text:
Masanosuke came to the city of Edo to prove himself as a warrior, but the man’s lack of confidence is so obvious that he’s perpetually unemployed and can barely afford to eat. So when the mysterious Yaichi offers him a job as a bodyguard - room and board included - the ronin jumps at the chance. But little did he know that his new employer is the head of the Five Leaves, a gang of kidnappers, and that his fees will be paid from the spoils of their crimes! Masanosuke never expected to find his home with a band of criminals, but as he grows more entangled in their world, his dreams of honor begin to fall by the wayside...
Saraiya Goyou, or House of Five Leaves, is the latest work by cult studio Manglobe. Now, while it isn't generally a good idea for a critic to speak personally, it bears mention that this is the first time I have ever seen anything by Manglobe, so I can't really comment on how it compares to their previous works. However, the fact that Manglobe already have a cult following in spite of only having four previous works to their name (Samurai Champloo, Ergo Proxy, Michiko to Hatchin and Seiken no Blacksmith) says quite a lot about this studio. Now, I don't know if Saraiya Goyou is in the vein of their other works, but this is likely considering that Manglobe are known for having a completely unique style and presentation, both in story and visuals, and Saraiya Goyou not only delivers on this, but it does so in spades. The show revolves around a swordsman for hire. Right now, you may well be thinking of some underrated master swordsman, a badass with amazing skill, who slays men in their thousands. This could not be further from the truth. Whilst the swordsman, our main character Akitsu Masanosuke (usually called "Masa" for short) is a competent swordsman, he is completely human. There is nothing truly special about him. He is, however, rarely hired, in part because he looks so harmless. But this all begins to change when he meets a strange man calling himself Yaichi, who actually agrees to hire him. However, as Masa soon discovers, he's been hired to work for a group of kidnappers. He initially tries to leave, but soon finds himself more and more immersed in the criminals' world. Now, it's worth noting that this show has a very unusual art style. This can be extremely offputting to some people, which, alongside with the slow pace of this show, probably account for the incredibly low ratings this show had upon airing. This is a great shame, because as of writing this is probably the best anime of 2010. It starts off quite slow, making it hard to rope viewers in, but it slowly but surely hooks the viewer. The pace is often considered to be the best and worst thing about this anime. It seems boring, but at the same time, utterly captivating. It's strange, but no matter how slow the show is, you never want to stop watching. At the same time, the slow pace can make the important moments all the more impressive and memorable. When it comes to the cast, most of them are good characters, and there are no bad characters in this show. However, the ones everyone remembers are the leading pair, Masa and Yaichi. Lesser characters like Ume and Matsu are memorable, but they aren't nearly as impressive. While Masa starts out as awkward, spineless, and mildly annoying, over the course of the series he gradually comes out of his shell. He comes to impact the plot strongly, form bonds with the Five Leaves, and prove his worth repeatedly in a fantastic display of character development. While he isn't as impressive as Rock from Black Lagoon, another character who started out in a similar fashion, he's certainly a character worthy of praise. Yaichi, on the other hand, is a riddle wrapped in a mystery inside an enigma. He is the mysterious leader of the Five Leaves, and a highly interesting character. To speak of his past is to ruin the entire plot of the show. Now, while the art style is offputting for some, it is by no means bad. It doesn't take long to get used to, and the art is produced to a high standard, as is the animation. Both are joined with an interesting style that focuses on a subtle, yet rich darkness. A large amount of the series is set at night, viewed only by candlelight, if even that. The daytime scenes are often indoors, under shadow. And the high-quality production extends to the soundtrack as well. The background music is distinct and memorable, giving a unique feel to the show. The opening theme, "Sign of Love", is a great song that grows on you more with each passing episode. The only problem I have with the soundtrack is the ending theme, a fun, bouncy song that invariably seems completely out of place at the end of each episode. While Saraiya Goyou is by no means a show for everyone, it is a great watch for those who can appreciate it. Some patience will be necessary for viewing it, but it will not go unrewarded. Final Words: Watching every other Manglobe show just shot up significantly in my priorities. Animation/Graphics: 9/10 Story/Plot: 9/10Characters: 8/10 Sound: 9/10 Overall: 9/10
This is an anime I most definetely enjoyed. It's different, most visibly in the unique art style but also in the content. It's a character-driven anime with some good character development. In some ways it reminded me of Samurai Champloo; what I really appreciated in SC was the subtle way in which the characters were portrayed and how the relationship between them was developed. And while not reaching the masterful level of SC, House of five leaves is on the same track. The story is quite simply about the relationship between two men with very different personalities and how their chance meeting affects each other and the people around them. The setting is feudal Japan. Our protagonist is a ronin who is incapable of keeping any job because of his "personality", he gets embarrassed when people watch him (usually succumbing to the urge to run away and hide) and totally lacks self-confidence - so he always comes across as an unreliable klutz, while as a matter of fact he is an extremely skillful and accomplished swordsman. The story starts when he meets Yaichi, the enigmatic and attractive leader of a band of kidnappers who appears to be fascinated by Masa's personality and decides to draw him into the band. Masa is initially very uncomfortable with this line of work, but nonetheless he finds himself increasingly drawn to Yaichi and to the people who surround him. There's more to the story which reaches its climax when the riddle that Yaichi himself is gets unravelled - I don't want to spoiler anything so I won't say more. But I will say that the storytelling is very good - despite being slow-paced. The plot is well thought out and through flashbacks and subtle hints it leads you to a satisfying end. I also commend the ending as it does not magically resolve all the characters' problems, it echoes real life where there never actually is a real end but things just go on as one day flows into the next. As for the characters, they are all portayed and developed well - main ones as well as side characters. The most interesting one is Yaichi, of course, as the core of the anime revolves around figuring out who he is and what his story is. As already said, I enjoyed watching how the relationship between Masa and Yaichi develops. The animation style is very distinctive and artsy. Different from the standard anime style. The soundtrack is also fitting; it combines different musical styles but it's never jarring. The voice actors did an excellent job, too. In conclusion, this isn't an anime that most people will enjoy because of the pacing and the lack of action, superpowers or romance. But for those of you who appreciate a good story and value character development, I'd recommend to give this a try.
This anime sure makes you expect things it ain’t. - First you see it has samurais so you expect it to be some action flick. Yet it’s not since there isn’t much action in it. - Then you see some really weird animation and colors and you think it will be some sort of mindfuck. Yet it’s not since everything weird in this show is just for aesthetics and it could easily be made with normal animation. - Then you hear it has gangsters and kidnaps and you think it will be a mystery thriller. Yet it’s not, there is mystery but doesn’t ever become exciting enough to be deemed thriller.- Then you hear it is slice of life and you expect it to be simple and almost storyless. Yet it isn’t because of ALL THE ABOVE. Ok, what is going on with this anime; it can’t be categorized at all; which in effect should be making it original in a way very cult-important… But it ain’t. Confusing? I bet it is; the entire show is made to confuse you. It messes with your expectations in an attempt to keep you looking for more. It worked for a few episodes up until you realize what this show is all about. An excuse to see flashbacks of people.That is the whole point of this anime; to see the backdrops of its main cast. Something triggers it, usually a kidnap, and then a flashback follows explaining what led a certain character to become a gangster in Five Leaves. Sounds exciting? Not if you realize most don’t have anything major to tell; it is basically simple tales of ALMOST everyday life that lead a man to turn to crime. In all honesty the story is very basic and the characters don’t seem to be much despite the immersion given to them. They are all still quite simple as personalities; they are just… looked into and thus feel better than the average stereotypes that are defined by their hair color or special attack. Still the show manages to be memorable and have its own value as an anime. - The most obvious one is the artwork, which makes everybody and everything to look un-anime like. It is not exactly experimental-level weird yet it surely looks like nothing else out there. With an almost minimalistic amount of motions and gradients, it becomes a one-of-a-kind as far as looks to and to be honest I doubt most would care about it if it wasn’t for that gimmick. Sounds like a minor detail but I personally like these sorts of unorthodox presentations.- After that comes the soundtrack which is full of tunes that fit the mood and era of the show, that of Feudal era. The voice actors are also doing a great job with their characters and bring out all they are. Is it a good show? Well, it is a lot simpler than it appears to be and when you get used to the weird artwork then you get to watch a rather nicely made slice-of-life running on flashbacks. It has no great fighting scenes or amazing plot twists and it’s basically about getting to know the gangsters. As unorthodox as it may sound it is not something I eventually enjoyed much. I only recommend this to slice-of-life fans who want to try something different.
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Question about 2001 Ford Taurus
Bank one is the engine cylinder bank near the engine firewall (see diagram). The bank one sensor one is the Oxygen sensor (O2) located in the exhaust pipe just of the engine cylinder bank at rear and before the Catalytic Converters.
Posted on Dec 28, 2010
A 6ya expert can help you resolve that issue over the phone in a minute or two.
Best thing about this new service is that you are never placed on hold and get to talk to real repairmen in the US.
The service is completely free and covers almost anything you can think of (from cars to computers, handyman, and even drones).
click here to download the app (for users in the US for now) and get all the help you need.
Posted on Jan 02, 2017
B1 means the sensor is located on the same bank of the engine that has the #1 cylinder. B2 is located on the opposite bank.
S1 means the sensor is located BEFORE the catalytic converter
S2 means the sensor is located AFTER the catalytic converter
You didn't say which engine you have, so I've included the diagrams of both 4 cyl and 6 cyl so you can see the banks
Posted on Oct 20, 2009
#1 is the egr position sensor #4 Is for single cylinder misfire so this could be the coil or a bad plug or wire ..but with fords should check for a vacume leak that can cause a misfire to .....#2#3 are 02 sensors before i would change them i would check the mass air flow sensor ..Hope this helps
Posted on Nov 10, 2009
If it was the upper o2 this is the one.This does not mean the o2 is bad,check the spark plugs and boots,and fuel pressure.The fuel ratio is not correct on that bank.
Posted on Apr 13, 2010
You will be told that it is passenger side 02 sensor before the cat,, but it is not .. Drivers side right after the manifold is the one you are after.
Posted on Jul 31, 2010
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In design circles, the name "Eames" is more or less inseparable from the word "chair". Between 1945-55, the Eames Office in Los Angeles produced a range of seating systems which - in the words of the Washington Post - "changed the way the 20th century sat down." This claim may be mildly hyperbolic, but not unforgivably so. In essence, the Eames chair introduced to the American psyche the idea of mass- production chic. The Eames Office - its products made of bent plywood or wire mesh, with such parodically utilitarian names as "DCM" (Dining Chair Metal) and "DCW" (Dining Chair Wood) - was able to harness America's post-war craving for technocratic newness to its spending power. The wistful admiration of Fifties' Europe for all things American meant that the trademark "organic" designs appeared in magazines like Domus, then in the fleshy curves of things like Gio Ponti's coffee machines.
But this fortunate timing does little to explain the lasting appeal of Eames furniture. More than half a century after the DCM first saw the spindly light of day, the chair remains in regular production; originals change hands for thousands of pounds. Another Eames piece - the Lounge Chair and Ottoman of 1956 - has netted its makers more than $100m. Proof of the immortal nature of Eames chic is on display in Waterloo's new international terminal; at the express command of its architect, Nicholas Grimshaw, the Eurostar waiting room is kitted out with row upon aluminium row of Eames Tandem Seating.
Explaining the apparently unstoppable nature of products like the DCM calls for a spot of deconstruction. The chair in question may be read in one of two ways. First, it is a piece of overt technology, a relic from the post-war cult of techno-optimism: the perverse bending of the DCM's plywood elements clearly suggests the triumph of technology over nature. (The Eames Office also designed plywood parts for aeroplanes.) Second, it is a piece of sculpture: an arrangement of linear planes and curves, tensely counterpoised in three dimensions.
The traditional way of reconciling this double act has been to split the genius behind it fifty-fifty, crediting Charles with the chair's technocratic elements, Ray with its decorative ones. This seemed sensible enough. Charles was a football star turned architect, the kind of man who was good with his hands; Ray was an artist whose work was heavily influenced by contemporary masters like Mir, Arp and Kandinsky. Look at the DCM chair on its pedestal in the Vitra Design Museum and its status as a piece of sculpture suddenly becomes clearer. It is a Calder stabile; the fact that it can be sat on seems almost coincidental. Arguably, the Eamesishness of the Eames chair lies with Ray's sculptural input rather than Charles's technologising.
Given this, the anomalous way in which history has treated Ray and Charles Eames may seem especially odd. In the index of any standard work of reference on the subject, listings for Charles outnumber those for Ray by a factor of 10 to one. When they were profiled on NBC's Today in 1956, Charles was introduced as the creator of the Eames Office; Ray was merely asked along as his helpmeet. Then it was Charles who was voted the world's most influential designer by the 1985 World Design Conference. Ray was allowed to attend the ceremony on his behalf - but then Charles had died seven years earlier. The US Library of Congress exhibition of their work - the same show that opens at the Design Museum this week - was entitled "The Work of Charles and Ray Eames", in that order.
This pro-Charles bias may seem faintly mysterious, but it is worth pointing out the precise nature of the Eameses' relationship. Ray was neither Charles's father, brother nor his son. She was his wife. The sexual ambiguity of her name is not without its ironies. (She was, for the record, baptised Bernice.) As Pat Kirkham notes in her excellent study. Charles and Ray Eames: Designers of the Twentieth-Century, the 1950s were a better decade for American consumerism than they were for American women. Ray Eames was a victim of the so-called "refeminisation" of women after a war in which they had been encouraged to do such hermetically masculine things as work in factories and make furniture. (Her own plywood sculptures grew out of work on lightweight splints for the US Army: their influence on the organic forms of the "Eames Look" is inarguable.)
Ray Eames was not the first wife to be unjustly overshadowed by her designing husband, but her exclusion seems particularly cruel. First, because the work of the Eames Office was in all other respects idealistic: forward- looking, rational, democratising. And, second, because the most iconically Eamesish qualities owe rather more to Ray.
This is not just to do with the way they look. Although one contemporary (female) critic suggested that "the prettiness of our lives now [is attributable] to Ray even more than to Charles," she only got half the point. Prettiness remained within the realm of the feminine; Ray's work for the Eames Office stepped smartly outside it.
While Charles worked on the MGM studio lot to make ends meet during the early 1940s, his wife was at home experimenting with plywood moulding systems. The specific technology that would allow the manufacture of, first, a suite of children's furniture, and then, the prototype DCM and Plywood Lounge chairs, was perfected not by the football-playing Charles Eames, but by his pretty little wife.
And what became of that pretty little wife? Ray outlived Charles by exactly 10 years. As in life, her posthumous reputation remains overshadowed by his. Although the Design Museum's exhibition is unusual in allowing Ray as much coverage as it does, the show's publicity material cites Charles's appreciation of her as a justification for doing so: "She has a very good sense of what gives a ... piece of sculpture its character ... She can see when there is a wrong mix of ideas." Ray's career as a fine artist and co-founder of the American Abstract Artists Group is alluded to and her likely influence on the Eames organic look hinted at. But the gender divide is somehow allowed to stand nonetheless. As you walk around the show, imagine how different things might have been had it been titled "The Work of Ray and Charles Eames". It would certainly have made for a snappier bumper sticker.
`The Work of Charles and Ray Eames': Design Museum, SE1 (0171 378 6055), Tues to 4 January 1999.Reuse content

domain: design


text:
Presentation on theme: "Solid and Hazardous Waste Chapter 21 Slides 51 -."— Presentation transcript:
Solid and Hazardous Waste Chapter 21 Slides 51 -
Where are Superfund Sites?
Stringfellow Acid Pits, LA , 34 million gal of DDT, acid, solvents, toxic metals dumped into ponds , 34 million gal of DDT, acid, solvents, toxic metals dumped into ponds Capped w/clay Capped w/clay Tainted water supply Tainted water supply Take 500 years to Take 500 years to clean up with pump clean up with pump and treat and treat
Chemical Accidents EPAs Emergency Response Notification System (ERNS) EPAs Emergency Response Notification System (ERNS) If toxins are spilled, ERNS must be notified If toxins are spilled, ERNS must be notified : 340,000 tons of toxic compounds were released during reported accidents : 340,000 tons of toxic compounds were released during reported accidents
DEALING WITH HAZARDOUS WASTE We can produce less hazardous waste and recycle, reuse, detoxify, burn, and bury what we continue to produce. Figure 22-16
Conversion to Less Hazardous Substances Physical Methods: using charcoal or resins to separate out harmful chemicals. Chemical Methods: using chemical reactions that can convert hazardous chemicals to less harmful or harmless chemicals.
Conversion to Less Hazardous Substances Biological Methods: – Bioremediation: bacteria or enzymes help destroy toxic and hazardous waste or convert them to more benign substances. – Phytoremediation: involves using natural or genetically engineered plants to absorb, filter and remove contaminants from polluted soil and water.
Conversion to Less Hazardous Substances Incineration: heating many types of hazardous waste to high temperatures – up to 2000 °C – in an incinerator can break them down and convert them to less harmful or harmless chemicals.
Conversion to Less Hazardous Substances Plasma Torch: passing electrical current through gas to generate an electric arc and very high temperatures can create plasma. – The plasma process can be carried out in a torch which can decompose liquid or solid hazardous organic material.
Long-Term Storage of Hazardous Waste Hazardous waste can be disposed of on or underneath the earths surface, but without proper design and care this can pollute the air and water. – Deep-well disposal: liquid hazardous wastes are pumped under pressure into dry porous rock far beneath aquifers. – Surface impoundments: excavated depressions such as ponds, pits, or lagoons into which liners are placed and liquid hazardous wastes are stored.
Long-Term Storage of Hazardous Waste Long-Term Retrievable Storage: Some highly toxic materials cannot be detoxified or destroyed. Metal drums are used to stored them in areas that can be inspected and retrieved. Secure Landfills: Sometimes hazardous waste are put into drums and buried in carefully designed and monitored sites.
Secure Hazardous Waste Landfill In the U.S. there are only 23 commercial hazardous waste landfills. Figure 22-22
Case Study: Lead Lead is especially harmful to children and is still used in leaded gasoline and household paints in about 100 countries. Figure 22-24
Case Study: Mercury Mercury is released into the environment mostly by burning coal and incinerating wastes and can build to high levels in some types of fish. Figure 22-26
Fig , p. 542 BIOMAGNIFICATION IN FOOD CHAIN SEDIMENT PRECIPITATION WINDS AIR WATER Inorganic mercury and acids (Hg 2+ ) Inorganic mercury and acids (Hg 2+ ) Organic mercury (CH 3 Hg + ) Inorganic mercury (Hg 2+ ) Hg 2+ and acids Runoff of Hg 2+ and acids Large fish Small fish ZooplanktonPhytoplankton Hg and SO 2 Hg 2 + and acids Human sources Incinerator Coal- burning plant Elemental mercury vapor (Hg) Photo- chemical Oxidation Elemental mercury liquid (Hg) Deposition Bacteria and acids Settles out Settles out Settles out Vaporization Deposition
ACHIEVING A LOW-WASTE SOCIETY In the U.S., citizens have kept large numbers of incinerators, landfills, and hazardous waste treatment plants from being built in their local areas. Environmental justice means that everyone is entitled to protection from environmental hazards without discrimination.
Global Outlook: International Action to Reduce Hazardous Waste An international treaty calls for phasing out the use of harmful persistent organic pollutants (POPs). – POPs are insoluble in water and soluble in fat. – Nearly every person on earth has detectable levels of POPs in their blood. – The U.S has not ratified this treaty.
Making the Transition to a Low- Waste Society: A New Vision Everything is connected. There is no away for the wastes we produce. Dilution is not always the solution to pollution. The best and cheapest way to deal with wastes are reduction and pollution prevention.

domain: chemistry


The Under Armour® Tide Chaser Fishing Shirt is created especially for anglers and is loaded with the technology you need to enhance your on-the-water experience. This Under Armour fishing shirt is made with stretch-woven polyester, a loose fit, and strategic shoulder seams that won't limit your motion. A button-down collar stays in place through wind and movement. 2 bellows-style chest pockets hold extra gear and under-arm vents offer air circulation. A Moisture Transport System, antibacterial treatment, and anti-stain fabric keep you feeling fresh and dry. The Under Armour Tide Chaser Fishing Shirt for Men offers UPF 30+ sun protection to help safeguard your skin. Machine wash. Imported.
Manufacturer style #: 1290743.
- 100% polyester
- Stretch woven fabric moves with you
- 2 bellows pockets with vent holes and button closures
- Short sleeves, button-down collar
- Moisture Transport System wicks sweat
- Anti-odor technology blocks bacteria growth
- Mesh shoulder vents allow air circulation
- UPF 30+ sun protection
- Stain release materials keep blood and guts from soaking in
- Loose, full fit
- Helps reduce odors; does not guarantee 100% odor elimination
Web ID: 2335435


text:
As much as i like it, i do think it's a tad overrated. As it goes on, the plot and especially the backstory becomes too ludicrous. Thankfully this is mostly remedied by the extraordinary character writing.
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domain: entertainment


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text:
Female surgeons had small but significantly improved 30-day mortality and other surgical outcomes over male surgeons, all other factors being equal.
Why does this matter?
Girls always told me in grade school they could do anything I could do, only better…turns out they were spot on regarding surgical mortality and other surgical outcomes (among many other things). In a prior study, female internists had better 30-day mortality rates for medical patients over their male peers. This study looked at surgical outcomes.
I’d like her to operate on me, please.
In over 100,000 patients in Ontario, with over 3,000 different surgeons, overall 30-day mortality was statistically better for patients who had a female vs. male surgeon. In fact, odds of death at 30-days was reduced 12% simply by having a female surgeon. Other surgical quality metrics, such as length of stay, repeat admission, and complications were also better for female surgeons. This was a retrospective study and may have had unrecognized confounders. But they, “matched patients for age, sex, and general comorbidity that had the same surgical procedure by a female or male surgeon of the same age with comparable annual surgical volume in the same hospital.” The other issue was similar to the critique of the article linked above about internists; namely, the surgeon was part of a very large team of people caring for the patient, all of whom had an influence on the outcome. Regardless of this objection, I think the results are valid. What I would like to know is why? What is it that, in the aggregate, female vs male surgeons are doing that improves outcome, and how can we all adopt these techniques for our patients’ benefit? Maybe the next study could be a detailed qualitative observation of female vs male surgeons to find out.
Comparison of postoperative outcomes among patients treated by male and female surgeons: a population based matched cohort study. BMJ. 2017 Oct 10;359:j4366. doi: 10.1136/bmj.j4366.
This was an excellent editorial on the #ILookLikeASurgeon campaign celebrating women in surgery – “the hashtag underlines the need to create a new surgeon ‘ideal’—not one that tries to make all surgeons like women, or indeed like a single image, but instead recognises the need for many images.”
Peer reviewed by Thomas Davis, MD.

domain: literature


Published 9 years ago.
About a 4 minute read.
National Geographic’s 2014 Greendex, released today by the National Geographic Society and GlobeScan, finds that concern about environmental problems has increased in most countries surveyed, and that more people expect that global warming will negatively affect them during their lifetime than in 2012. Despite this, the survey — a comprehensive measure of consumer behavior in 65 areas related to housing, transportation, food and consumer goods — shows that corresponding consciousness in consumer behavior has only grown slowly.
Results of the 2014 Greendex, which will be released later this morning at the New Metrics ‘14 conference in Boston, surveyed 18,000 consumers in 18 countries, and is the fifth iteration of the survey, which was first fielded in 2008.
Among the top findings in 2014:
“National Geographic developed the Greendex as an important tool for measuring sustainable behavior and changes in behavior around the world over time,” said Terry Garcia, chief science and exploration officer at the National Geographic Society. “The 2014 Greendex provides increased insight into what the drivers are for consumers to engage in more environmentally friendly behavior, such as peer influence and helping people see the connections between humans and the environment. This year we have seen that although change is coming slowly, consumers are showing positive change in their attitudes about sustainable food choices; this data can help inform behavior change in other sectors.”
Eric Whan, who directs the Greendex project at GlobeScan, added: “It’s vital that all actors work together to enable substantive reductions in the environmental impact of consumer behavior around the world. The research underlines that consumers need more encouragement from peers, as well as enablement and better leadership from companies and governments to lighten their own impact. That’s why the Greendex is so important.”
The Greendex was launched in 2008 to inform consumers worldwide and motivate sustainable choices. It explores individual consumer behavior and material lifestyle of 18,000 consumers in 18 countries around the world (14 in 2008), and measures the specific choices and behaviors that contribute most to a consumer’s overall ecological impact — the type of car you drive, the way you heat your house, the kind of foods you eat. A complex algorithm is applied to results to generate an index score — a Greendex score — for each individual respondent that reflects the relative environmental impact of his or her consumption patterns. Individual scores are averaged to create a mean score for consumers in each country. Combined with questions about cultural drivers and perceptions, the Greendex gives a comprehensive view into the state of sustainable consumption.
Consumers can calculate their own Greendex scores on the National Geographic website, and compare their scores to other consumers around the world. They can also examine the Greendex survey results by country, measure their knowledge of green issues and get tips on living a more environmentally friendly lifestyle.
While movement toward sustainable lifestyles seems to be taking hold at a disappointing pace in certain parts of the developed world, the growing presence, awareness and buying power of conscious consumer groups such as the Aspirationals and Generation World are reason to hope that subsequent generations will move the needle significantly.
Published Sep 26, 2014 1am EDT / 10pm PDT / 6am BST / 7am CEST


Metal-logic offers services for the construction of structures and profiles of stainless steel, carbon steel and aluminum. We introduce ourselves as a company focused on the subcontracting of cutting and deformation processes, as well as in welding and assembling of sets.
Our company was founded in 1997 as a local company, manufacturing several products and providing services for other industries. Focusing on long-term development concepts, today we position ourselves to be a specialized solution in the world of large capacity industrial processes, with the desire to serve the industries of the territory. Our company works on request and in detail, adapting to the needs of each client and offering a comprehensive service between design advice and diligent delivery.Mission
Metal-logic has more than 20 years of experience in subcontracting work for industries with a wide range of specific jobs. Below are a few sectors where our products have output.
Metal-logic offers services to manufacturing companies, with lines of production, transport tapes, maintenance and adaptation of existing machinery.
We offer curved, bending and welding services for the manufacture of boiler elements, ovens, chimneys and large pipes.
We offer an industrial service in specialized locksmiths for construction projects: metal profiles, frames, pre-frames, looms, supports, fencing, stairs, railings and any generic work from drawing.
Within the wide range of products that Metall-lògic offers, its most palpable field of specialization is that of industrial machinery. We present ourselves as a company prepared and focused for projects at the subcontracting level entrusted by external design and engineering teams.
Foundation of the society. Metall-lògic S.L was settled at the industrial site Susvalls, in Cassà de la Selva (Girona).
With the yearning to service the small locksmith industry, the company specializes in the world of construction, with the manufacture of metal profiles and assemblies.
Acquisition of the first 6000mm CNC buckle and 250 tonnes of pressure
Acquisition of the first CNC punching machine
Acquisition of the first punching machine / large format shear with automatic loading and unloading
Expansion of the existing ship up to 5000 m2 of production
Acquisition of a 7000mm bending machine with a pressure of up to 500t
Acquisition of a new electric punching machine with 7000x1500 cutting capacity with replacement and automatic loading and unloading
Construction of a new ship of 800 m2 of production
Acquisition of two laser machines of 6000x2000mm and 3000x1500mm with fiber technology and 6kW of power. With capacity for cutting up to 20mm thick in stainless steel
Since our foundation, the aim of METAL-LÒGIC has been to offer an integral service, based on the synergy of a team of professionals in metal constructions.
The value proposition we offer is the guarantee and the quality of having a park of state-of-the-art machinery, with agility to adapt to the demands of the market.Llegeix la nostra història


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text:
The assassination of former Japanese Prime Minister Shinzo Abe not only came as a tremendous shock to Japan, but it also leaves a tremendous political power vacuum. Although Abe resigned as leader in 2020, he had not only reasserted his role as the champion of the ruling Liberal Democratic Party’s (LDP) conservatives, he also formally assumed the leadership of his party’s largest faction.
Meanwhile, as a highly respected global statesman, he enjoyed a bully pulpit through the domestic and international media, a powerful tool to influence Japan’s policy agenda. This was never more clear than in February when he used an appearance on a Sunday talk show to raise the possibility of nuclear weapons sharing with the United States. Over the first nine months of Prime Minister Fumio Kishida’s tenure, Abe appeared determined to force Kishida to defer to his policy ideas.
The above excerpt was originally published in TIME.
Click here to view the full article.

domain: politics


text:
I am loving being able to harvest an overflowing garden basket every morning when I go out to my garden. This is the very best time of the year for healthy, gourmet eating! So tonight for dinner, Louisa and I put our harvest in a skillet and came up with a delicious garden-fresh dinner fit for a king!
Garden Skillet Dinner
- 1 gigantic zucchini, cubed (about 6 cups)
- 1/2 eggplant, cubed
- 3 Anaheim peppers (mildly hot), sliced (can substitute other peppers: bell peppers or 1 hot pepper)
- 1 clove garlic, minced
- 1/2 onion, chopped
- 3 tablespoons fresh oregano, minced (or 2 teaspoons dry oregano leaves)
- 3 cups cooked brown rice or quinoa
- Optional: 2 cups cubed cooked chicken or cooked ground beef
- 6 large garden tomatoes, chopped
- 1 cup sour cream or plain yogurt
- 1-2 cups grated cheese
1. Put veggies, garlic and oregano leaves in a large skillet. Cover and cook over medium low heat (no need to add water or oil).
2. When veggies are tender, stir in rice and meat. Heat through.
3. Spread tomatoes over the top of the contents of the skillet.
4. Stir 1 teaspoon powdered oregano, salt and pepper into sour cream and dollop on top of tomatoes.
5. Sprinkle grated cheese over all.
6. Cover and heat over medium low heat just until cheese is melted. Tomatoes will be warm but not cooked.
This recipe could easily be modified to use whatever your garden is producing. I like to have cooked grain like rice or quinoa in my fridge so I can make a quick meal. This only takes 30 minutes, start to table. Serves 6.
The gourmet, unique flavored “sauce” comes from the mix of the juice of the veggies with oregano and sour cream.
You might enjoy:

domain: food


text: June 21, 2012 by Tom McG It will be hard, hard, HARD…but ask him. Chances are he will be surprised at what you say. He might very well not realize that is what is happening to him. The good news is it might make him look at things differently and work on changing things for the better (which may be better for BOTH of you). The bad news is he may realize that what you say is the truth and he may decide to “go with it.” As difficult and painful as that will be for you…it will be better for you in the longer run. So talking to him is a win-win for you…even though you may not see it that way for a long time. Good luck, Sweetie.


text:
Here is our first recording "
Chasing the Dragon"
more to follow, enjoy
Recording some tunes at the end of June.
Should have them out mid July
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domain: hobby


text:
Vrhnika is a town, which is a centre of Municipality of Vrhnika. It is located by the old road from Ljubljana to Postojna. It lies on the slopes of Pokojnik plateau and on the western side of Ljubljansko swamp. The beginning and development of the city is connected with ships and traffic on the Ljubljanica River, which springs here on several places. Vrhnika is also situated on area, where is the shortest passage from Ljubljana basin over the karst and Inner Carniola forest plateau to the sea. The place of today's Vrhnika was already settled before the arrival of Romans. In written sources is first mentioned in 1300 and at that time was named Upper Ljubljana.
In the city we can see the following major attractions: the monument of greatest Slovenian dramatist, poet and writer Ivan Cankar (1876-1918), the birthplace of Ivan Cankar, Lavrencic House – the Old Post Office, a former Hotel by Black eagle, the Church of Saint Lenart, the Church of the Holy Trinity, the Church of St. Paul on the Hill and other.
The birthplace of Ivan Cankar is separated into a black kitchen, living room and chamber. It was proclaimed for a cultural monument. Lavrencic House belongs between the most important and oldest buildings in Vrhnika. It is located on the bank of the Ljubljanica River, where was sometimes a passanger port. A Hotel By Black eagle was built in 1850. By the Church of St. Lenart are buried Ivan Cankar's parents. The Baroque style church got in the 18th Century. It was built around 1640. The Church of Saint Paul is located on the place of the former Roman camp and was built in 1851.
Cankar's memorial house

domain: history


text:
is Largest Urdu Forum on net, Read & Share Poetry and a Lot more Register Now!
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This is a discussion on Wo Hamara Na Sahi within the Artist & Designer's Clubs part of the Art & Artist's Forum category of Urdu Poetry / Shayari | Islamic Art | Al-Quran & Hadith | Book Download | Gup Shup & more, Assalam-o-Alaikum Wo Hamara Na Sahi... tags:
Wahhhh Kya baat hay
Be hd Umda Design
and faaaaantastic Poetry
Zabardast Sohail bhai
Masha Allah good work......
Nice Design n Qitta as well....!
very nyshhhh....bohot khoob ;)
bahut achi sharing hai
bahot khoob bahot umda design sohail bhai

domain: artistic


text:
The Battle Bird Armada (バトルクック軍 Batoru Kukku Gun?, lit. "Battle Kukku Army") are the primary antagonists in Tails Adventure. They are an army of belligerent bird warriors lead by the Great Battle Kukku.
The Battle Bird Armada invades Cocoa Island to uncover the Chaos Emeralds which lay hidden there for ages. Tails fends off the invaders and defeats them. The Battle Bird Armada consists of uniformed birds, somewhat intelligent robot drones and advanced machinery. The army lives on a huge flying fortress that posed as an island throughout most of Tails Adventure.
- Great Battle Kukku, the dictator-like leader of the army. He is larger than most Kukkus, and is the final boss of the game battled in his flying fortress. He fights by throwing bombs all around him and throwing Tails himself if the fox gets too close.
- Battle Kukku XVI, aka Speedy, the son of the Great Battle Kukku. Speedy is a quick green Kukku who, despite his natural and fast aerial skills, sometimes wears armor equipped with an energy gun and a jet engine that lets him take even faster flight. He appears as a boss twice throughout the game, first on Pori Pori Mountain and then in the flying fortress just before the player faces his father.
- Dr. Fukurokov, the army's main scientist. He is the first boss of the flying fortress, but does not actually fight, as he instead lets his defensive machinery take care of Tails. His tendency to overlook little details is his greatest weakness.
Appearances in Other Media
- The Battle Bird Armada are the second villains (although the first chronologically) that Tails has fought single-handedly, the other being Witchcart.
- Given the name of Kukku Island when the game is set to English (Coco Island), it is possible that Kukku was meant to be read as "Cuckoo". On the other hand, it could have been mistaken for the name of the game's setting, Cocoa Island. However, "Kukku" was used in compilations and later the Archie Comics as part of the main villain's name, confirming its official spelling.
- In Ristar, another Sega game, both the first level miniboss and the end boss of Planet Sonata (Neuos in the Japanese version) bear a very uncanny resemblance to the bird troops.
- There is a similarity between Speedy, Bean the Dynamite and Jet the Hawk; they are three bird characters who are all green. Also, both the Great Battle Kukku and Bean use bombs as their weapon of choice.


text:
Pancuronium, vecuronium, mivacurium and rocuronium are nondepolarizing neuromuscular blocking agents. Although neuromuscular blocking drugs are designed to specifically block nicotinic cholinergic receptors at the neuromuscular junction, many bind to muscarinic cholinergic receptors on ganglia, nerve endings and smooth muscle . The principal action of nondepolarizing muscle relaxants is competitive antagonism against acetylcholine at nicotinic receptors in the neuromuscular junction and these agents are considered to have no direct actions on vascular smooth muscle .
Although they have a similar amino steroidal three-dimensional structure, experimental studies performed in different species have shown that these compounds affect the cardiovascular system with different potencies [3,4]. Pancuronium, which has been reported to have more sympathomimetic properties than vecuronium , is reported to increase heart rate and arterial blood pressure (BP) [6,7] by its positive inotropic and chronotropic effects [3,4]. Although rocuronium did not produce significant cardiac effects  except minor haemodynamic changes , vecuronium has been reported to induce bradycardia [9–11]. Mivacurium injection caused transient tachycardia and hypotension in healthy individuals . The mechanisms of action of these compounds have been explained by cardiac antimuscarinic effects, noradrenaline release and inhibition of noradrenaline reuptake [13–16].
The aim of this study was to investigate the relaxant effects and possible underlying mechanisms of pancuronium, vecuronium, mivacurium and rocuronium on isolated rat thoracic aorta along with their effects on the BP in clinical doses and compare their vascular actions with each other.
All experimental procedures were performed in accordance with the recommendations of the Guide for the Care and Use of Laboratory Animals and the experiments were approved by Cumhuriyet University Medical Faculty, Animal Care Committee. Twenty male albino Wistar rats (weighing 180–220 g) were injected with pentobarbital sodium (100 mg kg−1) and sodium heparin (5000 IU kg−1) intraperitoneally. The thoracic aorta was removed carefully and cleaned of fat and adherent connective tissues. It was cut into segments of 2–3 mm in length and mounted onto two stainless-steel stirrups immersed in a 10 ml organ chamber, containing Krebs–Henseleit solution (composition in mmol l−1: NaCl 120.0, KCl 4.6, CaCl2 2.5, MgSO4 1.2, NaHCO3 22.0, NaH2PO4 1.2, CaCl2 2.5, glucose 11.5) that was gassed continuously with 95% O2 and 5% CO2 and maintained at 37°C. The upper ends of the preparations were tied to an isometric transducer (Grass FT 03, Quincy, Massachusetts, USA) and preloaded with 1.5 g resting tension. They were allowed to achieve equilibrium for 60 min with the bath fluid being changed every 15 min. In some rings (n = 5), the endothelium was removed mechanically by inserting a polyethylene tube (PE50) into the lumen of the ring and rolling the vessel with the tube gently onto moistened gauze.
The aortic rings were precontracted with prostaglandin F2α (PGF2α) (10−7 mol l−1) and pancuronium (10−7–10−4 mol l−1), rocuronium (10−7–10−4 mol l−1), vecuronium (10−7–10−4 mol l−1) and mivacurium (10−7–10−4 mol l−1) were added to organ baths at cumulative concentrations in the presence or absence of a prostaglandin synthesis inhibitor, indomethacin (10−6 mol l−1), and a nitric oxide synthesis inhibitor, N(omega)-nitro-L-arginine methylester (L-NAME, 3 × 10−5) . The same protocol was applied to both endothelia (+) and endothelia (−) aortic rings.
Preparations precontracted with PGF2α (10−7 mol l−1) were stimulated with two parallel platinum electrodes at a frequency of 10 Hz as square-wave pulses of 50 V (0.2 ms) delivered by a current amplifier and a stimulator. Before electrical field stimulation (EFS), the tissues were treated with a noradrenaline reuptake inhibitor, desipramine (10−7 mol l−1), and a nonselective beta-blocker, propranolol (10−6 mol l−1) . Pancuronium, rocuronium, vecuronium and mivacurium were added to the organ bath at ineffective concentration of 10−7 mol l−1. Tetrodotoxin (10−7 mol l−1) was added to test whether the changes were depending on the neuronal response.
The drugs used were PGF2α, indomethacin, L-NAME, desipramine, propranolol, tetrodotoxin (Sigma Chemical, St Louis, Missouri, USA); vecuronium, rocuronium (N.W. Organon, Oss, Holland); mivacurium (Glaxo Smith Kline, Farma, Italy) and Pancuronium (Organon Teknika, Istanbul, Turkey). All drugs were prepared by dissolving in deionized water and were prepared freshly on the day of the experiment. The stock solutions were stored at −20°C.
All data are expressed as means ± SEM. Groups were compared statistically using general linear models of analysis of variance (ANOVA) followed by the Newman–Keuls test and t test when appropriate. A P value of less than 0.05 was considered significant. All analyses were performed with Statistica for Windows 6.0. (Statsoft, Inc., Tulsa, USA).
Pancuronium (10−7–10−4 mol l−1) and rocuronium (10−7–10−4 mol l−1) relaxed the preparations precontracted with PGF2α (10−7 M) in a dose-dependent manner but vecuronium and mivacurium did not. The relaxation effect of pancuronium was statistically more than rocuronium (P < 0.05) (Fig. 1a). There was no significant difference between their relaxation effects in the endothelium-denuded preparations (Fig. 1b). L-NAME (3 × 10−5) did not change the pancuronium (10−7–10−4 mol l−1) or rocuronium (10−7–10−4 mol l−1) effects but indomethacin (10−6 mol l−1) decreased their effect significantly (P < 0.05) (Fig. 2a and b).
EFS (10 Hz, 50 V, 0.2 ms) relaxed the preparations precontracted with PGF2αa (10−7 mol l−1); this relaxation effect was increased significantly by pancuronium (10−7 mol l−1), vecuronium (10−7 mol l−1), mivacurium (10−7 mol l−1) and rocuronium (10−7 mol l−1) (P < 0.05). Although desipramine, at a concentration sufficient to inhibit the uptake of catecholamine (10−7 M) by sympathetic nerve terminals , did not change EFS-induced relaxations, a nonselective beta-blocker, propranolol (10−6 mol l−1), decreased them significantly (P < 0.05). Tetrodotoxin (10−7 mol l−1), which blocks voltage-dependent Na+ channels, abolished EFS-induced relaxations (Fig. 3). Emax and pD2 values of pancuronium and rocuronium were calculated and are shown in Table 1.
The vasomotor effects of anaesthetics have been widely evaluated by the isolated vessel ring model. Various animal preparations have been used (rat aorta, canine mesenteric artery, porcine coronary artery and others). There are some studies with intravenous anaesthetics (propofol, thiopental and others) using this model .
Although neuromuscular blocking drugs are widely used with general anaesthetics, there are few studies evaluating the effects of them on vascular tone. Sai et al.  found that pancuronium caused relaxations in canine coronary and renal arteries partially contracted with PGF2α, whereas these arteries did not significantly respond to vecuronium.
The relaxant responses were independent of endothelium and abolished by treatment with indomethacin, a cyclooxygenase inhibitor, or tranylcypromine, a prostaglandin I2 (PGI2) synthesis inhibitor [20,21]. Among available prostanoids, only PGI2 relaxes canine coronary and renal arteries [21,22]. They concluded that these results might indicate that pancuronium releases vasodilator prostaglandins, possibly PGI2, from subendothelial tissues.
It has been reported that pancuronium stimulates the release of norepinephrine from nerves and simultaneously inhibits the neural uptake in canine-isolated saphenous veins  and in anesthetized dogs . Sai et al.  thought that the potentiation by pancuronium and vecuronium of the response to adrenergic stimulation appears to be due to the inhibition of the neural uptake of noradrenaline rather than the increased release of noradrenaline. In some studies, it was reported that, although vecuronium in clinical doses does not have the vascular action that pancuronium does [25,26], high doses of vecuronium may work as a sympathomimetic agent . Because of the endothelium-independent action, pancuronium might have some beneficial clinical effect, especially under pathologic conditions such as atherosclerosis and hypertension, in which the synthesis or action of nitric oxide [27,28] and endothelium-derived hyperpolarizing factor (EDHF) [28–30] are reduced. Sai et al.  reported that, in patients with heightened sympathetic activity, pancuronium and vecuronium also might elicit coronary vasodilatation through a potentiated action of noradrenaline on beta-adrenoceptors, whereas renal vascular resistance may be increased.
In another study , pancuronium produced a positive chronotropic effect. Vecuronium and rocuronium induced a positive inotropic effect; furthermore, vecuronium shortened the effective refractory period. All the changes in cardiac activity observed were induced by relatively high concentrations of the drugs.
There is only one study on the cardiovascular effects of mivacurium and in that study the authors reported that a slow injection rate of mivacurium (>30 s) might be used in hypertensive patients.
The plasma concentration of pancuronium administered to humans during the first 3 h is reportedly  500–100 ng ml−1 (about 90% free form , which is equivalent to 7 × 10−7 and 1.4 × 10−7 mol l−1, respectively). According to these data in this study, we used all of neuromuscular blocking drugs at concentrations similar to those in the study of Sai et al. . In this study, pancuronium and rocuronium relaxed aortic rings precontracted by PGF2α in a dose-dependent manner, but vecuronium and mivacurium did not. The relaxation effect of pancuronium and rocuronium was endothelium independent because there was not a significant response difference from the endothelium-denuded group. Their relaxation effects may be due to an increase in prostaglandin synthesis. The increased relaxation effect of pancuronium, rocuronium, vecuronium and mivacurium at EFS may be by decreasing the effect of noradrenaline reuptake from nerve endings because a noradrenaline reuptake inhibitor, desipramine, did not change this effect. Also, these neuromuscular agents may affect beta-receptors, because a nonselective beta-blocker agent, propranolol, decreased their EFS-induced relaxations.
In conclusion, pancuronium and rocuronium may have some clinical effect, especially under pathologic conditions such as atherosclerosis and hypertension in which endothelium is damaged. The mediation of prostaglandins in the relaxation effect of pancuronium and rocuronium may decrease their effect before surgical operations in the presence of prostaglandin synthesis inhibitors.
1 Bowman WC. Nonrelaxant properties of neuromuscular blocking drugs. Br J Anaesth 1982; 54:147–160.
2 Savarese JJ, Lowenstein E. The name of the game: no anesthesia by cookbook. Anesthesiology 1985; 62:703–705.
3 Iwatsuki N, Hashimoto Y, Amaha K, et al
. Inotropic effects of nondepolarizing muscle relaxants in isolated canine heart muscle. Anesth Analg 1980; 59:717–721.
4 Alvarez L, Escudero C, Silva L, Castillo-Olivares JL. Electrophysiological effects of atracurium and vecuronium
on normal and denervated hearts. J Cardiothorac Vasc Anesth 1992; 6:304–307.
5 Narita M, Furukawa Y, Ren LM, et al
. Cardiac effects of vecuronium
and its interaction with autonomic nervous system in isolated perfused canine hearts. J Cardiovasc Pharmacol 1992; 19:1000–1008.
6 Krol T, Siondalska-Kunicka E. Haemodynamic side-effects of pancuronium
. Anaesth Resusc Intensive Ther 1974; 2:161–165.
7 Cornet JP, Abiad M, Coriat P, et al
. Evaluation of the effects of rocuronium
bromide on haemodynamic and left ventricular function in patients under going abdominal aortic surgery. Eur J Anesth 1994; 11:78–81.
8 Marshall RJ, Muir AW, Sleigh T, Savage DS. An overview of the pharmacology of rocuronium
bromide in experimental animals. Eur J Anesth 1994; 11:9–15.
9 Milligan KR, Beers HT. Vecuronium
associated cardiac arrest. Anaesthesia 1985; 42:192–194.
10 Inoue K, El-Banayosy A, Stolarski L, Reichelt W. Vecuronium
induced bradycardia following induction of anaesthesia with etomidate or thiopentone, with or without fentanyl. Br J Anaesth 1988; 60:10–17.
11 Conzanitis DA, Lindgren L, Rosenberg PH. Bradycardia in patients receiving atracurium or vecuronium
in conditions of low vagal stimulation. Anaesthesia 1989; 44:303–305.
12 Salt PJ, Barnes PK, Conway CM. Inhibition of neuronal uptake of noradrenalin in the isolated perfused rat heart by panctrophysiological uronium and its homologues Org 6368, Org 7268, and NC45. Br J Anaesth 1980; 52:313–317.
13 Kobayashi O, Nagashima H, Duncalf D, et al
. Direct evidence that pancuronium
and gallamine enhance the release of norepinephrine from the atrial sympathetic nerve by inhibiting prejunctional muscarinic receptors. J Auton Nerv Syst 1987; 18:55–60.
14 Foldes FF, Kobayashi O, Kinjo M, et al
. Presynaptic effect of muscle relaxants on the release of 3H-norepinephrine controlled by endogenous acetylcholine in guinea pig atrium. J Neural Transm 1989; 76:169–180.
15 Appadu BL, Lambert DG. Studies on the interaction of steroidal neuromuscular blocking drugs with cardiac muscarinic receptors. Br J Anaesth 1994; 72:86–88.
16 Plaud B, Marty J, Debaene B, et al
. The cardiovascular effects of mivacurium
in hypertensive patients. Anesth Analg 2002; 95:379–384.
17 Sai Y, Ayajiki K, Okamura T, et al
. Comparison of the effects of pancuronium
in canine coronary and renal arteries. Anesthesiology 1998; 88:165–171.
18 Toda N. Interactions of bretylium and drugs that inhibit the neuronal membrane transport of norepinephrine in isolated rabbit atria and aortae. J Pharmacol Exp Ther 1972; 181:318–327.
19 Park WK, Lynch C, Johns RA. Effects of propofol and thiopental in isolated rat aorta
and pulmonary artery. Anesthesiology 1992; 77:956–963.
20 Gryglewski RJ, Bunting S, Moncada RJ, et al
. Arterial walls are protected against deposition of platelet thrombi by a substance (prostaglandin X) which they make from prostaglandin endoperoxides. Prostaglandins 1976; 12:685–713.
21 Toda N, Miyazaki M. Angiotensin-induced relaxation in isolated dog renal and cerebral arteries. Am J Physiol 1981; 240:H247–H254.
22 Toda N, Bian K, Akiba T, Okamura T. Heterogeneity in mechanisms of bradykinin action in canine isolated blood vessels. Eur J Pharmacol 1987; 135:321–329.
23 Vercruysse P, Bossuyt P, Hanegreefs G, et al
. Gallamine and pancuronium
inhibit pre and postjunctional muscarinic receptors in canine saphenous veins. J Pharmacol Exp Ther 1979; 209:225–230.
24 Domenech JS, Garcia RC, Sasiain JMR, et al
bromide: an indirect sympathomimetic agent. Br J Anaesth 1976; 48:1143–1148.
25 Marshall IG, Agoston S, Booij LH, et al
. Pharmacology of ORG NC 45 compared with other nondepolarizing neuromuscular blocking drugs. Br J Anaesth 1980; 52:11S–19S.
26 Morris RB, Cahalan MK, Miller RD, et al
. The cardiovascular effects of vecuronium
(ORG NC45) and pancuronium
in patients undergoing coronary artery bypass grafting. Anesthesiology 1983; 58:438–440.
27 Najibi S, Cowan CL, Palacino JJ, Cohen RA. Enhanced role of potassium channels in relaxations to acetylcholine in hypercholesterolemic rabbit carotid artery. Am J Physiol 1994; 266:H2061–H2067.
28 Van de Voorde J, Vanheel B, Leusen I. Endothelium-dependent relaxation and hyperpolarization in aorta from control and renal hypertensive rats. Circ Res 1992; 70:1–8.
29 Hayakawa H, Hirata Y, Suzuki E, et al
. Mechanisms for altered endothelium-dependent vasorelaxation in isolated kidneys from experimental hypertensive rats. Am J Physiol 1993; 264:H1535–H1541.
30 Fukao M, Hattori Y, Kanno M, et al
. Evidence for selective inhibition by lysophosphatidylcholine of acetylcholine-induced endothelium-dependent hyperpolarization and relaxation in rat mesenteric artery. Br J Pharmacol 1995; 116:1541–1543.
31 Melnikov AL, Malakhov KY, Helgesen KG, Lathrop DA. Cardiac effects of nondepolarizing neuromuscular blocking agents pancuronium
, and rocuronium
in isolated rat atria. Gen Pharmacol 1999; 33:313–317.
32 McLeod K, Watson MJ, Rawlins MD. Pharmacokinetics of pancuronium
in patients with normal and impaired renal function. Br J Anaesth 1976; 48:341–345.
33 Wood M. Neuromuscular blocking agents. In: Wood M, Wood AJJ, editors. Drugs and anesthesia: pharmacology for anesthesiologists.
Baltimore: Lippincott Williams and Wilkins; 1982. pp. 299–340.

domain: medical


text:
Help Wanted: The 8 Most Popular Jobs in the Marijuana Industry
Pot is a big business and only destined to get bigger. Legal sales last year reached $5.7 billion, up more than a billion dollars over the previous year. Sales this year are expected to top $7.1 billion.
This fall, we're likely to see marijuana legalization initiatives win in a handful of states—Arizona, California, Nevada, Maine, Massachusetts—which would more than triple the size of the legal marijuana market in the county. The combined population of the legal states so far is about 16 million; the population of California alone is more than 38 million. If all five initiative states vote for marijuana this year, the size of the legal market would grow to more than 55 million.
The already existing growth in the marijuana market combined with the prospect of a huge expansion in the near future is making pot a very hot industry. And that means job opportunities for people thinking about breaking into the field.
A number of marijuana industry job hunter websites have popped up in recent years to take advantage of the booming sector, and one of them has now put out a list of the hottest pot jobs. The website, 420careers.com, bills itself as "the marijuana industry's job listing site," and here's its list of the most popular jobs in pot:
- Budtenders – assist dispensary customers with purchasing marijuana. Basically pot shop sales clerks. Knowledge about different pot strains and products and their effects will be helpful, but it's still not likely to pay too much above minimum wage. Some listings offer hourly wages of $11-12 an hour; others put annual salaries in the mid-20s.
- Sales Reps – sell products (vapes, technology, edibles, etc.) to dispensaries. Go freelance or get paid on commission for peddling products. A classic sales gig where how much you make depends precisely on how much you can sell. Willie Loman, call home.
- Extraction Technicians – make marijuana concentrates. These jobs involve working in laboratory-type conditions and operating sophisticated CO2 or butane extraction systems to turn weed into cannabis oil. Job listers tend to be coy about pay offered in this field, but it requires some skills that should make it more remunerative than selling buds.
- Edibles Makers – make marijuana-infused foods and drinks. This is an entrÃ©e to the industry for people with culinary skills, such as cooks, bakers, and nutritionists. Relatively low-skilled work like being a line baker isn't going to pay very well, but there are also openings for food scientists, food chemists, and managers, with salaries of $60,000 to $80,000 and beyond
- Dispensary Security – patrol dispensaries for illegal activity. Wear a spiffy uniform, maybe even carry a gun, and get paid low wages. Median security guard salaries in Los Angeles are around $30,000 a year, but at least one LA dispensary was looking for guards willing to work for less than $20,000.
- Marijuana Growers – cultivate marijuana for dispensaries. These are not independent farmers, but employees of the dispensary, and the money is good. "Master Growers," the folks in charge of big-time grow operations, are being offered $100,000 a year and more. The folks doing the grunt work of maintaining and harvesting the plants don't get nearly as much, with hourly wages of $15 to $20 or so.
- Trimmers – trim and package marijuana flowers for dispensaries. Snip, snip, snip, all day long. Trimmers are being offered relatively low wages, around $15 to $20 an hour, in the legal marijuana industry. In the black or gray market, however, they tend to get paid piece rate (50 cents a gram or thereabouts), and a good trimmer can make $200 a day or so. Tax free.
- Dispensary Managers – manage all or various aspects of dispensaries. Doing essentially the same work as any other retail store manager, except for the exotic product. The job requires extensive management skills, as well as pot knowledge, with compensation linked to the size of the operation. A part-time manager job was being offered at $25,000 in Scappoose, Oregon, while a full-time in Sacramento was going for $60,000. Dispensaries with larger volumes will pay even larger salaries.
There are also openings for marijuana-related businesses and professionals. The five most popular auxiliary jobs in the US marijuana industry are::
- Consultants (cultivation, business management, etc.)
- Web Developers/Designers

domain: economics


text:
US 7659319 B2
Proton conducting membranes are made of sulfonated films comprising poly(arylene sulfide), an olefinic polymer, and an elastomer. They are used in PEM fuel cells operating at temperatures above 95° C., or at low relative humidity. According to methods of the invention, sulfonated poly(phenylene sulfide) (SPPS) films are provided with a wide range of physical properties, which depend in part on the ion exchange capacity of the films. In particular, the degree or level of sulfonation can be tailored by adjusting reaction conditions such as temperature and time.
1. A polyelectrolyte membrane, comprising an insoluble sulfonated film having a sulfonate content in meq SO3H/g of at least 0.64, wherein the film comprises
A) a poly(arylene sulfide),
B) an olefinic polymer comprising functional epoxy groups, and
C) an elastomer
wherein the weight ratio of A/(B+C) is from 70/30 to 95/5, and the weight ratio B/C is from 10/90 to 80/20.
2. A polyelectrolyte membrane, according to
3. A polyelectrolyte membrane according to
4. A polyelectrolyte membrane according to
5. A polyelectrolyte membrane according to
6. A film according to
7. A membrane electrode assembly comprising a proton exchange membrane film according to
8. A fuel cell comprising a membrane electrode assembly comprising a polyelectrolyte membrane according to
9. A film according to
10. A polyelectrolyte membrane according to
11. A polyelectrolyte membrane according to
12. A polyelectrolyte membrane according to
13. A polyelectrolyte membrane according to
14. A polyelectrolyte membrane according to
15. A polyelectrolyte membrane according to
16. A polyelectrolyte membrane according to
17. A polyelectrolyte membrane according to
18. A polyelectrolyte membrane according to
This application is a divisional of U.S. patent application Ser. No. 11/053,434 filed on Feb. 8, 2005, now U.S. Pat. No. 7,601,449. The entire disclosure of the above application is incorporated herein by reference.
The present invention relates to polyelectrolyte membranes and their use as proton exchange membranes in fuel cells. More particularly, the invention relates to treatment of poly(phenylene sulfide) films to provide a polyelectrolyte for fuel cell applications.
Fuel cells are increasingly being used as power sources for electric vehicles and other applications. An exemplary fuel cell has a membrane electrode assembly with catalytic electrodes and a membrane formed between the electrodes. Hydrogen fuel is supplied to the anode side of the assembly, while oxygen is supplied to the cathode. The membrane provides an electrical connection between the anode and cathode, and provides a medium through which fuel oxidation products are transported from the anode to combine with the reduced oxygen at the cathode. The overall reaction in the fuel cell is the combination of hydrogen and oxygen to yield water and an electromotive potential. Because the oxidation product of the fuel is essentially H+ or a proton, the polyelectrolyte membrane is also known as a proton conducting membrane or a proton exchange membrane (PEM).
Water management is important in a PEM fuel cell. A proton must be hydrated to pass through the proton exchange membrane to combine with oxygen at the cathode. According to various models, 7 to 11 water molecules are needed to account for the transport of one proton through the membrane. It has been observed that when relative humidity in the fuel cell is low, proton transport is less efficient and the current available from the cell is reduced. To avoid this, it is possible to humidify fuel cells to prevent the membranes from drying out. However, as temperature of fuel cell operation increases, pressurization may be necessary which leads to added expense.
PEM fuel cells operate at temperatures up to about 95° C. with external humidification at elevated pressures being required to maintain proton conductivity. As the membranes dry out at reduced humidity, proton conductivity deteriorates rapidly.
The industry is constantly looking for new membrane material that conduct proton efficiently at reduced humidity levels. It would further be desirable to provide membranes for PEM fuel cells with improved cost and durability characteristics.
New proton conducting membranes contain poly(arylene sulfide) polymers (PAS) bearing sulfonic acid groups. The membranes are prepared by the solid state sulfonation of films comprising the poly(arylene sulfide) polymers, an olefinic polymer containing epoxy groups, and an elastomer that improves the impact resistance, melt flowability, or flexibility of the film. A preferred poly(arylene sulfide) polymer is poly(p-phenylene sulfide). The membranes can be used in PEM fuel cells operating at temperatures above 95° C., or at low relative humidity. According to methods of the invention, sulfonated poly(phenylene sulfide) (SPPS) films can be provided with a wide range of physical properties, which depend in part on the ion exchange capacity of the films. In particular, the degree or level of sulfonation can be tailored by adjusting reaction conditions such as temperature and time. The SPPS membrane materials can be used as polyelectrolyte membranes in PEM fuel cells.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
In one embodiment, the invention provides an polyelectrolyte membrane comprising an insoluble sulfonated film. The film is made of three polymeric components, being A) a poly(arylene sulfide), B) an olefinic polymer comprising epoxy groups, and C) an elastomer. The weight ratio of A/(B+C) is from 70/30 to 95/5, and the weight ratio B/C is from 10/90 to 80/20 etc. The poly(arylene sulfides) are a known class of thermoplastic polymer. In various embodiments, the poly(arylene sulfide) comprises polymeric reaction products of polyhalogenated aryl compounds with a source of sulfur. In one embodiment, the polymer has a structure resulting from the reaction of para-dichlorobenzene and sodium sulfide, to form a preferred poly(p-phenylene sulfide).
The polyelectrolyte film can be produced as the reaction product of a sulfonation reagent such as chlorosulfonic acid and an extruded film containing components A) a poly(arylene sulfide), B) an olefinic polymer comprising epoxy groups, and C) an elastomer wherein the weight ratio of A/(B+C) is from 70/30 to 95/5, and the weight ratio B/C is from 10/90 to 80/20 etc. The polyelectrolyte film is insoluble in water, indicating the presence of some level of crosslinking in addition to the incorporated sulfonate groups. The sulfonate content of the polyelectrolyte film, also referred to as the ion exchange capacity (IEC), is preferably at least 0.64 milliequivalents per gram (meq/g). In preferred embodiments, the sulfonate content in meq/g is 1.7 or greater or 1.9 or greater.
The invention also provides a membrane electrode assembly comprising a catalytic anode, a catalytic cathode, and a proton exchange membrane disposed between and in contact with the electrodes. The proton exchange membrane is a polyelectrolyte film such as discussed above. The invention further provides fuel cells containing these membrane electrode assemblies.
In another embodiment, the invention provides a method for making a polyelectrolyte film suitable for use in electrochemical applications such as a fuel cell. The method comprises reacting a sulfonation reagent such as chlorosulfonic acid with an extended film comprising components A) a poly(arylene sulfide), B) an olefinic polymer comprising epoxy groups, and C) an elastomer. In one aspect, the method comprises immersing the extruded film in a solution of chlorosulfonic acid for a time and at a temperature sufficient to incorporate at least 0.64 meq/g SO3H. The temperature and time of the reaction can vary over a wide range, depending upon the concentration of chlorosulfonic acid, the degree of desired sulfonate incorporation, the desired turnaround, etc. For example, the temperature conveniently can range from about 20° C. to about 50° C. and the time from about 1 to about 60 hours. In one embodiment, the immersion of the film in the chlorosulfonic acid solution takes place at room temperature for a time of 10 to 30 hours.
After immersing the film in the chlorosulfonic solution, the film is exposed to water to hydrolyze chlorosulfonic groups to sulfonic acid groups. In one embodiment, the film is exposed to boiling water.
Fuel cells are provided according to the invention by using a polyelectrolyte film made by the above method as a proton exchange membrane. In preferred embodiments, the sulfonate content of the proton exchange membrane is 1.7 meq/g or greater, the liquid water conductivity at 30° C. is greater than 0.1 S/cm, and the conductivity at 100° C. is greater than 0.2 S/cm. In other preferred embodiments, the sulfonate content is 1.9 meq/g or higher.
A PEM fuel cell comprises an anode, a cathode, a proton exchange membrane disposed between the anode and the cathode, an inlet for hydrogen fuel adjacent the anode, and an inlet for oxygen adjacent the cathode. The proton exchange membrane comprises a sulfonated film, as described above, preferably having a sulfonate content of at least 0.64 meq/g SO3H. In various embodiments, the proton exchange membrane is an insoluble sulfonated film made by the method described above.
Suitable films containing components A) a poly(arylene sulfide), B) an olefinic polymer comprising epoxy groups, and C) an elastomer are described below and in U.S. Pat. No. 5,625,002 to Kadoi et al., the disclosure of which is incorporated by reference.
Suitable poly(arylene sulfides) useful as component A) a poly(arylene sulfide) include polymers represented by formula (I)
A preferred poly(arylene sulfide) polymer is poly(p-phenylene sulfide), also known as PPS. PPS has an idealized structure according to the formula
Mixtures of para- and meta-dichlorobenzene may be used with a source of sulfide to prepare poly(arylene sulfide) useful to make the polyelectrolyte membranes of the invention. In other embodiments, small amounts of 1,2,4-trihaloarylenes, such as 1,2,4-trichlorobenzene may be used. Use of small amounts of the tri-substituted arylenes introduces some branching into the polymeric structure. It is also possible to produce random copolymers containing paraphenylene sulfide and alkyl substituted phenylene sulfides.
In various embodiments, the PAS can comprise up to 30 mole % of recurring units represented by any of the following structural formulae:
As described above, the kind of PAS used in the present invention is not particularly critical, but in view of the affinity with an olefinic copolymer described below, preferably PAS which has been subjected to a deionizing purification treatment to remove ionic species is used. In various embodiments, the ion content of PAS expressed as the sodium content is not larger than 900 ppm, preferably not larger than 500 ppm. Non-limiting means for reducing the sodium content, include (a) an acid treatment, (b) a hot water treatment, and (c) an organic solvent washing treatment.
Acid treatment is carried out in the following manner. The PAS is dipped in or otherwise exposed to an acid or an aqueous solution of an acid, with appropriate stirring and heating. In a non-limiting example, a powdery PAS is immersed in an aqueous solution of acetic acid of pH 4, heated at 80° to 90° C., and stirred for 30 minutes. To remove the residual acid or salt, the acid-treated PAS is afterwards washed with water or warm water, preferably distilled water.
In a non-limiting example, hot water treatment is conducted by adding a predetermined amount of the PAS to a predetermined amount of water—preferably distilled water—and heating the thus-prepared mixture under stirring in a pressure vessel. Preferably the temperature of the hot water is at least 100° C., more preferably at least 120° C., most preferably higher than 150° C., and especially preferably higher than 170° C. A large proportion of water to PAS is preferred, and in general, a bath ratio of not larger than 200 g of PAS per liter of water is selected.
To avoid degradation of the polymer, the treatment is preferably carried out in an inert atmosphere. To remove the residual components, preferably the PAS that has been subjected to the hot water treatment is washed several times with warm water, maintained at a temperature of lower than 100° C., more preferably at a temperature of at least 10° C. but lower than 100° C.
Alternatively or in addition, organic solvents not having an action of decomposing PAS can be used for washing PAS. Non-limiting examples of solvents include nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, and piperazinone; sulfoxide and sulfone solvents such as dimethyl sulfoxide, dimethylsulfone, and sulfolane; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone, ether solvents such as diethyl ether, dipropyl ether, dioxane, and tetrahydrofuran; halogen-containing hydrocarbon solvents such as chloroform, methylene chloride, ethylene dichloride, trichloroethylene, perchloroethylene, monochloroethane, dichloroethane, tetrachloroethane, perchloroethane, and chlorobenzene; alcohol and phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Of these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide and chloroform are especially preferred. Further, these solvents can be used alone or as a mixture of two or more.
Washing with organic solvent is accomplished by immersing PAS in the organic solvent and heating or stirring as appropriate. The washing temperature for the organic solvent washing is not particularly critical, and an optional temperature can be selected of from room temperature to about 300° C. The washing efficiency is increased with an elevation of the washing temperature, but in general, a satisfactory effect is obtained at a washing temperature of from room temperature to 150° C.
Further, the washing can be carried out under pressure at a temperature higher than the boiling point of the organic solvent in a pressure vessel. The washing time is not particularly critical, and for a batchwise washing, a satisfactory effect is generally obtained if the washing is conducted for at least 5 minutes. Alternatively, the washing can be performed in a continuous manner.
In other embodiments, it is preferred to combine one or two of the other treatments. For example when, a high-boiling-point organic solvent such as N-methylpyrrolidone is used, the residual organic solvent can be easily removed by washing with water or warm water after the organic solvent washing, and preferably distilled water or deionized water is used for this washing.
In various embodiments, a satisfactory effect can be obtained by carrying out the above-mentioned acid treatment or hot water treatment alone. Alternatively a method can be adopted in which the acid treatment is first carried out and the hot water treatment is carried out thereafter, or a method can be adopted in which the hot water treatment is first carried out and then the acid treatment is carried out.
The epoxy group-containing olefinic polymer (B) used in the present invention is an olefinic polymer having an epoxy group in the side chain or main chain. Suitable polymers include olefinic polymers having a glycidyl group such as a glycidyl ester, a glycidyl ether or a glycidyl amine in the side chain, and olefinic polymers having a double bond epoxy-oxidized. A preferred epoxy group-containing olefinic polymer is a copolymer of an α-olefin with a glycidyl ester of an α,β-unsaturated acid. Examples of olefin include ethylene, propylene and butene-1. The glycidyl ester of the α,β-unsaturated acid is represented by the following formula:
Non-limiting examples, include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate. The content of the epoxy group in the epoxy group-containing olefinic polymer (B) is preferably 0.1 to 30% by weight, especially 0.2 to 10% by weight. If the content of the epoxy group is lower than 0.1% by weight, the desired effects cannot be obtained, and if the content of the epoxy group exceeds 30% by weight, gelation tends to occur at the melt kneading with PAS.
A minor amount of another olefinic monomer such as methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl acetate or vinyl ether can be copolymerized with the epoxy group-containing olefinic polymer (B) used in the present invention, as long as the effects of the present invention still can be obtained.
As described above, the impact characteristics can be improved in a PAS composition prepared by incorporating the epoxy group-containing olefinic polymer (B). Preferably, an elastomer (C) is incorporated into the components A) and B) to improve the impact characteristics and enhance the melt flowability and flexibility.
The elastomer (C) used in the present invention preferably does not include an epoxy group and an acid anhydride group and has a flexural modulus not larger than 10,000 kgf/cm2. The use of an elastomer containing an acid anhydride group is not preferred because it would tend to raise the melt viscosity of the composition and reduce the moldability of the composition.
The elastomer (C) can be any elastomeric substance that provides the benefits noted above. In preferred embodiments, the elastomer C) is selected from the group consisting of ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/propylene/diene copolymers, hydrogenated styrene/butadiene/styrene block copolymers, copolymers of ethylene with acrylic acid, methacrylic acid or alkyl esters or metal salts thereof, and polyamide elastomers. In various embodiments, other elastomers, such as butadiene/styrene copolymer, butadiene/acrylonitrile copolymer, polybutadiene, ethylene/vinyl acetate copolymer and plasticized polyvinyl chloride are less preferred.
The ethylene/propylene copolymer is a copolymer of ethylene and propylene having a melt flow index of 0.1 to 50 g/10 min as determined according to JIS K-7210, and preferably the ethylene content is 30 to 95% by weight, more preferably 40 to 90% by weight.
A suitable ethylene/butene copolymer is a copolymer of ethylene and butene-1 having a melt index of 0.5 to 50 g/10 min as determined according to JIS K-7210, and preferably the ethylene content is 30 to 95% by weight, more preferably 40 to 90% by weight.
A suitable ethylene/propylene/diene copolymer is a copolymer prepared by introducing a diene compound into an ethylene/propylene copolymer, and the iodine value as the factor indicating the quantity introduced of the diene compound is generally 5 to 30. As the diene compound to be introduced, there can be mentioned hexadiene, norbornadiene, and ethylidene norbornene.
A suitable hydrogenated styrene/butadiene/styrene block copolymer is a copolymer obtained by hydrogenating a part or all of the intermediate butadiene blocks of a styrene/butadiene/styrene copolymer elastomer, for example, according to the process disclosed in the specification of U.S. Pat. No. 3,413,323. The melt flow index of the copolymer is 0.5 to 100 g/10 min, as determined according to JIS K-7210, and the styrene content is preferably 5 to 60 mole %, more preferably 10 to 50 mole %.
Suitable copolymers of ethylene with acrylic acid, methacrylic acid, and alkyl esters in which the alkyl group has 1 to 5 carbon atoms, and metal salts thereof, include ethylene/acrylic acid ester copolymers such as an ethylene/methyl acrylate copolymer, an ethylene/ethyl acrylate copolymer, an ethylene/propyl acrylate copolymer and an ethylene/butyl acrylate copolymer, ethylene/methacrylic acid ester copolymers such as an ethylene/methyl methacrylate copolymer, an ethylene/ethyl methacrylate copolymer, an ethylene/propyl methacrylate copolymer, and an ethylene/butyl methacrylate copolymer, an ethylene/acrylic acid copolymer and an ethylene/methacrylic acid copolymer, and their metal salts such as Na, Zn, K, Ca and Mg salts.
Suitable polyamide elastomers include block copolymer elastomers having hard segments of a polyamide component and soft segments of a polyether component and/or a polyester component. Examples of the polyamide component, include
Of the foregoing elastomers (C), an ethylene/propylene copolymer, an ethylene/butene copolymer, an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, an ethylene/acrylic acid ester copolymer, and an ethylene/methacrylic acid ester copolymer are preferred.
The mixing ratio among the PAS (A), the epoxy group-containing olefinic copolymer (B), and the elastomer (C) is preferably within a range such that the (A)/[(B)+(C)] weight ratio is from 55/45 to 99/1, more preferably from 70/30 to 95/5, and the (B)/(C) weight ratio is from 95/5 to 5/95, more preferably from 80/20 to 10/90. If the ratio of the component (A) is lower than about 55% by weight, the strength and rigidity of the composition tend to be lowered, and if the ratio of the component (C) based on the sum of the components (B) and (C) is lower than 5% by weight, there tends to be little improvement of the melt flowability.
The method of preparing the film is not particularly critical. In one embodiment, PAS (A), the epoxy group-containing olefinic polymer (B), and the elastomer (C), are melt-kneaded at a temperature higher than the melting point of the PAS in an extruder, and the resulting kneaded mixture is pelletized. Thereafter a film can be extended or solution cast according to known techniques.
In general, preferably the melt-kneading temperature is higher than 280° C., to sufficiently melt the composition, and lower than 340° C. to prevent a thermal deterioration and gelation of the olefinic copolymer (B). Namely, preferably the melt-kneading temperature is 280° to 340° C.
A suitable film containing the three components A) a poly(arylene sulfide), B) an olefinic polymer comprising epoxy groups, and C) an elastomer is sold under the Ryton® 16C and XTEL-XE trade names by Chevron-Phillips.
Because PAS and PPS have limited solubility in many solvents, it is sometimes difficult or impossible to produce solution cast films of compositions containing them. However, the polymers are melt processable, so in a preferred embodiment extruded films are produced. Non-limiting examples of extruded films include 0.5 mil, 1 mil, and 2 mil films. PAS is insoluble in concentrated sulfuric acid. but readily disperses in oleum (fuming sulfuric acid consisting of 30% by weight SO3 in sulfuric acid) and in chlorosulfonic acid (CISO3H). The reaction with oleum leads to highly sulfonated polymers that are soluble in water, while reaction with CISO3H leads to the insoluble films of the invention.
PAS reacts with chlorosulfonic acid to introduce the chlorosulfonyl group (—SO2Cl) onto aromatic rings of the polymers. The polymer-bound chlorosulfonyl groups are subsequently converted to sulfonic acid groups upon hydrolysis, for example by exposing the sulfonated films to boiling water for one hour. The products derived from reaction with the chlorosulfonic acid are insoluble. This is believed to be due in part to a crosslinking reaction involving the formation of sulfone groups (—SO2—). The crosslinking provides advantages for the chlorosulfonation of preformed PAS films, because the crosslinking reaction reinforces physical properties and prevents the films from dissolving in water.
In various embodiments, a polyelectrolyte film suitable for use as a proton exchange membrane in a fuel cell is made by reacting an extruded PPS film with chlorosulfonic acid. The films contain components A) a poly(arylene sulfide), B) an olefinic polymer comprising epoxy groups, and C) an elastomer, as described above. For example, preformed films are immersed in a solution of chlorosulfonic acid in a solvent such as dichloromethane or 1,2-dichloroethane. Immersion occurs for a time and at a temperature sufficient to incorporate a desired amount of sulfonate or chlorosulfonyl groups onto the aromatic rings of the polymer. In one embodiment, at least 0.64 meq SO3H/g is incorporated. After immersing the film in the chlorosulfonic solution for a sufficient time, the film is thereafter exposed to water. This step converts the chlorosulfonyl groups to sulfonic acid groups by hydrolysis. The hydrolysis step can be carried out at elevated temperatures, such as in boiling water, to provide faster reaction kinetics.
After hydrolysis, the amount of sulfonic acid groups incorporated into the film can be determined by conventional means, such as titration with sodium hydroxide to a pH of 7. The number of mL of sodium hydroxide solution required to titrate the film to a pH of 7 is converted into meq SO3H/g of film by conventional methods.
Useful polyelectrolyte membranes in general have liquid conductivity measured in S/cm at 30° C. or 100° C. that are comparable to those of conventional perfluorosulfonic acids used as proton exchange membranes in fuel cells. For example, the commercially available proton exchange membrane, Nafion 112 from DuPont exhibits a liquid conductivity at 30° C. of 0.129 S/cm at 30° C. and 0.259 S/cm at 100° C. Such conductivity measurements may be made as described by Zawodzinski et al., J. Phys. Chem. 95 (15) 6040 (1991). The membrane is conditioned in 100° C. water for 1 hour and the measurement cell is submersed in 25° C. deionized water during the experiment. The membrane impedance (real) is taken at zero imaginary impedance.
According to another embodiment of the invention, a fuel cell is provided that contains the insoluble sulfonated film described above as a proton exchange membrane. Such fuel cells typically contain a catalytic anode, a catalytic cathode, and a proton exchange membrane disposed between the anode and cathode. The fuel cell also contains an inlet adjacent the anode for providing hydrogen fuel to the anode side of the fuel cell, and an inlet adjacent the cathode for providing oxidant gas (oxygen) to the cathode.
Referring generally to
The MEAs 13,15,14 and bipolar plates 16,18 are stacked together between aluminum clamping plates 32 at each end of the stack and the end contact terminal plate elements 20,22. The end contact terminal plate elements 20,22, as well as working faces 28,30 and 31,33 of both bipolar separator plates 16,18, contain a plurality of gas flow channels (not shown) for distributing fuel and oxidant gases (i.e., H2 & O2) to the MEAs 13,15,14. Nonconductive gaskets or seals (not shown) provide seals and electrical insulation between the several components of the fuel cell stack. Gas-permeable conductive diffusion media 34 press up against the electrode faces of the MEAs 13,15,14. When the fuel cell stack is assembled, the conductive gas diffusion layers 34 assist in even distribution of gas across the electrodes of the MEAs 13,15,14 and also assist in conducting electrical current throughout the stack.
An inlet for oxygen adjacent the cathode and an inlet for hydrogen adjacent the anode are also provided. Oxygen is supplied to the cathode side 36 of each fuel cell in the stack from storage tank 40 via appropriate supply plumbing 42 to provide an inlet for oxygen adjacent the cathode, while hydrogen is supplied to the anode side 38 of the fuel cell from storage tank 44, via appropriate supply plumbing 46 to provide an inlet for hydrogen adjacent the anode. Alternatively, air may be supplied to the cathode side 36 from the ambient, and hydrogen to the anode 38 from a methanol or gasoline reformer, or the like. Exhaust plumbing for the anode side 48 and the cathode side 50 of the MEAs 13,15,14 are provided. On the cathode side, the plumbing defines an exit side. Gas flow into and out of the stack is typically facilitated by fans 60, such as those shown in the exemplary configuration of
As shown in
The invention has been described above with respect to various preferred embodiments. Further non-limiting examples are given in the examples that follow.
Dichloromethane (50 mL, 66 gm) and chlorosulfonic acid (between 0.7 and 1.4 gms) are added sequentially to a wide mouth glass bottle (120 mL capacity, 2 inch diameter). 10 mL of this solution are added to dichloromethane (50 mL, 66 gms) in a wide mouth glass jar (410 mL, 3 inch diameter). To this mixture is added a 1 mil (0.001 inch, 0.0025 cm) colorless film of Ryton® 16C or XTEL-XE (Chevron-Phillips) consisting of a circle with a diameter of 2.75 inches and weighing between 0.14 and 0.18 gm. The jar is sealed with a screw cap lid and the film is allowed to react for various amounts of time at 25° C. while being suspended in the reaction solution. The insoluble colorless film is observed to turn blue-green and then black after several seconds of immersion in the reaction solution. After a variable time of reaction, the black film is then added to distilled water (200 mL) and the film turned light yellow. The film is washed extensively with more water (about 2 liter) and then boiled in water (250 mL) for about 1 hour. The film is then suspended in 1 molar sodium chloride (220 mL) and the amount of sulfonation is determined by titration with 0.01 molar sodium hydroxide to a pH 7 end point. The amount of sulfonation (in meq/g SO3H) with reaction time is 0.64 (1 hour), 1.27 (6.5 hours), 1.71 (16 hours), 1.86 (24 hours), 2.31 (48 hours), and 2.6 (60 hours). The sulfonated film with 1.9 meq/g SO3H had a liquid water proton conductivity of 0.131 and 0.337 S/cm at 33° C. and 100° C. respectively.
The reaction described above is repeated at 40° C. After 4 hours, the amount of sulfonation is determined by titration with 0.01 molar sodium hydroxide to be 2.36 meq/g SO3H. The physical properties of the film are better than those with membranes similar ion exchange capacities made at 25° C.
Polyelectrolyte films of Examples 1 and 2 are flexible enough to be handled and made into MEA's and fuel cells according to known methods. Comparable films made by chlorosulfonating a film containing component A) but not components B) or C) are too brittle for subsequent use in making fuel cells.
Although the invention has been described above with respect to various preferred embodiments, the invention is not limited to the embodiments disclosed. Variations and modifications as will occur to those of skill in the art upon reading the disclosure are also included in the scope of the invention, which is limited only by the appended claims.