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Beautiful necklace. Very white and shines a lot. Bigger than I expected. Goes perfectly with my 1/2 ct. Love earrings
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I was in love with this necklace as soon as I got it. It's gorgeous and for the price, well worth the buy! It's hard to believe this diamond was only 1/3 carat as it seemed bigger in person. I love white gold and felt the quality of this necklace was worth more than what I paid for. This is definitely a purchase I would make again
Necklace and pendant were true to size depicted on website. Very pretty pendant, and can be worn for dress or casual. Very versatile. Glad I made the purchase.
- How did the image on site compare with the actual product? Pretty Accurate
- How accurate was the sizing? right on the money!
- Please tell us about the quality of the product. Seems to be of good quality

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Rahul Says UP Riots 'Deliberately Engineered', BJP Hits Back
Rahul Gandhi's remarks about communal conflicts in UP being "deliberately engineered" has triggered a war of words between Congress and BJP, with both accusing each other of indulging in "communal politics".
While the Congress came out in support of Rahul Gandhi and blamed BJP for exploiting the situation for political purposes, BJP targeted Rahul saying it "reflected the party's communal thinking".
"Unfortunately ever since the BJP government has come to office at the centre, there is a growing realisation that the government is interested in keeping communal temperatures towards a degree just below the boiling point so that they can exploit religious polarisation for political purposes," senior Congress leader Manish Tewari said.
"And thus you have a situation in UP whereby, clustered around those 10-12 peaks where by-elections are scheduled, you have a series of incidents taking place. Its incumbent upon the central government to be proactive, to take it up with the state government and to ensure that if there is any communal polarisation anywhere around the country," a serious attempt is made to avert such a situation.
"Unfortunately the perception about the central government is completely opposite," he added.
Congress Vice President Rahul Gandhi had reportedly said, "Communal conflict is being artificially and deliberately engineered in our country, especially in Uttar Pradesh. This is a deliberate strategy to divide the poor of this country and pit brother against brother, to prevent people from uniting to fight the true enemy — inequality, poverty and lack of opportunity."
Hitting back, senior BJP leader Prakash Javadekar said whatever is happening in UP was because of Congress as it took support of the Samajwadi Party (SP), which is ruling the state.
"If any party does communal politics, it is Congress. They had alliance with Muslim League. In Hyderabad they had tie up with MIM. Even now, in both the houses of Parliament... by discussing communal situation, their motive is to increase communal tension," Javadekar said while condemning Gandhi's statement.
Javadekar further added, "Rahul's statement should not be given so much importance. Narendra Modi has already said one has to decide whether one would fight against poverty or Hindus and Muslims will fight against each other. The vision is to take everybody together."
"But Congress' thinking is totally communal and I condemn his statement because their communal thinking comes out of that," he said.
Meanwhile coming to the defence of Rahul Gandhi, while some Congress leaders said that there are "multiple elements" in UP who are spreading rumours with an aim to charge the atmosphere, others maintained that there is an attempt to create conflict between people and UP is being pushed into "pyre of politics."
"Rahul's comment is right. There are multiple elements in UP which are continuously attempting to spread rumours with an aim of continually charging the atmosphere. These occurrences are a major cause of worry not just for UP but for the entire country," senior Congress leader Shakeel Ahmad said.
"The entire country is aware of the hate politics prevalent in UP. There is an attempt to create conflict between people as seen in Muzzafarnagar, Moradabad and Saharanpur. UP is being pushed into pyre of politics," yet another Congress leader Rashid Alvi said.
Rallying behind the Congress Vice President's comment, Congress leader Rita Bahuguna Joshi said that her party does not believe in any politics which is "divisive" and Congress believes in "inclusive" politics.
"What Rahul Gandhi has said is absolutely true. The Congress party does not believe in any politics which is divisive. We believe in inclusive politics," she said.
"The entire nation knows that ever since the BJP government has come to power at centre, how they been trying to create communal divide in UP," she said citing the examples of Muzaffarnagar, Moradabad and Meerut where "smallest incidents like conflict between two people, were exploded into communal issue by the BJP."
"They are power seekers. Narendra Modi, his company and the Sangh Parivar shot to power through divisive politics. They should give the promise of growth to people instead of giving people Muzaffarnagar, Moradabad and Meerut. Its not about Rahul Gandhi finding a voice now. Rahul has a very strong voice and he is a leader and we are proud of him in the Congress party," she said.
Meanwhile Samajwadi Party leaders blamed the BJP for such communal conflicts and said that they have been trying to turn the state into "another Gujarat".
"BJP believes that since they are in power at the centre, they have got permission to create anarchy in UP. UP is a land of good faith with the mannerisms of Ganga and Yamuna. BJP has always tried to turn UP into another Gujarat," SP leader Rajendra Choudhary said.
However, stepping up the attack on Congress, BJP leaders called Rahul Gandhi "arrogant and autocratic" and said if the Congress vice president was so concerned with good governance, then he should ensure law and order in states governed by his party.
"Who takes Rahul Gandhi seriously in any case. If he was so concerned about good governance, why does not he ensure law and order in the states that are governed by Congress. He has no answer for that," said Shania NC, BJP leader.
She blamed the SP government in UP for failing to administer UP and said,"Clearly what has happened in UP is unfortunate. Post 2014, we have seen over 600 such cases, if they (SP) are unable to administer, they have no right to be in power."
"Rahul Gandhi should understand that his political secularism has been erased. He should stop using this formula of expired political secularism and introspect instead about political decisions of his party. If he remains arrogant and autocratic, he will not benefit," senior BJP leader Mukhtar Abbas Naqvi said.
Other BJP leaders maintained that both Congress and SP were "hands in glove" in the name of inclusive politics and blamed them for playing vote bank politics.
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- Daily Mail
Muslim League and MIM are deeply secular nationalist parties.Aug 10, 2014 10:23 AM Pradip Singh, stafford, uk
The guy who was out partying since the election, now wants communalise the politics when most of his party members have been accused in the riot. What a shameless hypocrite secular !Aug 10, 2014 01:59 AM Maha, NJ, United States
I did not know Imran Masood works for BJP.Aug 10, 2014 01:58 AM Maha, NJ, United States
> "BJP targeted Rahul saying it "reflected the party's communal thinking"."
The BJP has made UP a communal caudron but accuses Congress of communal thinking! Hypocrites!Aug 10, 2014 01:14 AM Anwaar, Dallas, United States
Court gave verdict favorable to Gurudwara and Muslims attacked Sikhs. So the court is a part of 'delibrate strategy'? Hindu girl abducted, raped and forcefully converted. Whose delibrate strategy it was?Aug 09, 2014 05:27 PM P.B. Joshipura, Suffolk, Virginia, United States
So Rahul admits to "deliberate strategy" in UP riots.Aug 09, 2014 03:33 PM K.Suresh, Bangalore, India
FROM OUTLOOKPoliticsThe Gujarat crisis could have wider repercussions for the BJP...more from outlook>>>
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text: Latest NewsYour club's Road to the Finals We're seven weeks out from the finals and the race for a place in the NRL Telstra Premiership top eight remains wide open. Can your team make the finals? Wed 20 Jul 2016, 7:00AMBy Jack Brady, National CorrespondentMen of League announce The Captains' Captain The Men of League Foundation, in partnership with the Australian Kangaroos, have announced the Captains' Captain. Tue 19 Jul 2016, 10:00PMMedia Release, NRLParramatta Eels administrator appointed NRL CEO Todd Greenberg today welcomed the appointment of a temporary administrator to replace the Parramatta Leagues Club Board. Tue 19 Jul 2016, 5:19PMMedia Release, NRLNo bad blood in Kangaroos Australian captain Cameron Smith says his Kangaroos side will have no problems coming together after a State of Origin series marred with bad blood. Tue 19 Jul 2016, 5:08PMBy Eden Richards, Queensland CorrespondentRound 20 NRL team lists The official team lists are in ahead of Round 20 of the 2016 NRL Telstra Premiership. Tue 19 Jul 2016, 5:01PMBoggitt family thankful for Men of League The story of Townsville-based Gavin Boggitt epitomises rugby league's community culture, and highlights the support networks at all levels within the game. Tue 19 Jul 2016, 4:30PMBy Steven Ross, North Queensland CorrespondentLive blog: Round 20 teams Join in the discussion as teams name their line-ups for Round 20 of the 2016 NRL Telstra Premiership season. Tue 19 Jul 2016, 4:00PMVunivalu's dream season continues Since making his NRL debut in Round 7, Melbourne winger Suliasi Vunivalu has taken the competition by storm, scoring 17 tries in 11 appearances. Tue 19 Jul 2016, 3:34PMBy Stephen Marson, Melbourne CorrespondentOne team change for Warriors Queensland prop Jacob Lillyman returns for the Warriors this week, replacing the suspended Charlie Gubb in their only change. Tue 19 Jul 2016, 3:20PMFour suspended, Gubb to challenge grading Four NRL players will sit out Round 20 with suspensions while Warriors prop Charlie Gubb will challenge the grading of his shoulder charge at the judiciary. Tue 19 Jul 2016, 2:20PMMore


text: Since I pretty much don't battle anymore outside of randbats format and theres a chance I might not again; I thought about posting my record against the smogon regulars I faced through my career for nostalgia purposes.. All records taken from my wonderful pokemon record sheet that I basically started the day I started pokemon online on the PBS, to netbattle :). Yes you probably don't give a fuck especially if we never battled so feel free to hit the back button. I still felt like posting this anyway!! :D I pretty much only put in the people I battled that I know post here. Acura 2-0 RUSA Win 6-4 RUSA Win 2-0 I rock your world, Eric Hayes. In the first game you quit early when basically your venusaur missed with sleep powder 3 times in a row :(. In won the second match 2-0 in December of 2004, which is pretty much when I started dating matches. Andii56 5-4 GSC Win 4-0 GSC Loss 0-4 GSC Loss 0-5 GSC Win 3-1 GSC Win 5-3 RUSA Loss 0-1 RUSA Win 5-0 RUSA Win 3-0 We had sort of a cool gsc netbattle legacy, all these GSC matches were pretty much me using gsc theme teams, which I loved to use on netbattle. Matches worth mentioning are the first in which I used my Christmas team to beat you and getting 2 kills with delibird, the 0-6 loss to you where apparently you owned my King theme team with UU and the 5-0 RS battle in which you used beat up Houndoom and lost to my ninjask/exploud combo. At the end.. I still end with a winning record against you . Articuno64 1-1 RUSA Loss 0-3 RUSA Win 3-0 Of course you remember our first match, it was in the Marble Palace Gemmatic Tournament and you and Celia scouted my team >:O! You totally fucked me up with blaziken and SPARK whiscash which I had no clue what it could do. I remember nothing about the 2nd match but I am glad to see I evened up the score. It is a shame we never RBY battled. chaos 1-6 RUSA Win 3-0 RUSA Loss 0-6 RUSA Loss 0-4 RUSA Loss 1-3 RUSA Loss 4-5 RUSA Loss 0-6 RUSA Loss 0-2 God you own my ass….. you and MrE are by far the 2 people that have the best record against me (0-5 against MrE)…. Aside from that ONE win I got at the beginning when you were pretty much giving rs its first shot on Netbattle and I took advantage of it, you basically always kicked my ass. In my second battle against you, you apparently stoped cold one of my best winning streak with a baton pass team. Then I pretty much always continued to suck against you.. The last battle was great though, it was in round 3 of the first smogon official tournament and it really came down to the last move.. it was one of the greatest battle I've had. Crazy Starwolf 4-6 RUSA Win 5-0 RUSA Loss 0-2 GSC Win 5-0 RUSA Win 6-5 RUSA Loss 0-2 RUSA Loss 3-5 RUSA Loss 0-5 RUSA Loss 3-5 GSC Loss 3-4 RUSA Win 5-0 It is a shame I started with a 3-1 record against you only to then lose 5 straight….. however… it doesn't matter at the end.. as I still won the last match between us ;D. Pretty much it sums up to my C gsc team and clefable getting a sweep in our first gsc match against your regular team and then you owning my ass everytime for a while. I recall you said you once beat me when in a hurry and half asleep or something . Fish 2-2 RBY Loss 0-1 RBY Win 3-0 GSC Loss 0-4 GSC Win 6-0 Lol… those 2 rby battles probably happened at the end of 2001 or early 2002, they are really old…. I battled you twice on the same tournament, losing to you first in round 6 in the winners bracket when you kicked my ass with several exploders, and then after making my way back to you to the finales, winning with luck against pretty much an UU team of yours… You actually had me beat with Focus Energy Hyper Beam machamp until starmie got a lucky freeze to put back the match in my favour. I also remember that last match, when you tested my gsc abilities to be in your team for sneak4, after losing you pretty much told me it wasn't anything amazing as you didn't try and all, it sort of hurt me :(. goofball 8-2 GSC Loss 1-2 GSC Win 4-0 GSC Win 3-0 GSC Win 5-0 GSC Win 1-0 GSC Win 5-0 GSC Win 5-0 GSC Win 5-0 RUSA Win 1-0 RUSA Loss 2-5 Ok now I fucking own you, eeveedude… after I guess I weirdly lost my first match using an eevee team, I pretty much raped the shit out of your all the time afterwards, beating you in a couple of tournaments like the Furret Cup, the Kabuto Kup and the Golden Girls Tournament, whatever that was. Ok you won the last match decisively but it doesn't make up for 8 straight losses :p. Green Pikachu 2-2 RBY Loss ?-? RBY Win 5-4 RBY Win 4-0 RBY Loss 0-2 I saw you started posting here so I'll post my record against you I guess! First 2 matches were in the SST, the first rby tournament I won :D, you beat me in the first and I kicked ass in the losers bracket and beat everyone afterwards, including you again. Guess what.. it ended 5-4 because you quit! These are actually all tournament battles, the other 2 being in the IMUT (I have no clue what that was) and the tag team Venonat Noober Pympz tourmanet thing. Hipmonlee 6-7 RBY Win 3-0 RBY Win 3-0 RBY Win 1-0 RBY Win 3-0 RBY Loss 0-5 GSC Loss 0-3 RBY Loss 0-1 GSC Loss 0-2 RUSA Loss 0-3 RBY Win 2-0 RUSA Win 4-0 RUSA Loss 3-5 RUSA Loss 3-5 Hip.. man.. I enjoyed our pokemon rivalry a huge lot and it turns out you edged me at the end by one win … I still 5-2 you at rby though which grants me bragging rights . We always won by streaks it seems, I won 4, you won 5, I won 2 you won 2 and we battled in a freakload of tournaments.. like in that monotype tournament when I beat your rock team with a fighting team, that grass monotype thing you eventually won, that freaking close win in that stage 1 tournament that came down to the last move when your haunter woke up JUST in time.. …… also that time when you owned my slowbro with a rhydon ONE ON ONE and where berserk gene tauros did the rest… that first RS battle between us… who also happened to be YOUR first ever rs match.. and I freaking lost that… that Dweedle Cup win in which I used 2 amnesiaers to beat you :D and that relatively recent loss where you beat me in an uu match with szizor and Persian in cs's uu tourney.. We've had awesome wars :) Icicle Knight 1-1 GSC Win 6-0 RUSA Loss 3-4 Wow I have matches against you? Pretty much all that's noted about them is that I swept with kangaskhan in the first and you apparently got a "fgt ch on my gyarados" in the second. Lol Last one actually apparently happened in july last year, which isn't too far back yet I remember nothing about it . Justin8649 6-3 RBY Win 3-0 RBY Loss 0-2 RBY Win 2-0 GSC Win 6-0 RUSA Loss 0-4 GSC Win 6-0 GSC Win 2-0 GSC Win 5-0 RBY Loss 0-2 So everytime you win, I win twice, that's what there is to remember from that record :D. First 3 battles are tournament matches in red's tournament and the monkey league… I remember you told me you were new in that first match to totally blow me off my mindset… but it didnt work :D! Then came the freaking I QUIT gsc match hahahaha, fuck man, that match and its stipulation was awesome… whoever was losing had to leave pokemon online forever… of course.. that didn't happen but you did leave for a while and it gave celia and a few others quite a scare . I won that match with luck though when my curselax beat yours with a CH . After that we've had a RUSA match in which you beat me with a REST gardevoir and a couple of UU matches… then you beat me pretty recently in a smogon weekly tournament thing back in like October. I still am 4-0 in gsc against you . lugiastorm 3-2 RUSA Loss 0-4 RUSA Win 4-0 RUSA Loss ?-? GSC Win 4-0 RBY Win 3-0 Uh…you will remember one of these 2 rs losses, probably the second one, you pretty much luckfucked me to the point I sent you a voice clip about the result of the battle!!! The 2nd match had ME getting insane lick in the Fire Leaf Cup when my magneton survived with 2hps to kill your jolteon, and my ptrap gengar survived with 1 hp to kill your own gengar :D. The RBY match was in the IBT in 2004, round 1 I used victreebel and sandslash in this!! Mcgraw 3-3 GSC Loss 0-1 GSC Loss 0-6 GSC Loss 0-5 RUSA Win 4-0 RUSA Win 1-0 RUSA Win 5-0 lol, so you're 3-0 against me in gsc and I'm 3-0 against you in rs. I especially liked that one rs match in which you were leading 5-1.. only to lose to salac reversal heracross for the 1-0 comeback :D MoP 1-1 GSC Win 2-0 GSC Loss 0-3 Actually not much to say.. you apparently battled my gsc T team twice with UU teams, won once, and lost once :p MrDodrio 2-0 RUSA Loss 0-3 GSC Win 4-0 RUSA Win 1-0 RUSA Loss 4-5 RUSA Loss 0-5 You own my ass at GSC, that is pretty much the story here, you totally destroyed me with taunt gyarados in the golden girls tournament and you kicked the ass out of my cb team. MTG 6-1 GSC Win 4-0 GSC Win 4-0 RBY Win ?-? GSC Loss 0-4 GSC Win 3-0 GSC Win 1-0 RUSA Win 5-0 All these battles are really old and yes I kick your ass at pokemon!… the last one being actually my first ever rs match, on the beta testing forms of the rsbots :D.. I swept with calm mind alakazam in it.. I also used recover medicham ._... another battle worth mentioning is the one before that.. which was for your badge in some TPM gym leader thing :D in a battle that was apparently decided on the very last move. Noobster 1-1 RUSA Win 6-5 RUSA Loss 0-2 Not much to say here, you quit early in the first after my magneton traped your skarmory and you beat my C team with complete standards in the second! Omni 3-1 GSC Win 6-0 GSC Win 4-0 RUSA Win 4-0 GSC Loss 0-4 Pretty much similarly to goofball, I beat you both in the Furret Cup and then in the Kabuto Kup as the Tampon Strings team rolled over you. I got 3 kills with lantern I our rs match, which must date back to rs 200 and then you (finally!) beat me in the last match in something called the summertime tournament.. a gsc uu tournament. Skarm 6-1 GSC Win 2-0 GSC Win 4-0 RUSA Win 2-0 GSC Win 3-0 RUSA Win 4-0 GSC Win 4-0 RUSA Loss 3-3 I am so proud of that record.. people regard you as one of the best and I happen to have a STELLAR record against you :D I have no clue why I always had your number. First win is in the Kabuto Kup and the second in the Metallic Standard Tournament, I don't remember that one though. You apparently almost beat me in the first with curse heracross however. I raped with gardevoir in our first rs match, which was 200 and then with zam in 386.. following gsc match was for the VAGINA BADGE back when you were the vagina gym leader :D! and yeah I regretted battling you in that last match with my B theme team against your real team, it ended up screwing an awesome record… but regardless, I probably would have lost with my real team anyway ;), that last match was also a stadium mode match for some reason O_o.. you beat my blastoise, bannette, blaziken combo with swamp, lax and salamence :o. Steelicks 2-0 GSC Win 5-0 RUSA Win 2-0 So in the first match, I beat then Devil Dan with my uu team, victreebell passing through you like my penis through your vaselined ass. And then my cb team beat you in round 1 of the 2nd official smogon tournament . 2-0 bitch :D This is my all time record for completeness!!! RECORD W L D TOTAL WINNING % RBY 211 53 0 264 79.9 GSC 1475 503 5 1983 74.4 RUSA 1009 278 3 1290 78.2 TOTAL 2695 834 8 3537 76.2 TOURNEY RECORD W L TOTAL WINNING % TOURNEYS RBY 70 31 101 69.3 TOURNEYS GSC 37 32 69 53.6 TOURNEYS RUSA 18 13 31 58.1 TOURNEYS TOTAL 125 76 201 62.2


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Dr. Blake graduated from the Indiana University School of Medicine in 1988. He works in Anderson, IN and 1 other location and specializes in Gynecology. Dr. Blake is affiliated with Community Hospital Of Anderson and Saint Vincent Anderson Center.
Medical School: Indiana University School of Medicine; Graduated 1988
Please verify insurance information directly with your doctor's office as it may change frequently.
*This physician has multiple office locations. See Office Information for details.
141 W 22nd St Ste 309
Anderson, IN 46016
13861 Olio Rd
Fishers, IN 46037
9660 E 146th St Ste 300
Noblesville, IN 46060
9660 E 146th St Ste 300
Noblesville, IN 46060
1000 N 16th St Ste 250
New Castle, IN 47362


text:
21 CSU athletes named to all-Mountain West team
13 individuals, 2 relay teams recognized for success at indoor championships
Track & field recap: Strong finishes on Day two at MW Championships
Competition resumes Saturday
Track & field preview: Rams head to MW championships
Meet kicks off Thursday
Track & field recap: Rams set quick pace at MW AF Open, Husky Classic
Head Coach Bedard impressed with the results
Track & field recap: Rams off to a good start in Nebraska
Events wrap up Saturday
MW Track & Field Indoor Championships
MW Track & Field Indoor Championships
CSU track & field at Tom Benich Invitational
CSU track & field at Tom Benich Invitational; March 22, 2013
2012 MW Track & Field Championships
2012 MW Track & Field Championships
Track & Field
- NCAA national qualifier - shot put - 2013
- NCAA national qualifier - hammer throw - 2013
- Fifth place - MW outdoor championships - hammer throw - 2013
- Seventh place - MW outdoor championships - shot put - 2013
- Seventh place - MW indoor championships - shot put - 2013
- Seventh place - MW outdoor championships - shot put - 2012
- Eighth place - MW outdoor championships - hammer throw - 2012
- Fourth place - MW indoor championships - weight throw - 2012
Top Collegiate Performances
- Hammer throw: 179-0.25 [54.57 m]
- Weight throw: 62-9.5 [19.14 m]
- Shot put: 53-6.25 [16.31 m]
- Discus: 148-0 [45.12 m]
Pueblo South High School
Ken lettered in track and football while attending Pueblo South High School in Pueblo, Colo. He was the 4A state champion in the shot put three times. He garnered all-state honors in track and all-league honors in football. He was also an honor roll student.
Ken was born to Mark and Jo Harriman on Aug. 19, 1990, in Pueblo, Colo. He has an older brother, Greg, and an older sister, Ashley. Majoring in economics.
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Jul 22, 2016 @ 6:30 AM
Connie Britton's Changing Looks
1. 1998
After graduating with an Asian Studies degree from Dartmouth, Britton made her debut in The Brothers McMullen before landing a role on Spin City.
2. 1999
A short (and short-lived) crop at for an L.A. fundraiser.
3. 2000
The star of the small-screen version of The Fugitive sported strawberry blond curls.
4. 2001
The Fighting Fitzgeralds actress went full-blown ash blond.
5. 2005
For the N.Y.C. opening of Sweet Charity, Britton let down her long russet waves.
6. 2006
Hello, good hair day! Britton hit the L.A. premiere of The Lather Effect with side-swept strands.
7. 2007
For a Friday Night Lights photo call, the actress glowed in peach makeup that complemented the hue of her blown-out mane.
8. 2009
She dropped by a network press party with sultry ringlets and glossy lips.
9. 2010
A rare updo drew focus to her deep blue eyes at the world premiere of A Nightmare on Elm Street.
10. 2011
Nominated for her role in Friday Night Lights, the American Horror Story lead hit the Emmys with loose waves.
11. 2012
She celebrated her Emmy nomination for American Horror Story with a glam '60s-inspired faux bob.
12. 2013
Hairstylist Rod Ortega was inspired by Rita Hayworth in the 1946 film noir Gilda when creating Britton's retro Golden Globes look. Before going through the hair with a one-inch curling iron, he spritzed fully dry hair with Leonor Greyl's Spray Structure Naturelle to make sure the coils stayed put. After the curls cooled, he brushed them out with a paddle brush. A few more pumps of the Spray Structure Naturelle guaranteed the waves would last all night.
13. 2014
Britton debuts lighter locks, complementing her new 'do with long layers.
14. 2015
The actress keeps up with her signature style.
1 of 14
After graduating with an Asian Studies degree from Dartmouth, Britton made her debut in The Brothers McMullen before landing a role on Spin City.
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What does BFM% stand for?
BFM% stands for Body fat mass percentage
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text:
|Publication number
|Publication type
|Application number
|Publication date
|May 1, 1990
|Filing date
|Aug 10, 1989
|Priority date
|Aug 10, 1989
|Fee status
|Publication number
|Laine E. Summers, Jeff J. Jurinak
|Original Assignee
|Conoco Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (8), Referenced by (66), Classifications (11), Legal Events (3)
|External Links: USPTO, USPTO Assignment, Espacenet
Epoxy resins and cements are used in a variety of oil field applications, which include primary cementing, casing repair, and water control. Epoxy materials may also be used for cementing wells which are employed to dispose of liquid wastes. An operation of this type is disclosed in U.S. Pat. No. 4,072,194. Epoxys may also be used in the leaching of minerals from subterranean formations to repair leakage through short-circuit passages formed between adjacent injection and production wells. Such a use is disclosed in U.S Pat. No. 4,438,976. Epoxy systems have high compressive strengths and excellent resistance to chemical and thermal degradation. Therefore, epoxys are well suited for the hostile conditions often encountered in subterranean formations.
In most applications, the epoxy formulations are based on the cured or final resin property requirements. To meet these objectives, hardeners may be used to accelerate curing once the resin is set and to optimize the resin properties. However, the placement of the epoxy in the subterranean formation is the critical and limiting step to the effective use of these systems in such formations.
Techniques for the placement of epoxy materials into subter, ranean formations; e.g., a casing annulus a gravel pack completion, or formations of the types described in U.S. Pat. Nos. 4,072,194 and 4,438,976, have been disclosed in numerous publications. All of these methods require that the epoxy material remain as a low viscosity fluid prior to and during the placement. Once in place, the epoxy must rapidly harden to form a rigid thermoset solid.
The principal manner of controlling the liquid epoxy viscosity and the hardening time of the epoxy is the selection of a hardener that is thermally activated. The increase in epoxy temperature caused by the thermal gradient in the well initiates the epoxy reaction once the activation or onset temperature of the hardener is exceeded. While variation in the hardener concentration provides a limited control of the set time, the amount of hardener used must be kept in a relatively narrow range for the resin to cure properly. With insufficient hardener, long set times result, incomplete reaction occurs, and resins remain uncured, If the amount of hardener is too great, the set time is too short to allow proper placement of the epoxy material. Also, with excessive amounts of hardener, the energy of the exothermic epoxy reaction is released very quickly. When this quick release of energy is coupled with the mass of resin required for many well operations, the energy released may produce extremely high temperatures in the resin. which can thermally decompose a portion of the epoxy material or damage underground equipment.
U.S. Pat. No. 4,072,194 to Cole et al. discloses the use of epoxy resins for completing wellbores used for waste disposal, in combination with a hardener which cures the resin after a latent period. and an accelerator The hardener is preferably present in a concentration less than the stoichiometric concentration to increase the latent period,
U.S. Pat. No. 2,904,530 to Steckler et al. discloses curing epoxy resins with a mixture of two aromatic polyamine hardeners.
U.S. Pat. No 3.759,914 to Simins et al. discloses compositions containing epoxy resin, a latent amine curing agent, and an accelerator. It is stated that an effective amount of the latent amine curing agent should be used to cure the epoxy material and that often, this effective amount will be the stoichiometric amount.
U.S Pat. No. 4,074,760 to Copeland et al. discloses resin containing composition for consolidating gravel packs containing a particulate material, an epoxy resin solvent mixture, a curing agent a coupling agent, an aqueous carrier fluid, and a surfactant. The curing agents may be mixtures of various amines. It is stated that the particular curing agent used and its concentration can easily be determined by a knowledge of temperature conditions and available working time.
U.S. Pat. No. 3,023,190 to Damusis describes a chemical curing of polyepoxy.polyhydroxy ether resins with a mixture of a catalyzing curing amine and a reacting curing amine. The reacting curing amines are primary amines and in certain cases, secondary amines. The catalyzing curing amines are tertiary amines.
U.S. Pat. No. 4,465,542 to Furihata relates to an adhesive composition including epoxy resins and corsercially available hardeners, Curing accelerators can be used together with the hardeners.
In accordance with this invention, a composition for use in a subsurface area is provided which comprises a liquid epoxy material and two hardeners for the epoxy material, each of which has a different activation temperature. The composition is further characterized in that the amount of each hardener in the composition is less than that required to totally react with the epoxy material, the epoxy material has a low viscosity at subsurface conditions of temperature and pressure, the epoxy material is substantially immsiscible with any fluids in the subsurface area, and the hardening time of the epoxy material is of short duration at subsurface conditions of temperature and pressure.
The composition of the invention is particularly useful in oil field applications and, more particularly, in gravel-packed completions. When used in such completions, the composition is further characterized in that the density of the epoxy material is greater than the density of the well fluid and the mixture of the epoxy material and hardener is essentially free of solids.
FIG. 1 is a sectional view of a typical wellbore containing a gravel pack.
FIG. 2 is a sectional view of the same wellbore after treatment with the composition of the invention.
FIG. 3 is a schematic diagram of a wellbore described in conjunction with a field test procedure.
FIGS. 4 and 5 are graphs of temperature increases with time for various combinations of hardeners and epoxy materials.
In carrying out the process of the invention, a composition comprising a mixture of an epoxy material and two hardeners for the epoxy material is delivered adjacent to a zone which is to be treated and the mixture is thereafter displaced into the zone and allowed to harden. The compositions and process of the invention find application in a variety of uses, including those mentioned previously in the background discussion. The invention, however, is particularly applicable to oil and gas wells containing gravel packs where water encroachment has led to advancement of water into the producing interval so that the well produces larger and larger quantities of water over a period of time. By plugging off the water zone, it is possible to reduce or even eliminate the flow of water, thus restoring the desired production of oil and/or gas from the well For convenience, the invention will be described in its specific application to a gravel-packed well.
The process of plugging off a water formation in such a well may be described by reference to the drawings. Referring to FIG. 1. there is disclosed a subterranean oil or gas zone and a water zone at 18 and 20, respectively. Although these are shown as separate zones, they may not be distinct and separate from each other but may tend to merge one zone into the other. Traversing these zones is a producing well having an outer production casing 8 and inner production tubing 2. A portion of the well adjacent zones 18 and 20 is isolated from the remainder of the well by upper packer 12. which is placed between tubing 2 and casing 8, and a lower packer 12 which is placed between slotted tubing 4 and casing 8 Contained in this isolated area is a slotted tubing 4, which is somewhat larger in diameter than production tubing 2. Around the outside of slotted tubing 4 is a wire.wrapped screen 6 which is supported and spaced from the slotted tubing by vertical rods (not shown). The isolated section of casing 8, which surrounds slotted tubing (4) and wire screen 6 is filled with gravel 10. This gravel fills not only the casing but also the perforations 16 extending from the casing through the primary cement 14 around the casing and into formations 18 and 20.
It is desirable that the well remain dormant during the operation of the procsss. If the well does not remain dormant, downhole fluid movement, or "cross-flow," between sand beds within the completion interval may cause the epoxy to be dispersed into portions of the well which do not require plugging. Also, the epoxy plug can become "honey-combed" if gas continues to trickle into the wellbore before the epoxy is completely hardened. If the well is not dormant, that is if there is gas flow, it may be eliminated or minimized by filling the well with fluid and maintaining a positive pressure; e.g., from about 300 to about 500 psi at the surface of the well. The fluid used may be fresh water, formation brine, seawater, or any other formation.compatible material. The first step of the process, therefore, if the well is not dormant, is to maintain a positive pressure at the surface of the well to ensure that the well remains essentially full of fluid. When the near wellbore area is sufficiently saturated with the displacement fluid, the migration of oil or gas into the wellbore is minimized.
In the next step of the process, the liquid epoxy material and hardeners are mixed together to form a liquid mixture and are introduced into the well and placed at a point adjacent to gravel-packed zone (10). Since the temperature in the well gradually increases from the top of the well down to the formation to be plugged, it is desirable to place the mixture of epoxy material and hardeners at the point of use as quickly as possible, thus ensuring that the epoxy material does not begin to harden until it is placed in the area of the zone which is to be plugged.
One method for moving the mixture of epoxy material and hardener to the desired location is to use a positive displacement dump bailer. This is a known mechanical device cylindrical in shape, which is filled with the mixture of epoxy material and hardeners and lowered into the well on a cable. The bailer is positioned at the desired depth and when activated, releases a metal bar in the top of the device. The bar falls downward inside the device and impacts the top of the fluid creating a downward-moving shock wave which travels through the fluid column contained by the bailer. The shock wave causes the shearing of metal pins in the bottom of the bailer and subsequent downward movement of a small piston which uncovers ports to allow the release of the contained material. The metal bar continues to fall through the bailer as fluid is released through the ports. The weight of the metal bar effectively adds to the weight of the fluid column being dumped. As the bar falls to the bottom of the bailer, the cylindrical bailer tube is wiped clean of the epoxy material/hardeners mixture.
Other types of positive displacement dump bailers, which operate in a similar manner, may also be used. It is also possible to deliver the mixture of epoxy material and hardener in an open bailer. This is a bailer which is open at the top and closed at the bottom. When activated, the bottom cover, which is held by metal pins, is sheared by an explosive or by other means thereby opening the bottom and allowing the mixture of epoxy material and hardener to flow by gravity from the bottom of the bailer and into the formation.
A coiled tubing may also be used to place the mixture at the desired point in the well. The coiled tubing is a 1-inch or other small pipe which is wound on a spool at the surface of the well. The mixture of epoxy material and hardener is placed in the end of the tubing and held in place by wiper balls at the top and at the bottom of the mixture. The tubing is then uncoiled and lowered into the well to the desired location, after which the mixture of epoxy material and hardener is pressured through the tubing and released at the selected location.
Referring again to FIG. 1, whatever apparatus is used for the purpose, the mixture of epoxy material and hardeners is placed in the apparatus and is delivered as quickly as possible to a point slightly above water zone (20). The apparatus is then activated to release the epoxy material/hardeners mixture which flows into slotted tube (4) and from there into the gravel pack (10) and perforations (16) At this point, a small amount of liquid may be pumped slowly into production tubing (2) to "squeeze" the epoxy material into the pore spaces of the formation rock or any voids in the primary cement (14) around the production casing. As the temperature of the mixture of epoxy materials and hardeners begins to approach the existing downhole temperature, the hardener with the lower activation temperature is activated and the epoxy material begins to react and increase in viscosity. As the temperature of the epoxy material increases still further, the second hardener reaches its activation temperature and the epoxy material continues to react. Eventually the epoxy material is completely reacted or cured.
FIG. 2 shows the same well as FIG. 1 after the epoxy material has hardened to form a solid plug (22) adjacent water zone (20). This plug fills the slotted pipe, the screen, the gravel, and may even enter the perforations (16) to effectively plug off production of water from zone (20).
The epoxy materials used in carrying out the invention have densities greater than the well fluid, which as previously pointed out may be fresh water, formation water, or other water containing salts. The epoxy materials are also essentially immiscible with the well fluid These two properties assure that the epoxy/hardeners mixture will not tend to rise through the formation fluid, nor will the mixture be diluted in any way by the formation fluid so as to prevent the epoxy from performing its proper function. Preferably, the epoxy will have a density of at least about 1 to about 11/2 pounds per gallon greater than the wellbore fluid.
The epoxy materials used will further have a relatively low viscosity at downhole conditions of temperature and pressure Thus the fluidity of the epoxy material and the density difference between the epoxy material and the wellbore fluid will facilitate the almost com. plete displacement of the wellbore fluid, saturating the gravel-pack in the zone to be treated. The viscosity of the epoxy material is usually between about 500 and about 1 centipoise at downhole temperatures of between about 75 and about 220 degrees Fahrenheit. The epoxy materials used are also essentially free of solids and, therefore, contain no materials to plate out on the gravel-packed sand face as does cement.
The epoxy material goes through several physical stages in the process of the invention. In the first stage, it is a flowable liquid of relatively low viscosity, particularly at higher temperatures. When the temperature of the epoxy material reaches the activation temperature of the hardener with the lower activation temperature, it begins to react and increase in temperature and viscosity. The hardener with the higher activation temperature then comes into play to cause further reaction of the epoxy material. Eventually the epoxy material hardens sufficiently that it ceases to flow. The point at which this occurs is called the "set point.". With additional time, the epoxy material continues to react and increase in viscosity until it becomes a solid. At this point, the epoxy is considered to be "hardened." The time required after the temperature reaches the set point for the epoxy material to become hardened is normally of very short duration--usually from between about 2 to about 20 minutes. With still additional time the epoxy material becomes completely reacted and harder and is considered to be cured. As with concrete, this final curing stage may take as much as several days, depending on the particular epoxy material/hardeners system.
In the application of the process of the invention, variation of the total combined hardener concentration in the epoxy material and the ratio of the hardeners is used to control the epoxy material viscosity and its set time over a wide range of conditions. As the epoxy material temperature is increased, the first hardener initiates a partial reaction of the epoxy material. This may produce a slight to moderate viscosity rise in the epoxy material. The change in viscosity can then be tailored to the specific application by varying the ratio of the hardeners. Once the epoxy material is in place and is at the treatment zone temperature, the second hardener initiates to complete reaction of the epoxy material. With additional curing at the treatment temperature, the strength of the solid epoxy material increases.
The set time of the epoxy material/hardeners mixture should be of short duration. Ideally, the epoxy material would begin to harden immediately after the mixture of epoxy material and hardeners have had a chance to completely displace the wellbore fluid in the area to be treated. Delayed hardening is desirable for two reasons. First, if the well does not remain entirely dormant from the time the epoxy material is placed until it is hardened, downhole fluid movement or cross-flow between sand beds within the treated area may cause the epoxy material to disperse into lower or upper portions of the well. Secondly, if the epoxy material remains in an ruihardened state, or if the reaction requires an extended period of time to complete, the integrity of the plug can be reduced if gas continues to trickle into the wellbore before the epoxy material is hardened. By proper selection of the epoxy material and hardeners, set times for the epoxy material can be designed to vary between several minutes to more than an hour. The set time of the epoxy material will be between about 1 and about 180 minutes and preferably between about 10 and about 60 minutes at bottom-hole conditions.
The amount of epoxy material used to plug off a interval depends on the size of the gravel packing and the portion of the gravel pack which it is desired to plug. Usually an amount of epoxy material between about 0.5 and about 2.0 gallons per foot of plugged interval is sufficient. Since the amount of epoxy material which a bailer or coiled tubing can deliver in a single operation is limited, it may be necessary to carry out the delivery process in two or more stages.
The hardener materials used in the process are those which are compatible with the epoxy material in that once the two are mixed, they form a liquid mixture which is substantially free from solids. Both hardeners employed in admixture with the epoxy materials have activation temperatures which are below the anticipated temperature in the treatment zone. Activation temperatures of hardeners can be accurately measured in calorimetry studies. Usually the hardener activation temperatures, as determined from calorimeter runs, will not be more than about 20� F. to about 30� F. below the temperature in the treatment zone. The hardener which is used for viscosity control has a lower activation temperature than the other hardener which determines the ultimate set time of the epoxy material. The amount of each of the two hardeners used in the compositions of the invention is less than that required to completely react with the epoxy material; however, the combination of the hardeners is sufficient to provide complete reaction and curing.
The total amount of the two hardeners used in the epoxy compositions usually is between about 2 and 15 parts per 100 parts of the epoxy material. The amount of each individual hardener used will vary from between about 1 to about 10 parts per 100 parts of the epoxy material. All parts herein are parts by weight.
Any epoxy material which meets the criteria previously set forth may be used in carrying out the process of the invention. A widely used class of polyepoxides from which the epoxy material may be selected are the resinous epoxy polyethers obtained by reacting an epihalohydrin, such as epichlorohydrin, epibromohydrin, epiiodilydrin, and the like with either a polyhydric phenol or polyhydric alcohol. The resulting resinous products may contain free terminal hydroxyl groups or terminal hydroxy groups and terminal epoxy groups.
Another class of polymeric polyepoxides from which the epoxy material may be selected are the polyepoxy polyhydroxy polyethers obtained by reacting a polyhydric phenol, such as bisphenol A, resorcinol, catechol, and the like, or a polyhydric alcohol such as glycenol, sorbitol, pentaerythritol and the like with a polyepoxide such as bis(2,3-epoxypropyl) ether, bis(2,3-epoxy-2-methylpropyl) ether, 1,2-epoxy-4,5 epoxypentane, and the like.
Another class of epoxides are the novolac resins obtained by reacting, in the presence of a basic catalyst, an epihalohydrin, such as epichlorohydrin, with the resinous condensate of an aldehyde; e.g . formaldehyde, and either a monohydric phenol; e.g., phenol itself, or a polyhydric phenol; e.g., bisphenol A.
Still another class of epoxides are the homopolymers and copolymers of epoxy containing monomers which also contain at least one double bond. Among such ethylenically unsaturated epoxy-containing monomers are vinyl 2,3-glycidyl ether, allyl 2,3-glycidyl ether, glycidyl acrylate, 2,3-epoxypropyl crotonate, glycidyl-oxystyrene, and the like. Suitable comonomers for copolysrization with these ethylenically unsaturated epoxy containing monomers include styrene, acrylonitrile, methyl acrylate, vinyl chloride vinyl acetate, diallyl phthalate, and the like.
Yet another class of epoxides are the di- and tri-epoxides, such as 3,4-epoxycyclohexylmethyl, 3,4-epoxy-cyclohexene-carboxylate. 3,4-epoxy,6-methylcyclohexylmethyl-3,4-epoxy-6-methyl cyclohexane carboxylate, bis(3,4-epoxy-cyclohexylmethyl) maleate, bis(3,4-epoxy-6-methylcylohexyl) methyl-succinate, ethylene glycol bis(3,4-epoxycyclohexane) carboxylate 2 ethyl-1,3-hexanediol bis(3,4-epoxy-6-methylcyclohexane carboxylate, and the like.
Another type of epoxides are the glycidyl ethers of alcohols and phenols, including such compounds as the diglycidyl or triglycidyl ethers of trimethyl propane, the diglicidyl ethers of 1,4 butanediol. 1,6 hexanediol, neopentylglycol resorcinol, hydroquinone, catechol, bis (hydroxyphenyl) methane, and the like.
Other monomeric polyepoxides which may be used include dicyclopentadiene dioxide, epoxidized triglycerides such as epoxidized glycerol trioleate, epoxidized glycerol trilinoleate, the diacetate of epoxidized glycerol trilinoleate and the like, 1,8-bis(2,3-epoxypropoxy)octane, 1,4-bis(2,3-epoxypropoxy) cyclohexane, 1,4-bis(3,4-epoxybutoxy)-2-chlorocy-clohexane, 1,3-bis(2,3-epoxypropoxy)benzene, 1,4-bis (2,3-epoxypropoxy)benzene, 1,3-bis(2-hydroxy,3,4-epoxybutoxy)benzene, 1,3-bis(4,5-epoxypentoxy),5-chlorobenzene, 4,4'bis(2,3-epoxypropoxy) diphenyl ether, and epoxy ethers of polybasic acids such as diglycidyl succinate, diglycidyl adipate, diglycidyl maleate, diglycidyl phthalate, diglycidyl hexachloroendomethylenetetrahydrophthalate, and diglycidyl 4,4'-isopropylidenedibenzoate, and the like.
It will be appreciated by those skilled in the art that the epoxides used in carrying out the invention are not limited to those selected from the above-described materials, but that said epoxides are merely representative of the class of epoxides as a whole.
The hardeners which are used in carrying out the process of the invention may be either liquids or solids. If present in the solid state, they may be melted and combined with the liquid epoxy material. or they may be dispersed in a solvent, or they may be converted to fine solids; e.g., by grinding, and then combined with the epoxy. In any event, the final mixture of epoxy material and hardener is a liquid and when used in packed completions, is characterized as being substantially free of solids.
Any hardener which has an activation temperature lower than the formation temperature at the zone to be plugged may be used. Examples of hardening agents are aliphatic and aromatic polyamines, acid anhydrides, the hydrazides derived from polycarboxylic acids, imidazole derivatives, dicyanodiamide, guanidine derivatives, and biguanidine derivatives. Typical examples of those hardeners are diaminodicylo methane, bis(4,amino,3,methylcyclohexyl) methane, diaminodiphenyl, methane, diaminodiphenyl,sulfone, 4,4'diamino-3,3'-dichlorodihexyl, methane, phthalic anlydride, chlorendic acid, and the like,
Hardeners which may be used also include primary and secondary polyamines, such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, aminoethyl ethanolamine, hydrazine, ethylene diamine, 1,3,propanediamine, 1,4,butane diamine, 1,6-hexane-diamine 3,3'-imino,bispropylamine, 1,2-propane diamine, 1,5-pentane diamine, phenylene diamine, and tertiary amines characterized by the formula: ##STR1## Wherein R, R', and R" are the same or different organic radicals such as dimethylethanolamine, dimethylpropylamine, dimethylbutylamine, dimethyloctylamine, dimethylethylamine, mono.methyl.diethylamine, diethylethanolamine, dimethyl decyl amine, monomethyl ethyl butyl amine, monomethyl dibutyl amine, monomethyl diprophyl amine, NN-dimethyl amino butyl amine, NN-dimethyl-amino hexyl amine, NN-diethyl amino butylamine, tetramethyl ethylene diamine, tri-methyl ethylene diamine, tetramethyl propylene diamine, tetraethyl ethylene diamine, triethyl ethylene diamine, tetraethyl propylene diamine, NN-diethylamino ethylamine, dimethylamino-propylamine, diethylamino-propylamine, dimethylaminomethyl phenol, and tri-(dimethyl-aminomethyl) phenol.
Other hardeners which may be used. some of which fall under the above classes of materials, are dicyanamide, thioameline, sodium phenylcyanamide, dithiobiurel, ethylenethiourea, dialkylmelamine, acetoguanamine, melamine, guarylurea, benzoguanamine, benzoyldicyandiamide, guanazole, 3-aminio-1,2,4 triazole, monomethyloldicyandiamide, thiosemicarbazide, adipamide, adipyl dihydrazide, isophthalyl diamide, isophthalyl dihydrazide, trisinomelamine, tetraminoditolylmethane, diamioacridine, phenylbiguanide, semicarbazide, 2oxoimidazoline-4.5-diacarboxamide, oxaldiimidic acid dyhydrazid, oxamidedioxime, diaminomaleonitrile, 2,3-diamino-5,6-dicyanopyrazine, stearic hydrazide, succiminide, and cyamoacetimide.
Still other hardeners include such materials as boron trifluoride-organic amine adducts; e.g., boron trifluoride amine complex, containing p-chloromiline and triethylene glycol.
The foregoing materials are not limiting; any hardener may be used which meets the previously described general requirements.
The use of multiple hardener systems with epoxy materials in oil field applications offers a number of advantages over the use of a single hardener. For example, varying the ratio of the hardeners allows viscosity control of the epoxy material that cannot be achieved with a single hardener. Increasing the concentration of the hardener with the lower activation temperature has the effect of viscosifying the epoxy fluid early in the placement process. This may be desirable in some applications to improve displacement of reservoir fluids or prevent overdisplacement of the epoxy material. Decreasing the concentration of the lower activation temperature hardener allows the epoxy material to remain a low-viscosity fluid for a longer period of time. Thus, additional flow time or reservoir penetration is achieved.
The use of multiple hardeners provides greater control of the hardening time of the epoxy material than single hardener systems. As with single hardeners, the hardening time can be varied by changing the combined hardener concentration. However, in dual hardener systems, a proportional increase in the higher activation temperature hardener produces further changes in hardening time. The transition from a low viscosity epoxy material to a solid material may be very rapid or can be delayed with multiple hardeners.
With a single hardener. concentrations below the hardener level required to completely react the epoxy material may be required in some applications in order to produce adequate flow or hardener times Undercured epoxy materials are susceptible to degradation and premature failure downhole However. with dual hardener systems, formulations with adequate flow and hardening times can be used that still produce completely reacted and more resistant epoxy materials.
Once the activation temperature of a single hardener has been exceeded, the reaction is initiated. Often the energy from the reaction is released very quickly, and the epoxy material in the wellbore heats up. If the hardener is in excess or if the effect of wellbore pressure accelerates the reaction, the temperature rise caused by the exothermic reaction may be uncontrolled and could degrade the epoxy material or damage the treated interval With multiple hardener systems, the energy evolved in the reaction is unchanged. but the rate at which it is released is significantly altered. The exothermic temperature rise can be controlled because the hardeners activate at different times. Thus. the heat evolved when the first hardener initiates reaction can be partially dissipated before the second hardener initiates further reaction of the epoxy material.
The following examples illustrate the results obtained in carrying out the invention:
An epoxy material, Heloxy-69, and two hardeners, Ancamine K-61-B and Curezol 2E4MZ-CN, were used in the following tests. Heloxy.69 is a resorcinol diglycidyl ether manufactured by Wilmington Chemical Corporation of Wilmington, Del. Ancamine K-61-B is a tertiary amine marketed by pacific-Anchor Chemical Company of Los Angeles, Calif. and Curezol 2E4MZ-CN is an imidazole compound manafactured by Shikoku Chemicals Corporation.
Tests were conducted that evaluated the flow time, the set time, and the exothermic temperature rise of several formulations at 190� F. Samples were prepared by weighing various combinations of hardeners and Heloxy-69 epoxy material on an analytical balance. Small samples of each formulation were then transferred into glass bottles and were placed in an oil bath. In addition, larger samples. 10 to 15 grams, were weighed into Nalgene bottles, a thermocouple was inserted into the epoxy fluid, and the samples were placed in the oil bath. The temperature of the oil bath was ramped from 85� F. to 190� F. in one hour to simulate the thermal gradient the epoxy would follow in a wellbore. Once at 190� F., the viscosity of the small epoxy samples was checked visually at five-minute intervals.
The temperatures of the oil bath and the epoxy samples in Nalgene bottles were measured and recorded every 30 seconds.
Flow and set time data from the tests are smmarized in Tables 1 and 2. The temperature increases associated with hardener initiation and epoxy reaction from several of the tests are shown in FIGS. 4 and 5. It should be noted that the effect of reservoir pressure is to decrease the flow and set times of epoxy formulations when compared to ambient pressure measurements
TABLE 1______________________________________SINGLE HARDENERHardener Flow SetConcentration Time Time(phr)1 Hardener (min) (min)______________________________________3.1 K-61-B .sup. 152 353.0 Curezol 25 35______________________________________ 1 phr Parts by weight hardener per hundred parts by weight of epoxy material. 2 Time after oil bath reached 190� F.
TABLE 2______________________________________DUAL HARDENERSHardener K-61-B/Curezol Flow SetConcentration Ratio Time Time(phr) (% of Total) (min) (min)______________________________________2.75 50/50 .sup. 301 552.75 34/66 35 552.75 17/83 35 503.0 50/50 25 503.0 34/66 30 453.0 17/83 30 40______________________________________ 1 Time after oil bath reached 190� F.
The flow time is define as the time that the epoxy remains as a low vicosity fluid. The set time is defined as the time required for the epoxy to stop flowing. The flow and set times of the individual hardeners are shown in Table 1. Although both samples have the same set time, the Curezol sample had a longer flowing time than the K-61-B sample. The activation temperature of the hardeners is the key to understanding this behavior.
Ancamine K-61-B is activated at temperature ranging from 120� F. to 170� F., and Curezol 2E4MZ-CN is activated at temperatures from 160� F. to 200� F. The activation temperature ranges are large because two different types of calorimeters were used to make the measurements.
In Table 1, the flow time of the K-61-B sample is less than the Curezol sample because the hardener initiates at a lower temperature. This results in a viscosity increase in the epoxy fluid but a delay in the ultimate set time because the hardener concentration is near the lower limit required to completely react with the epoxy. Therefore, the K-61-B hardener would not be a good candidate for some applications because the flow time is so short and there is little flexibility to alter the flow or set times. The Curezol hardener has a better flow time behavior but requires concentrations of hardener that produce an undesirable exothermic temperature profile (as shown in FIG. 2).
Formulations that used combinations of both hardeners produced longer flow times than the single hardener formulations. Different flow properties were achieved by varying the combined hardener concentration and the ratio of the hardeners. Increasing the K-61-B concentrations at a fixed hardener level decreased the flow time by viscosifying the epoxy fluid and increased the set time. In all cases, the formulations produced lower exothermic peaks than the 3.0 phr Curezol formulation.
The temperature increases associated with hardener activation and epoxy material reaction are shown in FIGS. 4 and 5.
FIG. 4 shows the oil bath temperature ramp and the temperature response of three epoxy formulations. FIG. 5 is a more detailed plot of the epoxy temperature responses. The differences in activation temperatures between the K-61-B and the Curezol hardeners are clearly shown. The K-61-B exotherm occurs between 5 or 10 minutes after the oil bath reaches 190� F. The Curezol exotherm was delayed until 30 minutes after the oil bath reached 190� F. However, the temperature rise of the Curezol sample peaked at 290� F., much greater than the K-61-B sample. This temperature rise was measured in a 10-gram sample. In a larger mass, the energy released would have resulted in a much greater temperature rise and ultimately may have thermally decomposed the epoxy material. The dual hardener system had a lower exothermic temperature rise than either of the single hardeners.
The well shown schematically in FIG. 3 is producing through perforations 19 at 11,948 feet to 11,980 feet. The well has a bottom-hole temperature of 205� F. and a bottom.hole pressure 4400 psi. The last test on the well showed a gas production of 1.2 mmcfd and a water production of 1,000 barrels per day.
Referring to the drawing, 2 7/8 inch production tubing (3) is connected in the bottom of the well with slotted tubing (7) which is covered with 124 feet of 4 1/2 inch, 6-gauge screen (9). A 7 5/8 inch production casing (5) is filled with gravel packing (17) surrounding the lower portion of the production tubing (3) and the screened slotted tubing (7). The extent of the gravel pack (17) is defined by an upper packer (11) around the production tubing and a lower packer (13), which seals the annulus between the wired slotted tubing and the production casing. The production casing (5) below packer (13) is sealed with a lower packer (15).
To seal off the water producing zone. which is in the lower portion of the production interval, the following procedure is followed:
1. A through tubing-bridge plug (not shown) is set at 12,000 feet
2. A 20-foot dump bailer is loaded with cement and is lowered to a position 10 feet above the bridge plug. The dump bailer is then activated to dump the cement, and sufficient time is allowed for the cement to set up.
3. The production tubing (3) is filled with salt water to a fluid level of about 1800 ft to essentially kill the well. It is important that the well remain dormant; therefore, the tubing and casing pressures are monitored before the treatment is carried out to ensure that the well remains relatively static for at least four hours.
4. A 40-foot positive displacement bailer is lowered into the well and loaded from the top with four gallons of Heloxy-69 epoxy material containing 0.90 parts of Ancamine K-61� B hardener and 1.35 parts of Curezol 2E4MZ-CN hardener. each per 100 parts of epoxy material.
5. The dump bailer containing the mixture of epoxy material and hardeners is run into the hole quickly to a position 10 feet above the tubing bridge plug. The dump bailer is then actuated to displace the resin/hardeners mixture.
6. After the epoxy material/hardeners mixture has had time to completely dump, the bailer is held stationary for several minutes and then pulled very slowly from the well. In order to keep the production tubing liquid full, additional liquid is added while the bailer is being removed to replace the volume occupied by the line attached to the bailer.
7. The epoxy material is allowed to harden for approximately four hours.
8. After cleaning, the bailer is filled with 4 gallons of epoxy material containing the same concentration of hardeners which have been thoroughly mixed.
9. The bailer is again run into the well quickly to a depth of about 30 feet above the tubing bridge plug and dumped again. After allowing time for the bailer to completely dump, one barrel of salt water is slowly pumped into the well.
10. The bailer is again slowly removed from the well with the well being maintained liquid-fluid full by replacing fluid displaced by the line connected to the bailer.
11. The epoxy material is again allowed to harden for approximately four hours.
12. The well is subsequently replaced in operation, and a test is carried out to determine production rates. As a result of the epoxy material treatment, the gas production is now 1.5 mmcfd and the water production is reduced to 100 bpd.
While the invention has been described in its specific application to a gravel-packed well, it is not limited to such use. The placement method disclosed herein may be used to plug any type of zone or formation in a well. In addition, it may be used to plug off other subterranean zones as previously pointed out. Ordinarily, a single epoxy material is used in the process. However, it is within the scope of the invention to use mixtures of different epoxys, particularly as this may be useful in obtaining the desired density difference between the epoxy material and the well fluid. Many of the epoxy materials are viscous at well surface temperatures. To facilitate mixing with the hardeners and introducing the mixture into the bailer, it may be desirable to heat the epoxy material to a temperature above ambient, usually, however, not higher than 110� F. to 120� F.
While certain embodiments and details have been shown for the purpose of illustrating the present invention, it will be apparent to those skilled in the art, that various changes and modifications may be made herein without departing from the spirit or scope of the invention
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|U.S. Classification
|166/276, 166/295, 405/264, 166/300, 523/130
|International Classification
|Cooperative Classification
|European Classification
|Aug 10, 1989
Owner name: CONOCO INC., 1000 SOUTH PINE, PONCA CITY, OKLAHOMA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SUMMERS, LAINE E.;JURINAK, JEFF J.;REEL/FRAME:005112/0269;SIGNING DATES FROM 19890807 TO 19890809
|May 1, 1994
|Lapse for failure to pay maintenance fees
|Jul 12, 1994
|Expired due to failure to pay maintenance fee
Effective date: 19940501


text:
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A Silent Air Purification System from The Sharper Image, this device cleans my the air in my room 24 hours a day, 7 days a week. Though not completely silent all the time, this air filter is by far the best on the market. The air it disperses smells fresh and tasty
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text:
Q1) show a lorrytraveling up a slop.
the angle of the slop is 4.8 with the horizontal and the weight of the lorry is 2.4 x 10^5 N. a resistive force of 1.2 x 10^4 N down the slop acts on the lorry as it travels up the slop at a constant speed 15ms^-1.
a) show that the componant of the weightr of the lorry down the slop is 2.0 x 10^4N.
b) calculate the rate at which the lorry does work against the resistive force.
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The "Call of the Wild", "White Fang" and Other Stories (Paperback)Jack London, James Dickey, Andrew Sinclair
Paperback Published: 26/01/1995
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"The Call of the Wild, White Fang and Other Stories" collects some of Jack London's most profound and moving allegorical tales. This "Penguin Classics" edition is edited by Andrew Sinclair with an introduction by James Dickey. "The Call of the Wild", London's masterpiece about a dog learning to survive in the wilderness, sees pampered pet Buck snatched from his home and set to work as a sled-dog. White Fang, set in the frozen tundra and boreal forests of Canada's Yukon territory, is the story of a wolf-dog struggling to survive in a human society every bit as violent as the natural world. This volume of Jack London's famed stories of the North also includes "Batard", in which an abused dog takes revenge on his owner; and "Love of Life", in which an injured prospector, abandoned by his partner, must struggle home alone through the wilderness, stalked by a lone wolf. In his introduction, James Dickey probes London's strong personal and literary identification with the wolf-dog as a symbol and totem. Andrew Sinclair, London's official biographer and the volume's editor, provides a brief account of London's life as a sailor, desperado, socialist, adventurer and acclaimed author. Jack London (1876-1916) was born John Griffith Chaney in San Francisco, California. By the age of sixteen he had left school, worked in a canning factory, spent time as an oyster pirate and been a member of the Fish Patrol in the San Francisco Bay. In 1893 he joined a sealing cruise, which took him as far abroad as Japan. In 1896 he was caught up in the gold rush to the Klondike river in north-west Canada, which became the inspiration for "The Call of the Wild" (1903) and "White Fang" (1906). If you enjoyed "The Call of the Wild", you might like Rudyard Kipling's "Just So Stories", also available in "Penguin Classics".
Publisher: Penguin Books Ltd
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"The Call of the Wild and White Fang - Jack London"
"It filled him with a great unrest and strange desires. It caused him to feel a vague, sweet gladness, and he was aware of wild yearnings and stirrings for he knew not what."
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