. The autoclave was sealed and placed into an oven that was pre-heated to 175� C. After 24 hours, the autoclave was removed from the oven and quenched with tap water. After cooling, the sample was taken out, washed with tap water first and then with DI water.
Trimer TPA was prepared by exhaustive alkylation of bis(hexamethylene)triamine (99+%, available from Aldrich, Milwaukee, Wis.)) with 1-iodopropane (99+%, also available from Aldrich, Milwaukee, Wis.) ). Approximately 450 milliliters of 2-butanone (99.5+%, HPLC grade, available from Aldrich, Milwaukee, Wis.), 72.6 grams of anhydrous potassium carbonate (99%, available from Aldrich, Milwaukee, Wis.), and 27.87 grams of triamine were added to a dry three-necked 1 liter flask equipped with a mechanical stirrer, a 60 milliliter addition funnel, and a reflux condenser. The reaction flask was then flushed with purified argon gas (99.999%, obtained from Merriam Graves, West Springfield, Mass.) and vented through a bubbler. 1-iodopropane, 101 milliliters, was transferred to the addition funnel. The reaction mixture was slowly heated to reflux (approximately 85� C.) under argon as the 1-iodopropane was added dropwise to the stirring mixture. The reaction was kept in the dark to avoid iodide oxidation. After approximately 10 hours, the warm, bright yellow reaction mixture was filtered to remove the potassium salts. 2-butanone was removed by rotary evaporation resulting in an off-white semi-solid. Cold 2-butanone was then added to the crude product and the solution was stirred for 1 hour. An equal amount of ethyl acetate (ACS Reagent, 99.5+%, from Aldrich, Milwaukee, Wis.) was slowly added to the stirring mixture. After standing for over 10 hours, the solid product was recovered from the solution by filtration. Traces of KI were separated from the product by dissolving the product in at least 200 milliliters of ethanol (pharmco, 200 proof absolute, obtained from VWR International, Bristol, Conn.). The KI was filtered and the solvent was then removed by rotary evaporation. The product was then recrystallized for a second time as described above, providing a 40 gram, 33% yield.
At this time, the solid product was checked using X-ray diffraction. Where the XRD crystal pattern for KI was detected, the procedure for KI removal and recrystallization using 2-butanone and ethyl acetate was repeated. The purity of the compound was verified using elemental analysis (C, H, N), electrospray ionization mass spectrometry (JEOL JMS700 MStation�, JEOL USA, Inc., Peabody, Mass.), and 13C-NMR (Bruker AVANCE� 400 DPX 300�, Bruker Biospin Corporation, Billerica, Mass.).
These studies showed that the resulting solid compound was in the form of trimer iodide. This was converted to hydroxide form by ion exchange. First, the solid trimer iodide was dissolved into DI water to make a 0.2 M aqueous solution. Then, 100 milliliters of the aqueous solution was mixed with approximately 15 grams of BIORAD AG� 1-X8 (20-50 mesh, commercially available from BIORAD Laboratories, Hercules, Calif.), a strong anion exchange resin in the hydroxide form. After stirring for over 10 hours, the resin was filtered from the solution and the OH− exchange efficiency was determined by standard titration with 0.0242 N HCl. This procedure was repeated twice more until the concentration of OH− in the structure-directing reagent solution remained constant.
Membrane Calcination
Finally, all membranes were calcined to remove organic SDAs. The calcination was carried out at 480� C. The calcination time depended on the membrane thickness. Usually, 10 hours or more was used for thick membranes (e.g., membranes about 10 μm or thicker) and 4 hours for thin membranes (e.g., membranes thinner than about 10 μm). Both the heating rate and the cooling rate were set to 0.5� C./min.
The steps of membrane formation through to membrane calcination are illustrated in
The porous membranes were then characterized using a variety of techniques, summarized below.
Scanning Electron Microscopy and X-Ray Diffraction
The samples were studied using scanning electron microscopy (SEM) and x-ray diffraction (XRD). Scanning electron microscopy images were taken using a JEOL 5400 Scanning Electronic operated at 15 kV. Before observation, the sample was sputter coated with a layer of gold-palladium alloy to increase conductivity. XRD data were collected using a well-aligned Philips X'Pert� diffractometer with λ(CuKα)=1.5406 Å.
Confocal Microscopy
Samples were studied using confocal microscopy. Confocal images were obtained on a Bio-Rad MRC-600/1000� confocal microscope equipped with an Ar�Kr laser with 488 nanometer, 508 nanometer, and 647 nanometer wavelengths and an oil-immersion objective lens with a numerical aperture of 0.85. Before observation, samples were immersed into fluorescent dye solution (0.1% wt fluorescein-Na in water) for about one week. Sample micrographs are shown in
Permeation experiments were carried out using the Wicke-Kallenbach mode. A detailed description of this setup and analysis procedure is described by Tsapatsis and co-workers in �Growth, microstructure, and permeation properties of supported zeolite (MFI) films and membranes prepared by secondary growth,� Chem. Eng. Sci., 54:3521 (1999). Results of the experiments are shown in
Results from experiments carried out using the Wicke-Kallenbach mode separating benzene from cyclohexane at various temperatures are shown in
It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.
Patent Citations
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health care
Objective Obamacare Info: Oakwood Hospital Hosts Seminars
The deadline to enroll for 2014 coverage is December 23.
Obamacare Key Dates In 2014
Implementation of the health reform law continues through 2014 with these key dates.
Metro Detroit Hospital Gets Germ Zapping Robots
A Metro Detroit hospital has a powerful new weapon in the war against germs.
Bill Forces Disclosure Of Law's Effect On Premiums
State legislators are sharply divided over an emerging plan to require Michigan insurance companies to tell policyholders the impact of the federal health care law on their premiums.
Sebelius: Obamacare Website Will Be Better By End Of Month
Just 1,300 state residents picked a plan in the first month, according to federal data, though Sebelius said many residents are still shopping.
Divided Mich. Senate Votes To Expand Nurses' Role
Michigan nurse practitioners and other nurses with advanced training could practice without oversight by physicians and prescribe drugs.
1,300 Michiganders So Far Enrolled In Obamacare
The state estimates at least 365,000 people could sign up on the market in 2014.
Romneycare Vs. Obamacare: Key Similarities & Differences
Can the nation expect to see the same positive results across the country as was seen in Massachusetts?
Mich. Asks Feds For Medicaid Expansion Approval
Michigan's Medicaid expansion plan needs approval because it differs from the basic option offered to states under the federal health care law.
Health On Wheels: Free Screenings In October
Wayne County's mobile health is rolling into a neighborhood near you.


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Plan Specification: HHF-4204
Total Square Footage: 1,578
Second Level: 644
Bedrooms: 1
Baths: 1
Garages: 3
Width: 39 ft Depth: 25 ft
Foundation: Slab
© copyright by designer
Plan: HHF-4204
This three-car garage plan can be an excellent addition to your existing home or built all by itself. The first floor garage plan has plenty of space including a first floor laundry room! The private second floor includes a large bedroom with a living area. The sloped ceiling along with the front dormer located in the living area adds an unexpected architectural element to the second floor.
Similar plans: 6768, 6769, 1854, 4205 More plans by this designer/architect
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bought for my daughter for her birthday. she was thrilled. i was very happy i could order it before it was released and it arrived on the day it was released. price was decent. much easier than looking for it in the store.
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Prathima Rajan
Prathima Rajan is an analyst based in Celent's Indian office. She specializes in retail banking, microfinance, rural banking and electronic payments.
Recent Stories From this Author
Bancassurance Taking Off as Distribution Channel
October 25, 2010 While many Asian consumers are staring to purchase policies from banks, the majority still prefer the personal touch of agents.
Is Bancassurance the Flavor of the Month?
August 12, 2010 Still slow to catch on in the United States, bancassurance is quickly becoming a major distribution channel in Asian markets.


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View NYCTEXASBANKER's Comments BY TICKER:
Latest | Highest rated
yes, it would take the afternoon to install in Shanghai but it might take 18 months to get the part from the States.Dec 12, 2014. 07:33 AM | 0 Likes |Link to Comment
http://1.usa.gov/P3cbtODec 11, 2014. 09:28 PM | 0 Likes |Link to Comment
LAGUARDIA IS OWNED BY THE CITY OF NY AND LEASED TO THE PORT AUTHORITY OF NY & NJ THAT IT TAKES ONLY A YEAR CONSIDER YOUR SELF LUCKY.Dec 11, 2014. 09:26 PM | 1 Like |Link to Comment
What everybody forgets is the two companies have different tax structures.
Maybe Nicholas Davout who has been filing out schedule d for 46 years might speak about how the K1 fit into sch dDec 10, 2014. 08:28 PM | 0 Likes |Link to Comment
Options that are hedges for underlining securities do not apply.Dec 8, 2014. 08:31 PM | 0 Likes |Link to Comment
club ford
Substantially identical comes into play in the non equity market securities. Bonds, Notes, derivatives and other non traditional securities.Dec 5, 2014. 09:52 PM | 0 Likes |Link to Comment
They are two different companies as defined by the SEC that what you tell the IRS auditor.Dec 5, 2014. 09:48 PM | 1 Like |Link to Comment
Why Clean Energy Fuels Looks Like A Good Bet At Its 52-Week Low [View article]
There have been trucks that ran on coal, just like we had electric trucks a 100 years ago but I doubt the EPA would approve them today.Dec 3, 2014. 03:48 PM | 0 Likes |Link to Comment
Wells Fargo In Focus [View article]
I guess your into Greek history however your knowledge of economic history is wanting. You seem to be a headline reader BANKS didn't need a bail out. Only some of the big banks needed a bail out. When less than 1%
of the number of banks needed help. I suggest you study economics, finance and statistics.
I do love your line:
Inflation doesn't affect the banks though, because they can print all the money they want, essentially making them richer.
When was the last time a commercial bank printed money?Dec 1, 2014. 10:03 AM | 2 Likes |Link to Comment
You comment
It is independent within the gov, not independent from the gov. Try again
Actually you need to try again.
The Federal Reserve System "is considered an independent central bank because its monetary policy decisions do not have to be approved by the President or anyone else in the executive or legislative branches of government, it does not receive funding appropriated by the Congress, and the terms of the members of the Board of Governors span multiple presidential and congressional terms
The federal government sets the salaries of the Board's seven governors. Nationally chartered commercial banks are required to hold stock in the Federal Reserve Bank of their region; this entitles them to elect some of the members of the board of the regional Federal Reserve Bank. Thus the Federal Reserve system has both public and private aspects The U.S. Government receives all of the system's annual profits, after a statutory dividend of 6% on member banks' capital investment is paid, and an account surplus is maintained.Nov 30, 2014. 02:51 PM | 0 Likes |Link to Comment
Microsoft Under New Assault For Tax Evasion [View article]Nov 27, 2014. 04:43 PM | 0 Likes |Link to Comment
Wells Fargo In Focus [View article]
The WFA platform is state of the art if your still back in the 1900's. There back office which is the key for good customer service is poorly trained and from my experience and two of my friends their service would not even get a f rating. Now myself and my two friends live in three different states so the only thought is they are consistently bad in customer service.Nov 27, 2014. 04:36 PM | 1 Like |Link to Comment
They do make consumer loans where have you been the last 20 years.
Why did you invest if you don't know what the companies division do?Nov 26, 2014. 07:04 PM | 1 Like |Link to Comment
GE would not be around today if the FED hadn't come to the aid of GECC
Jeff I and his merry bank of idiots was so taken by the CP market they became 82% the end of 2008.Nov 26, 2014. 07:03 PM | 1 Like |Link to Comment
Report: EPA plans to drop 2014 renewable fuel quotas [View news story]
I don't think coal will be a long term winner, because I doubt we will see a NEW coal fired plant built here. I do see it for the export market however but other nations will wise up eventually.Nov 21, 2014. 04:08 PM | 0 Likes |Link to Comment


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Slovenia Travel Guide
Articles about Slovenia
By Peter Koch
By Carren Jao
By Ingrid K. Williams
By Brooke Porter Katz
By Michael Luongo
By Scott Spencer
I may live to regret committing this piece of advice to print, but you should go to Slovenia and you should go soon, because eventually this all-but-unknown country, with its medieval villages, onion-dome spires, idealistic love of the arts, and v...
Hotels in Slovenia
After years when the only interesting lodging in town was the (admittedly rather cool) hostel converted from a former prison, Ljubljana finally has a decent hotel in the historic center.
Restaurants in Slovenia
Spajza has made is reputation on a romantic but relaxed candlelit ambience and excellent preparations of Mediterranean cuisine that range from Karst prsut (the prosciutto of Slovenia) and its signature horsemeat (try the truffled filet of horse) to fresh seafood from the Adriatic.
Things to do in Slovenia
Make a tour of the modern architectural masterworks of prodigious local talent Jo_e Plecnik, who took the Secessionists Art Nouveau style he learned in Vienna back home (via Prague) to remake his native city along his own, idiosyncratic lines.


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Feeders in RANKED?
So the last few games that i played in ranked i have gotten these kinds of people that actually troll/feed in ranked they go bottom of course and feed the other teams carry so they have an IE 10 minutes in. Riot needs to fix this problem i have lost so much elo because ONE person on my team feeds/trolls/is BAD.
must deal with it
One time a few months ago, for 11 games straight I had feeders, afkers, and/or leavers in EVERY single game.
I got an AP ashe, a jax that stacked dodge boots because he wanted to have 100% dodge all the time, etc.
I was ragging so hard in the last four games and even uninstalled the game. (next day due to not having DIABLO 3 out yet and bored to tears, I installed this game again).
I know this game was suppose to match you up in a balanced fight but sometimes I feel like riot hates me.
Don't get me wrong I'm not a super great player but at least I'm not going to rage quit on my team. When I'm good my team suucks and when I've lost my momentum and start doing badly my team gets a LITTTLE bit better.
GG TO THE KATARINA THAT STOCKED UP ON MANA POTS and Archangel Staff. Everyone yells out gg.
nice necro paShadoWn, how the hell you found this thread ? lol
Well newbs are getting worst nowadays..
This is one of the worst necros I've ever seen. Please don't necro QQ threads.
How'd I do?
For one, you replied to a necro thread with a serious question... to the OP... who opened this thread over a year ago. Think he's still around to answer the question?
Second, in this particular case, the search bar was used... by someone. How else would a year old thread make it back to the front page?
...and that'd be all fine and dandy, in fact, it'd be perfect, if there were an actual constructive discussion happening in this thread about something that players felt was still an issue today that needed constructive discussion in order to resolve the issue, or perhaps insight from a Red.
But that's not the case here. Look at the necroing post...
I mean... why? Now look at the original post...
The only thing that needs to happen to this necro thread is we all need to downvote the original post so that this thread gets locked.
|All times are GMT -8. The time now is 06:35 AM.
(c) 2008 Riot Games Inc


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Father and Son Crack Chemistry of Quasicrystals
For three decades, chemists and physicists have struggled to understand the structure of quasicrystals, particular crystals with a patterned but non-periodic structure formed by its elements. Stockholm University professor Sven Hovmöller worked for ten years on the problem without satisfying results. While others on his team moved on to other projects, Hovmöller continued his frustrating research until one day it came upon him to recruit his ten-year-old son, Linus, to help him with his work.
3-2-1, Balloons Away!
Who else held their breath as they watched Felix Baumgartner break the speed of sound on his recent epic skydive? We sure did! As my teammates and I watched his supersonic descent, my mind started to wander – what will happen to his giant balloon?
This is one
Blowing Stuff Up for Science
In case you missed it, Popular Science spent a few weeks profiling college laboratories where talented students are getting the opportunity to add to important academic research, learn about and prepare for highly skilled careers in the sciences, and, best of all, blow stuff up.
Popular Science's series "The Labs that Go Boom" features ten awesome laboratories and their work, providing an interesting look not...
Have you ever wanted to invent or create something? Making stuff is cool. I love seeing the interesting things that people dream up and construct themselves. They don't have to be big or grand to be inspiring – just innovative, creative, or plain old neat!
Here's something I came across recently that combines a cool accomplishment with a sense of sweet nostalgia – modern 3-D...
President Obama Announces 3-D Manufacturing Initiative
Last month, the Obama Administration announced the launch of a new institute in Youngstown, Ohio that will be dedicated to revitalization of American manufacturing through the emerging technology of 3-D printing.
The Department of Defense chose Youngstown to be the site of the pilot National Additive Manufacturing Institute (NAMII) and...
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GoDaddy will be leading the charge
Middle class Americans are the best at saving
Join the NASDAQ Community today and get free, instant access to portfolios, stock ratings, real-time alerts, and more!
This summer, it is raining gifts for
Time Warner Cable Inc.
) customers. This leading cable multi service operator (MSO) is
offering Dell laptops and gift cards to both existing and new
customers with selected service renovation and subscriptions.
This is part of a special promotion in association with Dell,
whereby Time Warner Cable will be giving out Dell Inspiron 11 3000
Series 2-in-1 laptops and a $100 Dell gift card to its customers.
This offer will be applicable till Oct 19, 2014.
The Dell Inspiron 11 3000 Series 2-in-1 laptop will compliment
the TV viewing experience for Time Warner Cable customers. It will
allow them to watch nearly 300 live TV channels and over 5,000 On
Demand TV shows through the TWC TV app.
For Time Warner Cable customers, the 'My Account' service
facility is also available in the Dell 2-in-1 laptop so that they
can connect to TWC WiFi hotspots.
We believe this promotional strategy will help the company
increase average revenue per user and also reduce churn rate. In
first-quarter 2014, Time Warner Cable significantly narrowed its
residential video customer loss to 34,000 from 217,000 in the
fourth-quarter of 2013. Notably, this figure marks the lowest loss
in the last five years. The company has also witnessed considerable
subscriber addition for its broadband and digital phone
Time Warner Cable currently holds a Zacks Rank #4 (Sell).
Other Stocks to Consider
Better-ranked stocks worth considering in this sector are
Comcast Corporation
Rogers Communications Inc.
) and
Charter Communications, Inc.
). All these stocks hold a Zacks Rank #2 (Buy).
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$24.95Out of Stock
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Legacy of the Dog is the finest, most comprehensive photographic guide to dog breeds ever published. The beauty and majesty of over 200 breeds are dramatically presented in more than 900 full-color images by acclaimed photographer Tetsu Yamazaki, w...
$16.99In Stock
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"I have a dog. Nothing exotic or special, just an ordinary dog. In fact, I always thought he was a boring dog. What I mean is, he can fetch, roll over, and shake hands, but mostly he sleeps and eats." Or so the little boy in this story thinks, until o...


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Nature Matters: Plenty Of Summer Activities For Kids At Hartley Nature Center In Duluth
Tuesday, Jul 5 at 4:48 PM
Summer vacation is a third of the way over and some kids are already chanting the children's mantra of "there's nothing to do." Hartley Nature Center has plenty of things for kids to do and Dave Anderson tells us about some of them in this week's "nature matters."
Park Point Third Cleanest Beach in America
Park Point Beach in Duluth is the third cleanest beach in the nation, according to the Natural Resources Defense Council. The ranking is based on frequency of water testing, and efficiency in notifying the public when the water does not meet health standards. Other top ranking beaches were in Delaware and New Hampshire.
Senator Jauch Vying for Greater Public Disclosure in Mining Legislation
HAYWARD, WI (Northland's NewsCenter) - While Gogebic Taconite waits on state legislation before starting work on a new mine in Northwest Wisconsin, Senator Bob Jauch says he's hoping new legislation puts the regulation of mining into the hands of the public.
Your Green Life: "Transportation Challenge"
In April we brought you the story of a family in Duluth who took on the challenge to cut their energy bill. In this week's "Your Green Life" Meteorologist Jeff Edmondson introduces us to a new climate idol family ready to take on the transportation challenge.
"Clean Clothes & Clean Environment"
Laundry may be on your list as one of the worst chores but if you want clean clothes it's a must–do. But clean clothes doesn't have to mean a dirty environment. In this week's "Your Green Life" Meteorologist Jeff Edmondson has a few tips to green up your weekly chore.
Stryker Bay Facelift
The Stryker Bay project to remove tar and other sediments in the bay has finally come to an end today.Jordan Weinand visited the new and improved site.
Watershed Festival at LSC
Duluth, MN (Northland's Newscenter) - Northlanders were given the opportunity today to purchase rain barrels and composters for their homes today to help fight storm water runoff.
WLSSD To Hold Rain & Compost Barrel Sale
Duluth, MN: The Western Lake Superior Sanitary District and the Regional Stormwater Protection Team will host a one-day rain barrel and backyard compost bin sale at Lake Superior College's lower east parking lot on Saturday, June 4th, from 9 am – 3 pm.
Your Green Life: "Top Green Cars, Summer 2011"
The price of gas has been like a roller coaster over the past few months. In this week's "Your Green Life" Meteorologist Jeff Edmondson takes a test drive with a few new cars which promise better gas mileage.
Your Green Life: "Spring Recycling"
You have probably heard the phrase "One's Mans Trash is Another Man's Treasure." In this Week's "Your Green Life" Meteorologist Jeff Edmondson takes a look at how to green up your spring cleaning.


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Wall panel alternative to cast iron hot water radiators?
We are thinking of replacing our cast iron hot water radiators with the "european style" flat panel radiators - primarily because the rooms are rather small, the radiators take up a lot of space and somehow end up being the focal point of the room. Looking to replace with something less obtrusive but with similar excellent heating capabilities. Was wondering if people had any experiences (good and bad) with Runtal, Myson, Veha or Buderus that could help narrow our choices. Runtal seems to be quite a bit more pricey than Veha for example so is that a reflection on the quality of the product?
Any advice would be much appreciated.
I'm not sure any of us have an answer for you. Not ignoring your post. Try the Heating forum, linked below. Hope they have an answer for you.
Here is a link that might be useful: Heating forum
Thanks emagineer,
I didn't imagine that I was being ignored :-) I think it might just be that these radiators are not so common in America so people don't have much experience with them. Thanks for your suggestion - I did post on the Heating forum but not much info there either. We will contact the Runtal people and see what we learn.
Thanks again
Runtal USA is pretty local to me so they get used quite a bit around here as an alternative to ordinary baseboard - in my previous house the plumber (plumbers mostly do the hot-water-based heating here, HVAC people are for forced hot air and AC) tried to talk me into a Runtal radiator/towel warmer for the bathroom. They just didn't have a style I liked. Buderus and Myson are also well known in the industry for good quality products; I've never heard of Veha and after getting into deep doodie with using a relatively unknown, bargain priced brand (Hudson-Reed) for the radiator/towel warmer in previous house's bathroom I'd personally stick with the big names. The bloody thing leaked nonstop and I canceled out the savings over a similar Myson by having the plumber back to tinker with it half a dozen times!