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Not really, GTA V is just a bumpy ride rather.
I hope things are straightened out with the current gen release.
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Posted 26 August 2014 - 06:16 PM
Not really, GTA V is just a bumpy ride rather.
I hope things are straightened out with the current gen release.
Posted 26 August 2014 - 06:39 PM Edited by Phoenix_Shit, 26 August 2014 - 06:40 PM.
Posted 26 August 2014 - 06:40 PM Edited by Agent Lynx, 26 August 2014 - 06:41 PM.
I'm not satisfied about what R* done with GTA 5. As Cowboy said it: R* is going to be the next EA - Ubisoft typed game developer.
They hyped people too much. I remember the first day I played the game. The texture resolution was so bad, I shut down the console and gave up for a few days.
You see, it's been almost 10 months since Online's release. Heist Pack is not yet released. Maybe, they supposed to put effort in Heist Pack instead of releasing sh*tty DLCs like Business, High Life, Hipster ect.
In my opinion, I believe Heist Pack is already done though but they don't release it to get more money from Shark Card bs.
Do you remember the DLCs for GTA IV? Not only new cars and new guns but new missions, new characters, new side missions, new events, new activities and a lot of new features. Yes, they weren't free but R* put real effort there. And it was worth it.
Posted 26 August 2014 - 06:54 PM Edited by Theburningfire, 26 August 2014 - 11:02 PM.
I think its sad that rockstar is going this "focus on online" path. lets just think back to 2004. GTA SA came out and everybody loved it, rockstar has put 100% effort into the single player. remember when in 2006, the fans created their own multiplayer (multi theft auto) and you know what?
the fans loved it. so if you wanna hear my opinion, YES. they are slowly digging their own grave with GTA:O i mean you don't need much braincells to see it was rushed back in october, the servers were a mess, and everyone (including me) was thinking ("cool! now i can show everyone how rich i am!")
but what happened? DNS Servers happened. everybody had billions of dollars, and if you think about it, this all happened because rockstar screwed up big time with the security of the servers. (correct me if i'm wrong) IMO, they should've just added the same multiplayer like in gta 4 like a fun mode sort of, without any money, friendly fire off and cops off.
we can do whatever we want. on the other side of the multiplayer, people could've played the normal mode (GTA:O) to discover new adventures with new possibilities.
and by the way if you're asking me, The servers will be filled with modders locking you in prisons and sh*t in a couple years. but if the modders are ALREADY there after a year of the release, rockstar is f*cked.
they really are. i don't even wanna know how it is in a couple of years...
Hide your kids, Hide your wife, lock your doors.
Posted 26 August 2014 - 10:03 PM
The fact that the product was not good enough is a good signal for R*, because there can't be anyone making a more basic game and taking their market. That's why R* attempted to do the most ambitious project ever, and continues to do so in the future too.
And you just can't be perfect with any aspect. That is what they aim for, but only with lots of good luck it will ever be possible. R* is pushing the limits of it's employees to pursue the impossible, because that makes sure that the company thrives in the future.
Most of the gamers are not hating or expressing their love, but they are satisfied with the game. Haters have been dissapointed, because they overestimated V, but those that express their love were served something so good they didn't expect possible.
Dissapointing a lot of people will deminish the sales in the future, but those gamers won't be buying the competior either, because they're inferior products with the same or higher cost. And those people who buy these inferior products will be buying the next gta too.
But GTA is not annualized like BF and CoD or GH and RB or AC and SR. That makes it possible to have time to create something never seen befor for next gta. And again to reach for the stars.
So to answer the question of OP: We don't know what the future holds for computer games, but since the new consoles are so young, there's plenty of time for R* to make the next GTA even more groungbraking than IV and V were on PS3 and XBOX360.
Posted 27 August 2014 - 12:38 AM
Highly disagree. To be honest, I'm sick of people crying about how R* haven't gave release dates etc.
1. Rockstar do not give many release dates, many release dates are given by Youtubers, and they are wrong then people rage about Rockstar although given the fact Rockstar didn't give a date.
2. Mostly I see people moaning because of Heists, yes I want them just as much as the next person, however I understand they want to make the Heists good for us and flawless and not full of bugs. So hence the delays.
3. To be honest, you're lucky the next gen are getting the game and shouldn't be moaning at all. They'll give release dates when they're ready and when they think the game is good enough for release.
1. just because some idiot youtuber on the web tells people what the release date is doesn't necessarily mean people will believe him or her. besides, why does that mean we shouldn't be annoyed at R*?
2. well, we've been waiting for heists for about how long... 11 months now? and they still haven't given us ANY INFO. not even a short trailer or some screenshots or something
3. f*ck next gen.
Posted 31 August 2014 - 12:53 AM
Rockstar games. No i cant say they've been going downhill but they arent going uphill either. People want heists but Rockstar is way to busy trying to make the games on Xbox 1 and PS4. And i really think the main reason is that Rockstar was making the next gen games right after the current gen games released. With all that, I could see why heists is delayed. But did it really take that long? I don't know, maybe. Moving on to Gta 5 online. The game was buggy from the start. Glitchers everywhere. People were farming the same mission over and over. Duplicating cars and selling them. Ugh terrible. Then Rockstar patched these glitches and bugs with small DLCs. However people complained and said why aren't heists out yet blah blah blah. Then the economy killer. People we're giving money out to everyone. I'm not gonna lie. I was living a hard GTA life. I owned a garage with 2 cars in it. i think the most money i had back then was about 50k. That money was a blessing and a curse. I wanted to be the virtual kingpin and get everything from scratch. Then the money came. I f*cking bought everything. Cars, boats I switched apartments 6 times that day. But then I realized i got everything and i said f*ck it. I stopped playing gta until the money was taken away. Damn unsecured servers. After it was patched i think 1 more dlc later, There i was back again. f*cking around in gta killing people stealing cars. It was fun again. Nothing big happened from there. Maybe the occasional tank douche that killed me. And the god mode people werent a big deal. To me that is. Jump to present day. I'm still doing missions with my friends making and spending money. The game itself wasn't a failure. It's the fact the people were upset with rockstar not fixing issues. GTA online was a great concept. If the servers were more secure and more people didn't want to get easy money, RP, and gives themselves god mode most of the problems in-game wouldn't be around.
Posted 31 August 2014 - 02:18 AM
They're not going downhill entirely. They seem to be focusing on a specific audience. They left out some basic features in GTA to appeal to a larger audience, but they ended attracting people who played FPS and other shooting games. Another thing they did is punishing people who just wanna have fun and focusing on people who want to play the game for what it is (Doing missions). This kinda ruined the online experience for me. Although I didn't like people who killed everybody with Buzzards in TBOGT online and I don't like people killing everybody with tanks neither, I'd like to be able to kill who I want and enter mission interiors like in IV.
Rockstar Games isn't going downhill, they're simply targeting a new, larger audience.
Posted 31 August 2014 - 03:45 AM
More like GTA kiddies are getting more melodramatic.
Precisely. You could add "spoilt, clueless and unappreciative" in between "like" and "GTA" as well.
Posted 31 August 2014 - 04:31 PM Edited by Spider-Vice, 31 August 2014 - 04:43 PM.
If no one can see it:
This is seriously getting a bit worrying for the future of Rockstar, I don't know what else they can do.
Edit: Here's a somewhat recent one from San Diego.
Posted 31 August 2014 - 05:23 PM Edited by Xerukal, 31 August 2014 - 05:24 PM.
Aye, the psychopathic management at studios like San Diego will be the end of Rockstar one day. There's only so much unnecessary verbal/mental abuse your employees can take before they spit in your face and declare they had enough of your bullsh*t.
Wouldn't be surprised if it escalates into someone wanting to physically attack Sam Houser, or whichever CEO is being so hostile (according to the reviews).
Posted 31 August 2014 - 05:28 PM
This isn't just at Rockstar San Diego, it's a bit in every studio. Just for curiosity I checked out reviews for 2K Games and et voilá, it's actually a bit of the same sh*t. Take-Two probably doesn't even know what is going on, or doesn't care. Every game company has a huge load of work and overtime and bad things like that, but limits are limits. After reading reviews for 2K Games, Irrational Games and Rockstar, I'm not sure whether it has to be Take Two taking action or each of the companies.
Rockstar has people who actually sort of like being there, so nothing will probably happen that soon.
Posted 31 August 2014 - 05:32 PM
Well I did say "studios like San Diego" and "one day".
Posted 31 August 2014 - 05:56 PM
I think you can define downhill more only with the meaning that the quality of GTA is going downhill. Because R* obviously doesnt. As they have released their latest titles successfully, there is no problem right now. Of course, as they only publish e. g. one GTA every 4 / 5 / 6 years, this has to get very good sale numbers, otherwise they would have a problem. So if their marketing of a new GTA or something else goes wrong, then I think they will have a big problem. I dont know about their financial management, but they made lots of profit the last years, so even though one GTA title would be a total fail, I guess they could survive to the title after that and then just hope that one after the failed one will sell better.
So for answering your question, R* definitely doesnt go downhill. GTA maybe.
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text:
Long Term Psych Meds And Dementia
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Long Term Psych Meds And Dementia

subset: commoncrawl


text:
Old-Time Stuff Is Not Forgotten on "History"
THE big names — Fort Sumter, Gettysburg, Lee, Grant — are getting much of the focus during television's Civil War spring and summer, as they always do when this pivotal conflict comes up. But to mark the 150th anniversary of the start of the war, the programming that resumes with a burst this weekend and continues over the next several months also has much smaller things on its mind: a child's doll, an aging tintype, a faded letter. And it is those things, 19th-century artifacts elevated to new prominence by a 21st-century television trend, that provide some of the clearest reminders of what the war was really about and how it remains with us today.
Finding new ways to look at the war is, of course, a sort of Ken Burns effect — an effort to clear the bar that Mr. Burns set so high in 1990 with his mini-series "The Civil War." Mr. Burns, for one, doesn't think the form is dead.
"I think there are still stories to be told," he said. "The Civil War is such a watershed moment, the watershed moment in the childhood of our country." Yes, there are limits on such documentaries — there's only so much you can do with still photographs and diaries — but that doesn't mean there can't be innovation. "It just forces us into new relationships with photographs, new relationships with voice, new relationships with narrative," Mr. Burns said....
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- Conference delves into effects of climate change on native people
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- Historian says the removal of Nazi-era art to Switzerland makes restitution unlikely
- Martin Kramer blasts MESA and Steven Salaita


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JOHN SEEWER – A judge will decide whether to send a former Ohio police captain back to prison a little over a year after he was freed from a life sentence and exonerated in his ex-wife's killing.
Former Akron officer Douglas Prade was ordered to appear in court Thursday, a day after an appeals court ruled that another judge was wrong to free him. Prade spent close to 15 years in prison for his ex-wife's killing before he was released in January 2013 when new testing of a bite mark cast doubt on his conviction.
Prosecutors want Prade sent back to prison immediately, but his attorneys are fighting to keep him free while he appeals.
Summit County Judge Christine Croce set a hearing for Thursday morning.
Prade was freed when now-retired Judge Judy Hunter decided there was convincing evidence of his innocence after DNA tests of the bite mark on Dr. Margo Prade's lab coat showed the DNA did not match that of her former husband.
But Ohio's 9th District Court of Appeals said Wednesday that the DNA testing only raised more questions than answers and that Prade's original conviction was based on overwhelming circumstantial evidence.
"Without a doubt, Prade was excluded as a contributor of the DNA that was found in the bite mark section of Margo's lab coat," the ruling said. "The DNA testing, however, produced exceedingly odd results."
Each sample produced completely different results, the appeals court said. "While it is indisputable that there was only one killer, at least two partial male profiles were uncovered within the bite mark," the ruling said.
Summit County Prosecutor Sherri Bevan Walsh on Wednesday sought a warrant to have Prade returned to prison. The prosecutor's office didn't know where he is currently living.
"In order to be exonerated, Prade and his attorneys needed to show clear and convincing evidence of his innocence – not simply create doubt," Walsh said. "They failed."
A message seeking comment was left with Prade's attorney. Prade has maintained his innocence.
Prade was convicted in 1998 of shooting his 41-year-old ex-wife, a family practitioner, inside her van in the parking lot of her Akron office. There were no witnesses and no fingerprints, and no gun was found after the November 1997 shooting.
A test of the lab coat fabric showed it contained at least two and as many as five DNA profiles and none matched the former police captain's DNA.
A Summit County assistant prosecutor told the appeals court in August that the findings showed a possibility that the bite mark evidence was contaminated, perhaps before Prade was convicted and sentenced to life in prison with parole eligibility in 26 years.
"The only absolute conclusion that can be drawn from the DNA results, however, is that their true meaning will never be known," the 71-page appeals court ruling said.
Prade's attorney said at the August hearing that new tests based on improved technology found only that the DNA came from a male, but not Prade.
Last month, Prade filed a lawsuit in federal court against current and former police officers, claiming he was framed.
He said after his release that he wanted to spend time with grandchildren he had never met and work with the Ohio Innocence Project, the group that helped free him, on cases of wrongfully convicted inmates.
"I'm just a jumble of emotions right now," he said then.


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Mar 24, 2014 at 5:59 am
GRANITE FALLS, Minn. (KNSI) The Yellow Medicine County Sheriff's office in western Minnesota is investigating the death of a person at an addiction recovery center.
The sheriff's office got a 911 call early Sunday morning on a report of an unresponsive person at Project Turnabout. The Granite Falls Ambulance responded, but the person was pronounced dead at the scene. Authorities say foul play is not suspected, but the case is under investigation. The victim's name has not been released, pending notification of family.
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Lamar Hunt U.s. Open Cup
Soccer: FC Tucson goes toe-to-toe with Dynamo but falls short in U.S. Open Cup
HOUSTON – FC Tucson refused to back down from one of Major League Soccer's most successful teams Wednesday, going head to head with the Houston Dynamo in a 2-0 loss at BBVA Compass Stadium.
Soccer: Upset of in-state rival won't get in way of FC Tucson's prep for league play
When you pull off arguably the most thrilling win in franchise history, what do you do for an encore?
FC Tucson: It's on: Local club to face Phoenix in U.S. Open Cup
Three members of the Tucker family, all wearing their blue Freedom Soccer Club uniforms, help with the April 25 groundbreaking ceremonies on a stadium being built at Kino Sports Complex North Field No. 1. From left to right, they are: Ellie Tucker, 9; Gabriel Tucker, 3; and Hannah Tucker, 6.
FC Tucson: It's on: Local club to face Phoenix in U.S. Open Cup
Are you ready for some May Madness?
Soccer: FC Tucson to open play in US Open Cup against Phoenix FC
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Come Down, Emmanuel
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Come Down, Emmanuel composed by Pepper Choplin. For SATB choir with optional rhythm instruments. Collection. Healing, Prayer, Advent, Sacred. Octavo. 12 pages. Published by Hope Publishing Company (HP.C5702).
With Appalachian musical roots, this compelling, original prayer is an earnest look at real day-to-day relationships -- pleading for Emmanuel to come down and be present in the lives of those facing difficult times. The text assures us of God's presence with sincerity and a relevancy that is often times hard to find, making this warm, folk ballad useful for Advent, or any time of the year. The Rhythm packet includes parts for Guitar, Bass, & Mandolin.
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Business | Investment
DIFC Courts appoint third Emirati judicial officer
Appointment supports development of national legal talent
Dubai: The DIFC Courts, Dubai's established English language, commercial common law judicial system, have announced the appointment of Maha Al Mehairi as a Judicial Officer. She has been promoted from her previous role as a Case Progression Officer. Maha will be working alongside Nassir Al Nasser, who was earlier appointed as the Courts' second Judicial Officer in December 2012. Maha and Nassir now provide judicial support to the Courts' bench by undertaking legal research, sitting on DIFC Courts' Small Claims Tribunal (SCT) proceedings and attending Case Management conferences and application hearings. Maha Al Mehairi recently qualified as an accredited mediator of the Royal Institution of Chartered Surveyors (RICS), the largest organisation for professionals in property, land, and construction issues worldwide.
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Murray State Racers Travel Gear at CBSSports.com Shop
CBSSports.com Shop - Everything Sports! Murray State Racers fans, score your new Murray State Racers Travel Gear from the Official Store of CBS Sports. Find your Murray State Travel Pillows and Bags and have your order shipped from the CBS Sports Store for a low flat rate.


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"but I have always been led to believe that the degree isn't as important as talent/know-how in graphic design..."
Here, without a degree, it's not likely anyone will ever know...
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Comment on Anyone else only have a diploma¿?Today, 08:51 PM
Comment on Anyone else only have a diploma¿?We don't even consider applications that don't list a degree where I work, though even people with degrees can have terrible portfolios. Out of probably 30 applicants from our most recent opening, maybe...Today, 08:37 PM
Reply to Standards of Graphic DesignHonestly, if you are unsure, it's better to under design. People who are new to design have this tendency to put everything they can think of into a design. Design is just as much about culling and restraint....Today, 08:31 PM
Reply to Crop Marks and Cutting PaperWe have a $250,000 digital printer and the backups can be up to 2mm out. That is within specifications.
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Is there a valid way to do this?Hi folks,
I haven't done much work on the web so some of my memories of CSS has faded a bit. I downloaded a copy of the css zen garden's exercise to refresh my memory.
I got everything to work, but one tag does not validate
html { overflow-x: hidden }Tags: None
Thanks for your reply Aestuo
I tried using the overflow: hidden property originally on the div but it seems to have no effect when I do that to the div itself. For reference:

div#extraDiv1 { margin-left: 5%; position: absolute; top: 0; z-index: -1; overflow: hidden; background-image:url(images/ss36-hires.jpg); background-position: 600px 0px; width: 1600px; height: 681px; } #extraDiv1 span { display: none; }
wait, what are you trying to do? backgrounds should never cause scroll bars, and are you testing in ie6 or something else? (i hope something else)
also, the overflow only affects content not the background of an element; a background image should automatically get cut off based on the size of the element.
Originally posted by Aestuo View Postwait, what are you trying to do? backgrounds should never cause scroll bars, and are you testing in ie6 or something else? (i hope something else)
also, the overflow only affects content not the background of an element; a background image should automatically get cut off based on the size of the element.
Is this possible using just an empty div and span tag? I'm trying to follow the zen garden exercise by not modifying the html document.
if you set the image as the background for the page it clips automatically. you just specify the image as the background in the body, and do not specify the width. if you have fixed width elements within the page, they will cause a scroll bar, but doing the background this way, you should have no issue.
Originally posted by Aestuo View Post(also, am i missing something? does everyone do the "Zen Garden Exercise"? - I've heard of the zen garden site before...)
I guess from your explanation that it can't be done with a div, and essentially can't be done at all with the stylesheet as a whole unless I get rid of that 5% margin (because otherwise everything would get a 5% margin to the left, no?) The 5% margin was not an absolute necessity, I was just experimenting using percentages instead of static numbers.
Thanks for the help on understanding overflow and its effect (or lack thereof)!
Edit: Scratch that, I can make it work I just forgot to remove the margin on the container div to achieve the same effect! Thanks again!Last edited by Garamond; 05-29-2009, 11:00 PM. Reason: D'oh


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Black History Museum To Have a Story for All
A central principle of the future National Museum of African American History and Culture will be that the varied stories of African Americans have broad meaning to all people. "The notion that African American history has limited meaning should be a concern for all of us," said Lonnie G. Bunch, the founding director of the planned museum that will be part of the Smithsonian Institution. For instance, he explained, he's been troubled by a survey in the 1990s in which 81 percent of white respondents said slavery had little to do with them, and in which 62 percent of the black respondents were uninterested in or embarrassed by slavery.
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- 1,000 + have signed a petition protesting US government plan to commemorate the 50th anniversary of the Vietnam War
- Historian and raconteur Raychauduri dies in UK
- Group is drawing attention to the historic swath between Gettysburg and Monticello
- Conference delves into effects of climate change on native people
- History professor says the Vikings never came to Newfoundland


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American Pie!
This great custom product in red from our department Men and Hoodie category can be printed just for you in the size and style you like. The design Orgasm Donor was created by CrewNeck and uploaded to Spreadshirt for you to have printed on a Hoodie. Next to a host of other great customized designs, you can find this Orgasm Donor design in Spreadshirt's Provocative category. If you are interested in topics like Orgasm Donor or american pie, then you'll love Orgasm Donor designs by CrewNeck. Spreadshirt also offers a huge selection of custom t-shirts, hoodies and accessories for the category Provocative as well as top crude jokes clothing. CrewNeck's designs have already impressed many of our customers, so we are sure that we've got right stuff for you! Spreadshirt is your destination for great designs of all kinds – whether it's Orgasm Donor, american pie or crude jokes. We are sure that you will find something nice in our shop, there are many amazing custom Provocative t-shirts, hoodies, or accessories for you to find! Tags: Design ID: 11875287
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This lightweight pullover hooded sweatshirt for men is comfortable and stylish. It has the classic kangaroo front pocket, drawstrings at hood and set-in sleeves. Reinforced cuffs and waistband add extra durability. The material is made from 50% cotton and 50% polyester and has a fabric weight of 7.8 oz.
still to fill


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text:
Abstract available in
Claims available in
Description (OCR text may contain errors)
1932- M. N. FREDENBURGH 87 51 nmacmon EMISSION MATERIAL Filed July 11, 1928 PREPARATION OF .BARIUM STRONTIUM CALCIUM CARBONATE BAR/um NITRRTE C]? 66.2. (51%. AMMmv/u/w CARE ONAT'E STRO/VT/UM N/TIFHTE C]? 4.3.0 6M3. C7 LUMP //00 GM 5. CALCIUM lV/TRATE GPA-2a Cims.
AMMoMu/v: HYDPGX/DE .DJSSOLVED IN DIST/LLED WATER 6.7 ($45.30) 470 6M5.
F/LTERED Tw/cE.
FILTERED Tw/cE.
SOLUTION No. I. SoLuT/oN No. 2,.
OO/WL. SOLUTION No. .2.
SOLUTION No.2 ADDED To SOLUTION No. AT'Co/vsTANT PAT: VV/TH sT'lRRlNCy So THAT TIME OF PRECIPITATION ls 5/Vl/N.
BAR/UM srno/vr/um CALCIUM Cameo/mm PLus WATER, PLUS Hm/wa/v/u/w lV/TRATE.
TRANsFERREpI 7'0 BucHMER FILTER.
WAsHEb W/rH .DISTILLED WATER fso-/aac.) UNTIL FREE FRO/v1 NITRATES.
PPT. DRIED A7- /oo- /2oc.
INVENTOR MN. FR EDENBURQH ATTORNEY Patented Au 9.1932
max N. rnn'nnnnunen, or East onmen, new
HOUSE LAMP COMPANY, A. CORPORATION OF PENNSYLVANIA nLns'raon niurssrorf i Application filed July- 11, 1928. sum in. 292,087.
This invention relates to electron-emitting:
electrodes and more particularly to electronemitting cathodes of the oxide coated type and comprisesessentially in a process (and the product) of producing substantially pure intimately admixed alkaline earth metal carbonates which may be employed in producing alkaline earth metal oxide coated cathodes for electron-emitting purposes. The products of this invention comprise admixed alkaline earth metal carbonates to which have been imparted a preferred and. definite crystalstructure'not heretofore obtainable andthe oxide coated cathode repared therefrom.
This invention is an improvement of the process of preparingelectron-emitting cathodes as set forth in the patent of Duncan MacRae,.'No. 1,812,103, entitled Electronemitting devices and method of making, which patent is assigned tothe Westinghouse Lamp Company, the assignee' of the present application;
' The process described in said patent contemplates applyinga coating of alkaline earth metal carbonates to the surface of a metallic cathode by forming an inorganic suspension of the carbonates in water or other suitable liquid which is inert with respect to.
the carbonates and which may be removed by heat without decomposition. Thereafter the composite cathode is suitably heated in an atmosphere of carbon dioxide to cause the coated material to adhere to the metal base and to remove'the 'susp ension medium. This coating process maybe repeated any number of'tinies so as to obtain heavier'deposits of the alkaline earth metal carbonates and may be made a continuous one if desired.
The resulting coating being comprised of unaffected by atmospheric gases and cathodes so coated may be kept indefinitely without deterioration before being incorporated in an electron discharge device. After being mounted in an electron discharge ,device, this carbonate coating may be rendered in an electronically active condition by highly heating the composite cathode during the exhaust procedure whereby the carbon oxide content of the 'coatingis substantially removed, leavalkaline earth metal carbonates is stable and ing a residue of anhydrous alkaline earth metal oxides which are adherent to the sin;
.\face of the metal base. In he practice of the in said patent ithas been found thatthe dispersion, purity, particle size, relative proportions 'of thecolnponent alkaline earth metal carbonates, etc., exert a considerable influence mam, Assrenon 'ro wasrnm rocess'as disclosed onthe application of the carbonate to the filament, as well as in effec the efiiciency and life'of the electron emissionof the hot composite cathode.
' In the process of coating as disclosed in said patent the preferred admixture of alkaline earth meta lcarbonates employed is com risedof barium and strontium carbonates, alt ough other admixtures of the alkaline earth metal carbonates are antici ated asfalling within the scope of the coating composition.
Thelcommon practice heretofore has been to employaiiy commercial grade of chemi- -cal1y pure alkaline earth metal carbonate as may be purchase'able upon the market, comminute the same, admix mechanically in the desired proportion and thereafter form an emulsion or suspension of the admixed materials in the desired medium for, coating. Separate aiid'independent lots of carbonate material as obtained on the market. were 1 found to vary widely in thedegree of purity; particle size, absorbtive properties towar the carrier fluid and density, etc., which caused variable results with respect to the life and efliciency of the resultant electron dis charge device within which the coated cathodes were employed. Moreover, at times dif-. ficulty was experienced in obtainin a uniform admixture of the carbonates wit out too finely comminuting the particles during the admixing process. Some difliculty was also experienced in maintaining durin the coating operation a uniform mix of t e component carbonates.
' One of the objects of this invention is to reduce the variable operating characteristics heretof gxide coated type. I
Another ob ect of this inventionis to provide a; high grade coating material for oxide coated cathodes which is comprised of umore encountered in hot cathodes of the formly admixed substantially pure carbonates I of the alkaline earth metals. tions and speed of mixing.
Another object of this invention is topro- .When barium carbonate alone is prepared vide a coating material for oxide coated filaby this general method the product proments comprised of intimately admixed alduced, regardless of the physical constants kaline earth metal carbonates which is uni of preclpitation when dried, is always more ture, pressure, concentration of the two soluform in composition, of a coarsely crystalor less flufly and'finely divided. When line structure and of a high degree of purity. strontium carbonate. alone is prepared by Another. object of this invention is to prothis general method, variation 1n precipita- 1o vide an'oxide coated cathode comprised of a tion conditions may produce a. material refractory metal filament base and a coating I either dense or light and fiuflt'y. When adof alkaline earth metal o'xidesin such a physmixtures of barium and strontium carical state of intimate admixture, purity, parbonates which heretofore have been emp 1oy-' ticle size, etc., that uniform operating results ed as a coatingmaterial in this process are 15 a bt i d th f formed by simultaneous precipitation, the
Anothe ct of this invention isto prodensity and phwre of the 5 vide a commercial process for preparing the cipitate may be us vary widely-by I substantially pure carbonates of the alkaline varying the precipitation conditions. T
earth metals in an intimately admixed state which process would be operable. to produce r effects primarily the absorbent or suspension this productconsistently.
properties of the material, thus altering the Other objects and advantageswill be .apcoating procedures considerably.
parentas .the process is more fully disclosed. I When calcium carbonate alone is prepared 5 In pre aring oxide coated cathodes of the by this general method the efi'ect of the phyinvention, the physical state of the admixed crystal structure of the resultant product is carbonates of the alkalineearth metals-has pronounced. By varying the precipitationa pronounced efi'ect upon the operating char conditions, two crystal forms or admixtures 3o acteristics of the composite. cathode. It is of these two forms of calcium carbonate may desirable from many standpoints to obtain a be obtained. a, highly-intimate dispersed admixture of the This variation in density'of the carbonates, I i
and in ,a coarse grained crystalline form due t0 variable precipitation conditions, 86
ao character fallm within the scope of this sical constants of precipitation pan the The more common and stable form is cal- V carbonate inaterialfi more intimate than is .cite which maybe precipitatednormally from obtainable bymechanical admixture. It is cold 'or medium ,warm solutions. Aragonite',
also desirable to retain a-relatively coarse but which is the second form of calcium caruniform particle size sof the admixed carbonate,may be precipitated. when the tem-' bonates, which' is practically impossible to perature of the calcium solution is held above obtain by 'mechanical admixture means. It 85 C. during precipitation.
j is necessary to retain a high degree of purity 40 in the components of the coating material. talstructure of the calcium carbonate may oughly understood as to which of the alkaline; taneously with either one or both of the other I earth metal oxides the phenomena of electron alkaline earth metal carbonates and that the emission. is due, recent researcheshaveindiprecipitation of thearagonite crystal form cated thati'n-a composite-oxidecoating such of calcium has a pronounced efi'ect uponthe as-may be formed by this process the emiscrystal structure of the simultaneously presion quality at 'the present operating tem-' cipitated admixed alkaline earth carbonates. per'ature's .is due to he barium component I have foundthat the addition of 'calclum thereof. It is commonly considered that the salts to admixed bariumand strontium solufunction of the remaining component or comtions and simultaneous precipitation of the ponents (SrO and -OaO) is in the nature of three alkaline earth metals under such con- I have determined that the aragonite crysw "Whereas heretofore it has not been thorbe obtained readily when precipitated simul-' an inert or'retaining structure serving either ditions thatthe ara'gonite type of crystal I as a carrier for the electron-emitting constitstructure is developed, completely alters the 9 uent, a, m t t o di e ing medium.- size of and the ysical state of the barium It is essential that the activating constituent and strontium carbonates and they partake of the filament BaO) be present in theof the sanfe type of crystal structure as the oxide coating in a finely dispersed condition calcium, and" form isomorphous crystals of for best electron emission results. strontianiteand witherite which also belong v The preparationof pure barium,strontium to the; rhombic system of crystallization.
' and calcium carbonates maybe accomplished Such a precipitation or formation of this s gby adding to an aqueous solution of thepure rhombic crystal structure is not normally ob- "nitrates, a solution \of alkali metal or .amtained by precipitating the barium and stron- I monium carbonates. The physical nature of tium aloneunderthesame conditions. This the precipitated material varies "with the efi'ect on the crystalstructure of theaggreconstantsof precipitation, such as temperagate precipitate .is increasingly pronounced with increased calcium content becoming apparent with as little as .5% CaCO and increasing until at approximately 10 to 20% calcium the desirable effect on the crystal structure which is desirable for the purpose of my invention is obtained. Larger percentages than 20 percent CaCO may be employed but are not essential to produce the effect which I have utilized in the practice of my invention serving only to increase the degree of coarsening of the individual crystals of the precipitated carbonates.
I have also determined that the rate of precipitation has a direct bearing upon. the
ultimate particle size and particle size contrast and for the purpose of my invention it appears desirable to effect the production of the admixed carbonates in such a manner as to cause the resulting crystals to be of nearly the same size and have at least a constant maximum particle size contrast. The per cent calcium present-in the solution (dilution) controls the maximum obtainable particle size whereas the rate of precipitation controls the particle size contrast.
It is common practice in many arts in order to obtain intimate mixtures of two or more components to simultaneously precipitate the components from aqueous solutions. Intimate admixtures of the alkaline earth carbonates may be prepared in this manner, but I have determined, however, that simultaneous precipitation of alkaline earth metal carbonates alone does not accomplish the desired effect as the crystal structure and particle size contrast of the material is an important factor in the'preparation of and subsequent activation of oxide coated cathodes by this method. Simultaneous precipitation of the carbonates must be accomplished under the certain conditions of temperature of solutions, dilution of solution, component admixtures, rate of precipitation, etc., so as to cause the formation of a definite physical state (particle size) and crystalline structure of the precipitate.
In order to ensure absolute purity in theresultant carbonate product, precipitation with alkali metal carbonates should be avoided. I prefer to employ ammonium carbonate and have found that the normal ammonium carbonate is a preferable compound to employ.
" ammonium compound are readily decomposed and volatle 1n vacuo.
- Another factor influencing my process from a commercial standpoint is the factor of dilution of solution, that is, the proportion of solids therein. Should the process of precipitation be conducted in too concentrat ed a solution, difiiculty in preventing occlusion of impurities in the crystal structure is encountered. This occlusion of impurities decreases with increased dilution until at approximately a concentration of 15.0 percent Greater or lesser dilutions may be employed however, without departing from the nature of myinvention. as regards the specific use of calcium as the extent of dilution has no apparent effect on the effect of the aragonite structure formation on the admixed barium and strontium precipitates.
Having broadly outlined the scope and nature of my invention I Will specificallydescribe my process as developed to form an admixture of alkaline earth metal carbonates which-may be utilized as the coating material on hot cathodes in electron discharge devices.
I first form a solution of the mixed nitrates of the alkaline earth metal containing approximately 15.0 percent total solids comprised as follows Barium nitrate (C. Pi'anhydrous) l 66.2 gins.
Strontium nitrate (C. P. anhydrous). l gms Calcium nitrate (C. P. 4 H 0) 4.4.2 gins. Distilled water 960 m. 1.
The nitrates are dissolved in the water contained in a Pyrex glass beaker of two liters capacity, by heating to 80 C. The solution is then filtered twice by gravity through a No. 14: l/Vhatman filter paper. This solution I'will refer to as solution #I.
As previously noted, other concentrations of solution may be employed if desired, but I have found that in general the difficulty'of washing free of impurities increases with increased concentration of total solids and that this concentration is most satisfactory from all standpoints.
I next prepare a solution of normal am monium carbonate (Spec. Grav. 1.130 at 25 C.) :This solution is prepared as follows Ammonium carbonate C. I. lump) 1100 gms. Ammonium hydroxide (C. P. S. G. Distilled water L 1987 m. 1.
beaker of 1 liters capacity, the ammonium carbonate is then added and the contents heated to and maintained at approximately 40 C., with occasional stirring until solution is complete. The solution is then filtered twice by gravity through a No. 14 Whatman filter paper. This solution I will refer to as solution #11.
In preparing theprecipitated. carbonates of the alkaline earth metals by my process I first heat solution #I in a'Pyrex glass beaker of two liters capacity to a temperature not less than 90 C. To this heated solution I add at a constant rate 200 m. l. of solution #II which has been preheated to. 30 (1., maintaining at all times a vigorous agitation of the solution during precipitation. With this particular proportionate mixture of alkaline earth metal carbonates I have found thatthe rate of addition of the normal aim-- monium carbonate solution to eifectpreclpi- 'tation of the carbonates should be such that total addition of the 200 m. L of solution II he efifected in approximately one minute.
.This rate of precipitation is the factor which difierences in the crystals of the precipitate appears to directly effect the. particle size and should be maintained a constant factor between successive precipitations.
With other dilutions of solution or relative proportion of barium to strontium to calcium therein this rate may be varied. The
temperature of the solution, however, must be maintained above 85 C. and.preferably between 90 and 100 C. at all times during precipitation in order to obtain the preferred I crystal structure of the precipitate.
After precipitation, the material is allowed to settle, the clear liquid decanted, and the material then washed into a Biichner funnel fitted with No. 50 Whatman filter paper- Thematerial should be thoroughly washed with hot water on the. filter until free from nitrates and the excess; moisture removed by application of vacuum to the filter. The particular coarsely crystalline structure which I obtain by myprocess facilitates washing free of impuritiesby permitting rapid passage of the washing fluid through the pores of the precipitate and filter.
The precipitate is then transferred to a Pyrex glass tray and dried at-approximately 110 C. When thoroughly dried and anhydrous, the composition of this material will be 50% barium carbonate, 30% strontium carbonate and 20% calcium carbonate. The material, although coarsely crystalline andrather dense, will readily pass a 325 mesh screen without any milling.
. This material is now ready for the coating process which is described in the previously mentioned patent of Duncan MacRae, No.
. 'necessity of-obtaining a coating material in 50 As before stated that in addition to the which the activating constituent thereof (barium) is finely disseminated throughout the mass, it is also necessary tomaintain a certain degree of coarseness or particle size within the coating material.
The exact reasons therefore are not at this time thoroughly understood but it is known b simultaneously precifitating the admixed a kaline earth metals in such a manner as to cause the formation of a coarsely crystalline product thereof and-by regulating the recipitating time interval to holdthe indivi ual particle sizes within a certain narrow par ticle size range, I am enabled to subsequently subdivide the said crystals 'toany preferred particle size by proper supervision overthe milling operation. In this manner I ,subdivide the crystalline precipitate to a degree which vives the best results when the material -is'appl1ed to and utilized one hot cathode in an electron discharge device.
I employ the following method in preparing a suspension of the carbonate material for coating a filament of the size which is employed in electron discharge devices of the power tube type, known to .the trade as the 171-A tube, in which the filament has thedimensional measurement of approximately .0047 X .00075 inches. 1
I prepare anadmixture of 95 grams of the dry anhydrous carbonates with 50 ml. distilled water. To this material I add a suitable binder material such as barium .nitrate or barium nitrite in amounts up to 5.0 per cent (by weight). I prefer to employ as a binder the barium nitrite (Ba (N0 as this compound melts and dissociates'in vacuo at a lower temperature than the nitrate compound giving thereby a bonding action at a lower temperature. I
- This mixture I place in a porcelain ball mill of approximately one quart capacity containing approximately 700 grams of flint pebbles of from A to inches in diameter. The mill is then revolved at a rate. of approximately '100 R. P. M. for a period of 1% to four hours. The ball milled carbonates are then placed in the coating cups and the filamentary cathodes coated by a continuous process substantially.
as described in the patent of Duncan MacRae, No. 1,812,103.
To obtain suitable deposits of the alkaline earthmetal carbonates upon the filamentary material above mentioned, it is not necessary to pass the filament through the process more than four times to obtain a deposit weighing approximately 1.0 m. .g. per 10 0. m. (i 10%). The speed through the coating cup'is' maintained at approximately 12 meters per minute and the temperature of the drying ovens through which CO is continually passed is maintained at from 700 to 900 C.
I am enabled to retain in the coating, the crystalline character of the carbonatematerial until it is subjected to complete decomposition during the evacuation procedure of the electron discharge device of whiclrit is an incorporated part.
Owing to the fact that the anhydrous oxides of the alkaline earth metals rapidly absorb moisture and CO from the air, it is difii cult to detect physical differences from oxide v 85 C. and simultaneously coated filamentary cathodes preparedfrom carbonates produced by'the practice -ofmy invention, and cathodes. repared from carybonatesproduced .by ot or processes after the same have been decomposed'invacuo to the alkaline earth 'metal oxides. I have found, that cathodes formed of carbonates prepared by my process exhibit. a greater uniformity in operating efliciency, life and maintenance over oxide coated cathodes heretofore prepareda- In addition thereto the electromc efiiciency, life and maintenance ofcathodes is more consistent and reliable from 'lot to. lot than heretofore obtainable.
- Whiledl do not wan't to be restricted to any theory I believe the unusual and excellent results Irobtain from the use ofthe. carbonate product of my invention is-due to the fact 0 that I obtain in the racticeof my invention, a coating material 1I1 Whl0h the activating constituent (barium) is finely andv uniformly dispersed throughout and in addition thereto the natureof the crystal structure ofthe precipitate and the permissible control orer the ultimate particle size thereof which'may comprise the actual coating on the cathode permits me to develop the maximum adhesive and electron emissive' properties of the coating material.
Whereas I have disclosed a specific; process for preparing an alkaline earth metal car bonate material for electron emission pur-/ poses and given the details of the process ofcoating the same upon a filamentary cathode,.
it is obvious that theremay be many variations made in the specific steps employed and a A the composition-of the'coating material employedtherein-without departing from the 40 nature of my invention and s'uch variations are anticipated as may fallvvith in the following claims. 3
-What is claimed is: '1. The method of forming intimate ad mixtures of alkalin arth metal carbonates which, comprises f rminga solution of barium, strontium and calcium salts in the desired proportion, heating the solution to temperatures approximating but in excess to V precipitating therefrom the alkaline eartli metals as a carbonate by the addition of avsplution ofnor- Inal ammoniumr carbonate.
2 The process of forming an intimate mixture of substantially pure barium and strontium carbonatescontaining not less than .5 per cent calciumcarbonates ina crystalline form isomorphous with the aragonite crystal structureof calcium carbonate which comprises admixing soluble salts of those metals in the desiredproportion-to form approximately 15.0 percent, solution, simultaneously precipitating the alkaline earth metal carbonates therefrom in a interval of- '@5 time through the addition thereto of a warm solution of normal ammonium carbonate, and maintaining during said precipitation procedure'a' solution temperature approximating but higher'than', C. v 1 *3. The process of formingintimate m'ixtures;of alkaline earth metal carbonates iso-,
morphous with respect to the aragonite'crystal structure of calcium carbonate which comprises forming a dilute water' solution of barium and strontium" nitrates in desired 5 relative proportions addingthereto -from .5% to 20% calcium nitrate, heatipg the solu: tion to .temperatures a proximating Sbut" :higher than 85Wneously precipi tating thealkalin metals as carbonates 8o therefrom by adding thereto at a constant rate. a warm solution of normal ammonium L'carbofiate. 4 .A". An electrode having a' coating, comprising a'mi'xtureof substantially-pure alkaline g5 earth-metal carbonates having a crystal strum ture isomorphous to'aragonite.
.5, A coated filament suitable for usein an je lectron discharge device formed; of about 50% of barium carbonate, 30% of strontium a. carbonate and about 20% of calcium carbonate, said carbonate material being-comprised of fractured crystals of substantially pure- 3- a'ragon'ite and isom orphous strontianite and witherite.
. I '95 6 An electrode haying a coatingcompris- I hr of the carbonatesof at leastone of the al aline earth metalsbarium or strontium associated with calcium carbonate in amounts structure of said material being substantial; 'ly isomorphous with calcium carbonate in, the aragonite crystal form. 7. As an article of manufacture, admixtures of alkaline earth metal carbonates con taining at least .5 percent calcium carbonate in which the 'calciumfcarbonate thereof is identifiable a's-b elonging to the-rhombicsystern of'crystal structure of the orthorhombic bipyramidal class, and the barium and strontium 'carbonates isomorphous' thereto.
81 As an article of manufacture, admix tures of alkaline earth metaLcarbonates-containing at least .5 percent calcium carbonate in, which the calcium carbonate thereof is identifiable as belonging -to the rhombic sys= tem of crystal structure of the orthorhom bio bipyramidal class, and the barium and strontium carbonates isomorphous thereto, said material containing up to .5 ipercent bariuni nitrite as a binder material;
QaA coating material for use in forming I cathodes of the oxide coated type comprised of approximately 50 per cent barium ,car-
bonate, approximately 30 per cent, strontium carbonate,'about 20% calciumcarbonat'e and containing approximately 5;% barium nitrite. f l
10. Themethod of forming i-ntimate admixturef of alkaline earth metal carbonates above approximately .5 percent the crystal 1 00 having a crystal structure isomorphous to calcium carbonate in the aragonite form,
' which comprises forming an aqueous solution of alkaline earth metal compounds admixed in the desired proportions, precipitating said solution with normal ammonium carbonate maintaining during said precipitation a so-' lution temperature of about 85 C.
1'1 .The method, of forming intimate admixtures of alkaline earth metal carbonates having a crystal,structure'isomorphous to. calcium carbonate in the aragonite form and h'avingia predetermined particle sizecontrast which comprises forming an aqueous solution of alkaline earth metal compounds ad-- mixed in the desired proportions, precipi-l tating said solution with normal ammon um carbonate, maintaining during said precipitation a-solution temperature of about 85 G.- and limiting the time interval of comple tion of said precipitation.
. 12. The method of forming coarsely crystalline intimate admixtures of alkaline earth metal carbonates which are suitable for use in the forming of electron emitting oxide coated type cathodes, which comprises forming an aqueous solution of barium and stron-,
tium salts in the desired proportions, adding theretofrom .5 to 20.0 per cent calcium salts,
precipitating said solution with normal am monium carbonate, maintaining during said precipitating reaction a solution temperature not less than about 85 G:
/ l3. The method of forming coarsely crysotallineintimate admixtures of alkaline earth metal carbonates suitable for use in the form-' ing of electron emitting oxide coated type cathodes which comprises forming a dilute aqueous. solution containing barium andstrontium salts inthe desired proportion,-
' adding thereto from .5 to 20 per cent water soluble calcium salts, precipitating said solution with normal ammonium carbonate,
maintaining a solution temperature during said precipitation of not less than 85 0., and limiting the time interval of the completion of theprecipitati greaction. v v
forming substantially 14. The method .0 pure coarsely crystalline'intimate admixed alkaline earth metal carbonate admixtures which comprises preparin gonite.
A. coating composition from .WhlClI about a 15 per strontium, and calcium saltsadmixed in the desired proportion with a'solution of normal ammonium carbonate, while maintaining solutlO! temperatures above approximately 85 r .16. The method of preparing coarsely crystalline intimate admixtures of alkaline earth metal carbonate compounds which comprises effecting the separation of said carbonate compounds at temperatures above about 85 C. from an aqueous solution containing their salts admixed in the desired proporduced(compr1sing a suspension of substantially pure alkaline. earth metal carbonate compounds the crystal structure of said carbonates being isomorphous to that of ara- 19. electronically active cathodes may be produced comprising a suspension of barium and strontium carbonate in approximately equal proportions and from .5,to 20 per cent'calcium carbonate, the crystalstruct'ure'of said calcium carbonatewbeing that of aragonite and the'crystal structureof the bariumand strontium carbonates isomorphous thereto.
4 In testimony whereof, I have hereunto sub- 1 scribed my name this 10th da of July 1928. MARK N. FREDIENBURGH.
cent aqueous solution containingbar'ium and strontium nitrates in approximately equal amounts and from .-5 to 20.0 'per cent calciun'i' nitrate, heating said solution to temperatures approximating 85 0., adding thereto a sQlution of normal ammonium carbonate in excess to efiect the separation of ,the alkaline earth metal carbonate compounds and recovering the precipitated carbonate compounds therefrom in any s'uitable manner.
"15., The method offorming coarsely crystalline intimate admixtures of alkaline earth metal carbonate compounds which comprises precipitating an aqueous solution 'o'f barium, I
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