3 In the case of tertiary amine catalysts, it is believed that the tertiary amine and isocyanate form an activated complex whichįacilitates the nucleophilic addition of the alcohol to the N=C 5 These compounds polarize either the isocyanate or hydroxyl compoundĪnd thus make the C=N bond more susceptible to nucleophilic addition of the hydroxyl group. Required to accelerate the additon reaction. The latter are much strongerĬatalysts than tertiary amines, i.e. Tin compounds like dibutyltin dilaurate (DBTL). Widely used catalysts include tertiary amines, such as triethylene diamine (TEDA),ĭimethylpiperazine (DMP), dimethylethanolamine (DMEA), and diazabicyclooctane (DABCO), Isocyanate reactions are very susceptible to catalysis that is catalysts greatly increase the rate of nucleophilic addition of compounds with active hydrogen to the C=N bond. > secondary alcohol > carboxylic acid > ureas > urethanes. > secondary aliphatic amines > aromatic amines > primary alcohols > water Typically decreases in the order: primary aliphatic amines The order of reactivity in uncatalyzed isocyanate (polymerization) reactions The rate of addition also depends on the type of nucleophile The same is true for other bulky side groups in ortho position. This is particularly true for diisocyanates in para position whereas diisocyanates in ortho position have somewhat lower reactivity due to steric hindranceīetween the two NCO-groups. Substituents lower the reactivity of the isocyanate group whereas a second isocyanate group in ortho or para position relative to the first group increases the reactivity Other substituents on the aromatic ring also affect the reactivity, that is electron withdrawing side groups in ortho or para position increase the reactivity and electron donating In the case of aromatic substituents, the negativeĬharge gets delocalized into the π electron ring system whichįurther increases the positive charge on the carbon atom:įor this reason, aromatic isocyanates are more reactive than aliphatic or cycloaliphatic isocyanates. Of alcohols whereas electron donating groups decrease the The carbon of the NCO group which facilitates nucleophilic addition 1-4Assuming a hydroxyl group acts as a catalyst,Įlectron withdrawing substituents increase the positive charge on Or six-membered transition state including one or two alcohol It is believed that the reaction proceeds via a four. Group (-N=C=O) is attacked by the nucleophilic oxygen of an alcohol group while its active hydrogen is added to the negatively charged nitrogen In the absence of a catalyst, the positively charged carbon of the isocyanate Polyol which leads to the formation of urethane bonds. The by far most important reaction, however, is step-growth polymerization of a diisocyanate with a polyol compound such as a polyester or polyether Polyisocyanates (N-substituted 1-nylons). (uretdiones) and trimers (isocyanurates) or they can be polymerized to Hydrogen atoms, like amines, alcohols, mercaptanes, water, andĬarboxylic acids or they can react with themselves to form dimers Important monomers that undergo a broad range of chemical reactions.įor example, they can react with compounds containing active Isocyanates, especially diisocyanates and polyisocyanates, are
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In addition, the product paper we print our panoramas on is certified for FCS sustainability and contains 10% post-consumer waste. Previously released plans included 400 residential units, 240 hotel rooms, 270,000 square feet of retail space, 246,000 square feet of office space and parking for 516 cars. Nearly 95% of production waste is recycled. Our building is partially powered with solar panels and utilizes LED lighting. 1001 S Miami Ave, Miami, FL 33130 (305) 909-6382 Visit Website CMC Group Panorama Tower Miami’s Panorama Tower in Brickell is on its way to becoming the tallest building in the city at. In addition to producing great products and supporting jobs in America, we try to be good stewards of our environment by following sustainability practices in our facility. Panoramic of Miami skyline seen from Watson Island, Miami, Florida, United States of America Cloudscape Copyspace Florida Architecture Country America. We offer framed and unframed prints that are "Made in the U.S.A." We continue to add to our growing collection of licensed college stadium panoramas and are an official licensee of the NFL, NHL and NASCAR. Our catalog includes licensed sports panoramas, city skylines, and many other fabulous sites from around the world.Ĭelebrating 30+ years in business, we remain committed to updating and expanding our collection. Blakeway Panoramas photographs, publishes and distributes the largest selection of high quality panoramic art prints in the U.S. Download high quality Miami Black City Vector Panorama clip art graphics. This year (as it was last year), the new promo isn't called FUTMAS, instead we're getting back-to-back Winter Wildcards! The World Cup is over, but we're getting new content almost every single (Fri)day in FIFA 23. Team 2 is live right now! The FIFA 23 Winter Wildcards will be crazy! | © EarlyGame / EA Sports Here you will find all the info about the recently released players as well as all the tokens during the swap event. We tell you which gifts one of our favorite Christmas promos has brought us this year. Will update the thread daily as more tokens are released.The FIFA 23 Winter Wildcards are here, instead of FUTMAS. 75.000 Coins or 500 Fifa Points.ġ1 - Stenmark (Released ) (Expires ): Obtainable by completing: FIFA 23 Winter Wildcards Challenge 2 SBCġ2 - Watts (Released ) (Expires ): Obtainable by completing: Winter Winning Objectives – Win 1 match in any FUT Game Mode.ġ3 - Fofana (Released ) (Expires ): Obtainable by completing: FIFA 23 Christmas Cheers SBCġ4 - Foti (Released ) (Expires ): Obtainable by completing: FIFA 23 Winter Wildcards Challenge 3 SBCġ5 - Kourfalidis (Released ) (Expires 2023.03.01): Obtainable by completing: FIRST OWNER FIESTA Objectives in Milestone – Win a match in the Live FUT Friendly: Homegrown Elevenġ6 - Kristof (Released ) (Expires ): Obtainable by completing: FIFA 23 Felix Passlack Winter Wildcards Silver Starsġ7 - Tiago Santos (Released ) (Expires ): Obtainable by completing: SBC Villareal vs Valencia in Marquee Matchupsġ8 - Uzodimma (Released ) (Expires ): Obtainable by completing: FIFA 23 Winter Wildcards Challenge 4 SBCġ9 - Tierney (Released ) (Expires ): Obtainable by completing: Winter Wildcards Cup Objectives – Play 2 Matches in the Live FUT Friendly: Winter Wildcards Cup.Ģ0 - Morgalla (Released ) (Expires ): Obtainable by completing: FIFA 23 Winter Wildcards Challenge 5 SBC.Ģ2 - Gordon (Released ) (Expires ): Obtainable by completing: FIFA 23 New Year’s Kick Off SBCĢ3 - Colaco (Released ) (Expires ): Obtainable by completing: FIFA 23 Winter Wildcards Challenge 6 SBCĢ4 - Chader (Released ) (Expires ): Obtainable by completing: FIRST OWNER FIESTA Objectives in Milestone – Win a match in the Live FUT Friendly: Homegrown Eleven.Ĭurrently Available Wildcard Swaps tokens:ġ - Larade (Released ) (Expires ): Free on login (If you haven't gotten it via the web/mobile app login via console)ĩ - Westbrooke (Released ) (Expires ): Obtainable by completing: Winter Wildcard Treasure Hunt ObjectivesĢ1 - Kelman (Released ) (Expires ): Obtainable by completing: Winter Draft Objectives – Play 1 FUT Draft Match.Ģ5 - Ballet (Released ) (Expires ): Obtainable by completing: FIFA 23 Janis Antiste Winter Wildcards Silver Stars ObjectivesĢ6 - Hwang Jae Hwan (Released ) (Expires ): Obtainable by completing: SBC Twente vs Emmen in Marquee Matchups Contains 1 Rare Gold Players rated at 86 OVR or higher and a Winter Wild Card Swap Token. You have to complete the "ENTIRE" Objective)ĥ - Barron (Released ) (Expires 2023.01.02): Obtainable by completing: By redeeming Winter Wildcards Swap Token pack with 20 stars in the new FUT Moments modeĦ - Vaananen (Released ) (Expires ): Obtainable by completing: FIFA 23 World Cup TOTT Challenge 2 SBCħ- Christogeorgos (Released ) (Expires ): Obtainable by completing: SBC Sweden vs Switzerland in Marquee MatchupsĨ- Svensson (Released ) (Expires ): Obtainable by completing: FIFA 23 Winter Wildcards Challenge 1 SBCġ0 - Cancar (Released ) (Expires ): Obtainable by buying Winter Cheer PACK in the Store. 15 Tokens - 85+ Winter Wildcards Player Pick (1 of 5)Ģ - Kunst (Released ) (Expired ) : Complete the "Fifa World Cup TOTT Challenge 1" SBCģ - Jinbao Zhong (Released ) (Expired ): Complete the 'Win 1' in the 'First Owner Fiesta' ObjectiveĤ - Jacobo Furlan (Released ) (Expired ): Complete the Silver Stars Objective ( N.B.10 Tokens - Winter Wildcards Sandro Tonali.5 Tokens - 3x 84+ Player Picks (1 of 4).2 Tokens - Winter Wildcards Kieran Trippier.It is likely that the additional 4 tokens will be released bringing the total to 30. Updated: An additional token was released on bringing the total released to 26. The first two were released on today with one as a free gift and a second as an SBC. There are 25 total FIFA 23 Winter Wildcards Swaps tokens that will be made available through the promotion. If you don't want to go with an Alternate book, the Pats' playbook also gives you that versatility. It's been the competitive standard for a bit now and nothing seems to have changed. Like many, we really love the Big Nickel package. It gives you several different nickel sets to work with, while letting you bring heavy pressure. It's probably not going to be the playbook you use online, but it's a good option for Franchise mode.įor us, the go-to defensive playbook is going to be the Alternate 46 playbook. They do a great job of getting use out of that four-man front. Face Of The Franchise & The Yard: The General Player Class Starting at Level 10 with a Tom Brady Gear Capsule. On the 4-3 side of things, you probably want to go with the Vikings. Buy the Madden NFL 22 MVP Edition and receive: Dual entitlement. The Bucs make use of fast linebackers who can quickly cover the field, while the Steelers' playbook comes with all kinds of different sets that you counter the offense. For players looking to run a 3-4 base front, we like both the Bucs and Steelers. Meanwhile, the Raiders have almost every formation you could want, making them very versatile.ĭepending on the defensive front you want to run, you have several good playbook options available. With the Pats building around Cam Newtown, they have some nice run options to shake things up, while also providing great mid-range passing. MUT 22: Bo Knows Release Date for New Players Bo Jackson already hit Ultimate Team with an 85 OVR card that every player will receive by logging into Ultimate Team between November 19, 2021. If you're running a more standard running attack, the Browns' playbook is our playbook of choice.įinally, for a more balanced approach we like both the Patriots and Raiders' playbooks. If you have a mobile QB like Lamar Jackson, the Ravens' playbook is a good choice because it has so many designed QB runs. This is our go-to when we want to bomb passes down the field.įor run-heavy teams we have a few options. "What better way to continue highlighting greatness in sport during the holidays than featuring Bo Jackson, the only athlete to be named an all-star in both professional football and baseball, and one of the greatest running backs ever in the NFL.If you're looking to air things out, we really like the Chiefs' playbook because it has a ton of deep passes to take advantage of Patrick Mahomes' cannon and Tyreek Hill's speed. Iran also gets to see precisely how its drones handle modern western air. "We revealed Madden NFL 22 with two of the greatest quarterbacks in history on the cover in Tom Brady and Patrick Mahomes," said Julie Foster, VP of EA Sports Brand. But now you know why Israel do adamantly bombs weapons transfers to Hezbollah. It's great the campaign has remained relevant for so many over the years and to see it revisited in Madden NFL 22 allows it to reach a whole new generation of fans." "The Nike Bo Knows campaign brings back a lot of nostalgia for me and many others. "It's great to be back in the game with Madden NFL and to appear on my first cover," said Bo Jackson. This is basically a chance for you to make sure Bo Knows Everything in every mode to make an impact. Jackson will also appear in the draft pool in the Superstar KO mode and a new Bo Knows Superstar X-Factor ability will be added. What's more, the new Nike x Bo Knows gear will drop in The Yard, which will also include the Nike Air Bo Turf worn by Jackson in the 90s. From November 19th to January 14th, Madden NFL 22 players will automatically receive an 85 overall rated Bo Jackson player item and Raiders uniform for the Madden Ultimate Team. Now you have a chance of getting Bo on your team in the modern era of the game. For a short period in time, the two-sport athlete was on top of the world, playing Running Back for the Raiders and a few different teams in the MLB. EA Sports decided to do a little bit of a throwback for Madden NFL 22 as they have the legendary Bo Jackson on a special cover and more. With most cloud storage tools, users are rewarded with extra storage space as they add more files to the services, allowing for a decent savings on HD space. 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It already included a program to demonstrate some of RVR’s features, so I ran it and watched RVR drive around with its LEDs changing color. Next, I looked at the introductory lesson on Sphero Edu. I was immediately able to drive the RVR around the room with no difficulty and manually change the color of the LED lights. Of course, the first thing I did was choose the drive option on the Sphero Edu app. Once the battery was installed, I powered on the RVR and easily connected it to my iPad. The app offers some beginning lessons and videos about RVR that I watched as I eagerly waited for all four lights on the battery to stop blinking. While waiting for the battery to charge, I was directed by the instructions to download and install the Sphero Edu app. Instructions showed me how to charge the battery and then install it into the RVR robot as well as how to attach the roll cage. The RVR robot is located in the center with a box containing the battery and USB cord on the right and the roll cage and mounting plate in a box on the left. Right at the start, as I opened up the box, I was impressed with the design of the packaging. RVR retails for $249 and can be purchased directly from Sphero’s recently redesigned website as well as other retailers. However, even just out of the box, RVR has a lot to offer. Unlike its previous products, Sphero has designed RVR to be compatible with other types of micro-controllers including Micro:bit, Arduino, and Raspberry Pi. Sphero RVR (pronounced rover) was first introduced last year as a successful Kickstarter campaign and began shipping in October of 2019. Known for its spherical robots, Sphero rolls out an all-terrain hackable robot with a pair of treads designed for beginners as well and experienced users. Image by Michael KnightĪpril 4-12, 2020 is officially National Robotics Week, so let’s take a look at one of the latest innovations in consumer robotics. Sphero’s RVR allows you to take robotics where it has not gone before. In October 2011, the Antwerp Court of Appeal overturned the Commercial Court's decision and ordered Belgacom and Telenet to initiate DNS blocks of 11 domains linked to The Pirate Bay or face fines within 14 days. BAF accused them of providing a safe haven for The Pirate Bay and appealed. ISPs said it was not their position to decide which websites their users can and cannot access. In July 2010, the Antwerp Commercial Law Bank ruled that none of the ISPs should block the pirate bay and described the idea of blocking wholesale locations as "disproportionate". After years of negotiations, legal action was taken. BelgiumĪfter the founders of The Pirate Bay lost their verdict in 2009, the Belgian Anti-Piracy Foundation (BAF) campaigned for two ISPs, Belgacom and Telenet, to block subscribers' access to the website. Starting in 2018, ISPs will have to block websites again. Austriaįrom May 30, 2016, Austrian ISPs will be able to unblock all previously blocked sites. Judge Nicholas said, "I am pleased that the relief from copyright infringement is evident and that the operator of the TPB websites has openly and deliberately disregarded the rights of copyright owners." Despite some success with ISPs blocking access, VPNs or changing DNS can still easily access sites like The Pirate Bay. On December 15, 2016, the Australian federal court ruled to proceed with the ban, forcing ISPs to ban access to The Pirate Bay, isoHunt, and SolarMovie, as well as the now-defunct Torrentz and TorrentHound, before January 5. In September 2014, the Australian government announced that it was discussing whether ISPs should be forced to block popular torrent sites, including The Pirate Bay. Using this order, the CNC had the ISPs block the IP range 194.71.107.0 to 194.71.107.255 in which The Pirate Bay operates and 12 different domains from The Pirate Bay. The order came about as a result of a lawsuit between the site and CAPIF (Argentine Chamber of Record Manufacturers). On June 30, 2014, the Argentine CNC (National Communications Commission) ordered the blocking of all domains of The Pirate Bay. The Pirate Bay has been blocked on many ISP's around the world.Ĭountries blocking access to The Pirate Bay where at least one internet service provider (ISP) formerly or currently censors TPB. Unblock The Pirate Bay with one of these proxy sites.Ĭountries blocking access to The Pirate Bay A proxy site allows you to bypass blocks setup by your Internet provider. Pirate Bay Proxy ListĬan't access The Pirate Bay? Try one of the proxy sites below. We periodically check our Pirate Bay proxy list against several major ISPs around Europe to make sure they have not been blocked. This is due to the help of information websites such as Torrent Proxy Portals that provide an up to date proxy list for ThePirateBay (TPB), and further information on how to avoid censorship using alternate methods. However their efforts seem to be counterproductive as Torrenting and other file sharing traffic is not decreasing. Since 2011 ISPs in the UK, Netherland, Belgium and now France have been blocking many file sharing websites including The PirateBay. Pirate Proxy List maintains a list of proxy sites that allow access to The Pirate Bay. Proxy sites are the easiest methods to bypass the block. Pirate Proxy List 2022: Unblock The Pirate Bay For example, websites with animated ads will now display them as static images- a small victory in our worlds, which are full of visual noise and disturbance. You’ll begin to see the immediate benefits of disabling Flash. Now we can install a new, non-Flash plugin. Log out of, and then back into your user account for the changes to take effect.Drag “Flash ugin” and “flashplayer.xpt” into your new Disabled folder.In your Library folder, create a new folder called “Internet Plug-Ins Disabled.” This will show you all installed plugins in your system: Enter the following path into the dialogue box: /Library/Internet Plug-Ins. So, once in the Finder, hit command + shift + g on your keyboard.If you try to access the Internet Plugins folder through your user account, you won’t see any files in the folder: You’re going to access the Internet Plugins in your system’s Library.After that will be some notes on Flash and Google Chrome. I’m going to first go over creating a Flash-free Safari. Now that we’ve enabled our Macs to show all system files, we can start the process of disabling Flash. Rule of thumb: if you don’t know what a file is, don’t touch it! You can also re-hide your system files by using the above Terminal command just switch YES to NO, and relaunch Finder. Note: You will see lots of files where you didn’t see them before, particularly one named. Click “Relaunch,” and Finder will restart: Hold down the Option key, and click the Finder icon in the Dock. For this change to take effect, you’ll need to relaunch Finder.Type the following command, and press Enter: defaults write AppleShowAllFiles YES.Scroll down, and double-click on the Terminal icon.(If you’re interested in learning how to use Terminal extensively, I recommend this guide.) It’s great for doing system administration, inspecting network traffic, etc. Terminal is a text-based program that allows you, the user, to send direct commands to the operating system. If you want to go Flash-free, though, you’re gonna have to get your hands a little dirty and do some work in the OS X Terminal. It’s a good safety precaution, preventing users from accidentally deleting a vital system file. Apple realized this, and forced OS X to hide system files by default. Most Mac users don’t go beyond checking email, listening to music, surfing the Internet, and perhaps writing the occasional document. READ THIS FIRST: HOW TO SEE YOUR HIDDEN SYSTEM FILES With the advent of Flash-less Macs, it’s high time for all OS X users to go footloose and Flash-free. It’s no wonder that the new MacBook Air line ships without a Flash plugin installed. Citing Adobe for catering to developers writing cross-platform applications as opposed to exclusively in Apple’s native Objective-C, “Thoughts on Flash” is a decided vendetta, swearing off any future contact with Adobe plugins. (And if you’re like me, you refuse to use any other browser because you’re in love with Safari’s multitouch features.)Īdobe, once one of Apple’s dearest busom buddies, has now taken on the role of the Cupertino company’s estranged wife. However, Flash is very good at crashing Safari, Apple’s Internet browser. The Flash plugin allows your Internet browser to display “rich” content such as video, rollover site features, and the most annoying of all, animation-based Flash websites. Jobs is referring to Adobe and their rich Internet application plugin, Flash. Viva la revolution!Īpple CEO Steve Jobs famously stated in his “Thoughts on Flash” manifesto, “We know from painful experience that letting a third party layer of software come between the platform and the developer ultimately results in sub-standard apps and hinders the enhancement and progress of the platform.” To help y’all out, we’ve created the below how-to guide to accomplish just that. We at Macgasm say go Flash-free! There are significant performance and battery life gains to be had by forgoing the finicky Flash plugin in OS X. What are everyday Mac users to do, stuck in the crossfire? Adobe is fighting back by working with smartphone manufacturers to create mobile, Flash-enabled devices. Flash war is still raging, with Apple shipping the new MacBook Airs sans Flash plugins. Twibbon can add a Pride ribbon to your Facebook and Twitter profile photos and help you coordinate messages of support and related content across both social platforms. Instagram also offers Pride-themed emojis, GIFs and stickers to add to your Story posts.Īnother way of showing support for LGBTQ causes is to create a campaign through Twibbon, a web tool that helps users get exposure for their brands, charities and initiatives. These include: Celebrate Pride: Rainbow Your Life, Pride Filter and Make Me Pride (Flag). If you don’t love any of Facebook’s Pride features, there are a handful of third-party apps that will help you put custom Pride filters over your favorite photo, then upload it to your profile. Once you find your keeper, click “use as profile picture” to finalize the edit. Just click on your profile picture and it will give you the option of adding a Pride-themed rainbow frame or filter.įrom here, you can browse different options and use the preview feature to test out each look. Its what we do, were a Transgender Pride filter app Its easy to use our profile picture maker to get profile picture effects and customize your profile picture. Well add the Transgender Pride effects for you. Facebook in particular makes it easy to add a little rainbow spirit to your profile. Transgender Pride Filter Just click the button up above to select an image from your photo library or take a brand new profile picture. Madison Malone Kircher Next, select the image (or images) you want to edit and share. Pride-themed products and symbols have seen an explosion in popularity, and now between stickers, T-shirts, buttons, bags, flags and magnets, you can quite literally show your stripes anywhere. Add filters & effects to create your style Choose from a range of stunning, adjustable filters for a style that sets your photo apart. First, open the Facebook app and tap the 'Photo' button at the top of your phone screen. Please look at the time stamp on the story to see when it was last updated.įor many people, it’s time to remember a key rule of Pride month: showing support for the LGBTQ community by plastering rainbows. This is an archived article and the information in the article may be outdated. Put the gay pride arcoriris flag on your photo online Select the effect to use Upload photo It's very easy just upload a photo and in a few seconds you will have the colors in your photo celebratepride Start Online editor to put gay pride colors in your profile image on facebook twitter or instagram. This effect is more pronounced if you have a high interest rate or if you start making extra payments early in the loan term. You can enjoy full vehicle ownership sooner.Īnother reason to make extra car loan payments is to save money on interest. First, it’s nice to get rid of a monthly payment. There are a couple of reasons to pay your car loan off early. Of course, this is a rough estimate because it doesn’t take your current month’s payment into account or any prepayment penalties that might be in your loan disclosures. In other words, you’d finish the auto loan 12 months early. This gives us 24, which is the number of months it would take to pay off $8,000 with your payment amount. Then, divide this $8,000 by your monthly payment amount of $333. You’d subtract that from the remaining balance of $12,000 to get $8,000. Now, say you want to pay an extra $4,000 this month. The result is the approximate number of months it would take to pay the loan off.Īs an example, let’s say you have $12,000 left on your loan and there are 36 months remaining in the term.Divide the remainder by your monthly payment.Subtract the lump sum from the current balance.Write down your current monthly payment.Write down the remaining months and current balance.However, you can find an estimate by doing your own calculations. What if you want to make a large one-time payment on your auto loan? Most auto loan payoff calculators calculate extra monthly payments, not a single lump-sum payment. |