text: Light and sensitive yet incredibly strong, the Penn Bluewater Carnage 7' Saltwater Jigging Spinning Rod is designed to handle the task of pumping tuna, snappers and groupers up from the depths. This rod features a 100% graphite blank with 9 Fuji® Deep Press Hardloy line guides, and triangular EVA Torque contoured grips that fit the hand and eliminate rod twisting while under a heavy load. 1-piece design.


text:
Spontaneous Combustion YKTTW Discussion
|Spontaneous Combustion
Do We Have This?, Needs More Examples Sometimes things just set themselves on fire. There's no warning. No explanation. They're just suddenly on fire. In real life, this is normally caused by a slow build up of heat that eventually sparks and causes a fire. In fiction this occurs because sometimes things just need to be on fire. This does not include people who create fire constantly, use their powers to set themselves or others on fire on purpose, or have an aura of flames that shows up as part of a battle mode. Those are all triggered and are not by definition spontaneous. Most of the origins of this trope are crouched in Urban Legends about spontaneous human combustion. Though there are no documented cases of people combusting, there are cases of buildings doing so if the conditions are right.
Examples:Comic Books
- A Judge Dredd story centered around a person who compulsively always had to one-up anyone around him who got more attention than him. One such person who got more attention than him was someone who spontaneously burst into flames at a dinner party, "and everyone figured that was about the coolest thing ever." The jealous main character of the piece did eventually do one better and went out with a nuclear bang... but he had to expose himself to radiation and get struck by lightning to do it, after vain attempts to will himself to explode were complete faliures.
- Happened to some of the drummers on Spinal Tap
- Krook in Bleak House, possibly the fictional Ur-Example though it was known of as "really" happening at the time, which is why Dickens used it.
- The Doctor Who Virgin New Adventures novel All-Consuming Fire features what appears to be a case of spontaneous human combustion, but ultimately turns out to have been murder-by-pyrokinesis.
- One episode of Fringe explored this. People who were used in experiments involving Pyrokinesis would burst into flames and explode if they couldn't focus their attention on other things around them when their power builds up inside of them.
- The X-Files suggested this as an explanation in the first-season episode "Fire", although there turns out to be an external cause. Also suggested as an explanation in "Soft Light" and "Trevor", both of which turn out to be something weirder.
- In the Bones episode "The Foot in the Foreclosure" they find ashes of a pair of lovers; Booth suspects SHC but Brennan says it's just an Urban Legend.
- An episode of Picket Fences wrote the depressed, alcoholic mayor out of the plot by having him spontaneously combust within his own house. He already figured his political career was over, apparently making him a literal burn-out was the final blow to the character.
- The a capella group The Bobs have a song about this, called "Spontaneous Human Comubstion".
- In one episode of South Park Kenny died via Spontaneous Combustion.
Replies: 30

subset: commoncrawl


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The best-selling 42ND STREET FOREVER series of vintage theatrical trailers returns in this "adults only" XXX-TREME SPECIAL EDITION! You asked for it, you got it! This compilation includes some of the sexiest, raunchiest and downright dirtiest trailers for classic X rated movies. Watch the original theatrical advertisements for the amazing sci-fi hardcore oddity ULTRA FLESH, the surreal head-scratching "F", and the gender-bending controversial classic PASSAGE THRU PAMELA!
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NEW YORK (AP) — U.S. stock indexes are mixed in afternoon trading Tuesday, taking a pause after five straight days of gains. DuPont soared on news that its embattled CEO will retire, while biotechnology companies sank again. Energy stocks climbed as the price of crude oil rose sharply.
By Nate Raymond and Joseph Ax NEW YORK (Reuters) - U.S. authorities charged a former president of the United Nations General Assembly, a billionaire Macau real estate developer and four others on Tuesday for engaging in a wide-ranging corruption scheme. John Ashe, a former U.N. ambassador from Antigua and Barbuda who was general assembly president from 2013 to 2014, was accused in a complaint filed in federal court in New York of taking more than $1.3 million in bribes from Chinese businessmen, including developer Ng Lap Seng. Manhattan U.S. Attorney Preet Bharara, who announced the arrests of Ashe and the other defendants, said the investigation could result in more charges as authorities examine whether "corruption is business as usual at the United Nations." "If proven, today's charges will confirm that the cancer of corruption that plagues too many local and state governments infects the United Nations as well," Bharara said.


text:
|Publication number
|Publication type
|Publication date
|May 28, 1963
|Filing date
|Dec 31, 1959
|Priority date
|Dec 31, 1959
|Also published as
|Publication number
|Clifford E. Milner
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (6), Referenced by (7), Classifications (14)
|External Links: USPTO, USPTO Assignment, Espacenet
United The present invention relates to photographic elements and more particularly it relates to photographic films. Still more particularly it relates to photographic translucent print films having improved antihalation and resolution characteristics.
Photographic emulsions on translucent to opaque film supports have a wide variety of applications in the fields of cartography, transilluminated display and mural Work, drafting and chart work, and technical and sales manuals.
It has been proposed to make such films by coating a photographic emulsion on one side of a transparent film support and coating on the opposite side of the support a translucent layer containing an opaque substance and which may or may not contain an antihalation dye. It has also been proposed to prepare such films by coating on one side of a transparent film support, in order, a slow speed emulsion containing an opalescent substance such as starch or rubber latex and a fast speed silver halide emulsion. On the opposite side there may be coated a plain gelatin layer or a layer containing an antihalation dye. Both of these proposals leave much to be desired in the way of good resolution and antihalation qualities. Further, it has been proposed to coat an antihalation layer between the emulsion layer and the support. This type of structure has some very serious disadvantages. When such elements are exposed and processed, the prints resulting therefrom are often stained in an unsightly manner which results in failure to obtain the desired white background for reflection viewing. This is caused by inadequate bleaching or color destruction during processing due to the presence of the emulsion layer which re tards diffusion of treatment solutions into and out of the non-halation layer. In addition, placing antihalation material in a layer contiguous with the silver halide layer often aifects the sensitometric characteristics by producing fog. Another proposal has been to coat a white water-resistant support with a silver halide emulsion on one side and tinted layer on the opposite side. An alternative method is to coat a tinted support with a white pigment coating on top of which there is coated a silver halide emulsion. These latter elements are also deficient in providing satisfactory resoution and antihalation qualities.
An object of this invention is to provide improved translucent photographic print films. Another object is to provide such films which have improved antihalation and resolution characteristics. Yet another object is to provide such films which are relatively simple in construction and embody commercially available and economical antihalation materials and pigments. A further object is to provide such films which do not produce objectionable stain when the exposed films are developed and fixed. A still further object is to provide such films which can be made by the use of conventional mixing and coating apparatus. Still further objects will be apparent from the following description of the invention.
The photographic elements of the present invention have (1) a transparent hydrophobic copolymer film base, (2) a translucent layer on one side of the base comprising dispersed finely divided particles of an inert inorganic white pigment having an average particle size in the range 0.1 to 2.0 microns in a water-permeable macromolecular atent ice organic colloid of high molecular weight as a binding agent, (3) a photographic silver halide emulsion layer on the translucent layer and on the other surface of the base (4) an antihalation layer comprising a binding agent, colloidal antihalation material, e.g., a dye or pigment, and finely divided particles of a white pigment is described for the translucent layer.
In general, the white pigment is present in an amount from 1.5 to 3.0 parts by weight per part of binding agent. The antihalation dye or pigment in general will be colloidal (in the range of 1 to 100 millimicrons) in their largest diameter. The amount of antihalation material present is that used in conventional antihalation layers and in general comprises 0.05 to 0.10 part per part of binding agent.
The support may be any conventional transparent hydrophobic film such as cellulose esters, e.g., cellulose acetate, cellulose nitrate, cellulose butyrate, cellulose mixed esters; vinyl polymers, e.g., polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrenes and copolymers thereof; polyamides, e.g., polypentamethylene sebacamide, polyhexamethylene sebacamide, polypentamethylene suberamide, polydecamethylene adipamide and superpolyesters, e.g., a highly polymeric linear polyester of a dicarboxylic acid with a dihydric alcohol. A prefered type of support comprises a polyester film as disclosed in Whinfield et al. US. 2,465,319 bearing a thin layer of an adherent film-forming essentially hydrophobic copolymer made and coated in the manner taught by Alles et al., U.S. Patent 2,627,088, and Alles, US. Patent 2,779,684, and patents referred to in the specifications of these patents. A film made according to Example IV of Alles US. Patent 2,779,684 which may or may not be coated with a thin gelatin substratum is coated on one surface with an aqueous gelatin dispersion comprising from about 30 to 50% of gelatin and from about 50 to of titanium dioxide based on total dry weight to give a layer having a dry coating weight of about 10mg./dm. of gelatin. Over this layer, any suitable light-sensitive layer may be coated. Gelatino-silver halide emulsions are preferred, however. For example, the variable gamma gelatino-silver halide emulsions dislcosed in Potter et al. US. Patent 2,280,300 have been found to be particularly useful. The type of light-sensitive layer will, however, depend on the manner in which the novel film elements are to be used. On the opposite side of the film there is coated an aqueous gelatin dispersion containing from about 50 to 70% of titanium dioxide and from about .25 to 10% of colloidal manganese dioxide. The layer is coated and dried in a conventional manner to give a dry weight about 70 mg./dm. of gelatin. To increase the utility of the novel film, delustering or matting agents, i.e., silica, starch, etc., may be added to the molten gelatino-silver halide emulsion as a final addition before coating to form a retouchable or drawing surface on the emulsion side of the film. For example, the highly porous siliceous compounds disclosed in Webster US. Patent 2,626,867 are suitable for this purpose.
Titanium dioxides of various crystalline forms may be used as the white pigment, however, the rutile crystalline form is preferred because of its greater hiding power (greater opacity for a given weight). Other white pigments such as barium sulfate can also be used. Likewise, while colloidal manganese dioxide is preferred as the bleachable non-halation coloring component, other bleachable non-halation dyes or pigments, i.e., Aur-amine (C. 1.655), Acid Blue Black (C. 1.246) and Nigrosine (C. 1.864) may be used. Other ingredients for various purposes may be added to any one or all of the layers. For example, so-called optical brightener, i.e., compounds which fluoresce under the influence of visible radiation to increase the brightness of the layers, may be added to the molten gelatino-silver halide emulsion, to the aqueous gelatin-titanium dioxide dispersion and/or to the aqueous gelatin-titanium dioxide-manganese dioxide dispersion as a final addition before coating.
The invention will now be illustrated in and by the following examples, but is not intended to be limited thereby.
Example I A dimensionally stable vinylidine chloride/methyl acrylate/itaconic acid copolymer-coated polyethylene terephthalate film made as described in Example IV of -Alles US. Patent 2,779,684 Was coated on one surface with an aqueous dispersion containing 3.5% gelatin and 7.0% of rutile'crystalline titanium dioxide (Du Pont Ti- Pure R-1-00) based on the total weight and to which had been added a small amount of an alkyl naphthalene sulfonate Wetting agent and a small amount of a bis-triazinostilbene compound as an optical brightening agent. The dispersion was coated at 56 feet per minute to give a dry gelatin coating weight of -mg./dm. Over this layer, there was coated a high speed variable contrast silver iodo-bromide emulsion containing 3% iodide and the rest being silver bromide and 73% gelatin based on total weight of dry solids. The emulsion was coated and dried in a conventional manner. The emulsion was made in the manner described in 'Potter et al. U.S. Patent 2,280,300 and contained 0.12 gram/gram of dry gelatin of highly porous S10 as a matting agent to provide a retouchable surface. There was also added to the molten emulsion before coating a small amount of the above optical brightening agent and 140 mg./mole silver halide of benzotriazole as an antifoggant. The dry coating weight was 33 mg./dm. of silver halide expressed as AgNO On the opposite side of the film there was coated an aqueous dispersion containing 6% gelatin, 12% rutile crystalline titanium dioxide, and 0.4% colloidal manganese dioxide. This aqueous dispersion was coated to give a dry gelatin coating weight of 70 mg./dm.
The resulting photographic film element was exposed by conventional projection enlarging equipment. The
exposed film was developed for 1 /2 minutes at 20 C.
in'a developer having the following composition:
Grams p-Methylaminophenol sulfate 2.5 Hydroquinone 10.0 Sodium sulfite (anhydrous) 37.5 Sodium carbonate, monohydrated 44.0 Potassium bromide 5.0
Water to make 1 liter.
The above developer .was used by diluting with two parts of water. The film was then fixed in a photographic fixer having the following composition:
Sodium thiosulfate grams 240.0 Sodium sulfite, anhydrous do 15.0 'Glacial'acetic acid ml. 47.0 Potassium aluminum sulfate grams 15.0
Water to make 1.0 liter.
ing the film elements for halation, they were exposed behind a neutral wedge with a density range of 0 to 7 over a length of 12 cm. and a mask with a 1 mm. slit with clean cut-edges parallel to theslope of the wedge. Sufficient exposure was given to cause inversion of the image by solaiization under the lightest part of the wedge. At this level of exposure the image of the slit is bordered on either side, at a distance which depends on the thickness of the film support, by two bands due to halation. The efiiciency of antihalation protection can be measured as the ratio of the exposures corresponding respectively to the threshold of halation and the threshold of blackening of the bands.
The resolution was determined by the method outlined in National Bureau of Standards Circular C248, A Test of Lens Resolution for the Photographer.
Opacity was determined as the transmission density to blue light. The measurements below show the comparison of the novel films of the inventions with known structures.
Reso- Anti- Backing Underlayer Opacity lution hala- Stain tion 1. White+bleach- White-l-bleach- 1.10 122. 44 Bad.
able color. able color. 2. White-l-bleach- White 1.10 107 40 None.
able col do 1.10 137 27 Do.
White+bleach-- 1.10 137 36 Bad.
ab color. 5. Single weight paper base 1.30 77 50 Good.
1 The larger the number, the better the antihalation characteristics.
Example I] Example I was repeated except that in place of the variable contrast silver iodo-bromide emulsion of that examplethere was coated a gelatino-silver chlorobromide emulsion. The emulsion contained about 34% silver chloride and the rest silver bromide. The .emulsioncont ained a delustrant-as a matting agent to provide a retouchable surface as is conventional in the art. The dry coating had a weightof 22 mg./dm. of silver-halide expressed as AgNO The backing was coated to a dry weight of v mg./dm. of gelatin (instead of 70 mg./dm; The resulting film had similar characteristics to the film of Example 1. Because of the warm image color and response to direct toning, the product was particularly suited to portrait and photomini-ature application requiring special effects.
Example III Example I was repeated except that in place of the emulsion of that example, there was coated a high contrast contact speed bromochloride emulsion containing 30% silver bromide and 70% silver chloride. The dry coating weight was 22 mg./dm. of silver halide expressed as AgNO The backing was coated to a weight of 40 mg/drn. of gelatin. A planar, non-curling film was obtained whichwas exposed in a conventionalcontact printer for 20 seconds at 15 feet using a single 50 ampere arc lamp. The film was developed for 2 /2 minutes at.20 C. in a developer having the following composition Grams .p-Methylaminophenol sulfate 1.5 Hydroquinone 6.0 Sodium sulfite, anhydrous 19.5 Sodium carbonate, monohydrated 28.0 Potassium bromide 0.8
Water to make 1.0 liter.
The film was then fixed for ten minutes in the fixing composition set forth in Example I. The film showed excellent sensitometric resolution and non-halation characteristics.
Example IV Example I was repeated except that-in place of the silver halide emulsion of that example, there was coated a high contrast direct positive silver chloride emulsion to a dry weight of 35 rng./dm. of silver halide expressed as AgNO The film was exposed through an amber filter to a high intensity mercury vapor lamp. The exposed film was developed for one minute in the developer described in Example '1 but diluted 1:1 with water. The film was fixed for 10 minutes in the fixing composition described in Example I. The resulting direct positive image showed good resolution and non-halation characteristics.
Other emulsions such as cold tone projection and contact speed emulsions may also be coated on the novel film structures to advantage.
All or a portion of the gelatin for the various layers may be replaced by other water-permeable colloids. For example, natural or synthetic, essentially hydirophilic polymers may be used to form the aqueous dispersions. Casein, albumin, interpolyamides, agar-agar, polyvinyl alcohol, polyacrylamides and polyvinylacetals may be used. In addition, certain other polymers or polymer mixtures such as polyvinyl-N-vinyllactams, butadiene-acrylonitrile copolymers, vinyl acetate-vinyl stearate copolymers, styrene-butadiene copolymers, alkyd and acrylic resins may be used in combination with gelatin.
Supports other than those mentioned above are polyethylene terephthalate/isophthalate of the British Patent 766,290 and Canadian 562,672 and those obtainable by condensing terephthalic acid or dimethylterephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane-1,4-dimethanol (hexadydro-p-xylene alcohol).
Other bleachable coloring materials may be used in place of colloidal manganese dioxide although it is preferred because of its greater stability under adverse storage conditionings. For example, the coloring materials disclosed in Baldsiefen, US. Patent 2,203,7 67 may be used.
Other white pigments may be used in place of the rutile crystalline titanium dioxide mentioned above, e.g., barium sulfate, calcium sulfate and zinc oxide.
The unexpected and advantageous result is that the antihalation and resolution characteristics of the novel structure are surprisingly good. The following is a comparison of the characteristics of prior art structures with those of the novel structures of the instant case.
Sensito- Backing Under layer Anti- Stain metric Halation Compati bility White-i-bleachable White+bleach- Good.... Bad... Poor.
color. able color.
Do Whflite pigment --do.--. None Good.
y. White only. White only P0or.... .do Do. Do White bleach- .--do Bad-.- Poor.
able color.
photographs, commercial displays, murals, education devices, etc.
For all applications, the planar, non-curling characteristics offer superior advantages over paper based products. For example, because of the durability of the films of the instant invention they are especially applicable to making sales manuals and instruction charts, etc.
In addition, because of the superior dimensional stability of the novel films they are especially useful in the field of aerial mapping and general survey mapping.
For transilluminated displays, a striking effect can be achieved by coloring only the side opposite the silver halide emulsion layer with appropriate colors. With reflection lighting only, the print appears black and white, but with transmission lighting the image appears in color. In this application, non-penetrating coloring matters are most suitable.
What is claimed is:
1. A translucent photographic print film comprising (1) transparent hydrophobic copolymer film base,
(2) a translucent layer on one surface of the base comprising dispersed finely divided particles of an inert inorganic white pigment having an average particle size in the range 0.1 to 2.0 microns in a waterpermeable macromolecular organic colloid of high molecular weight as a binding agent, there being 30 to 50%, by weight, of colloid and 50 to by weight, of said pigment,
(3) a photographic silver halide emulsion layer on the translucent layer, and on the other surface of the base (4) an antihalation layer comprising a water-permeable colloid binding agent, bleachable colloidal antihalation material and finely divided particles of the white pigment and having the particle size defiined in layer (2), said antihalation layer having a coating weight of 40 to mg. per sq. dm. of colloid, there being present about 50 to 70% of the white pigment and about 0.25 to 10% of the antihalation material, based on the colloid.
2. An element according to claim 1 wherein said pigment is titanium dioxide.
3. An element according to claim 1 wherein said pigment is titanium dioxide, the binding agent is gelatin and layer (2) has a coating weight of about 10 mg. per sq. dm. of gelatin.
4. A photographic print film as set forth in claim 1 wherein said colloid binding agent in each of layers (2) and (3) is gelatin.
5. A photographic print film as set forth in claim 1 wherein said antihalation material is manganese dioxide.
6. A photographic print film as set forth in claim 1 wherein said emulsion layer is a gelatino silver iodobromide emulsion layer.
References Cited in the file of this patent UNITED STATES PATENTS 1,597,727 De Sperati Aug. 31, 1926 1,631,421 Lohofer June 7, 1927 2,095,018 Wilmanns et a1. Oct. 5, 1937 2,313,570 Nadeau et al Mar. 9, 1943 2,698,235 Swindells Dec. 28, 1954 2,773,769 Goldschein Dec. 11, 1956
|Cited Patent
|Filing date
|Publication date
|Oct 19, 1923
|Aug 31, 1926
|Ig Farbenindustrie Ag
|Nov 3, 1923
|Jun 7, 1927
|Ig Farbenindustrie Ag
|Photographic film
|Oct 1, 1934
|Oct 5, 1937
|Agfa Ansco Corp
|Manufacture of antihalation layers
|Sep 25, 1940
|Mar 9, 1943
|Eastman Kodak Co
|Photographic layer capable of receiving writing
|Mar 16, 1950
|Dec 28, 1954
|Du Pont
|Photographic elements
|Jan 29, 1953
|Dec 11, 1956
|Goldschein Max H
|Instant drying photostat
|Citing Patent
|Filing date
|Publication date
|Mar 10, 1967
|Dec 10, 1968
|Polaroid Corp
|Novel photographic products and processes
|Sep 26, 1977
|Mar 13, 1979
|Agfa-Gevaert N.V.
|Photographic material for use in the silver complex diffusion transfer process
|Oct 3, 1978
|Sep 23, 1980
|Agfa-Gevaert N.V.
|Photographic material for use in the silver complex diffusion transfer process
|Sep 4, 1992
|Oct 12, 1993
|Eastman Kodak Company
|Photographic paper
|Aug 12, 1992
|Feb 22, 1994
|Hoechst Celanese Corporation
|Composite black and white substrate for color proofing films
|Jul 15, 1993
|Apr 5, 1994
|Eastman Kodak Company
|Photographic paper
|Nov 23, 1993
|Nov 1, 1994
|Hoechst Celanese Corporation
|Composite black and white substrate for color proofing films
|U.S. Classification
|430/510, 430/531, 428/323, 40/615, 430/517, 430/536, 430/950
|International Classification
|Cooperative Classification
|European Classification


text:
- Ticketmaster Reverses All-In Pricing Policy
- Ticketmaster Reverses All-In Pricing Policy
- Bitcoin and Ticketing: A Perfect Match?
- Donate to the Wounded Warrior Project and catch a ball game
- StubHub reverses course with "All In Pricing". Is preloaded ticketing soon to follow?
- New College Athletic Ticket Sales Group Completes First Annual Conference in Orlando
- Another NFL Team Cedes to Ticket Broker Lawsuit Pressure
- Warriors Score Big on Playoff Ticket Prices
- Lightning to Tampa Army captain – "You can sell your Stanley Cup tickets, but only to whom we approve"
- It's open season on the Secondary Ticket Market!
Toronto Maple Leafs tickets are NHL's most expensive
The Toronto Maple Leafs have the most expensive tickets in the National Hockey League, according to the latest numbers from Team Marketing Report (TMR).
The average cost of a non-premium Leafs ticket for the 2011-2012 season is $123.77 — the same amount as last season, but enough to lead the league for a second year in row. For the entire NHL, the average price of a non-premium ticket this season is $57.10, up 4.8 percent over last season.
The Winnipeg Jets, formerly the Atlanta Thrashers, have the league's second-highest average ticket price at $98.27. Rounding out the top five are the Montreal Canadiens ($88.67); the Edmonton Oilers ($70.13); and the Vancouver Canucks ($68.38). All prices are listed in U.S. dollars.
The team with the lowest average ticket price was the Dallas Stars ($29.95).
While the Maple Leafs did not see an increase in its average ticket price this season, the remaining four teams in the top five saw increases from last season to this season. Overall, 19 of the league's 30 teams saw average prices rise for 2011-2012.
The average cost for a family of four to attend a Leafs game is tops in the league, too, according to TMR. Under its Fan Cost Index — which looks at the combined cost of tickets, concession food, parking and souvenirs — the cost is $626.45, an increase of 1.3 percent this season.
The strengthening Canadian economy was the main reason for the increases among the top five teams, as more fans looked to attend games. Additionally, the league appears to benefiting from the excitement surrounding the Jets' return to Winnipeg.
Overall, the NHL is also receiving a bump from the continuing National Basketball Association lockout. In several cities, NHL and NBA teams share an arena.
"NHL [tickets] are moving great," Max Waisvisz, owner of Chicago-based Gold Coast Tickets, told TicketNews at the start of the season. "I think [the lockout] is going to help hockey 1,000 percent. People still want that event to go to."


text:
One Tree Hill News
One Tree Hill is returning for an eighth season. What will these new episodes focus on? The CW has revealed a lot in a recent press release.
Posted in: Spoilers
One Tree Hill Season Finale Clip: Going to Utah!
It's off to Utah for the characters on One Tree Hill next week. How will this show end its season? Tune in. Find out.
One Tree Hill Music: "What's In The Ground Belongs To You"
As we head into next week's One Tree Hill season finale, let's take a look back. We've collected the songs played on last night's episode, "What's In The Ground Belongs To You."
One Tree Hill Season Finale Preview
One Tree Hill airs its seventh season finale on Monday, May 17. Let's all just hope this isn't a series finale.
One Tree Hill Sneak Peek: A Surprise for Clay
One Tree Hill airs a new episode on Monday, May 10, 2010. In this clip from "What's In The Ground Belongs to You," Clay walks in to find an unwelcome guest in his house.
One Tree Hill Music, Quotes and New Promo
Another episode of One Tree Hill has come and gone. We've collected the latest music from the show and are also here to preview next week's installment.
One Tree Hill Clip: Naked Julian!!
One Tree Hill airs a new episode next week. You should really watch this sneak peek at it. Why? Julian is naked in it!
One Tree Hill Music: "Every Picture Tells a Story"
It's been far too long since we were treated to a new episode of One Tree Hill. This week's edition featured a number of hit singles.


text:
Adilibria brings Girl Power to the races
In Autumn/Winter 2006 adidas Women presents a unique women's collection offering high-quality sport performance products that underline the fusion of performance and design: Adilibria. The line is a complete range of women's apparel, footwear and accessories covering five different sports categories: Gym, Running, Yoga, Tennis and Swim. Supported by the adidas Women's ambassador team of world-class athletes such as Elena Isinbayeva, Allyson Felix, Ana Ivanovic and Gro Hammerseng, the collection is recognizable by the golden adidas Sport Performance trim.
Designed to encourage women to believe in their "Power from within" and find strength while concentrating on their wellbeing and themselves, the Adilibria collection focuses strongly on details and on combining unexpected features both in shapes and colours. Very soft non-sporty tones plus stylish and voluminous silhouettes are fully integrated in highly functional sport products.
The unique collection mirrors lightweight and fluent fabrics as well as fresh material mixes that assure comfort, breathability and extreme freedom of movement. Engineered constructions, Lycra additions and a variety of high-end technologies such as ClimaCool and ClimaWarm provide heat and moisture management through ventilation as well as thermal insulation in cold weather conditions. In addition, ClimaLite features soft, lightweight fabric for superior moisture management while ForMotion ensures enhanced power of movement and performance.
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text:
557 Rte 23 S
(973) 305-4805
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21 reviews
Moving to or from Wayne, NJ, 07470? Get FREE truck rental rate quotes at Wayne Storage. U-Haul rental trucks are specifically engineered from the ground up to assist moving families, not freight. Our moving trucks have more safety features than other moving trucks in the industry including gentle ride suspension and high visibility mirrors to assist the driver. Whether you are moving a smaller apartment or a large four-bedroom house, U-Haul truck rentals in Wayne, NJ will provide you with the moving truck rental you need to get from point A to point B. Find the perfect size moving truck to assist with your move, U-Haul is home of the $19.95 rental truck!
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U-Haul cargo van rentals and pickup trucks in Wayne, NJ are perfect for home improvement projects, deliveries and other small loads. Rent cargo vans or pickups to save money on local moving or deliveries. Cargo van and pickup truck rentals are popular with local business, college students and smaller housing moves in Wayne, NJ, 07470. Our moving van rentals include air conditioning, rub rails to protect your belongings and come equipped with a hitch to tow a trailer rental. U-Haul is the home of the $19.95 cargo van rental in Wayne, NJ, reserve a van for your moving needs from Wayne Storage!
This drop off was different than on my contract and I was not aware of the change. UHaul emailed me but I had no email avaiilability and I initially went with what was on the contract.
He came in on a Sunday for me even though he was closed on Sundays. He was very helpful and explained everything clearly. I'm very happy with this location.
Steve took the time to research other locations so I could get the right size truck and the time I needed it for... thank you.
The personnel in Wayne were okay, but were surprised by my call to confirm pickup for the following day. I asked for pickup 5 minutes from home on a Saturday afternoon and ended up with pickup 40 minutes away that had to be done by 7:30 a.m. If I knew when I made the reservation, that would be fine, but to find out later was not well handled by U-Haul reservations.
Never received additional items ordered (cart, blankets). Had to go to another Uhaul for one item...then I did not realize there were no blankets..to late. Had to pack truck without them ruined my furniture. Then I took back unused boxes still never received credit back. Then when I got to drop off location had to wait an hour because they had to clear why I had no blankets to return. Crazy and no excuse.
The rates surprise me
Location a little difficult to get to, staff/owners very nice and accomodating. Rented a 9' cargo van that had less than 3,000 miles on it and it was very comfortable and easy to drive. Had no problem picking it up or dropping it off. Would and most likely will rent from them again!
Had to sign a contract saying the tank was a quarter full before even been shown it was a quarter full, it was empty and had to fill it up. Was told the tank was 80 gallons and it needed to be a quarter full so I get 20 gallons, turns out 20 gallons is the size of the tank so I filled it up without making any dent in it and despite being lied to about it I won't get my money back for the gas because it's in the contract. Would never use u-haul again
Our customer service agent, Ryan, was absolutely the best! He went above and beyond the call of duty to meet our needs and exceeded our expectations. He is truly an asset to your organization.
Difficult access from the road, service was excellent and rent went uneventful
Excellent service. Steve made it very easy for me, took the equipment back without me waiting and emailed my receipt.
doing check-in online was simple and easy for the reservation , unless you want to deliver the trailer to my home also the system works fine .
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To reserve by phone, call 1-800-GO-UHAUL (1-800-468-4285)


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Tata Indica TDi: Pregnancy test
Go further in an Indica TDi.
Over 550 kilometres on a 37 litre tank.
Agency: Black River Football Club, South Africa
Writers: Khaya Dlanga, Mahle Kwababa
Art Director, Tefo Modisi
CD: Ahmed Tilly
10 comments
The piece's have nice use of white-space allowing the reader to create a punch line for themselves, lending to individual perspective.
-- Has the guy seen the test and feels the need to run?
-- Has the female just seen the test and realizes her life is about to change completely. new responsibilities that will effect her everyday. ie. many doctors visits, nutritionists, lamaze classes, baby clothes, food, diapers, ext.
It really doesn't matter if the original punch line is missed as long as the reader replaces it with one of their own, and the point is made;
"the car will go farther on less fuel".
I think its a good definition of a copy minimalist campaign.


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Performs exactly as described. I tried others, but this is simple, does what it says and there were zero issues. If I could hit 10 stars, I would. Definitely worth installing and trying out if you are looking to control how your categories are displayed.
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Works perfect!
I'm in Framework environment, everything it's ok
No problems...works as advertised.
Tried two others that were a bit confusing. This is simple and work great.
I dont know why this gets so many positive reviews, it doesnt work and I have the same issue as another poster from 5 months ago and they still dont have a solution!! Not much in the way of support clearly.
Works perfectly! Easy to use!
Nice and clean plugin. Just works!
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text:
'A Fool for Going to the War'
Kelly, Patrick J., VFW Magazine
Sanitary Commission Seeks Jobs for Vets
At a time when unemployment has hit record-high levels among recent war vets, it is instructive to consider the plight of Union vets in 1865-66 and see how one private agency-the U.S. Sanitary Commission-tackled the problem nearly 150 years ago.
"The United States Sanitary Commission (USSC)T wrote George R Fredrickson in The Inner Civil War, "was the largest, most powerful, and most highly organized philanthropic activity that had ever been seen in America." In some respects, it was the equivalent of a private forerunner of the VA.
President Abraham Lincoln signed legislation on June 18, 1861, creating the USSC as an official government agency (though it was privately run and funded). During the war, it operated 30 soldiers' homes, lodges or rest stops for disabled and transient Union soldiers. Its backbone was always the women volunteers who ran the USSC locally.
For a time after the war, it assisted Union vets in securing bounties, back pay and applying for pensions. Perhaps its least-known role was beating the drums among businesses for hiring veterans as valued employees.
In its network of temporary soldiers' homes, the USSC provided food, medical care and shelter to soldiers in transit, arranged for their safe transportation home and offered advice to ex-soldiers trapped in a maze of government paperwork.
Despite the best efforts of it and other of the North's voluntary associations, however, the rapid disbanding of the Union Army generated many painful individual dislocations.
Healthy veterans discovered that finding employment in the months following the Civil War was far from easy. Obtaining work was doubly difficult for war-disabled Union vets. Casual labor required a great deal of physical stamina and was a difficult, if not impossible, form of employment for men physically disabled by injury and disease.
Yet many disabled servicemen lacked the skills and education required for the physically less demanding white collar work - clerking, accounting, teaching or operating a telegraph. The economic outlook for unskilled veterans suffering from disabilities was, in short, bleak.
Desperate Circumstances
Forced into desperate circumstances, a number of veterans turned to begging. The sight of veterans with disabilities appealing for money on city streets, as well as on ferries and trains, became depressingly familiar in the years following the war.
In August 1865, Philadelphia's Public Ledger noted, "Quite a number of men in soldiers' clothes have made their appearance in our crowded thoroughfares, who, with arms in slings and support on crutches, hold out their hands to the passers for alms."
Early the following winter, a letter from a Union veteran to the New York Tribune reported: "I notice in passing through the streets of this great metropolis hundreds, aye, I might say thousands, of maimed soldiers, some with a leg or arm off, asking for alms. What attention is paid to them? I answer, none whatever; they are passed by in contempt. I do not mean to say by all, but by the majority.
"Answer, O ye wealthy, who roll by through the thoroughfares in your carriages, is this the way you treat those who have fought and endured all the hardships while you have been at your own firesides enjoying the sweets of this life?"
Attempting to scratch out a living, some of the war-disabled worked as crossing sweepers, while others strolled through the streets playing hurdy-gurdies (barrel organs).
Some private businesses attempted to assist war-disabled veterans and turn a profit at the same time. The Soldiers and Sailors Publishing Company printed a number of histories of the war and hired ex-servicemen with missing limbs to peddle these books.
Ex- soldiers, eager to play on public sympathy and profit from their wartime experience, wrote and published pamphlets with titles such as The Empty Sleeve and The Great War Relic. …


text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 13, 2004
|Filing date
|Sep 5, 2001
|Priority date
|Sep 5, 2001
|Fee status
|Also published as
|Publication number
|Steven M. Kuznicki, Richard M. Jacubinas
|Original Assignee
|Engelhard Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (14), Non-Patent Citations (3), Referenced by (4), Classifications (11), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to novel rare earth silicate molecular sieve compositions and to methods for the preparation thereof. More particularly, the invention is directed to high temperature stable molecular sieves constructed predominantly from chains of octahedrally coordinated rare earth lanthanides and actinides with tetrahedral bridging units such as from silicon.
Since the discovery by Milton and coworkers (U.S. Pat. Nos. 2,882,243 and 2,882,244) in the late 1950's that aluminosilicate systems could be induced to form uniformly porous, internally charged crystals, analogous to molecular sieve zeolites found in nature, the properties of synthetic aluminosilicate zeolite molecular sieves have formed the basis of numerous commercially important catalytic, adsorptive and ion-exchange applications. This high degree of utility is the result of a unique combination of high surface area and uniform porosity dictated by the "framework" structure of the zeolite crystals coupled with the electrostatically charged sites induced by tetrahedrally coordinated Al+3. Thus, a large number of "active" charged sites are readily accessible to molecules of the proper size and geometry for adsorptive or catalytic interactions. Further, since charge-compensating cations are electrostatically and not covalently bound to the aluminosilicate framework, they are generally base exchangeable for other cations with different inherent properties. This offers wide latitude for modification of active sites whereby specific adsorbents and catalysts can be tailor-made for a given utility.
In the publication "Zeolite Molecular Sieves", Chapter 2, 1974, D. W. Breck hypothesized that perhaps 1,000 aluminosilicate zeolite framework structures are theoretically possible, but to date only approximately 150 have been identified. While compositional nuances have been described in publications such as U.S. Pat. Nos. 4,524,055; 4,603,040; and 4,606,899, totally new aluminosilicate framework structures are being discovered at a negligible rate.
With slow progress in the discovery of new aluminosilicate based molecular sieves, researchers have taken various approaches to replace aluminum or silicon in zeolite synthesis in the hope of generating either new zeolite-like framework structures or inducing the formation of qualitatively different active sites than are available in analogous aluminosilicate based materials.
It has been believed for a generation that phosphorus could be incorporated, to varying degrees, in a zeolite type aluminosilicate framework. In the more recent past (JACS 104, pp. 1146 (1982); proceedings of the 7th International Zeolite Conference, pp. 103-112, 1986) E. M. Flanigan and coworkers have demonstrated the preparation of pure aluminophosphate based molecular sieves of a wide variety of structures. However, the site inducing Al+3 is essentially neutralized by the P+5, imparting a +1 charge to the framework. Thus, while a new class of "molecular sieves" was created, they are not zeolites in the fundamental sense since they lack "active" charged sites.
Realizing this inherent utility limiting deficiency, for the past few years the research community has emphasized the synthesis of mixed aluminosilicate-metal oxide and mixed aluminophosphate-metal oxide framework systems. While this approach to overcoming the slow progress in aluminosilicate zeolite synthesis has generated approximately 200 new compositions, all of them suffer either from the site removing effect of incorporated P+5 or the site diluting effect of incorporating effectively neutral tetrahedral +4 metal into an aluminosilicate framework. As a result, extensive research in the research community has failed to demonstrate significant utility for any of these materials.
A series of zeolite-like "framework" silicates have been synthesized, some of which have larger uniform pores than are observed for aluminosilicate zeolites. (W. M. Meier, Proceedings of the 7th International Zeolite Conference, pp. 13-22 (1986)). While this particular synthesis approach produces materials which, by definition, totally lack active, charged sites, back implantation after synthesis would not appear out of the question although little work appears in the open literature on this topic.
Another and most straightforward means of potentially generating new structures or qualitatively different sites than those induced by aluminum would be the direct substitution of some charge inducing species for aluminum in a zeolite-like structure. To date the most notably successful example of this approach appears to be boron in the case of ZSM-5 analogs, although iron has also been claimed in similar materials. (EPA 68,796 (1983), Taramasso, et. al.; Proceedings of the 5th International Zeolite Conference; pp. 40-48 (1980)); J. W. Ball, et. al.; Proceedings of the 7th International Zeolite Conference; pp. 137-144 (1986); U.S. Pat. No. 4,280,305 to Kouenhowen, et. al. Unfortunately, the low levels of incorporation of the species substituting for aluminum usually leaves doubt if the species are occluded or framework incorporated.
In 1967, Young in U.S. Pat. No. 3,329,481 reported that the synthesis of charge bearing (exchangeable) titanium silicates under conditions similar to aluminosilicate zeolite formation was possible if the titanium was present as a "critical reagent" +III peroxo species. While these materials were called "titanium zeolites" no evidence was presented beyond some questionable X-ray diffraction (XRD) patterns and his claim has generally been dismissed by the zeolite research community. (D. W. Breck, Zeolite Molecular Sieves, p. 322 (1974); R. M. Barrer, Hydrothermal Chemistry of Zeolites, p. 293 (1982); G. Perego, et. al., Proceedings of 7th International Zeolite conference, p. 129 (1986)). For all but one end member of this series of materials (denoted TS materials), the presented XRD patterns indicate phases too dense to be molecular sieves. In the case of the one questionable end member (denoted TS-26), the XRD pattern might possibly be interpreted as a small pored zeolite, although without additional supporting evidence, it appears extremely questionable.
A naturally occurring alkaline titanosilicate identified as "Zorite" was discovered in trace quantities on the Siberian Tundra in 1972 (A. N. Mer'kov, et. al.; Zapiski Vses Mineralog. Obshch., pp. 54-62 (1973)). The published XRD pattern was challenged and a proposed structure reported in a later article entitled "The OD Structure of Zorite", Sandomirskii, et. al., Sov. Phys. Crystallogr. 24(6), November-December 1979, pp. 686-693.
No further reports on "titanium zeolites" appeared in the open literature until 1983 when trace levels of tetrahedral TI(IV) were reported in a ZSM-5 analog. (M. Taramasso, et. al.; U.S. Pat. No. 4,410,501 (1983); G. Perego, et. al.; Proceedings of the 7th International Zeolite Conference; p. 129 (1986)). A similar claim appeared from researchers in mid-1985 (EPA 132,550 (1985)). The research community reported mixed aluminosilicate-titanium (IV) (EPA 179,876 (1985); EPA 181,884 (1985) structures which, along with TAPO (EPA 121,232 (1985) systems, appear to have no possibility of active titanium sites. As such, their utility, has been limited to catalyzing oxidation.
In U.S. Pat. No. 4,938,939, issued Jul. 3, 1990, Kuznicki disclosed a new family of synthetic, stable crystalline titaniumsilicate molecular sieve zeolites which have a pore size of approximately 3-4 Angstrom units and a titania/silica mole ratio in the range of from 1.0 to 10. The entire content of U.S. Pat. No. 4,938,939 is herein incorporated by reference. These titanium silicates have a definite X-ray diffraction pattern unlike other molecular sieve zeolites and can be identified in terms of mole ratios of oxides as follows.
wherein M is at least one cation having a valence of n, Y is from 1.0 to 10.0, and Z is from 0 to 100.
The original cations M can be replaced at least in part with other cations by well-known exchange techniques. Preferred replacing cations include hydrogen, ammonium, rare earth, and mixtures thereof. Members of the family of molecular sieve zeolites designated ETS-4 in the rare earth-exchanged form have a high degree of thermal stability of at least 450� C. or higher depending on cationic form, thus rendering them effective for use in high temperature catalytic processes. ETS zeolites are highly adsorptive toward molecules up to approximately 3-5 Angstroms in critical diameter, e.g. water, ammonia, hydrogen sulfide, SO2, and n-hexane and are essentially non-adsorptive toward molecules which are larger than 5 Angstroms in critical diameter.
A large pore crystalline titanium molecular sieve composition having a pore size of about 8 Å units has also been developed by the present assignee and is disclosed in U.S. Pat. No. 4,853,202, which patent is herein incorporated by reference. This crystalline titanium silicate molecular sieve has been designated ETS-10.
The new family of microporous titanosilicates developed by the present assignee including ETS-4, ETS-10, ETAS-10 (titanium aluminum silicates, U.S. Pat. No. 5,244,650), and generically denoted as ETS, are constructed from fundamentally different building units than classical aluminosilicate zeolites. Instead of interlocked tetrahedral metal oxide units as in classical zeolites, the ETS materials are composed of interlocked octahedral chains and classical tetrahedral rings. In general, the chains consist of six oxygen-coordinated titanium octahedra wherein the chains are connected three dimensionally via tetrahedral silicon oxide units or bridging titanosilicate units. The inherently different crystalline titanium silicate structures of these ETS materials have been shown to produce unusual and unexpected results when compared with the performance of aluminosilicate zeolite molecular sieves. For example, the counter-balancing cations of the crystalline titanium silicates are associated with the charged titania chains and not the uncharged rings which form the bulk of the structure. In ETS-10, this association of cations with the charged titania chains is widely recognized as resulting in the unusual thermodynamic interactions with a wide variety of sorbates which have been found. This includes relative weak binding of polar species such as water and carbon dioxide and relatively stronger binding of larger species, such as propane and other hydrocarbons. These thermodynamic interactions form the heart of low temperature dessication processes as well as evolving Claus gas purification schemes. The unusual sorbate interactions are derived from the titanosilicate structure, which places the counter-balancing cations away from direct contact with the sorbates in the main ETS-10 channels.
In recent years, scores of reports on the structure, adsorption and, more recently, catalytic properties of wide pore, thermally stable ETS-10 have been made on a worldwide basis. This worldwide interest has been generated by the fact that ETS-10 represents a large pore thermally stable molecular sieve constructed from what had previously been thought to be unusable atomic building blocks.
Although ETS-4 was the first molecular sieve discovered which contained the octahedrally coordinated framework atoms and as such was considered an extremely interesting curiosity of science, ETS-4 has been virtually ignored by the world research community because of its small pores and reported low thermal stability. Recently, however, researchers of the present assignee have discovered a new phenomenon with respect to ETS-4. In appropriate cation forms, the pores of ETS-4 can be made to systematically shrink from slightly larger than 4 Å to less than 3 Å during calcinations, while maintaining substantial sample crystallinity. These pores may be "frozen" at any intermediate size by ceasing thermal treatment at the appropriate point and returning to ambient temperature. These controlled pore size materials are referred to as CTS-1 (contracted titanosilicate-1) and are described in commonly assigned, U.S. Pat. No. 6,068,682, issued May 30, 2000. Thus, ETS-4 may be systematically contracted under appropriate conditions to CTS-1 with a highly controllable pore size in the range of 3-4 Å. With this extreme control, molecules in this range may be separated by size, even if they are nearly identical. The systematic contraction of ETS-4 to CTS-1 to a highly controllable pore size has been named the Molecular Gate™ effect. This effect is leading to the development of separation of molecules differing in size by as little as 0.1 Angstrom, such as N2/O2 (3.6 and 3.5 Angstroms, respectively), CH4/N2 (3.8 and 3.6 Angstroms), or CO/H2 (3.6 and 2.9 Angstroms). High pressure N2/CH4 separation systems are now being developed. This profound change in adsorptive behavior is accompanied by systematic structural changes as evidenced by X-ray diffraction patterns and infrared spectroscopy.
An example of a molecular sieve containing at least some rare earth atoms in octahedral framework positions is a titanium-based mineral called seidite. While an impure mixed material, seidite is clearly an octahedral/tetrahedral molecular sieve as is clear from the structure of the mineral given in Zap.Vseross.Mineral.0-va (1998), 127(4), pp. 94-106. The mineral seidite has a designated formula Na3CeTiSi6O17.5H2O based on a wet chemical analysis. Although in the aforementioned article, the cerium is described as occluded within the structure, it is believed that there may be some cerium in the framework positions. If a molecular sieve could be made with all or predominantly all of the octahedral chains as rare earth centers, qualitatively new, potentially more stable molecular sieves could result.
Kuznicki, et al. in U.S. Pat. No. 5,208,006 disclosed large pore crystalline molecular sieves having at least one octahedrally coordinated site comprising titanium and at least tetrahedrally coordinated silicon in the framework and wherein the molecular sieve has an X-ray powder diffraction pattern substantially the same as ETAS-10 or ETS-10. The octahedrally coordinated metal site can be titanium alone or mixtures of titanium and other metals, preferably zirconium, niobium, cerium, chromium, iron, lanthanum, hafnium, and mixtures thereof. The atomic ratio of octahedral titanium to the total of any other octahedral metals is disclosed as ranging from 99:1 to 1:10, preferably from 3:1 to 1:2 and most preferably from 2:1 to 1:1.
In U.S. Pat. Nos. 5,888,472; 5,891,417 and 6,007,790, assigned to UOP, there are disclosed what are designated crystalline molecular sieves having either zirconium or indium oxide octahedral units and silicate tetrahedral units. The zirconium and indium can be replaced, at least in part, by other metals including cerium. All these materials are described as microporous and being molecular sieves. However, it is most likely that these materials are simply layered materials without a three dimensionally porous framework and concomitant molecular sieving properties. Thus, in the only example in any of the mentioned patents directed to actual adsorption, so little oxygen was adsorbed, i.e., less than 2�% at −183� C., that it is doubtful the structure of a molecular sieve framework was formed.
In accordance with the present invention, a novel rare earth lanthanide or actinide silicate molecular sieve is formed comprising predominantly lanthanide or actinide octahedrally coordinated chains and tetrahedral bridging units, typically of silicon. In particular, a substantially pure rare earth silicate has been generated using a rare earth metal as a substitution for titanium in a typical ETS-4 type synthesis mixture. The molecular sieve which is formed, however, is unlike the mineral seidite and has a structure which does not parallel the titanium based ETS-4.
The rare earth silicate molecular sieve is formed in accordance with this invention by heating a reaction mixture containing a rare earth lanthanide or actinide source, a source of silica, a source of alkalinity, and water to a temperature of from about 100� C. to 300� C. for a period time ranging from 8 hours to 40 days. Concentration of the components contained in the reaction mixture are the same as that used in forming ETS-4 except that the rare earth source is used in place of the titanium source.
The rare earth silicate molecular sieves are adsorptive, ion-exchangeable and catalytically active. The novel materials exhibit dramatically increased thermal stability relative to ETS and aluminumsilicate zeolite compositions.
The present invention is directed to novel rare earth lanthanide or actinide silicate molecular sieve zeolites comprising rare earth octahedrally coordinated chains connected with tetrahedral silica bridging units. The rare earth silicates have a pore size of approximately 3-5 Å units and are the first molecular sieve silicate formed predominantly from rare earth oxides. The crystalline rare earth silicate molecular sieve zeolites of the present invention can be identified in terms of mole ratios of oxides as follows:
wherein X is a rare earth, or mixtures thereof; Z is silicon or silicon and at least one other tetrahedral framework atom; M is at least one cation of valence n; α is one half the valence of X; β is one half the valence of Z; c is >0 to 2; d is 1-10; and e is from 0 to 100. In a preferred embodiment, M is a mixture of alkali metal cations, particularly sodium and potassium, c is at least 1.0 and d is at least 5.0.
The original cations M can be replaced at least in part with other cations by well-known exchange techniques. Preferred replacing cations include hydrogen, ammonium, alkaline earth, rare earth and mixtures thereof.
In the above formula (I), X is a rare earth, or mixture thereof selected from the group consisting of the transition metals from the lanthanide and actinide series of the periodic table including lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium.
The rare earth silicate molecular sieve zeolites have an ordered crystalline structure and have substantially the same X-ray powder diffraction pattern regardless of the specific rare earth utilized in molecular sieve formation, although slight differences between the XRD patterns for the various rare earth silicates may be expected.
The rare earth silicate molecular sieve zeolites of the present invention are prepared in accordance with aforementioned U.S. Pat. No. 4,938,939 from a reaction mixture containing a rare earth source in place of a titanium source. Non-limiting examples of rare earth compounds which can be used include cerium chloride, cerium sulfate, cerium nitrate, cerium acetate, ytterbium chloride, ytterbium sulfate, ytterbium acetate, lanthanum chloride, lanthanum sulfate, lanthanum nitrate, lanthanum acetate, actinium chloride, actinium sulfate, actinium nitrate, and actinium acetate. The reaction mixture further contains a source of silica; a source of alkalinity such as an alkali metal hydroxide; water and, optionally, an alkali metal fluoride. The composition of the reaction mixture in terms of mole ratios fall within the ranges as set forth in Table 1.
Most Preferred
wherein X indicates a rare earth including lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium; and M indicates the cations of valence n derived from the alkali metal hydroxide and potassium fluoride and/or alkali metal salts used for preparing the rare earth silicate according to the invention.
In a preferred embodiment of the present invention, the reaction mixture is prepared as two separate mixtures that are then combined to form the reaction mixture. The first mixture contains a source of silica, a source of alkalinity such as an alkali metal hydroxide, water and, optionally, an alkali metal fluoride, e.g. KF. The second mixture contains the rare earth source, optional electrolyte and water. The combined reaction mixture is heated to a temperature of from about 100� C. to 300� C. for a period of time ranging from about 8 hours to 40 days, or more. The hydrothermal reaction is carried out until crystals are formed and the resulting crystalline product is thereafter separated from the reaction mixture by cooling to room temperature filtering and water washed. The reaction mixture can be stirred although it is not necessary. It has been found that when using gels, stirring is unnecessary but can be employed. When using sources of rare earth lanthanides or actinides which are solids, stirring is beneficial. The preferred temperature range is 150� C. to 250� C. for a period of time ranging from 12 hours to 15 days. Crystallization is performed in a continuous or batchwise manner under autogeneous pressure in an autoclave or static bomb reactor. Following the water washing step, the crystalline rare earth silicate is dried at temperatures of 100� to 400� F. for periods ranging up to 30 hours.
The method for preparing rare earth silicate compositions comprises the preparation of a reaction mixture constituted by sources of silica, sources of rare earth lanthanides or actinides, sources of alkalinity such as sodium and/or potassium oxide and water having a reagent molar ratio composition as set forth in Table 1. Optionally, sources of fluoride such as potassium fluoride can be used, particularly to assist in solubilizing a solid rare earth source such as CeO2 or Ce2O3.
The silica source includes most any reactive source of silicon such as silica, silica hydrosol, silica gel, silicic acid, alkoxides of silicon, alkali metal silicates, preferably sodium or potassium, or mixtures of the foregoing.
The rare earth source is preferably in the form of a soluble salt such as cerium chloride, cerium sulfate, cerium nitrate, cerium acetate, ytterbium chloride, ytterbium sulfate, ytterbium acetate, lanthanum chloride, lanthanum sulfate, lanthanum nitrate, lanthanum acetate, actinium chloride, actinium sulfate, actinium nitrate, and actinium acetate. Rare earth oxides can also be used in particular, rare earth oxides which can be rendered soluble in the reaction mixture. In-situ rare earth silicate molecular sieves prepared from insoluble solid rare earth oxides may be possible.
The source of alkalinity is preferably an aqueous solution of an alkali metal hydroxide, such as sodium hydroxide, which provides a source of alkali metal ions for maintaining electrovalent neutrality and controlling the pH of the reaction mixture within the range of 10 to 12. The alkali metal hydroxide serves as a source of sodium oxide which can also be supplied by an aqueous solution of sodium silicate.
The rare earth silicate molecular sieve zeolites prepared according to the invention may contain minor amounts of transition metals substituted for the lanthanides or actinides along the chain of octahedrally coordinated rare earth sites. Up to 45%, preferably up to 30%, and most preferably no more than 10% of the rare earths can be substituted with other transition metals. Non-limiting examples of transition metals which can be substituted for the octahedrally coordinated rare earth metals include Zr, Nb, Mo, Ru, Pd, Ag, In, Sn, Ta, W, Re, Ir, Pt, Au, Ti, Cr, Mn, Fe, Co, Ni, Cu and Zn.
The crystalline rare earth silicate as synthesized can have the original cations thereof replaced by a wide variety of others according to techniques well known in the art. Typical replacing cations would include hydrogen, ammonium, alkyl ammonium and aryl ammonium and metals, including mixtures of the same. The hydrogen form may be prepared, for example, by substitution of original sodium with ammonium. The composition is then calcined at a temperature of, say, 1000� F. causing evolution of ammonia and retention of hydrogen in the composition, i.e., hydrogen and/or decationized form.
The crystalline rare earth silicates are then preferably washed with water and dried at a temperature ranging from 150� F. to about 600� F. and may thereafter be calcined in air or other inert gas.
Regardless of the synthesized form of the rare earth silicate, the spatial arrangement of atoms which form the basic crystal lattices remain essentially unchanged by the replacement of sodium or other alkali metal or by the presence in the initial reaction mixture of metals in addition to sodium, as determined by an X-ray powder diffraction pattern of the resulting rare earth silicate. The X-ray diffraction patterns of such products will be essentially identical regardless of the rare earth metal used although some shifts in the peaks are to be expected between XRD patterns of varying rare earth silicates especially between those of large atomic size differences. Peak intensities, even for the same rare earth silicate may vary depending on the level of hydration of the sieve. Table 2 below sets forth the XRD pattern of cerium silicate.
The crystalline rare earth silicates prepared in accordance with the invention are formed in a wide variety of particular sizes. Generally, the particles can be in the form of powder, a granule, or a molded product such as an extrudate having a particle size sufficient to pass through a 2 mesh (Tyler) screen and be maintained on a 400 mesh (Tyler) screen in cases where the catalyst is molded such as by extrusion. The rare earth silicate can be extruded before drying or dried or partially dried and then extruded. For use as adsorbents, membranes of such rare earth silicates may be useful.
The novel rare earth silicate materials of this invention are useful as adsorbents to separate gaseous and liquid mixtures and as catalysts. When particularly used as a catalyst, it is desired to incorporate the new crystalline rare earth silicate with another material resistant to the temperatures and other conditions employed in organic processes. Such materials include active and inactive materials and synthetic and naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the new crystalline rare earth silicate, i.e., combined therewith which is active, tends to improve the conversion and/or selectivity of the catalyst in certain organic conversion processes such as the cracking of n-hexane. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and in an orderly manner without employing other means for controlling the rate of reaction. Normally, crystalline materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin to improve the crush strength of the catalyst under commercial operating conditions. These materials, i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in a petroleum refinery the catalyst is often subjected to rough handling which tends to break the catalyst down into powder-like materials which cause problems in processing. These clay binders have been employed for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays that can be composited with the crystalline rare earth silicate described herein include the montmorillonite and kaolin family, which families include the sub-bentonites and the kaolins known commonly as Dixie, McNamee, Georgia and Florida or others in which the main constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcinations, acid treatment or chemical modification.
In addition to the foregoing materials, the crystalline rare earth silicate may be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. The relative proportions of finally divided crystalline metal organosilicate and inorganic oxide gel matrix can vary widely with the crystalline organosilicate content ranging from about 1% to 90% by weight and more usually in the range of about 2% to about 50% by weight of the composite.
As is known in the art, it is desirable to limit the alkali metal content of materials used for acid catalyzed reactions. This is usually accomplished by ion exchange with hydrogen ions or precursors thereof such as ammonium.
In order to more fully illustrate the nature of the invention and a manner of practicing the same, the following examples illustrate the best mode now contemplated.
In this Example, the preparation of a ECeS-4 is set forth.
The following ingredients were mixed in a beaker.
173.59 grams
NaOH (s)
6.93 grams
26.01 grams
90.03 grams
N-Brand ™
1. N-Brand�
The following ingredients were separately mixed in another beaker.
54.55 grams
75.07 grams
36.09 grams
The mixtures from the two beakers were then blended together with H2O added as necessary to make a "creamy" homogenous gel with a pH of 1 gram in 99 grams of H2O equal to 10.7.
The mixed reactants were poured into Teflon-lined autoclaves, which were sealed. The amounts of gel in each autoclave was as follows:
Mass Gel
The autoclaves were heated to 225� C. and maintained at temperature for 3 days. The product from each autoclave was separately filtered and washed with hot water and dried at 100� C. Chemical analysis of the product was determined to be as follows:
Table 2 below shows the significant peaks of an X-ray diffraction pattern of the product formed as above-described. The XRD pattern for each sample was the same. The XRD pattern was formed on a Philips APD37320 diffractometer equipped with a theta compensator. The theta compensator maintains a constant area of illumination on the sample, so X-ray intensities obtained from a theta compensated unit are not directly comparable to those of a non-compensated unit. Thus, all values mentioned in the specification and claims with regard to the novel materials of this invention were determined by the theta compensated X-ray equipment. The radiation was the K-alpha doublet of copper, and a scintillation counter spectrometer was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle were read from the spectrometer chart. From these, the relative intensities, 100 I/I0, where I0 is the intensity of the strongest line or peak, and d, the interplanar spacing in angstroms, corresponding to the recorded lines, were calculated and recorded in Table 2.
Intensity* I/I0
*s = strong (>50);
m = medium (20-50);
mw = medium-weak (10-20);
w = weak (<10)
Once given the above disclosure, many other features, modifications, and improvements will become apparent to the skilled artisan. Such other features, modifications, and improvements are, therefore, considered to be a part of this invention, the scope of which is to be determined by the following claims.
|Cited Patent
|Filing date
|Publication date
|Sep 23, 1971
|Oct 30, 1973
|Grace W R & Co
|Process for the preparation of zeolitic alumino-metallo silicates
|Nov 16, 1984
|Jul 21, 1987
|The Standard Oil Company
|Process for the preparation of metallosilicates of tetravalent lanthanide and actinide series metals using heterpoly metallates
|Apr 10, 1986
|Oct 20, 1987
|Exxon Research And Engineering Company
|Rare earth stabilized aluminum deficient zeolite
|Jul 14, 1987
|Aug 29, 1989
|Mobil Oil Corporation
|Novel silicate
|Dec 11, 1989
|Jul 3, 1990
|Engelhard Corporation
|Preparation of small-pored crystalline titanium molecular sieve zeolites
|Apr 28, 1989
|May 14, 1991
|W. R. Grace & Co.-Conn.
|Crystalline group IVA metal-containing molecular sieve compositions
|Jan 24, 1992
|May 4, 1993
|Engelhard Corporation
|Large-pored molecular sieves containing at least one octahedral site comprising titanium and at least silicon as a tetrahedral site
|Jan 14, 1992
|Aug 3, 1993
|Research Institute Of Petroleum Processing
|Rare earth-containing high-silica zeolite having penta-sil type structure and process for the same
|Jun 19, 1996
|Oct 14, 1997
|Mitsubishi Jukogyo Kabushiki Kaisha
|Catalyst for purifying an exhaust gas
|Dec 19, 1995
|Feb 9, 1999
|China Petro-Chemical Corporation
|Rare earth--ZSM-5/ZSM-11 cocrystalline zeolite
|Apr 8, 1997
|Mar 30, 1999
|Uop Llc
|Zirconium silicate molecular sieves and process using the same
|Dec 15, 1997
|Apr 6, 1999
|Uop Llc
|Zirconium silicate and zirconium germanate molecular sieves and process using the same
|Aug 13, 1998
|Dec 28, 1999
|Uop Llc
|Family of microporous indium silicate compositions
|Title not available
|"The First Microporous Framework Cerium Silicate" By Rocha, et al., Alkewandte Casillie International Ed, 2000, 39, No. 18.
|"TSeidite-(Ce) Na4SrTiSi8O22F <K>5H2C-New Mineral with Zeolite Properties" Proc. RMS H 4, 1998.
|"TSeidite—(Ce) Na4SrTiSi8O22F K5H2C—New Mineral with Zeolite Properties" Proc. RMS H 4, 1998.
|Citing Patent
|Filing date
|Publication date
|Aug 17, 2006
|Jun 8, 2010
|Mitsubishi Jidosha Kogyo K.K.
|HC adsorbing material and device for judging deterioration of the HC adsorbing material
|Aug 17, 2006
|Mar 8, 2007
|Mitsubishi Jidosha Kogyo Kabushiki Kaisha
|HC adsorbing material and device for judging deterioration of the HC adsorbing material
|Apr 15, 2013
|Jun 3, 2015
|Sep 7, 2006
|Dec 5, 2013
|Mitsubishi Jidosha Kogyo K.K.
|Vorrichtung zum Beurteilen einer Qualit�tsabnahme eines HC-Adsorptionsmaterials
|U.S. Classification
|423/718, 423/713
|International Classification
|Cooperative Classification
|European Classification
|May 13, 2004
Owner name: ENGELHARD CORPORATION, NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KUZNICKI, STEVEN M.;JACUBINAS, RICHARD M.;REEL/FRAME:015331/0877;SIGNING DATES FROM 20010904 TO 20010905
|Jan 14, 2008
|Fee payment
Year of fee payment: 4
|Jan 21, 2008
|Maintenance fee reminder mailed
|Feb 27, 2012
|Maintenance fee reminder mailed
|Jul 13, 2012
|Lapse for failure to pay maintenance fees
|Sep 4, 2012
|Expired due to failure to pay maintenance fee
Effective date: 20120713


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