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Category: Free Android Apps >> Free Android Applications
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By Razor Jack On 14th October, 2019 Android Mobile Zone CONTRIBUTOR
Features of Truecaller: Caller ID, SMS spam blocking & Dialer Pro APK 10.52.7 - Android App
What's New in Truecaller: Caller ID, SMS spam blocking & Dialer Pro APK 10.52.7 - Android App
Play Store Link
Truecaller Caller Id Phone Directory Phone Call Calling App Phone Directory
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Weather Live v6.25 b187 (Premium) - Android App
Adguard Premium APK MOD Block Ads Without Root 3.3.50
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One of the sites I daily check for updates specially for latest ringtones. As per my opinion Android Mobile Zone is the first place where most of the latest ringtones are uploaded. Free to download option available and almost all contents are free to access, It's becoming more and more popular in 2014. Android Mobile Zone is daily updated website and I highly recommend to everyone.
Jaimin Dave | Co-Founder of CodeRiddles
Designed by Razor.


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There are various search engines for bots, such as Chatbottle, Botlist and Thereisabotforthat, for example, helping developers to inform users about the launch of new talkbots. These sites also provide a ranking of bots by various parameters: the number of votes, user statistics, platforms, categories (travel, productivity, social interaction, e-commerce, entertainment, news, etc.). They feature more than three and a half thousand bots for Facebook Messenger, Slack, Skype and Kik.
A chatbot works in a couple of ways: set guidelines and machine learning. A chatbot that functions with a set of guidelines in place is limited in its conversation. It can only respond to a set number of requests and vocabulary, and is only as intelligent as its programming code. An example of a limited bot is an automated banking bot that asks the caller some questions to understand what the caller wants done. The bot would make a command like "Please tell me what I can do for you by saying account balances, account transfer, or bill payment." If the customer responds with "credit card balance," the bot would not understand the request and would proceed to either repeat the command or transfer the caller to a human assistant.
Artificial neural networks, invented in the 1940's, are a way of calculating an output from an input (a classification) using weighted connections ("synapses") that are calculated from repeated iterations through training data. Each pass through the training data alters the weights such that the neural network produces the output with greater "accuracy" (lower error rate).
Dan uses an example of a text to speech bot that a user might operate within a car to turn windscreen wipers on and off, and lights on and off. The users' natural language query is processed by the conversation service to work out the intent and the entity, and then using the context, replies through the dialog in a way that the user can understand.
The most advanced bots are powered by artificial intelligence, helping it to understand complex requests, personalize responses, and improve interactions over time. This technology is still in its infancy, so most bots follow a set of rules programmed by a human via a bot-building platform. It's as simple as ordering a list of if-then statements and writing canned responses, often without needing to know a line of code.
The promise of artificial intelligence (AI) has permeated across the enterprise giving hopes of amping up automation, enriching insights, streamlining processes, augmenting workers, and in many ways making our lives as consumers, employees, and customers a whole lot better. Senior management salivates over the exponential gains AI is supposed to deliver to their business. Kumbayah […]
How can our business leverage technology to better and more often engage younger audiences with our products and services? H&M is one of several retailers experimenting with and leveraging chatbots as a mobile marketing opportunity – according to a report by Accenture, 32 percent of the world (a large portion of the population 29 years old and younger) uses social media daily and 80 percent of that time is via mobile.
The fact that you can now run ads directly to Messenger is an enormous opportunity for any business. This skips the convoluted and leaky process of trying to acquire someone's email address to nurture them outside of Facebook's platform. Instead, you can retain the connection with someone inside Facebook and improve the overall conversion rates to receiving an engagement.
"They're doing things we're simply not doing in the U.S. Imagine if you were going to start a city from scratch. Rather than having to deal with all the infrastructure created 200 years ago, you could hit the ground running on the latest technology. That's what China's doing — they're accessing markets for the first time through mobile apps and payments." — Brian Buchwald, CEO of consumer intelligence firm Bomoda
A chatbot that functions through machine learning has an artificial neural network inspired by the neural nodes of the human brain. The bot is programmed to self-learn as it is introduced to new dialogues and words. In effect, as a chatbot receives new voice or textual dialogues, the number of inquiries that it can reply and the accuracy of each response it gives increases. Facebook has a machine learning chatbot that creates a platform for companies to interact with their consumers through the Facebook Messenger application. Using the Messenger bot, users can buy shoes from Spring, order a ride from Uber, and have election conversations with the New York Times which used the Messenger bot to cover the 2016 presidential election between Hilary Clinton and Donald Trump. If a user asked the New York Times through his/her app a question like "What's new today?" or "What do the polls say?" the bot would reply to the request.
Like apps and websites, bots have a UI, but it is made up of dialogs, rather than screens. Dialogs help preserve your place within a conversation, prompt users when needed, and execute input validation. They are useful for managing multi-turn conversations and simple "forms-based" collections of information to accomplish activities such as booking a flight.
When one dialog invokes another, the Bot Builder adds the new dialog to the top of the dialog stack. The dialog that is on top of the stack is in control of the conversation. Every new message sent by the user will be subject to processing by that dialog until it either closes or redirects to another dialog. When a dialog closes, it's removed from the stack, and the previous dialog in the stack assumes control of the conversation.
One pertinent field of AI research is natural language processing. Usually, weak AI fields employ specialized software or programming languages created specifically for the narrow function required. For example, A.L.I.C.E. uses a markup language called AIML, which is specific to its function as a conversational agent, and has since been adopted by various other developers of, so called, Alicebots. Nevertheless, A.L.I.C.E. is still purely based on pattern matching techniques without any reasoning capabilities, the same technique ELIZA was using back in 1966. This is not strong AI, which would require sapience and logical reasoning abilities.

subset: commoncrawl


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Solar Plexus Chakra Collection
Is it time to open your Solar Plexus Chakra? Work through your emotional blockages with powerful crystal healing stones and welcome confidence and stability into your life. Learn more about your Solar Plexus Chakra and how you can use healing crystals to balance this energy center. Shop below for crystals and jewelry curated specifically for opening the Solar Plexus Chakra.
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This beautiful crystal necklace contains unique Mookaite Jasper stone pendant on a black leather cord. The pendant is a rich camel yellow tone, a...View full details$50.00Sold out
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The Phoenix designed by Oiva Toikka for Jalo is the world's first extinguisher designed specifically for the kitchen. It's sleek design means that it will look good on display in your kitchen and can be kept within easy reach in case of an emergency. The Phoenix Extinguisher utilizes the latest extinguishing technology and has been especially designed for extinguishing cooking oil fires, as well as other small household fires and even electronic appliances up to 1000 V. The extinguishant used in the Phoenix is biodegradable and is easy to clean off using water and ordinary household detergents. Please note that the Phoenix Fire Extinguisher is not refillable and it is strongly recommended that the product is disposed of after usage, even if it is not empty.
Phoenix Fire Extinguisher
Coming soon...Store price $114.36
We're working on getting a deal.
The more people who want it, the greater the chance to get it!
I want it!2 yrs ago
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Eichholtz Marathon Dining Table
Made from stainless steel this Eichholtz Marathon Dining table will dominate the space its in with its chunky legs and think glass top.
From the interior specialists Eichholtz. Eichholtz are the leading company in interior styling offering a wide selection of furniture, mirrors, ornaments, sculptures, lighting and much much more. If you see the Eichholtz name you can be assured the item is stylish and of the up most quality.
W 220 D 90 H 78 cm


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May God bless you and your...
Greatest guy ever!
I was lucky to be able to work with Matt and Carly to find their home. It was a fun journey.
Condolences to the family.
Sherry Schaffer
November 14, 2019 | Arlington, VA
Fairfax, Virginia
Sep 15, 1970 – Nov 4, 2019 (Age 49)
Matthew Joseph TroutSeptember 15, 1970 - November 4, 2019An adored father, husband, son, brother, uncle, and friend, Matthew Joseph Trout (age 49) was taken from us suddenly on Monday, November 4, 2019 at Inova Fairfax Hospital after emergency heart surgery. He was a light in this world and will...Read More
Not sure what to say?
Greatest guy ever!
I was lucky to be able to work with Matt and Carly to find their home. It was a fun journey.
Condolences to the family.
Sherry Schaffer
November 14, 2019 | Arlington, VA
I was lucky enough to go to middle and high school with Matt. We shared a love for baseball and baseball card collecting. Despite being a tough negotiator, he never had a cross word, was always positive, and fun to be around. Best wishes to the Trout family.
Todd Smith
November 09, 2019 | Jacksonville Beach, FL
Dear ChiChi and family
So sorry to hear of the loss of your son, so young, so loved, so special. I lost my son 3 years ago
He,too, was 49. I truly feel your
Pain! Treasure your memories
Patricia Schofield
November 09, 2019 | Lewes, DE | Friend
Our condolences are with the Trout Family. You are in our prayers.
Joe & Vickie Renda
November 09, 2019 | York, PA
Gretchen, Jason the Trout family and friends, I am sorry to see the passing of your loved one. I know the sadness you feel. We always hold hope as our lives move forward we will try to live productive, proper, and meaningful lives. In his short time in this world he has done all that and more. My deepest sympathy.
Wayne Trout
November 08, 2019 | Red Lion, PA
Matt was a friend of our late son, Steve, on their Little League team, the Tigers. I remember the two of them had fun together, and Matt was given the nickname - "Squirmy Bean". Warm thoughts and prayers are offered to Chi Chi and the other members of the Trout family. Bill and Ev Luckenbaugh
November 08, 2019
Matt played with my son, Steve, on their Little League team - the Tigers - which I coached. I believe he was the shortest fella on the team, and Steve gave Matt the nickname - "Squirmy Bean". That was about 40 years ago, but still a good memory of a fine fella. We lost Steve in 1996, so heaven has reunited the two childhood buddies.
November 08, 2019
So sorry to hear about the passing of Matt. He will be missed by all that new him. You couldn't ask for a better brother, friend, father and husband. Will always remember the Oriole games we went to with his dad and brother George. Our thoughts and prayers go out to his family and especially to Chi Chi.
Joshua and Cheryl Morrison
November 07, 2019 | Fort Myers, FL | Friend


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Thus, the main new idea arising from catastrophe theory as discussed so far is that it is worthwhile being alert to the possibility of unusual types of system behaviour, and that the techniques of the theory can be used to formulate models to handle such behaviour. In the next section, we begin a preliminary treatment of some examples and follow this with a slightly more formal treatment of the basic concepts. 1.2 A preliminary outline of some examples 1.2.1 A remark on scale
As usual in urban and regional modelling, it is important to distinguish the different scales at which models are to be developed. The usual distinction of micro-, meso-and macroscales is useful here as elsewhere. At the micro scale, we are concerned with individual behaviour of some kind, and decisions, possibly under constraints (and with the resulting behaviour being in some cases determined more by the constraints than any notion of choice). At the meso scale, we deal with urban and regional spatial structure, and this is the scale which is at the heart of geographical analysis (even though it has to be intimately connected to other scales). At the macro scale, the city or region is characterised by a small number of aggregate variables.


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BREAKING: Reports of active shooter, Joint Base Pearl Harbor-Hickam on lockdown
Wednesday, December 4th 2019, 9:40 PM EST by
UPDATE: KITV says the suspect in the shooting has been confirmed dead, according to sources two people have reportedly died. The lockdown was lifted, and the U.S. Navy is taking the lead on the investigation. KITV says according to a source, the shooter was an active military on-duty guard. The two other victims who died were civilians.
HONOLULU, HI (WENY) - WENY sister station, KITV says the entire Joint Base Pearl Harbor-Hickam is currently on lockdown, according to a Navy military service member.
According to KITV, reports of an active shooter near Dry Dock 2 came in after 2:30 p.m. after shots were reportedly fired. KITV says military police are on the scene responding.


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1.2 / September 26, 2016
App Information Shark Simulator 3D
- App NameShark Simulator 3D
- Package Namecom.appswallet.sharksimulator3D
- UpdatedSeptember 26, 2016
- File Size31M
- Requires AndroidAndroid 2.3 and up
- Version1.2
- DeveloperViolet Apps
- Installs500,000+
- PriceFree
- CategorySimulation
- Developer
- Google Play Link
Shark Simulator 3D Version HistorySelect Shark Simulator 3D Version :
Shark Simulator 3D 1.2 APK FilePublish Date: 2017 /1/31Requires Android: Android 2.3+ (Gingerbread, API: 9)File Size: 31.4 MBTested on: Android 7.0 (Nougat, API: 24)File Sha1: 4ad920d5d02ffa27e998fa2edddd711d5123d9a8
Violet Apps Show More...
Goat Simulator 2016 3D 1.5 APK
Goat Simulator 2016 3D.Now welcome you in Simulation world andbringing you in next-gen simulation technology.This Simulation Gameis just for fun and enjoyment. It is the hottest simulation game ofGoat with fun and adventure. You (player) act as a goat and targetdifferent objects, hit them smash and destroy objects.GoatSimulator 2016 3D makes your dreams come true act as a RealGoat...!The crazy and fancy goat is here, take a big breath andenter deep into smashing world of Goat.Play the toughest goat,climb, crash and hit all to have more fun, this crazy goat makesyou laugh...!Reach the targets, complete the targets and share withyour friends.Download to crash everything which comes on your wayand cause destruction in the city and different targets toachieve.Best of Luck...!Key Features - Simple and efficient controlsystem - Game physics of Goat - Being a silly goat face challenges- Funny goat simulator with realistic animations - Excellent 3Dstuffs and graphics - Level system, clear each level and unlocknext one - Yes! Goat Simulator is 100% free - Compatible with alldevices - Fun game as well as addictive and love-able...Game Play:- Game Contains 2 Environments ( Factory Area, Sea) - EachEnvironment has 2 Play modes ( Career Mode, Free Mode) - CareerMode in Each Environment has 5 Levels to clear in specified time -Free mode has no time limit, no level system, feel free and relaxduring game play - Radar help you to identify the targets in eachlevel - Different Objects target them, hit and smash - We will showyou remaining time, total target and hit targets, Score updateHowto Play: - Contains simple Control system - Tap Left side Gestureto control the Goat - Tap left side button above the controlgesture is for Pause GameImportant - City and Village Environmentwill be included in next version ... - Criticism is easy...! Soplease give suggestions for improvement of Game Play and notify anybug or game crash. - Any problem in installation process, Pleasereport to us. We will try to fix it ASAP. Thank You...!
Shark Simulator 3D 1.2 APK
When you are enjoying, relaxing and pleasuring of boating in thesea, suddenly, you never imagine a monster shark attack you andother. Do you survive from deadly, wild shark attack?Can youconceive a shark wanderings in the sea? This sea is encircled bysharks. Watch out and keep yourself alive...!Like the real shark inthe sea, take advantage of your hunter skills and fulfill the needsof the hungry shark. Play single player adventure shark game.Playwith the deadly Shark Simulator 3D, as the great white shark roamin the sea and always be on the lookout for food.Feel like a crazyshark, get on a shark run with wild shark simulation movements withyour smasher shark and you as a frightening hunter you are,unleashyour shark attack on the prey in the sea. Help the crazy, scaryshark make its way up the shark revenge challenges by target andkill multiple humans in this shark game.Control an angry, hungryand deadly shark through the sea and search for food. This hungryshark simulator contains realistic animated water combined with aextra ordinary terrain of mysterious deep-sea area which gives yourrambling with the angry, hungry shark an amazing and realisticfeeling.Key Features:- Amazing deadly shark revenge attack levels.-Real sharks features like shark bite and kill human.- Easy crazyshark simulator controls to move in the water.- Crisp sharkanimations and revenge game play.- Awesome 3D graphics withrealistic water view that include the open sea.- Sea attack withsurvival game. - Open world aquatic game.- Shark Simulator with atwist.- Highly detailed Interactive 3D sea environment of deadlysharks.How to Play: - Tap Left side Gesture to control the Shark -Tap right side corner button to Pause Game - Tap Camera button fordifferent viewsImportant : Any problem in installation processnotify any bug or game crash. Give your feed back and we fix it assoon as possible. Thank You...!
Watermelon Run 3D 1.0 APK
Are you ready for this superb adventure fun of watermelon run3D.Run, Jump and dash over and around tyrant Cleavers ( Obstacles )in this crazy new running game."I am a small but not my dreams" -Water Melon.Download it and join the battle with Watermelon to get"Freedom of Life" from tyrant Cleavers, in this uniquely tunedRunning game.You don't need to run aimlessly till the end of time.It does has an End.Stay tuned for this. Know what will be theWatermelon Run 3D.If you like racing, stunts, sprint, doodle,adventure and action games then you will definitely love WatermelonRun 3D.Watermelon Run 3D is the best 3D fruit running game...!Ifyou love running games then you will love this cool FREE Watermelonrunning game.
Front Commando Terror Target 1.0 APK
A commando warrior game to attack to target commandos andultimately loose theirhope to win their mission. Be careful toavoid from them as they can be harmful to your people and candestroy to your city buildings. Commandos come into differentstrategies as they sometime arrive their gunship helicopter andsometime by the jeep. They can any time attack on you and they haveheavy machine guns with AK-47gun.***How To Play***- Touch on thescreen anywhere to move your character in the game.- Joystick areavailable to move your character backward and forward.- A multitouch game to play and enjoy.**Game Features**- Awesome environmentwith HD graphics.- Amazing voice and music system.- Gunshiphelicopter to attack on you which the enemies soldiers have.- VIPlive menu with attractive graphics.- Sniper ready to attack you.-Different level selection and in every level senerio changes ofgame.- Realistic control of multiple guns.- Guns switching likeAK-47, Rocket launcher, Pistol.- Choose your weapon to kill thesoldiers.This game is available on the google play store and youcan download it easily from there.Best of luck...!
Car Parking 3D 2016 1.2 APK
Violet Apps presents New Season of Car Parking for 2016. Where youget to park car and tried to not hit different obstacle.Play thisfabulous game and check your car parking expertise. The parkingstand is on...! Make your way through stages, by parking car asvarious targets.For who seeks a parking game in high quality, ourprofessional have tested and analysed the games and put the bestones to this app.Car Parking 3D 2016 is an amazing car parkingsimulator games that require high precision. To put your vehicle inthe car park to the parking area of steering, acceleration and topneed to show your skills in the escape of the obstacles.An idealgame for those looking for real car parking game. It is a game withthe best in control and car physics driving games.****Gamefeatures***** Realistic vehicle controls,* Back to improve yourability to restore the park.* Steering Increases your mastery.*When you hit the obstacle car starts again.* Realistic car parkingexperience.* Excellent high quality graphics.* Enjoy driving withdifferent camera angles.* Real-car driving physics.* HD-qualitygames to enjoy.**How To play*** Accelerator is available to moveforward.* Paddle for backward.* Brake paddle for car stop.This gameis available on the google play store. Don't forget to download itfrom there.
Crocodile Simulator 2016 1.1 APK
Have you ever wondered what it is like tobeWild Crocodile? Now you finally have a chance to knowthatfeeling…!Crocodile Simulator 2016 game is full of anger and blaze oftheangry swamp crocodile. Use your animal instinct and attackpeopleswith vicious power and rage. Take control of most wildpredatorsreptile swamp monster, all animals in forest are scaredfrom thebloodthirsty hungry eyes, sharp teeth, deadly roar of thewildlifesimulator alligator rampage. Download this crocodilesimulator 2016and attack on peoples. Be a part of epic battlebetween survival ofthe fittest in animal simulators. Surviveagainst wildlife reptilesin this ultimate crocodilesimulator.Swim and Crawl…! Hunt and Attack…! Play as a huge crocodilepredatorand learn the fun of devouring your prey. With an appetiteas big asthe size of this water beast, you can hunt and eatanything. See theworld as an angry monster that will attackanything it sets itsbulging eyes on. Control this giant in waterand on land.This seemingly easy task is compromised by hunters ready to shootonsight. Attack the people on boats and on the beaches withyourmassive jaws to create some havoc before they escape.An angry giant renegade crocodile swim through swamp darkwaterfound its way out of woodland and entering in populated cityarea.People are screaming and running to save their lives frommightjaws of this predator deadliest hunters. Play as hungryalligatorcrawling to farm house and attack everyone comes on yourway.Attack people in the farmhouse or anywhere you get in this mapofanimal simulators. Crocodile attack, hunting and killthepeoples.You had played goat, snake, lion, horse, humpback whales,wolfsimulator now try your hands on controlling angrywildlifecrocodile simulator 3d. Swim in the swamp or crawl throughdarkwater or lush greenery environment with peoples. Crocodilearedeadliest hunters they eats people hunts down them inthisrealistic simulator.Brand new fun crocodile simulator 2016 game for entire familyallage youngster boys, girls and teens even mature people canenjoythis animal swamp crocodile realistic simulator withunlimitedfun.
Dolphin Rescue Simulator 3D 1.2 APK
Swim into the sea to your hearts content as a Dolphin RescueSimulator 3D...! Explore a vast sea world and rescue the humans andpets.Start your own family, and battle for your life against as areal rescuer of human and pets...!Download the Dolphin RescueSimulator 3D today while it's full of excitement of rescue ofhumans and pets...!HD GRAPHICS - Stunning High Definition graphicswill transport you to a remote aquatic ecosystem and surround youwith the sea beauty...!New Graphics Quality options allow you tocustomize the game to look amazing and perform great on anydevice...!HUGE 3D ENVIRONMENT - Your dolphins are free to roam amassive open-world environment that is more the double the size ofthe previous simulators...!Explore the humans, pets, and rescue ofthem by making planning...!NEW TOUCH-BASED CONTROLS - Brand newintuitive controls let you navigate your animal like neverbefore...! Pinch to zoom and play from yourdolphin's perspective orget a bird's eye view of the rescue action...!BECOME A DOLPHIN -Act like a dolphin by jumping out of the water and swipe the screento perform real rescuer like the Back flip and Reverse 360...!Useyour echolocation to hunt down fish and underwater predators!Useyour sonar and complete the quests, be alive one more day in thedolphins sea world...!Different quests, follow your dolphin rescueand go after humans and pets.If you liked living as a real Dolphinthen you'll love our other animal simulators...!Download theDolphin Rescue Simulator 3D to experience the exciting rescue lifeof the world's most intelligent and playful animal, the DolphinRescue Simulator 3D...!
Flying Heli Dog Simulator 1.2 APK
Violet Apps presenting the new Flying trend in simulationworld.Flying Heli Dog Simulator is a very challenging game with alot of fun and enjoyment in flying simulation.Also taking flight isexciting fun in the big city. Start with your helicopter dog flighttoday and as being the best pilot never in the city...!U have toeat your objects who are surrounded every where in the city beforeit's getting too late....!The ability to explore high in the skyabove the gorgeous representation of a real life big city make thisgame real fun to play.It's just you and your Flying Heli DogSimulator as you face the ultimate test of wit, cunning,and speedin this unique adventure puzzler simulation game. No scenes arealike, so be prepared for anything as you race to collect theobjects.***** FEATURES ****** Stunning 3D graphics of cityenvironment.* Highly realistic simulator surroundings.* Challenginglevels with integrated hint system. * Play with friends see who cancollect as many objects.* Steer your Helicopter Dog to safety.
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Shark Attack 3D Simulator 1.1 APK
Just when you thought it was safe to enter the water, from thedarkness rises a giant renegade Great White Shark. You control thisbeast as he terrorizes the waters, attack boats, eats people, huntsdown some humpback whales. If you enjoy playing free play simulatortype games, you will enjoy taking control of this huge 3Dshark.Features Include:--4 Giants Maps --Shark hunting day andnight--Open water Map with boats and whales--Beach Map with partypeople--Excellent sound effects--High Quality 3D graphics andexciting gameplay.Try to complete the objectives before time runsout. This shark especially enjoys the taste of humans. Go fishingfor people and whales and come back with a full stomach. If youenjoy games like Goat Simulator, Bear Simulator, Dinosaur Sim andHorse Simulator - you are going to love this 3D Shark Simulatorgame. It is created with high quality graphics and smooth controls.It all takes place in a fun 3D environment. The must have game ofthe summer vacation season. Happy hunting!
com.integer.SharkAttactSimulator3D APK
Shark attack the crazy shark simulator game is here. Become thekiller shark of the seas and munch on scared humans. Sharks haveevolved themselves so that they can tear apart their victim whenthey are hungry or angry. The beach is full of innocent people sothat the shark can eat them. Attack them when they are unaware sothat you guarantee a kill. The game is designed to give you thereal experience. Shark Attack Features: -Choose from variousaquatic themes -Realistic water effects Bloody Gore Animations-Exciting Oceanic Levels simulation -Optimized for Tablet -Classic attack strategy -Easy to use
Hungry Blue Whale Shark Attack: Shark Attack Games 1.0 APK
Survival against creature like shark take a lot of work for thesmall fish. Hungry and blood sucking sharks are hard to competewhen they attack with the fullest force. Explore through the bigocean and survive as the biggest bloody shark around. Sea worldhave rampages against small creatures. Shark attack hungry worldend in eating fleshy underwater fishes. Chase the prey through thesea underwater. Attack on the delicious food to have your share.White skin meat of fish sounds good to the sharks. Hammerhead sharkis among other kinds of the sharks in the game. Aquatic adventureof fish meat hunting underwater with crazy jawsome sharks. Darknessunderwater helps disguise and catch the prey unknown to the attack.No safe water for hunting these days, sharks attack near thebeaches killing people have riled them up. Shark hunter near beachlooking to kill some sharks. 3D effects and animation of huntingmakes all adventures more thrilling and blood rushing adrenalinepatches. Tourist swimmers consider entering it safe water aroundbeach area. Do not kill them. Shark attack beast sea animal isgiant and out of control. Biggest sea monster of beast underwatertaking lives is hard to capture. Under sea water waves sharksfloats silently and look for the boats to attack. 3D gameplay offishing objectives extraordinary in the graphics quality. Unlikeponds this ocean is dangerous full of dark. Commandos flying onhelicopters are on shoot all sharks order. Angry sharks are underthe monitoring of the precise sniper so they don't attack people.Sniper skills can kill all sharks including the hammerhead sharks.Best 3D animal under water is tiger shark with forceful attack onthe small fish and swimming tourists on the beach. Crazy whalesalongside the sharks throughout the big ocean are the worst rivalryand danger to the shark's kind. Shark Attack Hungry Worldfeatures:• Addictive shark attack on sea creatures underwater•Smooth 3D gameplay • Different levels of multiple hunting tasks. •Various aquatic themes to choose from• Play it on both smartphonesand tablets. • Make a strategy of pattern to catch the maximumInnocent people on the beaches, sharks attack is ready to take themas their delicious food. Victims makes the sharks hungry so theyattack people. Guarantee to be killed, beach has been locked.Underwater shark hunter killing machines are deployed byprofessionals. Shark attacks on mermaids is worst nightmare forthem. Take jetpacks and lasers to see better underwater. Shores andbeaches are full of survival attacks by the sharks. No proper foodunderwater brought Hungary attacking sharks up to the service.Submarines and whales frighten sharks, then they attack viciously.Shark swag boat smashing is crazy bosses move. Feast in a worldfull of meal deals. Ferocious sharks hungry attacks and mightybeast ready to eat fish. Sharks ruthless attacks are full of actionthrill and challenges. Raw attack moves while the sharks sailthrough salty sea waters. Keep killing and never stop chompingfresh fish meat. Warm waters full of swimmers on holidays. Underseapredator's lethal attacks on harmless people.
Angry White Shark Revenge 3D🐳 1.0.4 APK
Be the angry beast of the sea, an angry sea white shark or robotshark which is always on the lookout to attack a new prey tosatisfy its hunger as a hungry shark. Play as the white shark andexplore the depths of the sea as well as approach the shore to huntnew prey. In Angry White Shark Revenge 3D the mighty beast greatwhite shark or robot shark is out to seek some revenge, it willhunt, attack and eat any prey with its killer jaws. As the greatwhite shark or robot shark you will wait like a fish predator forunaware people enjoying in the sea, hunt them down and unleash yourdeadly jaw to devour your prey. But beware as there are somehunters as well all ready to a catch an angry shark. So with AngryWhite Shark Revenge 3D its time to feel like a crazy shark, angrysea white shark that breaks into a shark run when feel hunted orbetter yet show the shooter who the king of the sea is!This AngryWhite Shark Revenge 3D game gives you a chance to play as thevicious and deadly white shark and wreak havoc, get on a searampage, roam in the deep sea and always be on hunt like thepredator fish, hungry shark that you are. Help the crazy shark makeits way up the challenges of the shark simulator revenge game bykilling multiple humans. So download Angry White Shark Revenge 3Dand play as the angry shark nearing the shores, infuriated, wildand on a wild frenzy to unleash shark attack on any prey in reach.Key Features: • Realistic angry shark level• Try the all new killerjaws and shark bite features• Epic real 3D environment• Smooth andEasy Controls• Deadly shark animations• Works without internet.
Angry Shark 2016 1.6 APK
Control an Angry Great White Shark in this Action Packed OceanAdventure.Plays as a brutal shark and hunt to survive. Eateverything in your way and keep the killing spree going. Play thisbest in class 3D Shark Sim and become a ferocious hungry SHARK tokill ruthlessly and endlessly. Your mighty beast is ready to eatfish, humans and anything else in its path. Dive down to the depthsof the ocean and fight with other Sharks and Killer Whales, eatsome sweet dolphin and rare scuba divers to quench your hunger.Jump to the surface and scare the daylights out of innocentsunbathers, jet skiers, boaters and swimmers in these warm waters.Beware of the shooters, however, as they shoot on sight.The sharkis on a rampage! It will attack and destroy whatever gets in it'sway. Play as a furious shark and show no mercy. Chase your pray,attack and grab in your might Jaws to kill instantly. You canchange the skin of your shark to reflect your mood. Smooth and easycontrols allow you to control your beast effortlessly and killeasily. Keep killing and never stop chomping. Angry Shark 2016Features Includes:• Awesome 3d Sea and beach environment• Animatedferocious Great White Shark• Animated Aquatic animals includingShark, Orca, Whale, Dolphin, Jellyfish and more.• Exciting killingmissions• Magical underwater environment and effects• Smooth gameplay and easy controls• Awesome Visuals and sound Effects• Lots ofpeople to kill including Scuba Divers, Swimmers, Beach Goers,Fishermen, etc.**INSTALL NOW & START ATTACKING**AboutTapinator:Tapinator (Ticker: TAPM) develops and publishes games onmobile platforms. The Company's portfolio includes over 300 mobilegaming titles that, collectively, have achieved over 450 millionplayer downloads. Tapinator is headquartered in New York. For moreinfo, visit Tapinator.com
com.integer.sharksharkrun APK
Experience Shark Shark Run, the horrifying simulation of a deadlykiller shark who is on a rampage to gobble up all the holiday goerson the beach. They are known as one of the most dangerous wildanimals in the sea waters. So get ready to become the crazy maneater to devour all the people on the shores. This shark simulatoroffers us some great tactics to attack the tourists that come forholidays. But beware there are some hunters also who like teeth ofsharks so don't go near them. Like playing shark games, this one isfor you. Features : 3D Shark Models. Realistic environment. EasyControls Upgrade your shark. Newest shark simulator game. If youhave any problem in installation, please report to us firstname.lastname@example.com. we will try to fix it as soon aspossible.
Angry Blue Shark 2016 1.3 APK
Feel the rage of Angry Blue Shark Attack to take revenge as BlueHungry Shark from underwater species predator.Here's exciting newgame for ocean and water lovers.Swim as furious shark wreck theships with this monster fish species.Terrorize the ocean world withyour mighty jaws, sharp teeth and rage attack.This angry blue sharkis on rampage! It will attack and destroy whatever gets in way.Playthe Best of its type 3D Blue Hungry Shark Simulator and become aferocious hungry SHARK to kill ruthlessly and endlessly.Show nomercy, Chase your pray, attack and grab it in the might Jaws tokill instantly.This mighty beast is out to eat bulk of sea animals, fishes and lots of human.Become a Brutal Shark and hunt toSurvive.Experience of sea life at its finest.The new angry blueshark game has new shark attacking features.For the first time,youget to be on the evil side in this hungry shark game simulator,become a vicious blood thirsty and giant blue angry SHARKATTACK.You have to Pay more attention because this Shark attack 3dsimulator is not like other ordinary Angry Sea White Shark games.Show your fighting simulator skills in this angry blue sharkevolution game. Enjoy diving and swimming like realistic fish inwater as Angry Blue Shark Revenge sim.Hunt around the world ofKiller Whale, eat some dolphin and lonely scuba divers to clenchyour hunger.Angry Blue Shark Revenge offers you 10 underwatermissions for brutal hunting like great tiger shark.Scare small fishand make them your tasty meal.Try to complete the objectives beforetime runs out. This shark especially enjoys the taste of humans. Gofishing for people and boats and come back with a fullstomach.Complete all exciting missions and earn points in thisshark world!Clear levels by completing the objectives. Your missionmight be to destroy the ship or to kill the fishermen!May be BlueAngry shark is a hungry Shark too!!Play the most action packed gameAngry Shark simulator 3D. Intruders in the sea trying to attackShark home. Attack and defeat them by playing as an Angry Sharkattack.Angry Blue Shark 2016 features :- Breath taking actionpacked hunter missions- Free mode to swim, attack and diving likereal life shark in sea- Destroy boat, eat humans, small fishesfight with killer orca whale.- Realistic fish animation and physicsfor smooth gameplay- Intuitive controls with amazing backgroundmusic- Open water Map with boats and fishes- Beach Map with partypeople for Shark attack 3d simulator- HD underwater sea life withfish, species, whale, treasure and plantsYou may have played otheranimal attack 3d simulator games but this time its huge Hungry BlueAngry Shark.Take down predators before you become the prey.Humanhunters are boating over surface to kill this sea monster withmodern weapons make them scare with your jump attack without anymercy.Big sea animals, aquatic animals including Shark, Orca ,BlueWhale, Dolphin, octopus and Jellyfish.Play as crazy evil carnivorein Hungry Blue Shark Revenge 3D amazing simulation game in yourandroid phone and tablets.
Shark Attack 2019 : Shark Games APK
LIFE-LIKE SHARK BEHAVIOR! - True bite simulation with massive jaws.- Only shark games with advanced AI function. - Spear fishingmechanism with rope system. THE MOST EPIC, SHARK HUNTING! Play thenew Shark Attack 2018 - It's an angry shark simulator and get toexperience the underwater wildlife at its finest. See what it feelslike to hunt a vicious blood thirsty SHARK. Sharks have evolvedthemselves so that they can tear apart their victim when they arehungry or angry. Play the role of a diver in this shark huntinggames! Aim with your speargun, before pulling the trigger andshooting these sea predators! VARIOUS SPECIES OF SHARKS! Thishunting games lets you shoot an ocean full of variety - includingthe great white, hammerhead, and many more! This fishing games isawesome! REALISTIC! Experience the best underwater marine life,hunting sharks and becoming a shark hunter was never this fun.Enjoy overcoming shark attacks! Become an underwater hunter, killas many fish as possible; while avoiding to become their prey,watch out for sharkk lurking undersea in the shallows!
Whale Shark Sniper Hunter 3D 2.0.6 APK
Whale Shark Sniper Hunter 3D is an animal simulation game thatallows you to shoot all the crazy whales and white sharks, bullshark, orca whales along with sea monster from animal games with asniper shooter. In this modern sniper shooting simulation game, donot let vicious blood thirsty hungry sharks or megalodon sharkalong with crazy sharks even get closer to you or any other byusing your sniper 3d or american sniper along pro sniper assassinexperience as a trained sniper shooter. Target the white sharks orhammerhead shark and kill all the whale shark or blue whale alongorca whale from shark games one by one to proceed and save theentire city. Start your objective of targeting with shark simulatorand killing all the sharks in this angry whale shark attacksimulation game. This is one of the best animal hunter Game and allthe superhero sniper kill the shark in deep sea and save thepeople. You have been stuck in a boat in tropical, warm oceanswhich is full of hungry sharks like megalodon shark or bull sharkas live in open sea. Whale Shark Sniper Hunter 3D gives you anopportunity to target and kill great white sharks, tiger sharks,blue sharks and crazy sharks along blue whale with instant killcritical strike. There is no room for error as they are dangerouspredators or vicious sea monster and only one mistake can provelethal. Especially sudden angry shark can also proof to be lethal.So shoot them all down including blue whale and kill them beforeyou become their target. Use your precise sniper shooting skillsand kill them by using a single bullet. Start your ultimateunderwater hunting adventure and become a legendary sniper shooter.Get yourself ready for one of the most dangerous and horrifying seabattle and hunt down the giant hungry whale sharks and bull shark.Whale Shark Sniper Hunter 3D is for all the animal simulation game,hunting game, shark simulation game and sniper shooting gameslovers. Hunt the biggest sea hunter including hammerhead shark orblue whale along with tiger shark explore the sea water and come upwith an effective and unique strategy to become a legendary snipershooter with amazing shark simulator by killing and hunting all thesharks that are there in the waters. So what are you waiting for?Download Whale Shark Sniper Hunter free simulation game now andenter the world of ultimate animal hunting from hunting games. Thegame consists of six different and unique shark attack levels witha realistic environment and addictive gameplay. All you have to dois to use your snipe experience and precise sniper shooting skillsand kill all the sharks including hammerhead shark, megalodon sharkor deadly angry shark along with tiger shark Being a city trafficsniper is not that challenging and target do not attack you inthose games. Take up the most challenging task and become alegendary sniper shooter. Special Features: • Addictive underwateranimal hunter gameplay • 10 Different Levels with hungry sharksfrom shark evolution games • Realistic deep blue Sea Environmentfrom sniper fury games • Amazing Sound Effects from shark games
Crocodile Attack 2019 2.6 APK
It's JAWS...but with crocodiles! *CHOMP CHOMP CHOMP* This ravenouscrocodile lurks after its frantic prey. With an appetite as big asthis beast, you can hunt and snatch up anything. Swim, slither,crawl, and attack! Emerge suddenly from the waters, crawl onto theshore of the beach, and explore around the island looking for yournext meal, frightening the unexpecting humans and animals equally.Get them unawares! Control this giant in water and on land.Additionally, change the skin of your crocodile to cool themesincluding your country's flag (if you're feeling patriotic)! Putyour massive jaws to use and cause chaos! Your hunger must bequenched! Crocodile Attack 2016 Features: •Beautifully crafted 3Dgraphics & realistic water environments: including beaches,docks & open sea •Huge hungry animated 3D crocodile •Smooth andeasy controls to make the crocodile swim and attack •Fast actionpacked gameplay •Girls, Cows, Goats, Chickens and more •Plenty offun sounds and visual effects **INSTALL NOW AND START CHOMPING!!**About Tapinator Tapinator (Ticker: TAPM) develops and publishesgames on mobile platforms. The Company's portfolio includes over300 mobile gaming titles that, collectively, have achieved over 450million player downloads. Tapinator is headquartered in New York.For more info, visit Tapinator.com.
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Weed Firm 2: Back to College 2.9.87 APK
Weed Firm 2: Back to College by Manitoba Games. The sequel to thenow-legendary weed growing adventure, Weed Firm: RePlanted,featuring the next level in simulations for selling pot. In thisplant game you will: • Cultivate your weed farm empire withmultiple strains of marijuana, including the well-known White Widowand Purple Haze, as well as the amazingly powerful and extremelybeautiful Alien Weed • Market your pot to a range of eccentricclientele such as Jane the exotic dancer, Luni & Durte the rapduo, Sandy & Mandy the Cheerleaders, Ian the DJ, Rasta Bob, andmany more • Now featuring special customer Soulja Boy - Big Draco!• Grow your plantation and customize your shop with a series ofitems that will help kick up your buzz as well as keep you safefrom cannabis seeking intruders • Break into a new line of grassbusiness & expand your shop by growing magic mushrooms;including varieties such as Mexican, Ecuadorian, Alien, andIntergalactic • Open up a portal to another galaxy and sell yourfinest mushrooms to extraterrestrial alien visitors • Defend yourstash of 'shrooms and mary jane from the local Gangbangers and findcreative ways of shaking off corrupt cops and federal agents whoare ready to bust up your pot growing shop. • Expand your operationto the great outdoors and beyond. What will you find inside the RV?Diversify your business with blunts, rosin dabs, wax, and a varietyof edibles! In this follow-up to Weed Firm: RePlanted, the popularrole-playing weed growing and dealing adventure, expelled botanystudent Ted Growing heads back to his Alma Mater. This time he'snot there to hit the books, but rather to hide out from the copswho are hot on his trail. Ted sets up his grass grow-op in anabandoned gym and gets down to doing what he does best: cultivatingand selling cannabis. You get to be Ted as he expands his weed farmto new locations; planting new varieties of bud and magicmushrooms. Feel your pulse rising as Ted tries to keep his buzz upwhile growing his pot farm empire and selling to an ever-increasingclient base that demands R-E-S-P-E-C-T. Jah be with you! PeaceTwitter: http://www.twitter.com/TedGrowing Facebook:http://www.facebook.com/weedfirm Instagram:http://www.instagram.com/weedfirmgame Snapchat:http://www.snapchat.com/add/weedfirmgame
Unmatched Air Traffic Control 2019.22 APK
In this simulation game, you're an air traffic controller at a busyairport. The goal is to guide planes safely landing parking andtaking off, avoiding collisions between them. This game is muchlike the actual operation of a busy airport, but with easy andself-explanatory controls. Is a great hobby that stimulates memoryand reasoning. Have fun and good flights
Fallout Shelter 1.13.23 APK
** Google Play Best of 2015 ** Mobile Game of the Year - 2016 DICEAwards Winner 2015 Golden Joystick Best Handheld/Mobile Game "Mightjust be the best free-to-play game out there" - GamesBeat "Probablythe best game of E3 2015" – Gizmodo "Fallout Shelter is simple toplay and addictive as hell." - GameZone BUILD THE PERFECT VAULTCreate a brighter future…underground! Select from a variety ofmodern-day rooms to turn an excavation beneath 2,000 feet ofbedrock into the very picture of Vault Life. OVERSEE A THRIVINGCOMMUNITY Get to know your Dwellers and lead them to happiness.Find their ideal jobs and watch them flourish. Provide them withoutfits, weapons, and training to improve their abilities.CUSTOMIZE Turn worthless junk into useful items with Crafting!Customize the look of any dweller in the Barbershop. PROSPER Awell-run Vault requires a variety of Dwellers with a mix of skills.Build a Radio Room to attract new Dwellers. Or, take an active rolein their personal lives; play matchmaker and watch the sparks fly!EXPLORE THE WASTELAND Send Dwellers above ground to explore theblasted surface left behind and seek adventure, handy survivalloot, or unspeakable death. Find new armor and weapons, gainexperience, and earn Caps. But don't let them die! PROTECT YOURVAULT From time to time, idyllic Vault life may be disrupted by thedangers of post-nuclear life. Prepare your Dwellers to protectagainst threats from the outside…and within. Vault-Tec has providedthe tools, but the rest is up to you. What are you waiting for? Getstarted building your Vault today for FREE.
Episode - Choose Your Story 12.10.0+gn APK
Episode lets you LIVE your stories with love, romance, adventure,and drama. Wouldn't it be amazing if YOU were a character in yourfavorite story? Episode lets you do just that with over 100,000gripping stories, where you make choices that matter. With billionsof reads, Episode is the world's largest collection of interactivestories where YOU choose your destiny. Or become a creator andwrite your own! How does it work? • Customize your avatar anddesign your outfit • Develop relationships with your favoritecharacters - will they be rivals or lovers? • Change fate throughyour choices • Discover all of the different endings • Immerseyourself in thousands of diverse worlds, the options are endless!Not only can you read your favorite stories, you can also writeyour own! Write and publish your very own interactive stories onEpisode's platform, amassing millions of reads yourself. Some ofour favorites include: THE K*SS LIST is here! Kentwood Academy isripe for taking over. Continue your perfect streak of rulingschools by kissing 10 of Kentwood's HOTTEST singles! LOVE LIFE isyour wild romance in NEW YORK CITY! Ready to heat up your lovelife? Flirt, scheme, and party your way to true love in this NYCsizzling romance where YOU call all the shots and make your dreamscome true! THE BABY PROJECT. Your world is turned upside down whenyou're paired with a mysterious new *HOT* student for RiversideHigh's "Baby Project." This drama will leave you breathless. PRETTYLITTLE LIARS. Will you and the other liars be able to uncover themysterious "A" as she threatens to blackmail you? All is not whatit seems in this original twist on the TV series. POSITIVELYPRINCESS. Remember that time it turned out YOU'RE SECRETLY APRINCESS? Well, get ready, gurl: because eligible royals fromaround the world are lining up to marry you...and have your BABY?!DEMI LOVATO: PATH TO FAME. When you win a chance to tour with theone and only superstar Demi Lovato, your ability to balance love,friends, and fans is put to the test! Will you make it to the finalstage? PITCH PERFECT IN DEEP TREBLE™ You've always dreamed ofjoining the hottest acapella group in ACA-HISTORY, the Bellas! Nowyou're at Barden University and it's your time to shine. Will yoube able to balance auditions and showing off your vocal chops inthe riff-off, ALL while being torn between two new love interests?Other goodies include: • Mean Girls: Senior Year • The Royal Baby •My Brother's Best Friend • Clueless: School's Out • It Started Witha Bra • Falling for the Dolan Twins PLUS…more new stories EVERYWEEK! PRETTY LITTLE LIARS and all related characters and elements ©& ™ Warner Bros. Entertainment Inc. (s18) TM & ©2018Paramount Pictures. All Rights Reserved. ™ & ©2018 UniversalStudios PLEASE NOTE: Episode lets you purchase items within thegame for real money. Please disable in-app purchases on your deviceif you do not want this feature to be accessible.
Grand Truck Simulator 1.13 APK
Disclaimer: This is a beta version. The game was not finishedyet.Recomended hardware: Quadcore - 1GB RamGTS is a truck sim formobile. These are some of its features:Realistic physicsRealisticfuel consumeMods: You can make your own skins for trucks andtrailers or download from other guysYou can modify suspensions,lights (xenon), pente na turbina and automatic brake assist (onlyfor modern trucks)You can damage your body truck and brokeglassesFull working truck and trailer lightsFull working truckdashboardAirhornReal life truck sounds for engines, brakes, horns,Different types of trailers: Chassis, chassis + trailer, 3 axlesemi, 2 axle semi, 2+1 axle semi, bitren 7 axle, etc.Realistic sunsystem (Day and night)FogYou can hire drivers and buy deposits topark your fleet of trucksThe map is based on some little citys fromSao Paulo - BrasilYou start with a basic truck and by gettingexperience will get better trucks and jobsAnd remember, this gameis not finished but we are working hard to make your dreams true:)You can follow us on facebook to get the latest new about gamedevelopment or other playersskinswww.grandtrucksimulator.comhttps://www.facebook.com/GrandTruckSimulator?fref=tshttp://www.taringa.net/post/juegos/19001361/Skins-para-Grand-Truck-Simulator.htmlhttps://www.youtube.com/channel/UCPga7Hmi9KtlVuoH8ggDFZg
Bud Farm: Grass Roots 1.27.8 APK
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SimCity BuildIt 184.108.40.206178 APK
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text:
Brand New Ballads
first edition Paperback
1885 · London
by Leland, Charles G
London: Fun Office, 1885. 1st. Paperback. Hal Ludlow, Thomas Dalziel, and the Author. Bound in publisher's original almond wrappers printed in brown. Chipped at head and heel of spine, wrappers lightly soiled, otherwise very good. Two states of wrapper were printed, sequence undetermined. This copy reads 'Fun" on the front. (Inventory #: 25673)


text:
Set in London The Scene offers self-catering accommodation with free WiFi. The unit is 5 km from Olympic Stadium.The kitchen comes with a dishwasher an oven and a microwave as well as a kettle. Towels and bed linen are provided in this self-catering accommodation. There is a private bathroom with a bath.Victoria Park is 6 km from The Scene while Emirates Stadium is 7 km away. London City Airport is 10 km from the property.
รูปถ่าย ของ
แสดง โรงแรม The Scene บนแผนที่
51.58485 -0.020372


text:
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Monthly Archives: November 2011
Gary Speed
Until he took his own life, I'd never heard of Gary Speed. Although he was Manager of the Wales Football Team, and I am Welsh, I am not a football fan. However, the intensity of the shock at his death … Continue reading
Posted in Eleanor's Opinion, Healing Tagged depression, Gary Speed, healing, mental illness, Suicide 4 Comments
This Week I Have Been Mostly Happy
Mostly very happy actually. I've found myself walking around with a huge smile on my face, and singing lots (alone in the car, I wouldn't subject anyone else to that). I feel as if the clouds have thinned out to … Continue reading
A Ten Minute Walk in the Fresh Air
On Wednesday I had my first appointment for Cognitive Behavioural Therapy. Because of my work patterns, it's more convenient for me to attend at another surgery, the other side of the Wye Valley in the Forest of Dean. Wednesday afternoon … Continue reading
Posted in Healing Tagged Cognitive Behavioural Therapy, depression, healing, hope, love 3 Comments
Exhaustion and Recuperation
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Posted in Uncategorized 8 Comments
All's going well. I'm seven weeks into my antidepressants, with very few side effects, and slowly, really slowly, my energy levels are rising. I'm still tired all the time, and not sleeping as much as I feel I need to, … Continue reading
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Raman spectroscopy is among the primary techniques for the characterisation of graphene materials, as it provides insights into the quality of measured graphenes including their structure and conductivity as well as the presence of dopants. However, our ability to draw conclusions based on such spectra is limited by a lack of understanding regarding the origins of the peaks. Consequently, traditional characterisation techniques, which estimate the quality of the graphene material using the intensity ratio between the D and the G peaks, are unreliable for both GO and rGO. Herein we reanalyse the Raman spectra of graphenes and show that traditional methods rely upon an apparent G peak which is in fact a superposition of the G and D' peaks. We use this understanding to develop a new Raman characterisation method for graphenes that considers the D' peak by using its overtone the 2D'. We demonstrate the superiority and consistency of this method for calculating the oxygen content of graphenes and use the relationship between the D' peak and graphene quality to define three regimes. This has important implications for purification techniques because, once GO is reduced beyond a critical threshold, further reduction offers limited gain in conductivity.
Graphene has become a primary research focus in many current fields of science as evidenced by the recent announcement from the European Commission of €1 billion funding for the commercialisation of graphene research over the next ten years1. This, coupled with the recent proliferation of publications on graphene and graphene oxide (GO)2,3,4, suggests that research on 2-D graphitic materials will increase. Raman spectroscopy has proven to be one of the most powerful techniques for the characterisation of graphene, as its phonon modes provide explicit insights into changes in layer structure, dopants, conductivity etc5,6. For practical reasons, materials scientists and engineers developing devices and larger-scale materials often work with GO and reduced graphene oxide (rGO), which are easier to process due to improved solubility, better control over size and more scalable processing methods7,8,9,10,11,12. Unfortunately the tools that are used to extract physicochemical information from the Raman spectra of graphenes have not proven directly applicable to these materials. In particular, the ID/IG ratio, which has been validated as a measure of inter-defect distance in graphene, is unreliable when applied to GO and rGO13,14,15,16. Ferrari and Robertson defined an amorphisation trajectory, in which the ID/IG ratio of amorphous carbon (that was still sp2 bonded) would increase with the removal of defects, proportional to the square of the crystallite size17. In this way they define a transition between carbons that have a crystallite size smaller than ~2 nm, which should obey the Ferrari–Robertson relation and those with larger crystallites, which obey the Tuinstra–Koenig relation. The discontinuity in the ratio-to-structure relationship is attributed to the complete distortion of the aromaticity at very high defect densities; however, this proposal has been vitiated for GO and rGO as high-resolution STM imaging has shown areas of aromaticity up to 8 nm2 even in raw GO18.
Results and Discussion
The D' peak is present in all defective graphenes and is therefore attractive as a measure of quality. However, due to the superposition of the G and D' modes (giving rise to an apparent G peak, the Gapp), it is impractical to measure the position or intensity of the D' mode. The second order transition (2D', observed at ~3,200 cm−1) does not coincide with other modes and is an allowed mode even without defects, in the same way that the 2D is and so can be observed even in pristine graphene. After GO is reduced the 2D' peak occurs at higher energy, shifting by as much as 40 cm−1 from GO to graphene19, therefore, the difference between the 2D' and the apparent G (Gapp) positions (2D' − Gapp) increases. Also, by simply halving the energy of the 2D' mode we can get the energy of the inferred D' mode (D'inf) as it is not expected to vary as greatly as the 2D and D modes can6. The difference (D'inf − Gapp) is more reliable than the absolute 2D' or D'inf position, which is subject to natural variation within samples, laser spot locations and measurement conditions. Figure 1(a,b) shows this clear relationship between the energy difference and the C/O atom ratio, as determined by X-ray photoelectron spectroscopy (XPS) or elemental analysis, for samples of rGO produced using various reduction methods and for pristine monolayer graphene (whose Raman spectrum displays no D mode). In contrast, the ID/IGapp ratio is not clearly correlated to the C/O atom ratio for the same samples (Fig. 1c), illustrating the difficulty in using the ID/IG ratio across the full range of graphenes.
The correlation of the D'inf − Gapp with the C/O ratio also allows us to quantitatively describe the previously ill-defined boundaries between GO, rGO and graphene. We can define the three types of graphene derivatives by defining two points along the curve that mark the boundaries for three regions (see Fig. 1b):
Considering the unreliability of the ID/IG –structure relationship for GO and rGO, it is apparent that the contribution of the D' mode to Gapp had not been appropriately taken into account. In GO, the peak being measured as the G peak is actually the superposition of two peaks, the G and D' peaks. The latter is a defect-derived peak that is observed in graphene at ~1,620 cm–1 19,20. In graphite, the intensity of the D' peak is proportional to the crystallite size and hence the amount of defects21. For GO and rGO, which have comparatively high defect densities, the D' peak is therefore expected to be much more intense and thus contribute significantly to the Gapp peak. In the Raman spectra of graphene samples, even those that have been subjected to ion bombardment to introduce lattice vacancies, the D' peak remains distinct from the G peak22, but the properties and spectral signature of defective graphene do not closely approach those of even highly reduced GO. Ferrari and Basko predicted that the high defect density present in GO and rGO would produce D' peaks whose energy was low enough to coincide with the G mode at ~1,600 cm−1 6. The half width at half maximum above the Gapp centroid position is larger than expected for many GO samples, implying that the G mode is accompanied by an extra peak at slightly higher energy15. Further increasing the density of defects is predicted to give D' modes at energies as low 1,580 cm−1, which would theoretically make it appear at lower energy than the G peak. The origins of this large shift in the energy of the D' mode remains unclear, but could depend on the second-nearest neighbour force constants19. The impact of such a large position shift on the position and intensity of Gapp has not been explored.
When the peak at ~1,600 cm−1 is understood as arising from two modes, rather than interpreted as a single mode (Fig. 2), the observed peak positions and intensities are redefined and the spectral differences between GO and rGO are clarified. Upon GO reduction, the position of the G peak increases and both the intensity of D' and the ID/IG ratio decrease, all of which are expected consequences of greater graphitisation following reduction (Table 1). The change in ID/IG is particularly important, as interpreting the spectra in Fig. 1 based upon a single Gapp peak would produce an increase in the ratio rather than a decrease, as was reported by Stankovich et al.16. This peak overlap greatly limits the utility of ID/IG as a measure of defect density in GO and rGO.
Excitation-energy-dependent position shifts (dispersion) of the Gapp peak have been measured in graphene samples with a high density of lattice vacancies to be ~6 cm−1eV−1 22. This dispersion has been predicted, without explanation, to apply to all highly defective nanocrystalline graphites6. We contend that the dispersion of the Gapp peak is another artefact of the superposition of a nondispersive G and an intense and dispersive D' peak. The D' peak has well-described dispersive behaviour; whereas the G peak has no known mechanism for dispersion. Pimenta et al. measured the dispersion of the D' peak to be 10 cm−1eV−1 in graphene23, this is the same dispersion we measured for the Gapp peak of rGO (Fig. 3). The dispersion was slightly higher (13 ± 2 cm−1eV−1) for the as-produced GO sample (i.e. the most defective material), allowing for some minor dispersion in the actual G peak. Thus, the net dispersion of Gapp is most likely due to the dispersion of the D' peak.
The peak commonly labelled 'G' in the Raman spectra of GO and rGO samples is in fact a superposition of the G and D' peaks (the Gapp peak). This superposition renders the ID/IGapp ratio an unreliable measure for the reduction of GO and has prevented it from accurately describing some of the recently reported GO and rGO samples. We propose that the best measure of GO reduction is the difference in the positions of the D'inf and Gapp peaks, i.e. D'inf − Gapp or the equivalent 2D' − Gapp. The strong correlation that exists between the C/O atom ratio and D'inf − Gapp, illustrated for a range of GO and rGO samples from different laboratories and using different reduction techniques (Fig. 1), demonstrates the value of this simple and robust tool for the analysis of the degree of reduction in GO. This correlation also provides for the quantified definition of GO, rGO and graphene based upon a simple and rapid Raman spectroscopic measure.
In addition to demonstrating a superior methodology for the characterisation of graphene materials, we have shown for practical purposes we can define three regions of reduction: A material with D'inf − Gapp < 0 can be defined as GO, one with 0 < D'inf − Gapp <25 is defined as rGO and samples with D'inf − Gapp > 25 can be defined as graphene. We have shown that the D' and 2D' modes, which have been overlooked in the Raman spectra of GO and rGO, provide valuable insight into all defective graphene materials. The amount of reduction can be predicted from the energy difference between the Gapp and D' or 2D' peaks. We suggest that the consideration of the second-order Raman modes is vital to fully and accurately characterise graphene and its derivatives.
Spectroscopy and analysis
All Raman spectroscopy was performed on an in Via Renishaw Raman spectroscope, using dry samples on a glass substrate. A 50x objective was used for all measurements and the system was used unpolarised with a 514 nm argon ion laser unless otherwise stated. The laser power was reduced to avoid sample damage; thus 1% power was used at 488 nm, 5% at 514 nm and 10% at 633 and 785 nm. All spectra were gathered over 10 s exposures and 1 (488 nm and 514 nm) or 2 accumulations (633 nm and 785 nm). For spectral analysis each peak was fitted to a single Lorentzian (except in Fig. 2 and Table 1 as explicitly described) using the standard fitting functions within Origin Pro 8 using the automatic parameter initialization, the fits all achieved an R2 greater than 0.98. The four spectra presented in Fig. 2 and Table 1 used a two-Lorentzian peak fit for the Gapp peak, using the same software. The Raman spectra taken from the literature were interpolated using GraphClick software and then analysed as above. XPS analysis was carried out on an ESCALAB250Xi Thermoscientific spectroscope, using focused monochromated Al Kα radiation. The spectra were fitted using Avantage software.
Reduction of GO
GO samples were synthesised using the modified Hummers method as described in9,24. The synthesised materials were washed in water with centrifugation, this process being repeated until the solution reached neutral pH. GO was reduced using two primary techniques: thermal and chemical. Two types of thermal reduction were used. The first was reduction in a furnace under nitrogen flow at 400, 600 and 800 °C for 4 h and 1,000 °C for 2 h, with a ramp rate of 4 °C min−1. The second was performed in a commercial microwave under vacuum (4 × 10−4 mbar) for 2 or 6 s. For the chemical reduction ascorbic acid was mixed with GO in a ratio of 10:1 by mass and stirred at 85 °C for ~24 h until the reaction reached completion, then heated in the microwave at 150 °C for 30 min (ramp rate 1 °C min−1). The same process was used for reductions with ethylene glycol. Samples of 1 mgml−1 GO in ethylene glycol were prepared and diluted with twice as much deionised water by volume prior to reduction as above. Pristine single layer graphene was purchased and used as is from Graphenea.
Additional Information
How to cite this article: King, A. A. K. et al. A New Raman Metric for the Characterisation of Graphene oxide and its Derivatives. Sci. Rep. 6, 19491; doi: 10.1038/srep19491 (2016).
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The authors thank Dr Elizabeth Carter and Mr Joonsup Lee of the Vibrational Spectroscopy department, USYD and Dr Bill Gong at the Surface Analysis Facility, Mark Wainwright Analytical Centre, UNSW for technical support. A.A.K.K. thanks the Gritton Scholarship for funding. N.N. gratefully acknowledges the financial support by CSIRO-National Research Flagships Program for providing the Postgraduate Scholarship (Future Manufacturing Flagship; No. FlagshipPhD12/03743). A.T.H. acknowledges continued support from ARC future fellowship. J.M.R. gratefully acknowledges support from ARC future fellowship.
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King, A., Davies, B., Noorbehesht, N. et al. A New Raman Metric for the Characterisation of Graphene oxide and its Derivatives. Sci Rep 6, 19491 (2016) doi:10.1038/srep19491
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Processing influence on dielectric, mechanical, and electrical properties of reduced graphene oxide-TPU nanocomposites
Journal of Applied Polymer Science (2019)
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