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DoItYourself.com Community Forums > Heating, Cooling, Air Conditioning, Ventilation and T-Stat Controls > Heat Pumps and Electric Home Heating
Geothermal can produce hydrogen?
CarlR
Location: Mid-Michigan
"Hydrogen can be produced using diverse, domestic resources including fossil fuels, such as natural gas and coal (with carbon sequestration); nuclear; and biomass and other renewable energy technologies, such as wind, solar, geothermal, and hydro-electric power."
- http://www1.eere.energy.gov/hydrogenandfuelcells/production/
So how could you use an open loop geothermal system to produce hydrogen to create power for your house?
Find all posts by CarlR
airman.1994
Can't be done! They are made to heat and cool your home.
Find all posts by airman.1994
stickshift
Location: WI/MN
Forget about it - significantly higher cost to capture, process and utilize than worth even thinking about.
Find all posts by stickshift
Do you know how the process is done, or possibly any links, so that I could see for myself whats involved?
GregH
Location: Manitoba
You are talking about two different things.
An open loop geothermal system can not produce hydrogen.
Geothermal is used to transfer heat, hydrogen production is a chemical process.
Use Google and you will find many links for what you want to know.
Visit GregH's homepage!
Find all posts by GregH
Ya guys do understand that the quote was directly from the Department of Energy's website, and not my own words, right???
I know what Geothermal is used for, but when I came accross this from the governments website, I had to clear it up......................
There's plenty of examples of people using geothermal wells to produce hydrogen. Buses in Denmark, German engineers, Iceland, to name a few.
Also here's a link to an article about a resort in Alaska that runs their buildings, and vehicles on hydrogen that was produced with geothermal heat.
http://www.autobloggreen.com/2007/07/09/alaska-resort-using-hydrogen-to-fuel-appliances-and-vehicles/
Also I know it's not hydrogen related, but I was wondering if something like this could be scaled down to power a house. It seems like a simple concept.
Could get the picture to show, but there's the link.
http://www.dodgetalk.com/forums/attachment.php?attachmentid=154949&stc=1
Concretemasonry
Heat Pumps and Electric Heating > Geothermal can produce hydrogen?
I think the plants you are referring to use the geothermal (heat) as an energy source to supplement other energy sources like gas and electricity. The process of producing hydrogen is nothing new, but it does require energy and a big investment because of the technology, equipment and materials.
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Heat Pumps and Electric Home Heating
Does this quote make sense?
abunai on Jun 09, 2007
I recieved the quote of 5300 on installation of the following trane system: 4TWR3024A1000A 4TEE3F31A1000A BAYHTR1410BRKB HONEYWELL PRO 8000 Wanted to know if the units made sense and if the price was within range. Additionally I can not replace the old R22 pipes, and this looks like R410A system, should i go back and ask for an R22 system.?
Charging your heat pump.
mattison on Aug 16, 2007
Since it is illegal for anyone not certified by the EPA to handle refrigerants and we here at Do It Yourself have no way of knowing if a user is certified or not, or if another reader may take the info and perform illegal activities we will not give any information on charging procedures, or any type of sealed circuit repairs. Charging procedures include how to properly charge your system, what the proper pressures should be, etc... Sealed circuit repairs include any work that requires the handling of refrigerant such as changing an a-coil, moving a condenser unit yourself, changing out a heat pump unit yourself, etc... General questions on what the effects of too much refrigerant or too little refrigerant in the case your system is freezing or a tech added refrigerant and it's not performing properly are welcome but repair remedies will not be given if it pertains to the refrigerant circuit. We will tell you what to look out for when a tech is working on your unit but no step by step or technical information. Posts or threads violating this sticky will be edited or deleted.


It is pretty cool seeing Whistler mapped by Google Street View. The runs looks quite difference in street view than when I am skiing on it. I guess when I am skiing, I was too focus on not falling down. I didn't take a good look at the scenery on both side of the run.


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Q: Why is vlookup returnig N/A I have a excel file which has 4 columns on Sheet1 and I need to check If Email from Sheet 1, matches Email from Sheet2, then write the Date (B) column from sheet2 in sheet1
Tried something like that but it is returning N/A everytime
=VLOOKUP(C2,Sheet2!$B:$E,2,FALSE)

Sheet1
First Name (A)| Last Name (B)| Email (C)| Phone (D)
Sheet2
First Name (A)| Date (B)| Last Name (C) | Phone (D)| Email (E)

redpajama_set_name: RedPajamaStackExchange


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A prickly pair – the bull rout and the pogge
What a lot of bull
Despite its other name, the bull rout does not have a poisonous sting in its tail. Instead it has extremely sharp – but not venomous – spines on its head and body. There's no need to kill the fish for fear of being 'stung'', but any wound should be cleaned as soon as possible.
The bull rout varies in colour from mottled green-brown to pale grey and has dark blotches on its back and head. The fins are quite distinctive with a bumblebee like yellow and black pattern on them. It also has a membrane (flap of skin) stretching across the throat, joining the gill covers.
The belly of the male is yellow but during spawning the fish changes dramatically. Most of the body turns a coppery colour while the belly becomes deep red, spattered with white polka dots.
The bull rout reaches about 30cm (12in) in length. It is found all around Britain but occurs nearest to the shoreline in its more northerly ranges. Specimens approaching the 2/4 lb (1.2kg) mark have been caught off the North Sea coast.
You'll find it from a depth of about 4m (13ft) inshore down to 60m (200ft) on almost any type of sea bed. In the southern parts of its range it penetrates estuaries and appears among rocks and seaweed. A gluttonous predator, it feeds heavily on shrimps and crabs as well as herring, sandeels, whiting and gobies.
Bull rout spawn in mid to late winter. The orange eggs, laid in clumps among rocks and seaweed, are guarded by the male fish. After hatching the young fry live near the surface until they are about 15mm (%in) long. Bull rout grow quite fast – reaching 17cm (7in) long after three years and up to 30cm (12in) at six years.
This little pogge
The pogge is an easily identified little fish. Its body is completely covered with bony, armour-like plates and there are a large number of bristle-like barbels under its lowerjaw.
It is called the hooknose because it has a pair of small hooked spines on the tip of its snout. There are also long curved spines on each of its lower gill covers. It is smaller than the bull rout – usually l-2oz (28-56gm) in weight and growing to a maximum length of about 15cm (6in).
A bottom-living fish, it can be found from a few metres of water down to about 200m (660ft). The pogge spends much of its time on the bottom, using its barbels to find food buried in the sea bed. Young pogge feed on sandhoppers but as they grow they take small shrimps, shore crabs, brittlestars and herring eggs.
Pogge spawn from February to April, when the female lays yellow eggs in small clumps among large brown seaweed. The eggs are not guarded and take almost a year to develop before hatching. This fish has a small mouth and is only likely to be taken by anglers fishing close to the sea bed with small hooks. It often appears in the catches of shrimp trawlers or in sprat nets.
As bold as wrasse: the rock cook and corkwing
The speckled brill -sea-bed chameleon
Conspicuous cuckoo
Favourite plaice
Black bream: deep water dwellers
The spiny spurdog
The free-loading sea lamprey
Plaice Fishing Tips
A glittering prize
The red mullet
Skate Fishing
The extraordinary John dory
← A glittering prize
Ailing eels, poorly pike and peaky perch →

redpajama_set_name: RedPajamaCommonCrawl


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December 6, 2005 No comments MJEOL BULLET
Astonishing Jackson Trial Discussion w/ Mesereau – MB#290
Part 1 | Part 2
DECEMBER 6 2005 — "You can't be afraid of your case especially if you have the truth on your side," said Attorney Thomas Mesereau as he was speaking in front of a crowd at Harvard Law School Nov 29 2005.
During his appearance on the discussion panel, the philanthropic attorney talked about the Michael Jackson trial which resulted in an acquittal on 14 counts (10 felony and 4 misdemeanor) earlier this year. Dan Abrams was also on the panel. More about his contentions will be in Part 2 of this special MJEOL Bullet.
Mesereau spoke on a number of issues and gave advice to future lawyers about how to think independently and to customize their defense depending on the case they are trying. One of those issues was race and how it can play a part in the justice system.
He said what happened to Jackson earlier this year was "absolutely unjust" and that the "case", in his opinion, was a "total fraud". No arguments here.
He laid into prosecutors like only he can, lambasting their zeal to get a conviction against Jackson by almost any means necessary. Again, no arguments here.
In conservative, libertarian Santa Maria, Jackson is extremely popular among all age groups, according to Mesereau, who spent time in Santa Maria before the trial.
"White people, latino people, young, middle aged, old, children, loved Michael. He was their celebrity. He could have lived anywhere in the world, he had chosen their community. He had done kind things for people in that community," he said.
Jackson wasn't prosecuted for his race, but rather, because he is a mega-celebrity, Mesereau said. And he didn't want Jackson to be identified with a racial issue because it may have separated him from the community that stood in judgment of him during the trial.
He also learned most people in Jackson's community thought the D.A. was on a vendetta to get Jackson; a vendetta which goes back to the 1993 investigation.
As discussed in MJEOL Bullet #289 (Stunning Revelations about 1993 Accuser via Mesereau — MB #289), there were stunning revelations around the 1993 accuser's accusation revealed by Mesereau. He was not one of Jackson's lawyers at the time.
Through the course of his investigation for this past trial, he came upon some information about the 1993 accuser.
He says there are witnesses who say the 1993 accuser, Jordan Chandler, told them that Jackson did not molest him. Further, these witnesses say that Chandler was so angry at what his parents made him do, he said he would never speak to them again.
On top of that was the fact that he filed for legal emancipation from his parents. From the appearance:

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MESEREAU: Now the one you're talking about never showed up. He's the one who got the settlement in the early 90s. And my understanding is prosecutors tried to get him to show up and he wouldn't.
If he had, I had witnesses who were going to come in and say he told them it never happened. And that he would never talk to his parents again for what they made him say.
And it turned out he had gone into court and gotten legal emancipation from his parents. His mother testified that she hadn't talked to him in 11 years. So, you know, there was a problem there as well.
(see Harvard U. , Nov 29 2005)

The media is thus far completely mute on these latest revelations. I assume it's because it does not fit the 'wacko-jacko-molester' image they continue to try to sell the general public.
That undeserved image now hinges on the 1993 allegation, which has gotten less and less credible throughout the years to those who believed it in the first place. And this appears to be another 18 wheeler-sized hole in the collapsing dam of suspicion.
Children usually don't file for legal emancipation for no reason. The typical basis for such an action is to keep parents from haphazardly misusing money belonging to the child or having access to their finances, and to prevent them from being in a position to make decisions on behalf of the child.
Additionally, Mesereau told the audience he found out the grand jury in the 90s had serious problems with the validity of the Jordan Chandler's allegations. He said he spoke to a member of the 1993 Los Angeles county grand jury who relayed that they thought the Chandlers wanted to get money out of Jackson.
Continuing to lay down the facts around the 1993 investigation, he said the D.A. flew to two different countries looking for someone to accuse Jackson after the 1993 investigation. Further, law enforcement had a website at the sheriff's department looking for information on Jackson, Mesereau reported.
All of this wouldn't be so creepy if Jackson were actually a criminal. But since he's not, this type of behavior seems to have an obsessive undertone to it. That is, if the vindictive obsession isn't outright apparent.
__…so ridiculous it could have been a protracted Benny Hill skit__
The dimpled attorney said he believed they had the truth on their side and he saw no reason not to hit prosecutors over the heads with it. Again, no argument here.
This case was totally ridiculous. There were people claiming to be kidnapped and held hostage while they were out shopping (spending Jackson's money), getting body waxes, being put up at posh hotels, talking to the Dept of Children & Family Services, going to doctor appointments, and meeting with civil attorney Bill Dickerman among other things.
Not to mention they were staying with Maj. Jay Jackson and being flown to Florida on a jet chartered by Chris Tucker. Oh yeah, that's what I call kidnapping! It was a ridiculous allegation to make and an asinine allegation to believe.
Gavin Arvizo claimed he was laying up in Jackson's bed getting "molested" at a time when his mother is complaining to witnesses — Azja Pryor for example — that Jackson's people are keeping the family away from him.
Last time I checked, you actually have to be around a kid for there to be any possibility of molestation. I suppose he was seconds away from alleging to have been molested telepathically? Ludicrous.
The children were behaving like destructive little &!#@ all while playing the roles of innocent and later corrupted little victims of Jackson. Never mind the fact they acted like holy terrors on the flight back from Florida….at the dentist's office…at actress Verne Watson-Johnson's house….on the set of Chris Tucker's movie in Las Vegas….at Neverland when Jackson was away….at Neverland when Jackson was there…..etc.
And those are only a few of the many things wrong with the trial before we get into the preposterous actions of the prosecution!
Mesereau admitted he didn't want to play the traditional "reasonable doubt" card which so many defense attorneys use. He said he did not want to appear as if he was playing with technicalities in front of the jury. From his appearance:
MESEREAU: …I wanted to be the bearer of truth; not them. I did not want to look like someone who was playing with technicalities. Let them look like it.
(Harvard U, Nov 29 2005)
Prosecutors did look like they were playing fast and loose with the facts and benefiting from technicalities, commented some observers who also heard Mesereau speak.
In my opinion, technically Janet Arvizo could assert her 5th Amendment right not to testify, for fear of incriminating herself concerning issues of welfare fraud. But the public knew how it looked.
She was essentially leveling allegations without being forced to answer questions about illegalities in which she's been involved. Add on top of it the fact Tom Sneddon claimed in his opening statement that she was going to admit to breaking the law, but she didn't.
Another technicality, again in my opinion, concerned the now infamous 1108 so-called "evidence".
Decade old 3rd party-allegations became a part of this trial. But technically — and at the allowance of the judge — it did seem rather ridiculous that prosecutors didn't have to produce the now grown men who these 3rd party witnesses claimed were molested.
Prosecutors would use testimony from a set of witnesses with zero credibility and skirt the issue of the absence of said "victims". But the public for the most part — and the jury — evidently saw right through it. And so did the defense.
Taking on the role of truth bearer, the defense contacted the prosecution-alleged "victims" who ultimately came in and testified that Jackson didn't touch them, didn't show them any pornographic material, and didn't give them alcohol.
Oops! I can only assume prosecution didn't bank on the defense being able to get Brett Barnes, Wade Robson, Mac Culkin, or their families, to come in to testify.
Mesereau addressed the issue of whether or not he should have put on a defense case. If you remember, there were talking heads saying the defense should have rested right after the prosecution rested its case.
The seasoned attorney told the audience if he would have done that, the jury would have probably been a hung one. He advised the future lawyers in the crowd not to be afraid of their cases or walk on eggshells, especially if they have the truth on their side.
"But again I felt we had the truth. I felt we had the evidence, so I did not rest", he said.
He advised that jurors want to know what the truth is and they think the lawyers know what really happened—whether the lawyer does or not.
When attorneys use only the reasonable doubt defense, Mesereau said, jurors are most likely thinking 'his client's guilty, he just thinks he can stop them from proving it'.
Had the defense not put on a defense, many people would have been wondering why not. In addition there were questions they wouldn't have addressed, but could have.
For example, there is nothing more striking than having someone who prosecutors claim is a "victim" come to court and testify that Jackson never touched them. And further, to get on the record that they told prosecutors the same thing over 10 years ago. It is simply too pertinent not to get that information before the jury.
__Asset grabbing?__
During the question portion of the discussion, an audience member asked Mesereau if the desire to get Jackson's assets may have played a role in the "case" materializing.
Jackson has quite a few assets, but the main points of desire for some are his half ownership of the Sony/ATV catalog and that 2700 acre ranch in the heart of wine country.
Mesereau said the desire to obtain Jackson's assets, like the ATV catalog, would have been significantly enhanced if Jackson was convicted. He says:
I happen to fervently believe there are people who were waiting in the winds hoping he would be convicted so they would simply walk in and grab assets.
Can I tell you definitely that people who want the catalog are in that group? No I can't.
There were people trying to grab assets even before any of this materialized. So it's not a huge leap to conclude those same people weren't going to lift a finger to help or public support Jackson. They may have even been acting against him.
As discussed in a previous MJEOL Bullet, Las Vegas attorney David LeGrand started an investigation into the people around Jackson looking for illegalities and irregularities in how Jackson's money was being disbursed by his advisors.
None of them came in to testify for the defense. Two of them, Marc Schaffel and Dieter Wiesner, are currently suing Jackson. And Jackson has already filed a countersuit against Schaffel.
__You can't judge a book by its cover__
Mesereau never thought the jury would penalize Jackson for not fitting some clean-cut, 'boy-next-door' image although the media continued to portray him as "strange" and allege jurors would punish him for being "weird".
I specifically remember Geoffrey Fieger — currently caught up in a scandal of his own — morphing into a total lunatic while ranting about how the jury would be likely to convict partially because of the way Jackson looks.
For those who still want to cling to the notion that Jackson "bleached" his skin, Mesereau slapped that issue down as well. He confirmed for the purposely stupid that Jackson does in fact have vitiligo. He said he's seen the evidence of it himself. From his appearance:
MESEREAU: I never thought this jury would penalize Michael Jackson cause he has long hair; because he has a serious skin condition which I have witnessed.
It's called vitiligo. He has shown me his skin. If you look at the — his back, you will see brown patches and white patches. It's changing and eating pigment in his skin.
He's very embarrassed with that. He chose to put white makeup on his face rather than have these splotches all over his face. That's his choice. I don't think it's a crime to do that.
(see Mesereau Vid Webcast Part 2 Nov 29 2005)

During the question section of the discussion, one audience member mentioned the contrast between the way the media generally covers Jackson, and the way they cover other celebrities.
This unidentified audience member said there did seem to be a racial component in coverage of what he called Jackson's "artistic eccentricities".
In Jackson's situation, this collective group of reporters, editors, and producers we call "the media" do seem to cover his artistic eccentricities to make him look like a mentally challenged buffoon, while his white counterparts are respected as creative geniuses.
For instance, I don't see too much hateful criticism about Richard Branson trying to shoot people off into space nor do I see that same level of criticism after a tv special on the wild life of some rock star.
In Branson's case, he's a pioneer and an innovator. If Jackson made a statement that he wanted to make space travel affordable for the average person, it would be cause for more media ridicule.
Does Jackson have some fault in the way the media portrays him or are they simply selling the story which garners them the most advertising dollars and ratings?
One needs only to look at the recent spate of ridiculously unfounded Jackson stories — everything from crack in underwear to an Islamic conversion — to know the answer to this question.
In Part 2 of this special MJEOL Bullet, we will discuss Mesereau's comments about the media coverage and get into some of the most asinine statements I've ever heard out of the mouth of MSNBC's Dan Abrams.
-MJEOL
Previous Post:Michael Jackson reveals new single releases
Next Post:Part 2: Astonishing Jackson Trial Discussion w/ Mesereau – MB#290


With the emergence of tablets and smartphones, today, individuals and businesses alike no longer entirely rely on computers to store and access files. You may be using your computer in the office, your laptop at home, and your mobile device while on the road, making cloud storage a growing need.
With the usage of multitude of devices, it's very unpractical to keep your files all in one physical storage. This is where cloud storage comes in as a very handy solution. Most cloud storage services are now making it easy for users to access files through all of these devices.
However, features of one cloud storage provider will surely differ from another. And a user will be the only judge to its effectiveness and efficiency, depending on their needs.
Dropbox is one of the most popular cloud storage services today. Apart from the free 2 GB storage (it's free on most cloud storage anyway), it lets users have more free storage by simply referring a friend and have them use the software (extra 500 MB for each referral) or by linking your account to social media sites (extra 1 GB). Alternatively, users can opt for a monthly subscription of $9.99 for 100 GB of storage.
Apart from being available on Windows, Linux and Mac operating systems, Dropbox can also be used on mobile operating systems such as iOS, Android and BlackBerry. Of course, you can also access Dropbox on your mobile browser.
Google Drive is the default cloud storage for Gmail users, which gives them a generous 15 GB of free space. It has its built-in document collaboration app, Google Docs, where all files created though it is instantly saved on its cloud storage. Users can also opt to make these files public or share it with peers.
There is no option to increase the space for free, unlike Dropbox, but its huge free space could compensate for it. For those who want to upgrade to a bigger storage, you can purchase 100 GB for $1.99 a month, 1 TB for $9.99 and 10 TB for $99.99.
The cloud storage app is available on Windows, Mac desktops and on Android and iOS mobile devices.
If you've heard of SkyDrive before, that now is what's known as OneDrive. It's Microsoft's foray into cloud storage and is available as a built-in app for all Windows 8 and 8.1 PC users. Users of older Windows OS versions can get it, too, by downloading the app.
Despite being a Microsoft-owned company, the cloud storage app is also available in Mac desktops and in iOS, Android and of course, Windows Phone and Nokia X mobile devices as well as the Xbox. OneDrive offers free 7 GB storage and can have an increase of 3GB when the automatic photo upload feature is used, and additional 500 MB for every friend referred.
Users who want more storage can get 50 GB for $25 a year, and 200 GB for $200 a year.
Apart from storage options for consumers, these cloud storage apps have their respective enterprise counterparts as well.


Brett Danielson is a registered and licensed Professional Civil Engineer specializing in design and analysis of commercial, industrial, residential, and institutional buildings, industrial devices, and bridges. Before founding Inland Northwest Engineering in 1996, he worked as a design engineer for PPL Coffman Engineers and as an engineering consultant for ABKJ, Inc. In 1996, he founded Inland Northwest Engineering, Inc., and began using his experience to build and shape the business to what it is today.
Brett Danielson has licenses for Professional Civil Engineering in Washington (1992), Idaho (1996), and Oregon (1998). He graduated from the University of Texas, Austin in 1987 with a B.S. in Architectural Engineering.
Gwen Danielson began working for Inland Northwest Engineering as a drafter in 2011. Before joining INE, she was involved in the Blender 3D modeling community as a moderator on Blender Stack Exchange, and contributed to a few minor open source coding projects. She also manages INE's website.


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This web-based handbook is formatted so that students can access college-specific information, via the links across the top of the page, or general information that applies to all students, regardless of academic program using the menu to the left.
Welcome to the Student Handbook Online. This web-based document provides access to information about services and resources for students as well as policies and procedures. Policy at an academic institution is a complex and dynamic thing. It changes periodically, as it should.
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Slower Eagle Ford Growth Seen, Actually More Beneficial to Region
Despite as many as 100,000 lost jobs since its peak in 2014, the annual report on the Eagle Ford Shale by the UTSA Center for Community and Business Research shows the shale field is still an incredibly important, and productive, piece of the Texas economy, News Radio 1200 WOAI reports.
UTSA economist Tom Tunstall says the shale field south of San Antonio still employs about 100,000 people, and has a $55 billion impact on the state's economy.
"The worst of the things appear to have happened last year," Tunstall said. "Now, as companies bring people back, they are clearly going to be more cautious about what positions to fill, they have become a lot more efficient."
Gross output from the 21 county Eagle Ford region fell from a peak of $123 billion in 2014 to $50 billion last year, when oil prices bottomed out below $30 a barrel.
But Tunstall says the slower growth we are seeing today as oil prices rebound will actually be more more beneficial in the long term for the small towns that dot the shale region.
"They have taken it on the chin the last couple of years, but things are coming back in a more incremental and manageable fashion."
Tunstall says the boom on oil production between 2012 and 2014, when nearly a quarter million workers poured into the sparsely populated area led to the creation of 'man camps,' caused significant damage to roads and infrastructure, and didn't prodive the small towns with the opportunity to plan ahead.
Tunstall says now there is a more controlled growth in the region, with more permanent sources of revenue, with sales of natural gas to Mexico, for example.


Beaumont Foodie News – Suga's Deep South Cuisine sets the stage with first class appetizers and cocktails.
Appetizers can set the tone for a fine Southeast Texas restaurant experience.
Beaumont diners looking to move beyond the ho hum appetizers you find at many chain restaurants enjoy the inspired Southeast Texas appetizers offered by Suga's Deep South Cuisine.
Nestled in the heart of downtown Beaumont, Suga's offers appetizers that are definitely a cut above.
Pair your choice with a Suga's hand crafted cocktail, and enjoy.
Suga's Southern Fried Green Tomato Stack. Fried green tomatoes are a Southern staple. Most Southeast Texas diners picture their grandmother's fried green tomatoes, which are great. Suga's starts with those same core ingredients and adds some Suga's twists, taking Granny's fried green tomatoes to the next level. They layer their fried green tomatoes with lump Gulf crabmeat, tomato relish,mango nectar,and peach hollandaise. Delic ate, delicious, elegant.
Suga's Goat Cheese Stuffed Shrimp. Suga's commitment to matching high quality fresh ingredients with inspired culinary vision makes an appetizer like this possible. They start with large Gulf shrimp and stuff them with herbed goat cheese made right here in Texas. Suga's goat cheese stuffed shrimp are served with tomato relish and chive oil. Texas shrimp, Texas goat cheese, Texas flavor.
Suga's Southern Egg Rolls. Egg rolls have been popular in Beaumont Chinese restaurants for generations. In the last few years, a few non-Chinese restaurants have tried putting their own spin on the egg roll concept. Beaumont foodies agree that one of the bestis the Suga's Southern Egg Roll. Suga's starts with a tasty egg roll wrapper and stuffs it with chicken, tasso ham, and braised greens. Yum. Suga's southern egg rolls are served with spicy mustard and red pepper sauce for a double barrel blast of heat. A perfect blend of East meets South.
Click here for the Suga's Deep South Cuisine Dinner Menu to browse their current appetizer offerings.
Set the tone for your next fine meal with inspired appetizers from Suga's Deep South Cuisine.
Come on the weekends for live music Friday night, Saturday night, Sunday brunch, and Sunday night.
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A judge in the Berks County magisterial district was recently arrested for driving under the influence and careless driving. Reading police say they received a call complaining about a car swerving into oncoming traffic while it was driving down Kutztown Road and North Ninth Street, both within city limits. When the police pulled her over, they noticed she was likely intoxicated.
The responding officers said they could smell alcohol on her breath. When they conducted field sobriety tests, they determined she may have been driving under the influence. As such, they arrested the judge and took her to the Penn State St. Joseph Medical Center. There, a blood test revealed her blood alcohol content was .188 percent. The legal limit in Pennsylvania is 0.08 percent.
Being arrested for driving under the influence is undoubtedly stressful. Your mind races with questions and concerns, and you aren't exactly sure what to do next. There are steps to take after a DUI arrest that can better prepare you for what lies ahead. Read on to discover what you should do after your arrest.
What's done is done. Now you have to take a deep breath and prepare yourself. Many people who are arrested for DUI experience feelings of embarrassment, desperation and shame. The thought of telling family members and even co-workers about your arrest can cause anxiety. These feelings are not unusual. In fact, they are experienced by almost everyone who is arrested. Now is the time to get ready for the emotions you will be dealing with.
How Much Does a First Time DUI Cost in Pennsylvania?
Driving under the influence in Pennsylvania can have a high cost in terms of potential harm to human lives, but it also carries with a quite literal cost if you are arrested. People worried about getting a DUI or who have just gotten their first one may wonder exactly what the damage is in terms of dollars and cents.
On paper, laying out such numbers would seem easy, but in real life the costs are much more wide-ranging. Some even estimate that the first time costs to be in excess of five figures when factoring in costs like court fees and increased insurance premiums. These prohibitive costs illustrate why not driving under the influence is so important and also why hiring a Pennsylvania DUI lawyer could pay off if you can get your charges reduced or dropped.


text:
Nc/Nga is an inbred mouse model bred in Japan at Nagoya University in 1957. It is used as a human atopic dermatitis model for its biological properties.

If kept under so called conventional conditions these mice develop skin lesions clinically and histologically very similar to human atopic dermatitis. The hair of these mice is rougher—especially on the head and dorsal skin. Erythema, haemorrhage, excoriation, erosion, scaling, and dryness are observed almost everywhere on the body—mainly on the face and ears. These symptoms do not develop if these mice are kept under specific pathogen free (SPF) conditions. This supports the theory that atopic dermatitis development is influenced by both genetic predisposition and environment. The production of serum IgE is several times higher in mice kept under conventional condition than in those from SPF conditions. High level of serum IgE is typical for human dermatitis too.

The lesional skin shows hyperkeratosis in the epidermis. Another trade mark is heavy cell infiltrate in the dermis. This infiltrate consists mainly of Cd4-positive t-lymphocytes with less Cd8-positive t-lymphocytes and macrophages. Infiltration of these cells leads to higher activation of mast cells. Higher production of certain chemokines, cytokines, and respective receptors is also typical. Notably production of TARC (thymus- and activation-regulated chemokine) is significantly higher. This chemokine plays an important role in lesion pathogenesis. Cells infiltrating dermis produce cytokines typical for Th2 polarization especially IL-4 and IL-5. Considering receptors, CCR3 and CCR5 are expressed in both lesional and nonlesional skin but CCR5 is higher in lesional skin. CCR4 is receptor typically expressed in lesional skin only. CCR4 is a receptor for TARC. These differences in chemokines and cytokines production are observed only in Nc/Nga mice kept under conventional conditions.

Genetic determinant responsible for atopic dermatitis-like skin lesions is located on chromosome 9. This quantitative trait loci (QTL) was named derm1 and is surrounded by seven genes possibly involved in atopic dermatitis onset and pathogenesis. These seven candidate genes are:

- thymus cell antigen 1 theta (Thy1)

- CD3 antigen delta, epsilon and gamma polypeptide (Cd3d,e,g)

- interleukin-10 receptor alpha (Il10ra)

- interleukin-18

- C-terminal Src kinase (Csk).br>

All these genes or their products more precisely are involved in T lymphocytes development.

Derm1 region is conserved on human chromosome 11q22.2-23.3 and 15q21-25. Nevertheless, no gene directly involved in atopic dermatitis development was located into this locus in human.

References

Atopic dermatitis
Medical tests
1957 introductions
Immunology mice

redpajama_set_name: RedPajamaWikipedia


text:
Physicochemical Analysis and Synthesis of Nonstoichiometric Solids
By V. P. Zlomanov, A.M. Khoviv and A.Ju. Zavrazhnov
Submitted: June 5th 2012Reviewed: November 2nd 2012Published: June 10th 2013
Home > Books > Materials Science - Advanced Topics
chapter and author info
V. P. Zlomanov
Department of Chemistry, Moscow State University, Moscow, Russia
A.M. Khoviv
Department of Chemistry, Voronezh State University, Voronezh, Russia
A.Ju. Zavrazhnov
*Address all correspondence to: zlomanov@inorg.chem.msu.ru
From the Edited Volume
Materials ScienceAdvanced TopicsEdited by Yitzhak Mastai
Materials Science - Advanced Topics
Edited by Yitzhak Mastai
Technological progress is intimately associated with creation of new materials, such as composites, piezoelectrics, ferroelectrics, semiconductors, superconductors and nanomaterials with preset functional properties. For the synthesis of these materials, it is necessary to study the chemical processes that lead to the composition, structure, and accordingly desired properties. Investigation of the interrelation between the composition, structure and properties of matter and determination of synthetic conditions for obtaining substances with preset composition and structure are the major problems of physicochemical analysis. Although significant progress has been made in understanding several challenges remain for further advancements. These challenges and new approaches include some definitions – stoichiometry, nonstoichiometry, deviation from stoichiometry, substance, phase, component as well as the use of phase diagrams in selecting conditions for the synthesis of nonstoichiometric solids. Since nonstoichiometry is associated with defects, attention is also paid to their classification and formation. Synthesys of solid involves control over phase transformations. For this reason some features of the P–T–x phase diagrams are discussed. The following inportant features of P–T–x phase diagrams will be considered: highest maximal melting point Tm,ABmaxof the solid compound SAB , noncoincidence of the solid, liquid and vapor compositions (xL ≠ xS ≠ xV ) at this temperature, factors determining the value of the homogeneity range, some features of the terms congruent and incongruent phases and phase processes. Criteria for evaluating the homogeneity of nonstoichiometric solids are also considered.
The term Physicochemical analysis was introduced in [1] and defined as the field of chemistry dealing with the interrelation between the composition and properties of matter [1]. The foundations of physicochemical analysis were in [1-6].
It has been realized that it is necessary to study the thermodynamic properties of solids and the phase diagrams of the systems in which these solids occur. Because the properties of solids depend significantly on their composition, great attention has been focused on the physicochemical analysis and foundations of the directed synthesis.
2. The essence of physicochemical analysis — Some definitions
Investigation of the interrelation between the composition, structure, and properties as well as determination of synthetic conditions for obtaining solids with preset composition and structure are the the basic problems of physicochemical analysis.
The subject of chemistry is the conversions of substances. What is a substance, and what is its conversion? A substance is a multitude of interacting particles possessing certain characteristics: composition, particle size, structure, and the nature of chemical bonding. It is these characteristics that determine the properties of the substance (Figure 1).
Interrelation between the basic characteristics and properties of a substance.
Composition is defined as the kinds of particles constituting the substance. For example, a sodium chloride crystal is built of sodium and chloride ions occupying cationic sites (NaNa+) and anionic sites (ClNa+), respectively. The constituent particles can be not only atoms or ions, but also molecules (e.g., I 2 molecules in iodine crystals and water molecules in ice), coordination polyhedra (e.g., SO42−tetrahedra in potassium sulfate), and other entities.
Structure is some ordered arrangement of the above particles in space.
The properties of a crystal, such as the lattice energy and electrical, optical, and chemical properties, are determined by the composition and structure of the crystal. Different spatial arrangements of the same particles, such as carbon atoms in diamond and graphite, are characterized by different lattice energies and, accordingly, different properties, including melting and boiling points and hardness.
The chemical bond is understood as the forces binding the particles together. These forces arise from the the Coulomb interaction of electrons and nuclei. Depending on the electron distribution among nuclei, there can be ionic, covalent, and metallic bonds.
The particle interaction energy depends on the particle size. At the nanometer level (1–100 nm), it changes markedly, making possible the formation of new physical and chemical properties of the substance. This is explicable in terms of surface physics and chemistry (dependence of the surface energy on the particle size).
A conversion of a substance is a change in one or several characteristics of the substance (Figure1). This process is accompanied by a change in energy (dU) in the form of heat transfer (δQ) or work execution (δА):
dU=δQ–δА.E1
The main purpose of directed synthesis is to obtain substances with the preset composition, structure, and, hence, properties.
The direct synthesis of solids includes control of phase transitions. Therefore, thermodynamic data characterizing phases and their transitions are necessary to estimate the optimum synthetic conditions.
Now let us consider some specific features of the concepts of a phase and a component.
2.1. Phase and component
A substance is made up of particles or their interacting sets with a certain structure and chemical bonding. Energy is an equivalent or measure of these interactions. In thermodynamics, the state of a system is defined using a set of variables, or coordinates, such as pressure Р, temperature Т, and volume V. For a thermodynamic state of a system characterized by a set of coordinates (intensive thermodynamic properties), Gibbs suggested the term phase of matter [7, 8]. This definition emphasizes that the phase of matter is size- and shape-independent. Later, the word combination phase of matter gave way to the term "phase."
The equation of state of a phase in terms of pressure (Р), temperature (Т), and composition (х) is written as (2)
dG=−SdT+VdP+∑i=1k(∂G∂xi)P,T,xjdxi,E2
where G, S, and V are the molar Gibbs energy, molar entropy, and molar volume of the phase, espectively; x i is the mole fraction of the i-th component k; x j means the constancy of the mole fractions of all components but not the i-th component. The phases can be individual solid, liquid, gaseous compounds, or solid solutions, including nonstoichiometric compounds, whose thermodynamic properties are described by equations of state like Eq. (2) and are continuous functions of P, Т, and х.
Note the following specific features of the concept of a phase. Firstly, existing phases should be distinguished from coexisting phases. The properties (Gibbs energy G, enthalpy, etc.) of an existing phase, such as a solution containing different concentrations of the same substance, are continuous functions of composition. By contrast, the properties of coexisting phases (i.e., phases that are in equilibrium) are equal in all parts of the system. The second specific feature is associated with the definition of a phase as the homogeneous part of a heterogeneous system. This definition is inexact because it does not specify whether homogeneous parts of a heterogeneous system are one phase or different phases. Thirdly, the concept of a phase is broader than the concept of a physical state (gas, solid or liquid). Finally, the fourth specific feature of the concept of a phase is associated with the issue of the minimum set of particles describable in terms of one equation of state like Eq. (2). From the standpoint of kinetic molecular theory, this set should be sufficiently large to allow regular particle energy distribution. Estimates demonstrate that the number of particles must be at least several tens. The properties of such a phase will be affected by surface tension [9].
The components of a system are the types of particles constituting this system. They are called constituents, and their number is designated n. If the concentrations of the n constituents are related by m independent equations, then k = n – m is the number of independent constituents, or, simply, the number of components. For example, the system NH 3(g) + HCl(g) = NH 4 Cl(s), which consists of three substances (n = 3), whose concentrations are related by one equation (m = 1), is two-component since k = n–m = 3–1= 2.
The components are subject to the following constraints:
their concentrations must be independent of one another;
they should completely describe the concentration dependence of the properties of the system;
their number should satisfy the electroneutrality principle.
2.2. Stoichiometry, nonstoichiometry, deviation from stoichiometry
The properties of a substance depend on its composition. The great focus of materials sience are the concepts of stoichiometry, nonstoichiometry, and deviation from stoichiometry.
The proportions in which substances react are governed by stoichiometric laws (stoichiometry). These laws, which characterize the composition of chemical compounds, were discovered by systematizing experimental data. The fundamental laws of stoichiometry include the law of constant composition and the law of multiple proportions.
The law of constant composition, established in the 19th century by the French chemist Joseph Louis Proust, states that the chemical composition of a compound is independent of the way in which this compound was obtained. The law of multiple proportions, formulated by the English chemist John Dalton in 1807, states that, when two elements combine with each other to form more than one compound, the mass fractions of the elements in these compounds are in a ratio of prime numbers. Both laws follow from atomistic theory and suggest that the saturation of the chemical bonds is necessary for the formation of a molecule from atoms. Any change in the number of atoms or their nature or arrangement indeed means the formation of a new molecule with new properties.
Are the law of constant composition and the law of multiple proportions always obeyed? They are valid only for the substances constituted by molecules. In fact, the composition of a substance can vary significantly, depending on the preparation conditions. It was long believed that only those chemical substances exist whose composition obeys the law of multiple proportions. They are stoichiometric and are called daltonides in honor of John Dalton. However, as methods of investigation were making progress, it turned out that the properties of solid inorganic substances, such as vapor pressure, electric conductivity, and diffusion coefficients, are composition dependence. In some composition range, the structure, i.e. the arrangement of the components in space remains invariable, while the component concentrations vary continuously. This range is called the homogeneity range or the nonstoichiometry range. These substances are referred to as nonstoichiometric or variable-composition compounds. Earlier, they were called berthollides in honor of Claude Louis Berthollet, Proust's compatriot. A nonstoichiometric compound can be treated as a solid solution of its components, such as cadmium and tellurium in the compound CdTe.
The homogeneity range is characterized by the corresponding deviation from stoichiometry. The stoichiometric composition of a solid compound, e.g., АnBm, where n and m are prime numbers, is the composition that obeys the law of multiple proportions. The deviation from stoichiometry or, briefly, nonstoichiometry (Δ) is defined as the difference between the ratio of the number of nonmetal atoms B to the number of metal atoms A in the real A n B m+δ crystal (δ ≠ 0) and the same ratio in the stoichiometric crystal А n B m [10]:
Δ=m+δn−mn=δn.E3
For the three-component system A–B–C, the composition of the solid phase (А1–х Вx)1–у С у is conveniently expressed in terms of the mole fraction of the binary compound (х) and nonstoichiometry (Δ).
In this case, the nonstoichiometry Δ can be viewed as the difference between the ratio of the equivalent numbers of nonmetal and metal atoms in the real crystal and the same ratio in the stoichiometric crystal. For example, for (Pb1–х Ge x )1–у Te y crystals with a NaCl structure,
Δ=y/(1 –y) – 1/1 = (2y– 1)/(1 –y).E4
The mole fraction (molarity) of the binary compound determines the fundamental properties of nonstoichiometric crystals, including the band gap and heat capacity. The concentration of carriers—electrons and holes—and, accordingly, the galvanomagnetic and optical properties of nonstoichiometric crystals are also associated with nonstoichiometry.
3. Directed synthesis of nonstoichiometric solids
The strategy of directed synthesis of substances with the preset nonstoichiometry, structure, and properties is based on physicochemical analysis and includes the steps presented in Figure 2.
Steps of the directed synthesis of nonstoichiometric solids.
Synthesis is the consequence of processes involved in the conversion of the starting compounds into products. It includes selection and preparation of the starting chemicals (precursors), homogenization of the growth medium (melt, vapor, etc,), the nucleation of the desired phase, nucleus development (growth), and cooling (heating) of the product from the synthesis temperature to room temperature.
Each synthesis step depends on certain conditions or operating parameters. These include the chemical nature and composition of the growth medium, temperature, pressure, diffusion coefficients, heat and mass transfer, and the driving forces of chemical reactions (such as concentration, temperature, pressure, and chemical potential gradients). Figure 3 presents the most important operating parameters of the synthesis.
Operating parameters of solid synthesis.
Provided that the analytical relationship between the rate of solid synthesis (growth) and the operating parameters is known, this process can be carried out under computer control. This problem has been solved for the Czochralski growth of silicon and germanium crystals and for the Bridgman growth of transition metal oxide crystals [10-14].
Solid synthesis involves phase transitions. For this reason, synthesis conditions are selected using phase diagrams (see section 4). The phase diagram of a system indicates the number of compounds forming in this system and the regions of their stability, specifically, the temperature, pressure, and composition intervals. Thus, using the phase diagram, it is possible to choose the medium (melt, vapor, etc.) for the synthesis of the desired solid, the synthesis conditions (temperature, pressure, and growth medium composition), and the way of carrying out the necessary conversions.
The thermophysical and chemical properties of the starting substances, final synthesis products, and the growth medium to be used (melt, vapor, other solid phases) should be known along with thermodynamic data.
The conversion of a synthesis medium into a solid phase (crystallization) includes the nucleation and development of crystallization centers. Accordingly, it is related with heat and mass transfer and interfacial reaction kinetics. The general problem of analytically describing the crystallization process has not been solved. Furthermore, it is not always possible to evaluate the skill and equipment factors or to establish an unambiguous correlation between the properties of a nonstoichiometric phase and its molecular composition. In this sense, directed synthesis is regarded as being an art [13, 14].
4. Phase diagrams as a key to selecting conditions for synthesis of solid with well-defined nonstoichiometry
The synthetic conditions for nonstoichiometric solids (S AB ) coexisting with a vapor (V) and a melt (L) can be estimated using Р–Т–х diagrams or their Т–х projections [15-17]. Let us consider the following features of the Т–х diagrams: the highest (maximal) melting point Tm,ABmaxof the solid S AB ; the compositions of the phases at this point; some features of the solidus, liquidus, and vapor lines; the nonvariant points of congruent melting (Tmc), sublimation (TSc), and evaporation (Tec); and, finally, congruent and incongruent phases and phase processes.
4.1. Maximal melting point Tm,ABmaxof a nonstoichiomertic solid S AB
The Gibbs energy of a phase in a two-component system A–B is given by Eq. (2), so the phase equilibria in this case are represented graphically in a four-dimensional space. This space is explored as four three-dimensional projections: G–P–T, G–P–x, P–T–x, and G–T–x.
To clarify the features of the T–x diagram let us consider the derivation of part of the Т–х projection from the G–T–x diagram. For this purpose, it should be considered the relative positions of the G-surfaces of the solid phase S, liquid phase L, and vapor V. In order to determine the arrangement of these three surfaces, we will traverse them with isothermal planes. The projections of the sections of the G-surface on the G–x plane will appear as G S , G L , and G V curves representing the dependence (5) of the Gibbs energy (per gram-atom) on composition at a constant temperature (Figure 4):
GA1−xBxS=(1−xBS)μAS+xBSμBSGA1−xBxL=(1−xBL)μAL+xBLμBLGA1−xBxV=(1−xBV)μAV+xBVμBV}E5
where μASand μBSare the chemical potentials of the components A and B in the solid phase, μALand μBLare those of A and B in the liquid phase, μAVand μBVare those of A and B in the vapor phase, and x B is the mole fraction of the component B.
Let us consider the effect of temperature variation on the relative positions of the G–x curves. At T 1 >Tm,ABmax(Figure 4a), the solid phase S AB is metastable and the two-phase system L + V is stable because a common tangent line can be drawn for the corresponding G curves, indicating the equality of the chemical potentials of the components in the equilibrium phases.
As the temperature is decreased, the arrangement of the G curves changes. Since the temperature dependence of the Gibbs energy is determined by the entropy(∂G∂T)P,x= –S and the entropies of the vapor and melt are higher than the entropy of the solid phase, S V > S L > S S , the G curves shift upwards upon cooling and the G V and G L curves do so more rapidly than the G S curve. As a consequence, a common tangent for the G S, G L , and G V curves can appear at some temperature T 2 = Tm, ABmax(Figure 4b). This temperature Tm, ABmaxis referred as the highest maximal melting point of the solid SAB.
(G–x) sections of the G–T–x diagram: (a) T 1 > T m , A B max ; (b) T 2 = T m , A B max ; (c) T 3 < T m , A B max ;(d) part of the T–x projection near T m , A B max .
From the definition of a phase as the totality of the parts of the system whose properties are described by the same equation of state, it follows that the properties of the system are homogeneous functions of composition, pressure, and temperature. Therefore, upon further cooling, for example, to Т 3 <Tm,ABmax, it will be possible to draw two tangent lines for each of theGABS, G L , and G V curves (Figure 4c). The coordinates of the equilibrium phases are designated as V, L, and S in Figure 4d. The subscripts (') and ('') are given to the phase compositions to the left and right, respectively, of the composition corresponding to Т <Tm,ABmax.
As the temperature changes, the G V -, G L - and G S -curves, shifting upwards and to the sides, describe three surfaces: G V = G V (Т, х), G L = G L (Т, х) and G S = G S (Т, х) − and the projections of the tangency points on the Т–х plane draw the solidus line S'–S'', the liquidus line L'–L'', and the vapor line V'–V'' (Figure 4d). Thus, Figure 4d shows part of the Т–х projection of the Р–Т–х diagram near the highest melting point of the SAB compound. The points V', L', and S' and the points V'', L'', and S'', as examples, represent the compositions of the vapor V, solid phase S, and liquid phase L that are in equilibrium at the temperature Т = Т 1 and are called conjugate points. The lines VV'', LL'', and SS'' and the lines VV', LL', SS', as examples, formed by series of these points, are called conjugate lines. The lines connecting conjugate points, such as V′L'S' and V''L''S'', are called tie lines. Note that, among the various intersection points between the vapor, liquidus, and solidus lines (Figure 4d), only the intersections points of the conjugate lines (VV'', LL'', SS'', V V ′, LL ′, SS ′) have a physical meaning, as distinct from those of the lines LL ′ и VV'', etc.
4.2. Specific features of the solids, liquidus and vapor lines
Here, let us consider the continuity of the solidus, liquidus, and vapor lines; the factors determining the homogeneity range; the issue of whether this range must include the stoichiometric composition; the causes of the retrograde character of the solidus line; and the concepts of a pseudocomponent and psevdobinary section in multicomponent systems.
The Т–х and Р–Т projections of the Р–Т–х diagram of a two-component system having a compound AB [10, 15] are shown in Figure 5. The Gibbs energy of any phase is a homogeneous function of composition, so the solidus line S'S'', the liquidus line L'L'', and the vapor line V ′V'', which represent the temperature dependence of the compositions of the equilibrium phases, are continuous lines having no inflection points.
The homogeneity range of a solid compound is bounded by the solidus line. It is determined by the coordinates of the tangency points of the common tangent line for the G curves of the equilibrium phases (Figure 4), i.e., by the equality of the chemical potentials of the components. Therefore, in the general case the homogeneity range (Δ in Eq. (3)) is determined by the relative positions of the G S , G L and G V curves (Figure 4) (i.e., the properties of all coexisting phases) and by the shape of the (G–x) P,T curves. Thus the nonstoichiometry value depends not only the specific features of the nonstoichiometric solid, namely the radius value, electronic configuration and electronegativity of the constituents species, but on the properties of all coexisting phases.
In the case of the compound AB formed from solid components A and B,
AS+BS= ABS; ΔfG0E6
the homogeneity range can be estimated using the following relationship [17]:
f(δ' / k) –f(δ''/k) =−ΔfGо,E7
where Δ f G° is the standard Gibbs energy of reaction (6), f is the monotonic function of composition δ, the subscripts ' and '' refer to the left and right sides of the homogeneity range, and k is a tеmperature dependent parameter. It follows from Eq. (7) that, the more negative the Gibbs energy Δ f G°, the larger the difference f(δ'/k) – f(δ''/k) and, accordingly, the broader the homogeneity range δ'' – δ'. For crystals dominated by covalent bonding, such as those of the A III B V compounds GaAs, InP, etc., δ'' – δ' is on the order of thousandths of an atomic percent. For crystal with polar bonds (CdTe, PbSe, SnTe), the homogeneity range is between a few tenths of an atomic percent and several atomic percent.
(a) T–x and (b) Р–Т- projections of the Р–Т–х diagram of a two-component system with a congruently melting compound (S АВ ).
The homogeneity range may include the stoichiometric composition or not. Since the δ' + δ'' value defines the position of the center of the homogeneity range, the expression
f(δ'/k) +f(δ''/k) = [μB(B) –μA(A)] /RT– [μB(δ=0) –μA(δ= 0)] /RTE8
describes the dependence of the position of the homogeneity range center on the difference between the Gibbs energies of the pure components (first term in (8)) relative to the isolated atoms in their ground states and on the difference between the chemical potentials of the components in the stoichiometric solid (second difference in (8). If the latter quantity is neglected in a series of crystallochemically similar compounds, the center of the homogeneity range, (δ' + δ'')/2 will shift in the direction in which the difference μ B (B) – μ A (A) increases. This can easily be illustrated by examples of nontransition metal chalcogenides.
In the general case, the stoichiometric composition does not correspond to the minimum of the free energy of the solid phase and can fall outside the homogeneity range. When this is the case, the stoichiometric compound does not exist. For example, strictly stoichiometric ferrous oxide can be obtained only at high pressure.
The temperature dependence of the solidus SAB'SABmaxSAB"(Figure 5), which defines the boundaries of the homogeneity range of the nonstoichiometric compound S AB , is described by the following equation [16, 18]:
(dxSdT)P=(∂S/∂x)P,TS−(SL−SS)/(xL−xS)(∂2G∂x2)P,TE9
where S L and S S are the molar entropies and х L and х S are the compositions of the solid phase (S) and melt (L). The solubility of the components in the nonstoichiometric solid А 1-х В х = =А 1/2−δ В 1/2+δ can be retrograde: it can initially increase with increasing temperature ((dx S/dT)>0) and, on passing though a maximum, decrease ((dx S/dT) Р < 0). The maximum solubility (x S)max is found from the extremum condition for function (9) ((dx S/dT) Р = 0) since (∂2G∂x2)P>0, according to the phase stability criterion. The retrograde solubility is due to the difference between the rates at which the entropies S L and S S, including their configurational components, grow with increasing temperature.
The liquidus line (LQ1LmaxLQ2) and vapor line (VQ1VmaxVQ2) in Figs. 4 and 5 represent the temperature dependence of the compositions of the melt (L) and vapor (V) in equilibrium with the nonstoichiometric solid S AB .
4.3. Noncoincidence of the phase compositions at the maximum melting point of a nonstoichiometric solid S AB
Both pressure and temperature extrema at Т = const and Р = const, respectively, exists in a three-phase two-component system provided that the following condition is satisfied [16]:
(xL-xS)/(xV-xS) = (SL-SS)/(SV-SS) = (VL-VS)/(VV-VS)E10
Thus, if the coexisting phases have different molar volumes V and entropies S, the composition of one of them will be a linear function of the compositions of the two others: x L = βx S + (1 – β)x V where β is a coefficient depending on the pressure and temperature and independent of the composition. Since V L ≠ V S ≠ V V and S S ≠ S L ≠ S V in the general case, at Т = Tm, ABmaxthe composition of the solid phase SAB does not coincide with the composition of the melt L and vapor V: х S ≠ х L ≠х V . This is in agreement with the phase rule:
c=k+ 2 –r–α,E11
where k is the number of components, 2 is the number of external fields (baric and thermal), r is the number of phases, and α is the number of independent constraints imposed on the intensive variables (с). Indeed, if it is assumed that, at Т = Tm, ABmaxх S = х L = х V , then α = 2 in Eq. (11) and с = 2 + 2 – 3 – 2 = –1 < 0, which is impossible. Unfortunately, this mistake is frequently encountered in the literature [18-21].
In the case of lead, germanium, tin, and cadmium chalcogenides, the vapor phase consists mainly of a chalcogen, so it can be accepted that х S –х V = –0.5. At Р ≅ 1 atm, V S– V V ≅ 10–3 V S and V S – V L ≅ 5∙10–2 V S. Therefore, х S – х L = 2.5 × 10–5; that is, the compositions of the phases at the highest melting point do not coincide, even though they are very similar [14, 22, 23].
4.4. Nonvariant congruent melting, sublimation, and evaporation points of the three-phase equilibrium S AB + L + V
Since the solid, liquid, and vapor phases are characterized by different temperature and concentration dependences of the Gibbs energy, the following intersection points of the conjugate liquidus, solidus, and vapor lines can appear on the Т–х projection. The temperature of the intersection point of the conjugate liquidus and solidus lines refers to solid and liquid phases of equal compositions (x S = x L ) and is called the congruent melting point Tmcof the S AB phase. The temperature of the intersection point of the solidus and vapor lines refers to a solid phase and vapor of equal compositions (x S = x V ) and is called the congruent sublimation point TSc. The temperature of the intersection point of the conjugate liquidus and vapor lines refers to a liquid phase and vapor of equal compositions (x S = x V ) and is called the congruent evaporation point Tec. The temperatures Tmc, TScand Tecdo not correspond to the stoichiometric composition (δ = 0) of the solid phase А 1/2−δ В 1/2+δ, where х = 1/2 + δ and δ is the deviation from its stoichiometric composition AB. For example, congruently melting lead telluride contains (2.8 ± 0.3) 10–4 mol excess Te per mole of PbTe [22, 23]. Because the formation energies of the defects responsible for the nonstoichiometries δ > 0 and δ < 0 are different, the G S curve (Figure 4a, 4b, 4c) is asymmetric relative to the δ = 0 composition. Accordingly, the coordinates of the common tangency points of the G curves in the general case do not coincide with the δ = 0 composition.
The equality of the compositions of two phases of the three ones involved in the equilibrium means the appearance of one more relationship α = 1 between independent variables (degrees of freedom) in the phase rule expression (11). Therefore, the equilibrium at the points Tmc, TScand Tecis nonvariant: с = 2+2–3–1 = 0. The solid S AB , which has a homogeneity range at these points, can be considered a pseudocomponent whose properties are composition-independent, and the sections through ternary, quaternary, and other multicomponent systems involving the S AB solid can be considered as pseudobinary.
4.5. Congruent and inconguent phases and phase processes
The concept of congruence is of great significance in the synthesis of nonstoichiometric solids because, in the case of noncoincidence between the synthetics medium (vapor, melt) and solids compositions, there are fluxes of rejected material and the corresponding kinetic instability of the crystallization front.
A phase can be congruent and incongruent in different temperature intervals. A phase obtainable from the phases that are in equilibrium with it by mixing them in appropriate proportions is called a congruent phase. A phase that cannot be obtained from the coexisting phases is called incongruent [24, 25]. As an example, let us consider the phase S AB (Figure 5a) in the three-phase equilibrium S AB + L + V at different temperatures. Above the congruent melting point (Tm,⥄ABc< T < Tm, ABmax) the solid phase S AB is incongruent. In the temperature range TSc< Т <Tm,⥄ABc, it is congruent with respect to the vapor and melt. In designations of three phase equilibria, a congruent phase is written in the middle. Thus, in the former case, the three-phase equilibrium is designated VLS AB ; in the latter case, VS AB L.
The concepts of congruent and incongruent phases should not be confused with the concepts of congruent and incongruent phase processes.
Phase processes are changes in the state of the system such that the masses of some phases increase owing to the decrease in the masses of others without changes in the intensive parameters (temperature, pressure, phase compositions) [26]. A phase process in which one phase forms or disappears is called congruent. A phase transition in which more than one phase forms or disappears is called incongruent.
The same phase, for example, S AB (Figure 5a), can be involved both in congruent and in incongruent phase processes. At a temperature or pressure corresponding to the three-phase line Q 1 Q 2 in Figure 5b, the solid phase S AB melts congruently, yielding a melt and a vapor: S AB = L + V. The compositions of the phases involved in this congruent phase process are different and are represented by the solidus, liquidus, and vapor lines in the Т–х projection (Figure 5a). The melt and solid phase compositions coincide only at the congruent melting point Tmc. At the temperatures corresponding to the eutectic nonvariant points TQ1and TQ2(Figure 5a), the S AB phase is involved in the incongruent phase processes
V + SA= L + SAB and SAB+ L = V + SB.
Thus, S AB phase can be said to melt congruently only in a certain temperature range.
Now let us consider the usage of the terms congruently melting compound and incongruently melting compound in the literature. Firstly, this differentiation is not strict, because the same compound (e.g., S АB ) can be involved in congruent and incongruent phase processes, depending on the temperature. Sometimes, a congruently melting compound is understood as a compound melting without dissociation or decomposition. However, a solid–melt phase transition is accompanied by the breaking and relaxation of chemical bonds in the crystal and by long-range disordering. Therefore, the term melting without decomposition is not quite correct, and it should be understood as the identity of the overall compositions of the coexisting phases. In the strict sense, the overall compositions of the phases coincide only at the congruent melting pointTm,⥄ABc, which is below the highest melting point Tm, ABmax:Tm,⥄ABc< <Tm, ABmax.
An incongruently melting compound is sometimes understood as a solid compound that decomposes into a solid phase S B and a liquid L upon melting (Figure 6). The compositions of the resulting phases differ from the composition of the parent phase. However, in some temperature range, such as TQ1< T < T Р , the "incongruently melting compound" is involved in the congruent melting process S AB = L + V.
An essential feature differentiating congruently and incongruently melting compounds is that the highest melting point of a congruently melting compound is higher than the temperatures of the nearest nonvariant points: Tm, ABmax> TQ1and TQ2(Figure 5a).
The highest melting point of an incongruently melting compound is intermediate between the temperatures of the nearest nonvariant points of the system.
Supersaturation and synthesis of a nonstoichiometric solid at a fixed vapor pressure of the volatile component can be produced by cooling or, conversely, heating the three-phase system. The latter case corresponds to the temperature range Т 1 < T < Т 2 in Figure 5b. For example, cadmium telluride crystals were obtained by heating cadmium enriched melts [10]. Note that the composition of the crystals that were grown using the vapor–liquid–crystal technique always lies in the solidus line, i.e., at the boundary of the homogeneity range [15].
T–x projection of the Р–Т–х diagram of a two-component system with an incongruently melting compound (S АВ ).
5. Nonstoichiometry and defects in solids
Solids like S AB are grown from the vapor, melt (solution), or solid phases, which are called growth media. Crystallization can be viewed as the transfer of atoms of the components A and B from the growth medium (g.m.) to their regular sites AAxand BBxin the crystal lattice of the S AB compound:
Ag.m.=AAx+VBx; ΔG1; K1=[AAx][VBx]aA= exp(−ΔG1/kT),E12
Вg.m.=BBx+VAx ; ΔG2; K2=[BBx][VAx]aB= exp(−ΔG2/kT)E13
where [ ] designates concentrations and a A and a B are the activities of the components in a growth media. The generation of VBxand VAxvacancies via reactions (12) and (13) is explained by the principle of conservation of the ratio of the numbers of sites characteristic of a given crystal lattice.
Because of the size and energy differences, the Gibbs energies ΔG 1 and ΔG 2, the equilibrium constants of reactions (12) and (13), and, accordingly, the numbers of atoms A and B in the crystals turn out to be different: К 1 ≠ К 2 and [AAx] ≠ [BBx]. Thus, nonstoichiometry appears; that is, the difference between the B-to-A ratios in the real and stoichiometric crystals becomes nonzero.
Note that the properties of crystals are affected not by the nonstoichiometric atoms AAxand BBxthat occupy their regular sites, but by the defects (resulting from a disordering of the ideal structure).
These defects may be the vacancies VAxand VBxor the interstitial atoms Aixand Bix
Аg.m..=Aix+ΔG3,E14
Bg.m. =Bix+ΔG4.E15
This circumstance is due to the fact that the AAxand BBxspecies do not change the energy structure of the crystal, but complete it in a way. Near the defects (VAx, VBx, Aix, Bix), the energy field and, accordingly, the electrical, mechanical and other properties of the crystal are altered (Figure 7). Thus, defects play an important role in the description of the real structure and properties of nonstoichiometric solids.
Model of the energy spectrum of (a) an ideal and (b) a nonstoichiometric crystal containing V A vacancies.
6. Classification and formation of defects
Defect formation processes and defect classification are significant points in control of the defect composition of solids in their directed synthesis.
An ideal, or perfect, solid is one in which all particles making up the substance or structure elements (atoms, ions, molecules, etc.) occupy their regular sites in the lattice. Under heating, irradiation with a beam of high-energy particles, or mechanical treatment, the regular arrangement of particles over their sites undergoes disordering: some particles can leave their sites. The resulting disorder in the arrangement of particles over their normal sites is called defects [27].
In terms of geometry and size, all defects are divided into point and extended defects [27, 28] (Figure 8).
Classification of defects.
The size of point, or zero-dimensional, defects is comparable with the interatomic parameter. The zero-dimensional (OD) defects include electronic defects (holes, electrons, exitons), energy defects (phonons, polarons), and atomic point defects (APDs). The APDs in nonstoichiometric AB crystals include VAxand VBxvacancies (absence of atoms or ions in lattice sites); interstitial atomsAix, Bixand Fix, where F - foreign atoms (the upper symbol х means the neutrality of the defect with respect to its environment), the lower symbol means the defect location.
The formation of an APD is an endothermic process requiring a small amount of energy: 0.5 ≤ E f ≤ 3 eV. Therefore, APDs are equilibrium defects and their concentration depends on synthesis conditions, namely, the temperature and the partial pressures of the components. The size of an APD is 0.1–0.5 nm; however, APDs polarize their environment in the crystal structure, causing slight displacements of neighborions, and largely determine the physical and chemical properties (diffusion, electric conductivity, etc.) of the nonstoichiometric crystal.
Vacancies, interstitial and antistructure (ABx, BAx) defects are classified as intrinsic defects of a crystal. The concentration (c j ) of these defects takes on a thermodynamically equilibrium value at any Т > 0 K: c j ≈ exp(–W j /kT), where Wj is the defect formation energy, 0 < W j < 3 eV. The higher the temperature, the higher the APD concentration c j . As the crystal is cooled to room temperature, part of the APDs can annihilate via various mechanisms. However, many APDs persist even at exceptionally low reactions (12)–(15), but also from the irradiation of the crystal with high-energy (>1 MeV) electrons at very low temperatures.
Oppositely charged APDs can be attracted to one another to yield new APDs as electroneutral association species, such as (VA -VB+), (VA -FA+), (VAx)n. Dipole–dipole interaction leads to the formation of APD clusters, which can serve as nuclei of other phase in the nonstoichiometric crystal.
Extended defects include linear (1D), or one-dimensional, and two (2D)- and three-dimensional (3D) defects [29, 30] (Figure 8). Let us consider some specific features of these defects.
Linear defects, or dislocations, are similar to point and two-dimensional defects in the sense that their size is comparable with the unit cell parameter. In the third dimension, the dislocations are fairly long or even infinite. The simplest kind of dislocation is the edge dislocation.
The most important two-dimensional (2D) defects include solid surface, block (domain) boundaries, stadling faults and crystallographic displacement planes, which are surfaces in which coordination polyhedra of two contacting ideal are rearranged.
An example of periodic intergrowths is provided by the family of tungsten bronzes, A x WO3 (A = alkali metal). In these compounds, WO3 layers are intergrown with hexagonal bronze bands. The formation of intergrown bronzes is likely favored by the synthesis conditions. The boundaries of intergrowths can be periodic (ordered) or nonperiodic (disordered).
Note the following specific features of two-dimensional defects. Firstly, their formation energy is fairly high (>3 eV) and they are kinetically stabilized nonequilibrium defects. The "frozen" state of these defects is responsible for their "memory" for preparation history. Secondly, these defects do not change the stoichiometry of the substance. Thirdly, planar defects result from APD interaction and exert a significant effect on on the reactivity and physical properties of nonstoichiometric solids.
The size of three-dimentional defects (Figure 8) exceeds the lattice constant in all three directions. These defects are, in essence, macroscopic imperfections of the crystal structure and are formed during crystal growth and subsequent processing. Three-dimentional defects include separate blocks; mosaics (totality of a large number of small- and large-angle boundaries); inclusions (microdeposits) resulting from phase transitions, such as the decomposition of a solid solution; magnetic domains (crystal zones with the same orientation of spins or electric dipoles); Guinier–Preston zones (parallel platelike formations as thick as a few unit cells, separated by different distances and having the same composition as the crystal); cavities; and cracks. Three-dimentional defects can be viewed as resulting from defect association and ordering. For example, pores can be considered to result from the association of a large number of vacancies. Bulk defects also include elastic tensile and compressive stresses.
Deviations from stoichiomrtry may be so large that defect interactions become significant leading to direct ordering, clustering, superstructure formation, long-range ordering, and the formation of new nonstoichiometric phases differing in symmetry, energy and other aspects from the parent phase. In such systems defects are intrinsic components of the crystal structure rather than being statistically distributed imperfections. The crystal-chemical and thermodynamic aspects of nonstoichiometric compounds with narrow and broad homogeneity range as well the approaches for controlling the nonstoichiometry and considered in [31].
7. Substance homogeneity criterion in physicochemical analysis
The Gibbs energy (G) of a crystal is a statistical quantity related to the distribution function. The mean G value determines the most likely distribution of zero-, one-, two-, and three-dimensional defects. Fluctuations around the mean value are possible, and, in a closed system (solid substance with a constant net composition at a fixed temperature), the configurational fluctuation can manifest itself as a change in composition within a small region as a consequence of a random motion of particles inside some volume element or to its surface. This brings up the question of what substance can be called homogeneous. The degree of heterogeneity of a solid phase is characterized by the statistical distribution of structure elements from which the crystal is built. These structure elements are the atoms of the components of the system in their regular sites, as well as various zero-, one-, two-, and three-dimensional defects in their regular positions (Figure 8).
A quantitative estimate of the degree of heterogeneity can be based on the following three types of distributions:
distribution of structure elements in some measurable volume,
distribution of these volumes in the crystal, and
distribution of measurement data and properties of the solid phase.
Let σ be the confidence interval and c i be the concentration of structure elements in the ith microvolume. If
|ci−1/N∑i=1Nci|≤σE16
the solid substance can be called homogeneous. If there is an i value at which this inequality is invalid, the solid phase should be considered to be heterogeneous. For practical use of a material, of significance are such deviations of the property in a given object from the weighted average value for the entire system that go beyond the confidence interval. In this sense, heterogeneity can be understood as the totality of property values, measured in all microvolumes, that fall outside the confidence interval. An analysis of generalized heterogeneity criteria in terms of an autocorrelation function was carried out by Nikitina et al. [32]. A thermodynamic analysis of defect ordering and an interpretation of the concentration dependences of physical properties taking into account short- and long- range order parameters were made using a model based on the above stricture elements or cluster components [33].
Some features of homogeneity criteria, physicochemical analysis, thermodynamics in materials science and inorganic crystal engineering are discussed in [34-37].
Technological progress is intimately associated with creation of new materials, such as composites, piezoelectrics, ferroelectrics, semiconductors, superconductors and nanomaterials with preset functional properties. For the synthesis of these materials, it is necessary to study the chemical processes that lead to the desired properties
Physicochemical analysis is the field of chemistry dealing with these processes, the interrelation between the composition, structure and properties of matter and determination of synthetic conditions for obtaining such substances. Several challenges and new approaches have been discussed. They include the concepts of a substance, phase, component, directed synthesis strategy as well as some definitions. Attention was paid to nonstoichiometry, classification and formation of defects.
Synthesis of nonstoichiometric solid involves control over phase transformations. The P–T–x phase diagram is a key to selecting conditions for synthesis of solid with well-defined nonstoichiometry. For this reason the following features of P–T–x phase diagrams were considered: highest melting point of a nonstoichiometric compound ( Tmax m,AB ), noncoincidence between the solid-, liquid-, and vapor-phase compositions (x L ≠ x S ≠ x V ) at this temperature, factors determining the nonstoichiometry range, the terms congruent and incongruent phases and phase processes. Criteria for evaluating the degree of heterogeneity of nonstoichiometric solids were also considered.
Glossary of Abbreviations
Tm,ABmaxmaximal melting point of a nonstoichiometric compound AB
(NaNa+) cationic sites
(ClCl−) anionic sites
U internal energy
Q heat
А work execution
δ nonstoichiometry
Tmcnonvariant point of congruent melting
TScnonvariant point of congruent sublimation
Tecnonvariant point of congruent evaporation
S solid phase
L liquid phase
V vapor
μASchemical potential of the component A in solid phase
μBSchemical potential of the component B in solid phase
μALchemical potential of the component A in liquid phase
μBLchemical potential of the component B in liquid phase
μAVchemical potential of the component A in vapor phase
μBVchemical potential of the component B in vapor phase
xB mole fraction of the component B
SV entropy of vapor
SL entropy of melt
SS entropy of solid
GV Gibbs energy of vapor
GL Gibbs energy of liquid
GS Gibbs energy of solid
ΔfG° standard formation Gibbs energy
k number of components
r number of phases
α number of independent constraints imposed on the intensive variables (с)
AAxregular sites of atom A in crystal lattice of the SAB
BBxregular sites of atom B in crystal lattice of the SAB
К 1 equilibrium constant
VBxand VAxvacancies
Aixand Bixinterstitial atoms
c j concentration
W j defect formation energy
σ confidence interval
(VA -VB+) electroneutral association species
(VA -FA+) electroneutral association species
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2.The essence of physicochemical analysis — Some definitions
3.Directed synthesis of nonstoichiometric solids
4.Phase diagrams as a key to selecting conditions for synthesis of solid with well-defined nonstoichiometry
5.Nonstoichiometry and defects in solids
6.Classification and formation of defects
7.Substance homogeneity criterion in physicochemical analysis
© 2013 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
V. P. Zlomanov, A.M. Khoviv and A.Ju. Zavrazhnov (June 10th 2013). Physicochemical Analysis and Synthesis of Nonstoichiometric Solids, Materials Science - Advanced Topics, Yitzhak Mastai, IntechOpen, DOI: 10.5772/54815. Available from:
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One of the Commonwealth's greatest coin rarities, the 1920 Kookaburra Square Halfpenny design type 1
Choice Uncirculated with a sculpted three dimensional design on both obverse and reverse. And stunning mirror fields.
Noble Auctions July 1986. Noble Auctions July 2007. The Madrid Collection of Australian Rare Coins.
If there is one coin that represents the aspirations of all collectors it is this 1920 Kookaburra Halfpenny. It is the ultimate Australian numismatic rarity. For as long as auction records have been kept, the coin has been referred to as 'one of the Commonwealth's greatest coin rarities'. A kookaburra halfpenny was trialed at the Melbourne Mint in 1920 and 1921. This example was struck in the former and as it so happens, '1920' is regarded as the glamour year of the Australian numismatic industry. Furthermore, it is extremely rare, known by three examples only. And the quality is simply stunning. You would be forgiven for thinking that this coin was struck to proof quality. As a point of note it is the finest (by far) of the three known examples. The coin's last appearance at auction - in July 2007 - was as exciting as it was momentous. Frenetic bidding saw the coin rapidly move beyond its original pre-auction estimate of $150,000, leaving an exhausted bidding audience to absorb the final sales result of $380,000.
The glamour of the year '1920'
The year '1920' is indeed a glamorous one for the industry for it hosts some of the rarest and most famous coins of the Australian numismatic industry, a stunning line-up that includes:
Australia's rarest florin, the 1920 Star Florin.
One of Australia's most valuable shillings, the 1920 Star Shilling.
Australia's most valuable sovereign, the 1920 Sydney Mint Sovereign.
The 'Crowned Head' 1920 Kookaburra Penny, the only square penny in the series to depict the monarch wearing a crown.
This coin, the 1920 Kookaburra Square Halfpenny, the rarest halfpenny of the series and throughout history has always been known as one of the great Commonwealth coin rarities.
When the Kookaburra Square Penny and halfpennies were created, Australians were recovering from the war and determined to lessen the ties with Great Britain. The mood even filtered through to our coinage! The Government planned to introduce a square penny and halfpenny with our native bird on the reverse. And the monarch minus his crown on the obverse! Provocative and contentious but uniquely Australian.
Australia entered a modern age post World War I. For many Australians, it was a time for breaking out socially, of questioning and changing old values and behaviour and enjoying the good life. It was a time of great change. People forgot the old and embraced the new in an attempt to leave the hardship and struggles of the war behind them.
New technology was being created, like toasters and cars, things that today we take for granted. The fashion world was exploding, great changes were being embraced in styles of dress. Australians were identifying with their own culture, keen to lessen the emotional and cultural ties with Great Britain.
Creating a new, totally Australian coinage was a part of the deal which is why the Government floated the idea of the Kookaburra Penny and Halfpenny envisaging a coin that would be unique to Australia.
The Government's plan was to discard the British-styled penny and halfpenny and to create a coin with a typically Australian design featuring the nation's native bird, the kookaburra. To maximise impact, a new shape was planned with the move from circular to square. And bronze was to be discarded and a new metal taken up, that of cupro-nickel.
Tests began at the Melbourne Mint in 1919 and continued for three years, ending in 1921.
Today there are approximately 200 kookaburra coins held by private collectors, making it on a par for rarity with the 1813 Holey Dollar, the nation's first silver coin. And the 1852 Adelaide Pound, the nation's first gold coin.
The best thing for collectors is that the 200 kookaburra coins do not bear the same design. The Melbourne Mint tested thirteen different styles introducing enormous interest, personal choice and procurement challenges into the series, for some designs are far rarer than others.
Aside from the concept of adapting every vending machine to accommodate a new square shape, the impracticalities of the kookaburra coinage is demonstrated with the size of the halfpenny. The bird is sculpted and three dimensional. The fields stunning.
Even without the crown, this portrait of George V is commanding and regal. It could almost be a proof striking, the details and fields are so good.
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