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The Stolen Slave— It's dark, she's tied...
The Brothers— Newlywed wants her brothers before the wedding.
His Birthday Plaything Pt. 02— She may be J's creature now, her boyfriend isn't in charge.
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Gwennalyn's Sexual Awakening Ch. 01— A princess is ravaged by orcs & enjoys it.
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Shemale Sisters Ch. 01: Creating a Slut— Jasmine is lured into having sex with 3 shemales.
Gotham Nights Ch. 06— Can the new Batgirl Stephanie handle Red Robin and Red Hood?
Jamaican Resort Day 04— Carol continues her wild ways. I love it.
Smoking for Money Pt. 03— Coed smoking fetish model does DP on camera for first time.
Weekend with Judy Pt. 02— Judy's husband lets her live out yet another fantasy.
Mollie's Family's Follies— Three Kids, Two Parents, One Happy Family.
The Oldest Ball "Kid"— Cliff learns the danger of hunting with the competition.
Shruti - A Complicated Woman— My erotic journey with a complicated woman Shruti.
The School Fete— Two mothers are ambushed by senior students.
Gotham Nights Ch. 04— Batgirl initiates the new Robin, Stephanie Brown!
Taylor's Locker Room Gangbang— A high school girl gets gangbanged after boyfriend loses bet.
The Gambler— He couldn't stop. What about her?
Sex Games 06 Pt. 02— The gang(bang)s all here.
The Four Sluts Pt. 05— Rachel likes to whore herself around.
Many Men for Her Birthday— Wife gets surprise domination for her birthday.
The Gallery— A woman's life-changing experience at a popup dating service.
Sex Games 06 Pt. 01— Boating with two Boaters.
Private, Don't Look Ch. 10— A kinky wild night. Then our world is made right.
Strapped Tight Ch. 03— Toy-happy leather guy does Jimmy with Ted and Mr. G.
Darkness— Two men show a woman what can happen in the dark.
Jessie's First Threesome— The events leading up to and including my first DP.
The Sheriff Pt. 02— Finally getting what I needed.
Left Out— Skye and Bobbi comeback from a mission.
You're Mine Ch. 01— She belongs to her Master.
Backpacker Ch. 01— Two best friends become closer when they meet French babe.
Wild Vacation Tryst Ch. 01— Foursomes and moresomes adventure in paradise.
Between Operations— What happens in the doctor's room stays in the doctor's room.
Mixed Swirl...— Two filthy construction workers drill office slut.
Private, Don't Look Ch. 06— The girls move in, more sex, Kim gets DPed, I get pegged.
She's All Grown Up— Twin brothers reunite with their adopted sister.
Arin's Inheritance Pt. 11— Arin's turn in the basement.
After Poker— Everyone gains and loses from a poker party.
Uniques Bachelor Party— Old friend gets unique bachelor party.
From Swapping to Hotwife Ch. 03— Wife moves on to being a Hotwife.
Cum Lover and Steve Pt. 11— Sara has Lesbian sex and two cocks.
Sex Games 02— We continue to escalate our sex games.
Morning After— Cara models for Daddy & Uncle Johnny in a sexy photoshoot.
Fitting in with the Upper Crust Ch. 09— Diane's incestuous sex & threesome with her son and Buddy.
A Fantasy Fulfilled— Couple realize a fantasy while on vacation.
Not the Only One— I teach my cocktease daughter-in-law a lesson.
The Four Sluts Pt. 04— Elizabeth is a wannabe slut, but being 18 changes things.
Our Sexy Adventure Ch. 01— Married seduction of a young man
Learning How to Be Black Ch. 03— A cheerleader's father falls to Darrel's might.
Happy Birthday...— She lives out her fantasy being taken by two men at once.
The Mud— An adventure with magical mud, inhibitions be damned.
Construction Grime & Catcalls— Redhead airs her grievances with construction project.
Beer Pong— A high stakes beer pong tournament leads to sexy debauchery.
Judge Lust— Corrupt judge indulges in debauchery and decadence.
Draxon Ch. 03: Reckoning— In a new realm, our heroine meets Draxon's brother...
Early Summer— 3 friends in Miami party with Kate Upton and Aubrey O'Day.
The Boys in the Box Ch. 49-51— Getting to know a new slave, and a master/slave threesome.
Roni Takes a Road Trip— On her way to a family reunion, Roni puts on a show.
That's Entertainment— Blackmailed by stepfather into entertaining clients.
Academy Girl Serafina— Serafina, late and alone, is seduced by the wild and woods.
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Elle's Group Fantasy— Elle, her husband, a friend, her lover plus another.
Landica Bk. 01 Ch. 03— Maria takes another man to her bed.
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A Weekend at the Cabin Ch. 02— The couple continues to be tormented.
The Erikson Twins Big Summer Pt. 04— More fun for the twins and a new career path.
Ryan and Pierce— Her divorce comes through and her lovers celebrate.
Piano— Jane and Sarah earn the money to repair an old piano.
The Erikson Twins Big Summer Pt. 03— Two 18-year-old twin boys have more fun in Cougarville.
The Erikson Twins Big Summer Pt. 02— The Twins have more fun.
Our Fantasy Develops Pt. 01-04— Our developing sexual fantasies.
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Becky G Does An Epic Dubsmash & Sends A Message In A Bottle With ANDPOP
ANDPOP Rounds Up The Top 5 & 1/2 Dogs Of Instagram
Bryan Cranston Talks Stripper Names & Choosing Roles
Icona Pop Talks 1D Make-Outs, Worst Emergency & Party Cup Tricks
10 Reasons Why We're Counting Down The Days Until Pentatonix's Album
These Upcoming Netflix Originals Can't Come Fast Enough For Us
MUST FOLLOW MONDAY: Pentatonix's Mitch Grassi
ANDPOP Talks "Full Out," Selfie Tricks, And "Degrassi" Friendships With Ana Golja
7 Lines We Would Love To See Role Reversed From "Twilight"
ANDPOP'S Top 11 ABC Family Shows Over The Years
8 Badass, Prime Time Leading Ladies To Watch This Fall
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Brittany Mahaney is a regular contributor to ANDPOP.com and the former Online Editor. She obsesses over cat videos and boy bands, and often ends up on the weird part of the internet. You can follow her on twitter at @britt_mahaney or brittanymahaney.com.
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Francis, Mary and Elizabeth are chosen among 12 favorite Royals from @andpop #Reign https://t.co/2AB1P6a7vV
@andpop Can't pick!!!! Ryan T is OFF THE CHARTS.... Like picking fav child- no can do! LOL :O LUV @OneRepublic
Omg I wrote the article, this is me https://t.co/zidak3xt1J
@andpop @Spencermusic1 this is a great interview!
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JD came by to talk about a new dope artist he has named Royce Rizzy who you can peep right here. However, the bulk of this 75 minute Juan Ep is spent discussing the amazing career of JD. We start out discussing his role as a kid on the Fresh Fest tour, continue through the formation of Kriss Kross, stories of how he had TLC before they were on LaFace, Biggie and Da Brat talk.
Cowboys to bring in Michael Sam
Michael Sam is flying into Dallas on Tuesday night and will take a physical for the Cowboys on Wednesday, a source told ESPN NFL Insider Adam Schefter.
If Sam passes his physical, the Cowboys intend to sign him to their practice squad, the source said.
Sam, who is seeking to become the first openly gay athlete to play in the NFL, was cut by the St. Louis Ramson Saturday.
The Rams spent a seventh-round draft pick, No. 249 overall, on him in May's draft. He put together a solid preseason performance, coming up with 11 tackles and three sacks. In Thursday night's preseason finale against Miami, Sam finished his preseason work with a team-high six tackles.
Sam cleared waivers Sunday and is free to sign with any team.
The Rams finalized their 10-player practice squad on Monday, and it did not include Sam.
Coach Jeff Fisher had suggested that a lack of bodies at positions with little depth could leave the defensive end on the outside looking in when the team added to that unit.
The Cowboys announced Tuesday that rookie defensive end DeMarcus Lawrence, their second-round pick, has been placed on injured reserve with a designated to return tag. That means Lawrence, who is recovering from surgery to repair a broken foot suffered early in training camp, is ineligible to practice for six weeks and must sit out the first eight games. The Cowboys signed defensive end Jack Crawford, a two-year veteran cut last week by the Oakland Raiders, to take Lawrence's place on the roster.
The Cowboys also signed offensive tackle John Wetzel and defensive back Jemea Thomas, who were both cut by Dallas after making the initial 53-man roster, to the practice squad. The Cowboys now have 10 players on the practice squad, meaning they would have to release one to make room for Sam.
allhiphop.com exclusive: Jermaine Dupri Introduces His New Artist Royce Rizzy
AllHipHop got to sit down with CEO of So So Def Records & "Mayor of ATL" Jermaine Dupri and new artist Royce Rizzy who just signed with him this year.
We caught up with them while they were on a promo run in NYC to push Rizzy's single "Gah Damn" Remix Ft. K-Camp, Jermaine Dupri, Twista & Lil'Scrappy. The single will be on his forth coming project Determination coming out in September. JD explains about Rizzy and his latest hit:
The song basically speaks to me because thats how I talk … he's not from Atlanta ..but if you are you know thats how most people speak" says about "Gah Damn"
Watch as JD introduces him to the world and talks about how Rizzy's music attracted him, the new JD single coming out and what to expect in 2015 from So So Def. "Music! Music, thats it."
Take a look at Royce Rizzy Ft. K-Camp, Jermaine Dupri, and Twista "Gah Damn"
Usher (@Usher) The UR Experience Tour Dates
Usher reveals the full list of cities he'll be stopping through this fall.
The UR Experience will kick off in Montreal, Quebec on Nov. 1 and close in Tampa, FL. on Dec. 14. The 27-city tour will include special guests and a setlist full of hits covering Usher's 20-year discography. Here's what Usher had to say about his upcoming tour:
"With The UR Experience, I want to give my fans an ever-changing live show full of surprises and special guests," Usher says, via a press release. "I am really excited to be with my fans and give them an Usher experience like they've never seen or heard before."
Tickets for select markets go on sale on Monday, Sept. 8. Check out details over at Usher World or Live Nation.
Usher's upcoming eighth studio album, rumored to be titled UR, is slated to drop this fall.
Check out the dates for The UR Experience below:
Date City Venue
Nov. 1 Montreal, QC Bell Centre
Nov. 2 Toronto, ON Air Canada Centre
Nov. 4 Detroit, MI The Palace of Auburn Hills
Nov. 5 Cleveland, OH Quicken Loans Arena
Nov. 7 New York, NY Madison Square Garden
Nov. 10 Washington DC Verizon Center
Nov. 11 Philadelphia, PA Wells Fargo Center
Nov. 13 Boston, MA TD Garden
Nov. 14 Uncasville, CT Mohegan Sun
Nov. 15 Atlantic City, NJ Boardwalk Hall
Nov. 17 Chicago, IL United Center
Nov. 18 St. Paul, MN Xcel Energy Center
Nov. 21 Los Angeles, CA Staples Center
Nov. 22 Las Vegas, NV MGM Grand Garden Arena
Nov. 24 San Jose, CA SAP Center at San Jose
Nov. 26 Seattle, WA Key Arena
Nov. 27 Vancouver, BC Rogers Arena
Nov. 30 Edmonton, AB Rexall Place
Dec. 2 Broomfield, CO 1STBANK Center
Dec. 4 Dallas, TX American Airlines Center
Dec. 5 Houston, TX Toyota Center
Dec. 6 New Orleans, LA Smoothie King Center
Dec. 8 Memphis, TN FedEx Forum
Dec. 9 Atlanta, GA Philips Arena
Dec. 12 Orlando, FL Amway Center
Dec. 13 Miami, FL American Airlines Arena
Dec. 14 Tampa, FL Tampa Bay Times Forum
Stalley (@Stalley) On Ebro In The Morning
Stalley sits down with Ebro and Laura Stylez on Hot 97′s Ebro In The Morning. Stalley talks about MMG, LeBron James returning to Cleveland, his new single Jackin Chevys, cars, his debut album Ohio, the other single Always Into Something featuring Ty Dolla $ign, and working with producer Rashad.
Kevin Gates (@Kevin_Gates) The Breakfast Club Interview
Kevin Gates makes his way to The Breakfast Club to sit down with DJ Envy, Angela Yee and Charlamagne Tha God. Kevin talks about the music industry, his childhood in Louisiana, his partnership with Atlantic Records, being inspired by Birdman, his children, and his time in prison.


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The 25 Most Anticipated Albums Of 2012: Madonna, Usher, Green Day
What sets are you most excited about? Mumford & Sons, Justin Bieber, U2, Jay-Z...
Crossover queens: Nicki Minaj and Janelle Monae
Nicki Minaj and Janelle Monae both managed to make funky urban albums that also made waves, too, in the pop sphere. The former will drop her sophomore set "Pink Friday: Roman Reloaded" on Valentine's Day (Feb. 14) in 2012, while Monae is crafting her follow-up to 2010's "The ArchAndroid" -- make that plural, follow-ups. She told Back To Rockville that she wants to release two new albums in 2012, dates to be determined by her "soul clock."
Photo Credit:
Kevin Feige and the Russo brothers reveal why no Avenger got killed off in 'Captain America: Civil War'


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Kaszuby, Poland in pictures
I had a chance to spend few days in Kaszuby earlier this year and it was as pretty as I imagined. I stayed in the heart of the region, in a small village Wdzydze Kiszewskie. It was mid May so there weren't all that many people around, only some school groups. Sadly, even if there're less than 200 inhabitants in the village, Wdzydze looked like a summer nightmare place that I wouldn't like to visit in the peak season. But May seems like a perfect time to be there. It was quite and peaceful, singing birds woke me up early in the morning, lakes were empty – everything a person needs to relax in a beautiful landscape.
Wdzydze is also known for the oldest open-air museum in Poland, showing the old architecture typical for Kaszuby region. While I preferred the museum in Sierpc I enjoyed this one as well. I always like wandering this kind of museums and imagining how the life used to look like all these years ago. This one had a really nice location, in the forest at the shore of the lake and at some points I really felt like I moved back in time!
Another attraction of Wdzydze that I really enjoyed was a watch tower. A pretty high one – 36 meters – and located next to the point where four lakes meet, offers a breathtaking view of the area. I went there twice and it still wasn't enough for me, I could spend hours just staring at this perfect view. But as well I could spend hours just sitting in the pier, with my feet in the lake, reading a book or staring at the endless surface of the water in front of me…
Do yo also like exploring your own country? Which place there would you recommend?
If you think of visiting Poland or just want to read more about the country take a look what else I wrote about it!
If you enjoyed that post why don't you share it with your friends? That would mean so much to me! Also be sure to join 18.000+ fellow travelers and follow me on Facebook, Twitter, G+ or Instagram for travel updates and even more pictures! If you don't want to miss new posts sign up to my newsletter!


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Buy factory-fresh MREs (Meals, Ready to Eat)
Our MREs are not the ancient military rations you heard stories about as a kid. Meal Kit Supply MREs (Meals, Ready to Eat) are not your grandpa's combat rations—they're tougher, they last longer, and they taste a heck of a lot better. Each 1,200+ calorie MRE consists of a three-course meal of America's favorite comfort food, with entrees like Beef Ravioli, Chili, Spaghetti, and Meatballs, as well as side dishes like Fried Rice and Potatoes Au Gratin. Unlike many MRE and 19FD-01-IRAT (Rations, Initial Deployment) retailers, we offer four breakfast meals in every case of 12 MREs. Some breakfast entrees include Pork Sausage Patty and Apple Maple Oatmeal, with sides and desserts like Poptarts, Strawberry-Banana Milkshakes, Pound Cake, and Hashbrowns with Bacon.
Meal Kit Supply's factory-fresh MREs have the widest variety of food items commercially available because we know that even in an emergency you've got taste buds. Each MRE includes the following food items:
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We assembled our MREs—which contain 100 percent U.S. military MRE food components—with you in mind. When emergency strikes, you're not going to have the time or resources to generate boiling water, or even track down a utensil. That's why we include a flameless ration heater, spoon, and napkin in every MRE: so you can have a hot meal any time, any where, without a stove or boiling water. And the water you use to trigger the flameless ration heater doesn't even have to be clean: it could come from a puddle or lake.
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If you were wondering what kind of emergency food you should have on hand, wonder no more. Buy Meal Kit Supply MREs and get the most reliable, factory-fresh, shelf-stable food commercially available. It's easy—like emergency preparedness should be.
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Why buy MREs from Meal Kit Supply?"5.0 out of 5 stars Great Product to Prepare for Hurricane Season. Great product. The meal kit contains 12 complete Ready-to-Eat meals which include entree, side dish, bread, drink mixes, instant coffee, condiments, napkin and spoon and dessert! A flameless ration heater is also included with each MRE to warm the food. This kit is the perfect item to have on hand for the upcoming South Florida hurricane season. The best part? The food actually tastes good! This meal kit may be slightly more expensive than others out there, but the quality of the food along with the great taste makes it well worth the few extra dollars you might spend, and with a 5 year shelf-life, this kit is actually a pretty great bargain. My shipment arrived quickly and the box tucks away neatly in my pantry to have ready in case of emergency. I would recommend this product to anyone as a good insurance policy to have on hand. 5 Stars, all the way."
Lisa H.


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Athletic Field Marking Paint - Wh. - 36 pk.
by Sport Supply | Item #: 949008 | Model #: 0792PACK |
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^Free shipping (if noted above) is available within the continental U.S. only. Offer excludes Alaska and Hawaii. Shipping to AK or HI adds a location surcharge to the regular rate. Delivery estimates, taxes, and fees are based on ZIP Code. Club Pickup orders are based on your club's current price and item availability on the day of payment.
About this itemThirty-six white athletic field marking paint cans that will work in most striping machines.
Athletic field marking paint does not contain lead, CFCs and a low VOC. Thirty-six (20 oz.) aerosol cans per case. Will work in most striping machines in use today. Approximately 150 yards of stripe per can. Cannot be shipped by air.
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Health Safety Consultants Worcester Park
2 results for Health Safety Consultants in Worcester Park
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Sun February 10th, 2013
Main Space
Minimum Age: All Ages
Doors Open: 6:30PM
Show Time: 7:30PM
Event Ticket: $13
Day of Show: $15
free for members
Billband: "Towards Daybreak" album release concert
All-star octet plays music of Bill Ryan
Composer Bill Ryan is known to many as the force behind the Grand Valley State University New Music Ensemble, the student group that gained widespread praise for recordings of Steve Reich's Music for 18 Musicians (2007) and Terry Riley's In C with remixes (2009). With Towards Daybreak, the sophomore release from Ryan's ensemble Billband, the focus turns back to his own work. Out Tuesday January 29 on Innova Recordings, the CD is by turns contemplative, roiling, elegaic, and aggressive – a reflection of experiences in Ryan's life, from the birth of a child to the loss of his parents. His post-minimalist musical language is personal and expressive, poised on a knife edge between lushness and reticence. It is a music that reveals itself gradually, working its way deeper with each listen.
Individually, Billband members have an astonishing list of performing credits, including working with Sting, Yo-Yo Ma, the Bang on a Can All-Stars, Blue Man Group, So Percussion, and the Steve Reich Ensemble, among others. And as a collection, they take no prisoners.
Bill Ryan, composer
Ashley Bathgate, cello
Vicky Chow, piano
David Cossin, percussion
Michael Lowenstern, bass clarinet
Pablo Mahave-Veglia, cello
Jonathon Nichol, saxophone
Doug Perkins, percussion
Todd Reynolds, violin
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Ashley Bathgate
American cellist Ashley Bathgate has been described as an "eloquent new music interpreter"(New YorkTimes) and "a rising star of her instrument"(Albany Times Union) who combines "bittersweet lyricism along with ferocious chops"(New York Magazine). Her "impish ferocity", "rich tone" and "imaginative phrasing" (New York Times) have made her one of the most sought after performers of her time. The desire to create a dynamic energy exchange with her audience and build upon the ensuing chemistry is a pillar of Bathgate's philosophy as a performer. Her affinity to dynamism drives Bathgate to venture into previously uncharted areas of ground-breaking sounds and techniques, breaking the mold of a cello's traditionally perceived voice. Collaborators and fans alike describe her vitality as nothing short of remarkable and magical for all who are involved. Bathgate is a member of the award winning, internationally acclaimed sextet, Bang on a Can All-Stars, and is also a founding member of TwoSense,a duo with pianist Lisa Moore, and Bonjour, a low-strung, percussive quintet with fellow new music mavens Florent Ghys, James Moore, Eleonore Oppenheim and Owen Weaver.
Most recently Bathgate gave the world premiere of a new Cello Concerto by Australian composer Kate Moore with the ASKO|Schönberg ensemble at the Gaudeamus Festival in Utrecht, NL. She subsequently recorded an album of Moore's solo cello works which will be released in 2016 on Cantaloupe Music. This past season also brought the world premiere of What Moves You, a collaborative performance project with jookin' dance sensation Lil Buck at the Spoleto Festival USA inCharleston, NC. Bathgate is currently embarking on a collaboration with the Brooklyn-based composercollective Sleeping Giant, who is writing her a six-movement suite for solo cello to premiere next year on the Metropolis Resident Artist Series in NYC. Other upcoming commissions include works by Doug Cuomo, Michael Gordon, Erdem Helvacioglu, Scott Lindroth, Jascha Narveson, Todd Reynolds, and Neil Rolnick. Bathgate's radio/television appearances include performances on WQXR FM's Young Artist Showcase, WQXR's Meet the Composer podcast with Nadia Sirota, NPR's Performance Today, WYNC's New Sounds Live, SiriusXM, Late Night and The Tonight Show with Jimmy Fallon. Her recorded work can be found on Albany Records, Cantaloupe Music, Innova Recordings, La-La Land Records, Naxos, Nonesuch and Starkland.
Equally at home in both the concert hall and the rock club, Bathgate focuses on presenting concerts thatdraw from a wide range of musical genres. Her dedication to performing traditional music is equally matched by her passion to promote new music by today's composers. That dedication has led her to work with an esteemed list of composers and musicians such as John Adams, Louis Andriessen, Nik Bärtsch, Iva Bittova Martin Bresnick, Don Byron, Jace Clayton, Bryce Dessner (The National), Arnold Dryblatt, DJ Spooky, Ben Frost, Philip Glass, Michael Gordon, Annie Gosfield, Ann Hamilton, Glenn Kotche (Wilco), David Lang, Lori Lieberman, Meredith Monk, Richard Reed Parry (Arcade Fire), Questlove and The Legendary Roots Crew, Lee Ranaldo (Sonic Youth), Steve Reich, Terry Riley, Trio Mediaeval, Julia Wolfe, Shara Worden (My Brightest Diamond) and Nick Zammuto (The Books). Bathgate has toured the U.S., South America, Russia, Australia, Europe, and Asia with the Bang on a Can All-Stars and has collaborated with several notable ensembles including the Choir of Trinity Wall Street (Julia Wolfe's Anthracite Fieldsat Avery Fisher Hall), Red Fish Blue Fish (Steve Reich's Musicfor 18 Musiciansat Disney Hall), the Kronos Quartet (Brian Eno's Music for Airportsat MIT, Cambridge) and eighth blackbird (Reich's Pulitzer Prize winning Double Sextetat Carnegie Hall & TheBarbican).
Bathgate studied at Bard College with Luis Garcia-Renart (B.M.) before continuing her education at Yale University with renowned cellist Aldo Parisot (M.M. & A.D). Originally from Saratoga Springs, NY, Bathgate began her cello studies with the late Rudolf Doblin, principal cellist and assistant music director of the Buffalo Philharmonic in the 1950's. After his passing, she resumed her tutelage with Ann Alton at Skidmore College. A member of the Empire State Youth Orchestra at the time, Bathgate was also the unprecedented two-time winner of the Lois Lyman Concerto Competition, performing the Saint-Saens and Schumann Cello Concertos with the orchestra at Troy Savings Bank Music Hall. While at Bard College, she was invited to perform both the d'Albert and Barber Cello Concertos with the American Symphony Orchestra under the direction of Leon Botstein and then went on to win Yale University's Concerto Competition in 2008, performing with the Yale Philharmonia in New Haven's legendary Woolsey Hall.Bathgate resides in New York City.


text:
|Publication number
|Publication type
|Publication date
|Apr 18, 1972
|Filing date
|Aug 26, 1969
|Priority date
|Aug 26, 1969
|Publication number
|Johnson Robert C, Merrifield Richard E
|Original Assignee
|Du Pont
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (2), Referenced by (11), Classifications (9)
|External Links: USPTO, USPTO Assignment, Espacenet
United States Patent Johnson et al.
15 3,656,835 [451 Apr. 18, 1972 MODULATION BY A MAGNETIC FIELD OF ELECTROMAGNETIC RADIATION PRODUCED BY THE DECAY OF TRIPLET STATES Inventors: Robert C. Johnson; Richard E. Merriiield,
both of Wilmington, Del.
E. I. du Pont de Nemours and Company, Wilmington, Del.
Filed: Aug. 26, 1969 Appl. No.: 853,183
Related US. Application Data Continuation-impart of Ser. No. 724,420, Apr. 26, 1968, abandoned, which is a continuation-impart of Ser. No. 648,883, June 26, 1967, abandoned.
U.S. Cl ..350/l60 Int. Cl ..G02f l/I6 Field of Search ....350/160 P; 252/300, 301.2, 252/30 1 .3
[5 6] References Cited UNITED STATES PATENTS 3,214,382 10/1965 Windsor ..350/l60 P 3,214,383 10/1965 Moore et al. ..350/160 P Primary ExaminerWilliam L. Sikes AttorneyJames H. Ryan [57] ABSTRACT Thisdisclosure describes a process and devices for modulating electromagnetic radiation, e.g., visible light, by means of variation in a magnetic field on a substance, e.g., anthracene, pyrene, diphenylanthracene, etc., in which triplets can be created, with the triplets subsequently decaying and thereby causing said substance to emit electromagnetic radiation, e.g., to fluoresce.
16 Claims, 15 Drawing Figures P'ATENI'EIJAPR 18 me I SHEET 1m 4 FIG. In
1 5.0 I00 I50 IIACIIETIC FIELD STREIICTH IKILO-OERSTEDSI FIG. lb
MAGNETIC FIELD STREIICTII (KILC-OERSTEDS) INVENTORS ROBERT C. JCRISCII RICIIARD E. IERRIFIELD ATTORNEY PATENTEDAPR 18 me 3, 656,835
SHEET 2 [IF 4 LEGEND 3 ROBERT c 10m? &',( R memo E. IERRIFIELD NOH-IRRADIATED ANTHRACENE BY W 14.1
ATTORNEY PATENTEmPmalsvz SHEET 0F 4 FIG.9
FIG. l0
FIG-ll INVENTORS JOHNSON RICHARD E. HERRIFIELD ROBERT ATTORNEY RELATED APPLICATION This application is a continuation-in-part of our copending application Ser. No. 724,420 filed Apr. 26, 1968, as a continuation-in-part of Ser. No. 648,883, filed June 26, 1967 both prior applications now abandoned.
BACKGROUND OF THE INVENTION 1 Field of the Invention This invention relates to, and has as its principal objects provision of, a process and devices for modulating or changing the intensity of the light resulting from the decay of triplet states.
2. Description of the Prior Art An exciton in a crystal or region of a crystal is an internally mobile, electronically excited state which can internally transport energy but not charge. A triplet exciton is one in which the electronically'excited state in question bears one unit of spin (arising from two unpaired electrons). Excitons, once created in a crystal, do not persist indefinitely, but decay by a monomolecular process characterized by a lifetime 1. In the case of triplet excitons, the energy given up in this monomolecular decay process can either appear as heat or as light (phosphorescence).
The rate of monomolecular decay process is usually increased if impurities are added to a pure crystal. This shortening of the triplet lifetime is called quenching. Paramagnetic species, e. g., free radicals, are particularly effective quenchers of triplets. Paramagnetic impurities can be introduced into a crystal by cocrystallization with the host material or by diffusion of the impurity into a pure crystal or they can be produced in situ by exposing a crystal to high energy radiation, e. g., X-rays. Examples of paramagnetic impurities are oxygen, nitric oxide, substituted hydrazyls such as diphenylpicrylhydrazyl, nitroxides such as di-tert-butyl nitroxide, and N- nitrosodiarylamines such as N-nitrosodiphenylamine. The impurities can be incorporated in the pure crystals in amount and by procedures well known to those skilled in the art. The quenching of triplet excitons in anthracene crystals by free radicals produced by X-irradiation of the pure crystal is disclosed by C. Z. Weisz et al., Mol. Crystals 3, 1968 (1967).
In some crystals,triplet excitons can also disappear by a second, bimolecular, process, termed mutual annihilation, in which a pair of excitons meet and combine their energy to yield a single, higher energy, singlet exciton (one with zero spin, i.e., all electrons paired). This singlet exciton, which normally has a much shorter lifetime than the triplet exciton, subsequently disappears with emission of light. The light produced in this manner is usually termed delayed fluorescence to distinguish it from the more usual prompt fluorescence which results when the singlet exciton is produced directly by absorption of light.
Crystals in which triplet excitons can be created can be classified according to whether they show phosphorescence, delayed fluorescence, or both. These classes of crystals are discussed in more detail below.
The process of mutual annihilation of triplets leading to delayed fluorescence and the process of phosphorescent emission from triplets can take place in fluid systems as well as in crystals. In the former case the triplets involved are simply triplet states of molecules rather than excitons. In the following the term triplet will refer to a molecule in a triplet state for fluid systems and to a triplet exciton for crystalline substances.
The exciton has been studied extensively, both theoretically and experimentally. See, for example, Dexter and Knox, Excitons, Interscience Publishers, Inc., New York (1964), and Knox in Solid State Physics, Academic Press, New York, Suppl. 5 (1963). The triplet-triplet annihilation process is discussed in some detail by R. G. Kepler, .l. C. Caris, P. Avakian and E. Abramson, Phy. Rev. Letters, 10, 400 (1963) and by P. Avakian and E. Abramson, J. Chem. Phys. 43, 821 (1965). The process of triplet-triplet annihilation in fluid systems is described by C. A. Parker, The Triple! State, A. B. Zaha7n, Ed., pp. 353-359, The University Press, Cambridge (l9 DETAILS OF THE INVENTION AND DRAWINGS In accordance with the present invention, it has been found that, when a substance in which triplets can be created is excited to produce triplets and a magnetic field is applied thereto, the intensity of' electromagnetic radiation resulting from the decay of the triplets changes with variation in the strength of the applied magnetic field. The triplets can be either triplet excitons in the case of a crystalline substance or molecular triplet states in the case of fluid system, e.g., a solution. The electromagnetic radiation that is influenced by the magnetic field includes, in the presence of paramagnetic quenching, both delayed fluorescence and phosphorescence, and is restricted, in the absence of such quenching, to delayed fluorescence.
For triplet excitons in a crystalline substance in the absence of paramagnetic quenching, the delayed fluorescence intensity increases in low magnetic fields, reaching a maximum increase at some field strength ca. 1000 De or less. Further increase in the field strength results in a decrease in delayed fluorescence intensity up to a field of ca. 5000 0e, at which point the intensity has decreased to less than the zero-field value.
In some crystalline substances one or more peaks in intensity, in addition to the initial low-field peak, are observed as the field strength is increased. For sufficiently high field strengths very little further change in intensity takes place as the field strength is increased.
The intensity of electromagnetic radiation also depends on the direction of the applied magnetic field, and in some crystalline substances there are observed to be directions of applied magnetic field for which one or more of the peaks in intensity of electromagnetic radiation are not discernible as the field strength is increased.
The effect of a magnetic field on the exciton annihilation process does not depend on the source of the triplet exciton. Thus, optically created triplet excitons in which activating radiation of one wavelength excites the emission of radiation of a different wavelength are useful as shown in detail below. The process, however, is equally operable with excitons created in any other manner, e.g., by recombination of electrons and holes which are introduced into the crystal by means of injecting electrodes. For example, in the case of crystalline anthracene, an electron-injecting electrode can consist of a solution of the sodium salt of anthracene in tetrahydrofuran while a hole-injecting electrode can consist of a solution of anthracene and AlCl in nitromethane. Production of triplet excitons in anthracene by the injection process is disclosed by W. Helfrich and W. G. Schneider, J. Chem. Phys. 44, 2902 (1966).
The effect of a magnetic field in changing the emitted electromagnetic radiation, i.e., delayed fluorescence, resulting from the mutual annihilation of triplet excitons, results in crystals of any material in which the mutual annihilation process takes place. Such materials include both:
1. Crystals showing delayed fluorescence but not phosphorescence: 9,10-diphenylanthracene, 9,9'-bianthryl, naphthalene, phenanthrene, p-terphenyl, trans-stilbene, tetracene and Z-methylpyrene; and
2. Crystals showing both phosphorescence and delayed fluorescence: anthracene, 4,5-iminophenanthrene, and 4,5- methylenephenanthrene.
In the case of delayed fluorescence in fluid systems, operable solvents are those in which triplet-triplet annihilation leading to delayed fluorescence can take place. These solvents must dissolve the solute to some extent, must be inert to the solute, and must be transparent to exciting and emitted light. Inoperable solvents are those which quench molecular fluorescence, e. g., by reacting with the solute or by containing iodine. Specific operable solvents include alcohols, such as methyl, ethyl, isopropyl, tert-butyl, and 2-ethylhexyl alcohols; hydrocarbons such as methylcyclopentane, heptane, isooctane, and toluene; ethers, including polyethers and cyclic ethers, such as ethyl ether, butyl ether, l,2dimethoxyethane, tetrahydrofuran, and dioxane; esters, such as ethyl acetate, methyl propionate, and ethyl isobutyrate; ketones, such as acetone, Z-butanone and cyclohexanone; and fluorinated and chlorinated hydrocarbons, such as chloroform, ethylene chloride, chlorobenzene, fluorobenzene and l,l,2-trichloro- 1,2,2-trifluoro-ethane.
With materials in which triplet-triplet annihilation leading to delayed fluorescence takes place, the introduction of paramagnetic impurities leads to a change in the magnetic field dependence of delayed fluorescence intensity as a result of the combined effects of the field on the annihilation and quenching processes. This change consists of a more rapid increase of delayed fluorescence intensity at low fields, a greater maximum increase, and an extended range of field strengths which produce an increase in intensity.
For materials in which the monomolecular decay of the triplet is accompanied by the emission of light (phosphorescence) the introduction of paramagnetic impurities also leads to a magnetic field-dependence of the phosphorescence lifetime and intensity, regardless of whether or not the material is one in which triplet-triplet annihilation takes place. The phosphorescence lifetime and intensity are typically a minimum at zero field and increase as a field is applied up to a field strength of ca. 2000 Oe, above which field little further change takes place. This effect is observed in crystals of the second class of crystals numbered above, and in addition in crystals of a third class, i.e., those showing phosphorescence but not delayed fluorescence. Examples are carbazole, N-phenylcarbazole, benzophenone, dibenzofuran, and triphenylene.
The effect of a paramagnetic impurity results from the fact that the quenching of triplets by a paramagnetic species is altered in the presence of a magnetic field. The quenching is a maximum at zero field and decreases as a magnetic field is applied, typically decreasing to ca. 90 percent of the zero-field quenching rate for a field of ca. 2000 Oe. Little further change in quenching rate takes place as the field is increased beyond this value. The field dependence of the quenching is manifested by a corresponding field dependence of the triplet lifetime. (Triplet lifetimes in pure materials or when quenched by nonparamagnetic impurities are insensitive to magnetic fields of these magnitudes at room temperature.)
The effects of magnetic fields on phosphorescence lifetime and intensity discussed in the foregoing two paragraphs can also take place in solution. Operable solvents are the same as those, discussed above, in which triplet-triplet annihilation leading to delayed fluorescence can take place.
The invention will be understood in more detail from the remainder of the specification and from the drawings wherein the common numerals represent the same parts and in which:
FIG. la is a plot of annihilation luminescence intensity v. magnetic field strength in an anthracene crystal (roughly 7 X 9 X 14 mm. in size) at room temperature (ca. 25C.);
FIG. lb is a plot quite similar to that of FIG. 10 except that the anthracene crystal was at 4.2I(. (see Example 1, below);
FIGS. 2a, b and c are plots of delayed fluorescence activity v. magnetic field strength in anthracene crystals (3 X X mm.) irradiated (solid line) with 4 X l0 rads of X-rays and unirradiated (broken line). In each plot, the field is in the plane of the a and b crystal axes; in a it is parallel to the a axis, in b it is at an angle of 25 with the b axis, and in cit is parallel to the b axis. The X-rays generate free radicals in the crystal which serve as quenching agents;
FIGS. 30 and b show solenoids (air core and soft iron core, respectively) in magnetic contact with, Le, magnetically coupled to, an operative crystal. I-Iere crystal 10, e.g., of anthracene, is magnetically coupled to a field set up in a coil 11 with terminals 12 and 13 and, in 3b, an iron core 14. Conventional exciting means (not shown) is also provided. When the crystal is excited, variation in the current in the solenoid causes variation in the intensity of the light emitted from the crystal. The excited crystal can be used to determine the presence or absence of an electrical current in the solenoid and, when calibrated, its magnitude;
FIG. 4 shows a permanent magnet 15, e.g., in a magnetic tape, magnetically coupled to an anthracene crystal 10. If there are variations in the strength of the field over the magnet, they are optically detectable on the crystal;
FIG. 5 shows a system for modulating light. In this system, light from a lamp 16 is passed through an input lens 17 and then through an input filter 18 to remove wavelengths shorter than those necessary to create triplet excitons in the crystal. This light is focussed by the input lens 17 into a small region of the crystal 10. Some of the annihilation luminescence from crystal 10 is collected by the output lens 17 and directed through the output filter 19 which rejects the exciting light passed by the input filter. The intensity of this annihilation luminescence light can be modulated by the magnetic field of the solenoid which, in turn, is controlled by the magnitude of the electric current passing through the solenoid terminals 12 and 13;
FIG. 6 shows a system for reading out magnetically stored information. In this system, light from lamp 16 is passed through input lens 17 and input filter 18 to remove wavelengths shorter than those necessary to create triplet excitons in the crystal 10. The light is focussed into a small region of the crystal by input lens 17. Magnetic tape 20 is in close proximity to crystal 10. The magnetic fields from the magnetized material of the tape encounter the illuminated region of the crystal and modulate the intensity of the annihilation luminescence of the crystal. Some of the annihilation luminescence from the crystal is collected by the output lens 17 and directed through the output filter 19 into the photodetector 21. Output filter 19, as before, rejects exciting light passed by input filter 18. The electrical output follows the annihilation luminescence intensity which, in turn, responds to the changes in magnetic field strength corresponding to informa' tion stored on tape 20. The electrical output can be processed electronically by conventional means (e.g., an oscilloscope, not shown) to present the information which has been read out of the magnetic tape through terminals 22 and 23 of photodetector 21;
FIGS. 7 and 8 show circuit elements and means for exciting the crystal. In FIG. 7 (compare FIG. 3b), anthracene crystal 10 is excited by visible light, e.g., having a wavelength of6320 A. The magnitude of electric current which controls the magnetic field of the electromagnet controls the annihilation luminescence intensity (output light) which is emitted by the crystal under irradiation by the input light;
In FIG. 8, the crystal is excited electrically and triplet excitons are created in crystal 10 by recombination of charge carriers. The charge carriers are injected at electrodes 24 and 25. Electric current through terminals 12 and 13 control the magnetic field of the electromagnet which, in turn, controls the annihilation luminescence intensity (output light). The electrical input, at the injecting electrodes 24 and 25, determines the zero magnetic field intensity of the annihilation luminescence;
FIG. 9 shows a complete apparatus for determining the ef fects of field intensity on fluorescence emission from a crystal to give results such as those shown in FIGS. 1 and 2. In FIG. 9, a ISO-Watt Xenon lamp 26 directs a light beam 27 (incident or exciting light) through a plate glass plate 28, neutral density filters 29 and 30, heat absorbing glass 31, and color filter 32 (Coming C. S. 2-62) into converging lens 33 which focuses the beam onto crystal 10 held in a vacuum box 34 provided with glass 35 (actually another Corning glass filter C. S. 2-62) and transparent. support 37. Emitted light beam 36 passes through transparent support 37 and into a Crofon (Crofon is a bundle of jacketed Lucite [poly(methyl methacrylate)] fibers frequently used as a light guide) light guide 38 and filter 38' in box 39 and eventually into photomultiplier tube 40 (RCA 6199) coupled through output line 41 to a high voltage power supply (not shown) and a suitable recording device, e.g., Leeds and Northrup Speedomax Type G recorder, not shown. When magnetron horseshoe magnet 43 is brought into proximity with the crystal 10, variations in the output from photomultiplier tube 40 is plotted in FIG. 1 are observed;
In FIG. 10, incident light from a Xenon lamp (not shown) is fed through red color filters 32 and glass window 50 in a vacuum box 51 provided with several sealing rings 52, and Crofon light guide 55. Light guide 55 extends into a closed metal tube 56 fastened through fastener 57 to box 51 and sealed with O-ring 58. Opaque partition 59 extends almost the length of tube 56 and divides the same into two lightproof chambers. A light beam coming through light guide 55 is directed around partition 59 and onto crystal 10. This incident light causes emitted light to leave the crystal. The emitted light can be modulated by solenoid 60 in a cryostat (not shown) at low temperatures. Emitted light strikes Crofon light guide 61 extending back up into box 51 where opaque partition 62 prevents light from guide 55 from interfering with that in guide 61. Guide 61 directs the emitted light through filters 63 and 64 into photomultiplier 40 and the light is recorded as above; and
FIG. 11 shows a film for determining the magnetization of a surface, the film consisting of usable crystals 70, e.g., of anthracene, embedded in an inert matrix 71, e.g., of photographic gelatin, on nonmagnetic support 72. Other suitably transparent nonmagnetic materials such as cellulose acetate, Mylar, etc., can be substituted for gelatin and, if strong enough, eliminate the need for support 72.
There follow some nonlimiting examples in which tests on various usable crystals are recorded. In low-temperature experiments, helium gas (exchange gas) in the vacuum box 51 was maintained at low pressure to facilitate cooling the crystal.
EXAMPLE 1 In the apparatus of FIG. 10, an anthracene crystal was placed in a l-meter long stainless steel tube in the core of a Varian superconducting solenoid. Light from a xenon lamp was filtered with two Corning glass color filters, C. S. 2-62, to remove wavelengths shorter than 5900 A. and passed to the crystal through a Crofon light guide. Luminescence from the crystal was led through a second Crofon light guide and one each of Coming glass filters, C. S. 5-56, 5-57, and 4-72, to a photomultiplier tube, the output of which was amplified and recorded by conventional means. The tube containing the crystal was positioned within the core of a solenoid in a cryostat. The crystal was cooled to 4.2 K. by helium exchange gas in thermal contact with liquid helium.
The intensity of luminescence from the crystal was measured continuously as the magnetic field strength was increased from 0 to 3000 De, results of the tests being shown in FIG. 1b. The intensity of luminescence increased as the field strength was increased from zero, reached a maximum increase of 4 percent at a field of 420 Oe, and decreased upon further increase of the field returning to the zero-field value at 726 Oe and decreasing to 85 percent of the zero-field value at 3000 0e.
EXAMPLE 2 In the apparatus of FIG. 9, an anthracene crystal contained at one end of a l-meter copper tube was illuminated through two Corning glass color filters, C. 8. 2-62, with focussed light from a 150-Watt Xenon lamp. The luminescence of the crystal was led into either a Crofon or aluminum foil light guide to a photomultiplier tube in the manner described in example 1. The crystal was at room temperature throughout the experiment. A magnetron permanent magnet was brought up to the crystal so that the magnetic field varied from zero to a maximum of about 2000 Oe. The dependence of luminescence intensity on field strength was qualitatively the same as that observed in Example 1.
EXAMPLE 3 An anthracene crystal with arrangements for illumination and detection of luminescence equivalent in all essentials to those of Example 2 was placed in an air-core solenoid. The
' same field strength in Examples 1 and 2.
EXAMPLE 4 The experiment of Example 3 was essentially repeated with a pyrene crystal replacing the anthracene crystal. The results were essentially the same as those found in Example 3.
EXAMPLE 5 A pure anthracene crystal (about 3 X 5 X 10 mm.) was exposed to a dose of 4000 rads of X-rays and quenching free radicals generated therein. Triplet excitons were created in the irradiated crystal by illumination with He-Ne gas laser (Spectra-Physics Model 125) and the resulting delayed fluorescence was observed with a photomultiplier. The exciting light was interrupted periodically by a mechanical chopper at a frequency of ca. cycles per second. The output from the photomultiplier was fed through a fixed bandpass tracking filter (Ad-Yu Electronics, Inc., Type 1034 Dual Channel Synchronous Filter driven by Type 1036 Synchronous Converter) and digital phase computer (Ad-Yu Electronics, Inc., Type 524A3) in order to measure the phase angle between the exciting light and the delayed fluorescence, said phase angle being a measure of the triplet exciton lifetime. The triplet lifetime in the irradiated crystal was measured to be 1.55 msec. compared to 22 msec. in the unirradiated crystal. A permanent horseshoe magnet was then brought up to the crystal, subjecting the same to a magnetic field of ca. 2000 Oe, and the triplet lifetime was found to be increased by ca. 8 percent over the zero-field value.
The irradiated crystal with arrangements for illumination and detection of luminescence equivalent in all essentials to those of Example 2 (FIG. 9) was placed in the magnetic field of an iron-core electromagnet, the field was varied from zero to 3500 0e, and the resulting change in delayed fluorescence intensity was measured for several directions of the field relative to the crystal axes with the results shown in FIG. 2a, b and c, which also shows the results of the same measurements made on an unirradiated, but otherwise identical, crystal.
EXAMPLE 6 In apparatus essentially that of FIG. 5 except that crystal 10 was replaced by a liquid sample, a solution of anthracene in ethanol (10 molar) was placed into the core of a l-inch long solenoid with 10 layers of No. 20 enamel-coated magnet wire wound on a :-inch-diameter fiber tube. Light from a xenon flash lamp was filtered with a Corning glass filter, C. S. 7-54 and focussed onto the sample by means of a lens. Luminescence from the sample was led through a Pyrex light guide, a camera shutter (Synchro Compur OMX) which shielded the photomultiplier during the flash, and one each of Coming glass filters, C. S. 4-72 and 5-58, to a photomultiplier tube (EMI 6255S/A), the output of which was amplified and differentiated with operational amplifiers (Tektronix Type O) and stored in the memory of a Computer of Average Transients (Varian CAT Model C-l024). The contents of the computer memory was recorded with an xy-recorder (e.g., Mosley Model 135A).
Following the release of the shutter, closure of the shutter contacts fired the flash lamp through a flash lamp triggering circuit. An auxiliary photodetector (RCA lP28 photomultiplier) upon detection of the flash triggered the solenoid pulser circuit which applied to a current pulse of 0.1 millisecond duration to the solenoid in which a peak field of up to 7000 e was developed. In response to the magnetic field pulse, a corresponding pulse was observed in the differentiated delayed fluorescence signal from the sample demonstrating the modulation of the delayed fluorescence by the magnetic field.
EXAMPLE 7 A pure anthracene crystal was exposed to a dose of ca. 1200 rads of X-rays. The apparatus used was essentially that of FIG. 9 except that the irradiated crystal was placed between the wheels of a phosphorescope rotating at ca. 22 cycles per second. Triplet excitons were created for a half period with an He-Ne gas laser (Spectra Physics Model 125) and the decay of the resulting phosphorescence was observed during the other half period, through a Crofon light guide and a pair of Coming glass filters, C. S. 2-64, with a red sensitive photomultiplier (EMI 95588, $20 response). The output of the photomultiplier was amplified with operational amplifiers (Tektronix Type O) and stored repeatedly in the memory of a Computer of Average Transients (Mnemotron CAT Model 400, Technical Measurements Corporation) operated by an external address advance of l X seconds per channel from a waveformpulse generator (Tektronix Type 162 and 163). The contents of CATs memory were read out with a printer (Technical Measurements Corporation, Printer Model 500), and normalized on a computer.
The triplet lifetime in the irradiated crystal was measured to be ca. 3.6 msec. to ca. 23 msec. in the unirradiated crystal. A permanent horseshoe magnet was then brought up to the crystal, subjecting it to a magnetic field of ca. 2000 Oe. With otherwise the same procedures as before, a slower decay of phosphorescent emission was obtained corresponding to an increase of ca. 6 percent of triplet lifetime over the zero field value.
EXAMPLE 8 A 9,10-diphenylanthracene crystal with arrangements for illumination and detection of luminescence equivalent in all essentials to those of Example 2 was placed in the magnetic field between the pole pieces of an electromagnet. The magnetic field strength could be varied continuously from 0 to 24 kilooersteds. The direction of the magnetic field could be changed by rotating the electromagnet. The crystal was at room temperature throughout the experiment.
The intensity of luminescence from the crystal was measured continuously as the magnetic field strength was increased from 0 to 24 kilo-oersteds. The intensity of luminescence increased as the field strength was increased from zero, reached a maximum of 113 percent of the zero-field value at a field of ca. 700 Oe, and decreased upon further increase of the field returning to the zero-field value at ca. 1700 Oe and decreasing to 80 percent of the zero-field value at ca. 4000 Oe. The intensity increased with further increase of the field to a maximum intensity of 84 percent of the zerofield value at ca. 5400 Oe and decreased upon further increase of the field to 74 percent of the zero-field value at ca. 7700 Oe. The intensity increased with further increase of the field to a maximum intensity of 80 percent of the zero-field value at ca. 1 1,000 Oe and decreased upon further increase of the field to 70 percent of the zero-field value at ca. 19,000 Oe. The intensity increased with further increase of the field to a maximum intensity of 74 percent of the zero-field value at ca. 22,200 0e and decreased upon further increase of the field.
The modulation of delayed fluorescence by constant or slowly var ing fields decreases in magnitude when the tri let concentra ion becomes so large that virtually all of the trip ets produced disappear by mutual annihilation rather than by monomolecular decay. The preferred operating range for triplet concentration in these processes is a concentration less than that given by the reciprocal of the product: (annihilation rate constant at zero magnetic field) X (triplet lifetime). The magnetic field effect still occurs above this exciton concentration, but with diminished magnitude. The preferred concentration range depends on parameters characteristic of the particular material being employed and will thus be difierent for different materials.
Since obvious modifications and equivalents in the invention will be evident to those skilled in the art, we propose to be bound solely by the appended claims.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for modulating the intensity of electromagnetic radiation which comprises:
a. generating triplets in a system in which triplets can be created, and in which said triplets subsequently decay with emission of electromagnetic radiation derived from delayed fluorescence or, in the presence of paramagnetic quenching, phosphorescence, and
b. changing a magnetic field strength on said system thereby causing a change in the intensity of the emitted electromagnetic radiation.
2. The process of claim 1 wherein the system is a crystalline solid.
3. The process of claim 2 wherein triplet excitons are generated in the crystalline solid by exciting electromagnetic radiation.
4. The process of claim 2 wherein triplet excitons are generated in the crystalline solid electrically.
5. The process of claim 2 wherein the crystalline solid is anthracene.
6. The process of claim 2 wherein the crystalline solid is pyrene.
7. The process of claim 1 wherein the system is a solution in an inert transparent solvent of a substance in which triplets can be created.
8. The process of claim 7 wherein the system is a solution in ethanol of anthracene.
9. In combination in a device for modulating the intensity of electromagnetic radiation:
a. a system in which triplets can be created with subsequent decay and the emission of electromagnetic radiation derived from delayed fluorescence or, in the presence of paramagnetic quenching, phosphorescence;
b. means for generating triplets in said system;
0. means for establishing a magnetic field in said system; and
d. means for varying the strength of the magnetic field and thereby varying the intensity of emitted electro-magnetic radiation.
10. The device of claim 9 wherein the system is a crystalline solid.
11. The device of claim 10 wherein the means for generating triplets is electromagnetic radiation.
12. The device of claim 10 wherein the means for generating triplets is electrical.
13. The device of claim 10 wherein the crystalline solid is anthracene.
14. The device of claim 10 wherein the crystalline solid is pyrene.
15. The device of claim 9 wherein the system is a solution in an inert transparent solvent of a substance in which triplets can be created.
16. The device of claim 15 wherein the system is a solution in ethanol of anthracene.
|Cited Patent
|Filing date
|Publication date
|Sep 26, 1962
|Oct 26, 1965
|Trw Inc
|Process for incorporating phosphorescent triplet state organic compounds in plastic media
|Sep 26, 1962
|Oct 26, 1965
|Trw Inc
|Process for incorporating phosphorescent triplet state organic compounds in plastic media
|Citing Patent
|Filing date
|Publication date
|May 3, 1972
|Oct 22, 1974
|Du Pont
|Method and apparatus for modulating light with a magnetic field
|Aug 1, 1973
|Nov 26, 1974
|Du Pont
|Modulation by a magnetic field of electromagnetic radiation produced by the decay of triplet states
|Nov 17, 1978
|May 26, 1981
|Siemens Aktiengesellschaft
|Process and apparatus for displaying an image in front of an optical contrasting background
|Jan 26, 2002
|Apr 18, 2006
|Sicpa Holding S.A.
|Luminescence characteristics detector
|Nov 21, 2006
|Mar 20, 2012
|Giesecke & Devrient Gmbh
|Apparatus for checking the authenticity of banknotes
|Jan 26, 2002
|Apr 1, 2004
|Milan Vasic
|Luminescence characteristics detector
|Nov 21, 2006
|Jan 29, 2009
|Thomas Giering
|Apparatus for Checking the Authenticity of Banknotes
|Aug 6, 2012
|Nov 14, 2013
|University Of Calcutta
|Static magnetic field induced differential fluorescence emission
|Feb 21, 2015
|Aug 25, 2016
|Audi Ag
|Beleuchtungsvorrichtung mit einem Konversionselement f�r ein Kraftfahrzeug und Verfahren zum Betreiben einer solchen
|Mar 1, 2001
|Sep 4, 2002
|Sicpa Holding S.A.
|Improved luminescence characteristics detector
|Nov 21, 2006
|May 31, 2007
|Giesecke & Devrient Gmbh
|Apparatus for checking the authenticity of banknotes
|U.S. Classification
|359/284, 359/296
|International Classification
|Cooperative Classification
|European Classification


text:
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Either way, enjoy.
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