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Casey Reinhardt and Mahsa Townsend didn't have a tough task when they coined the name for their radio show. All they needed was a short phrase that encompassed the cupcake business, the real estate business and the general topic of love and relationships.
The answer was simple: "The Sweet Spot." Or, at least, it's simple in Reinhardt's telling.
"I'm, obviously, in the sweets business — cupcakes," explained the co-host of KX 93.5 FM's Sunday night show, which launched shortly before the new year. "And then Mahsa is in real estate, so it's a spot."
That's "spots," of course, as in decent spots to call home. And it's not the only way Reinhardt and Townsend play up their dissimilarities. The show's official logo shows two silhouetted figures, one sporting a pink apron and holding a giant cupcake and the other leaning casually in what appears to be business attire. The show's description on the station website trumpets the hosts' "totally different backgrounds."
In terms of comparing those backgrounds, a two-column chart might work better than a paragraph. Reinhardt works in confections as the owner of Casey's Cupcakes, Townsend in real estate. Reinhardt hails from Laguna Beach, Townsend from Iran, which her family fled amid political turmoil. Reinhardt is single, Townsend married with a son.
OK, when it comes to age, they are not too far apart. Reinhardt is in her late 20s, Townsend in her early 30s.
On the other hand, they're both savvy businesswomen. And they both believe in a combination of modernity and chivalry, which is to say that they pursue lucrative careers while preferring that the man pick up the dinner check.
It's that delicate chemistry, for "The Sweet Spot" creators, that keeps their program exciting week after week. And it's what convinced Tyler Russell, the founder and program director of KX, to take a chance on a pair of first-time hosts.
Russell met Reinhardt, a Newport Beach resident whose company owns six Southern California locations, at a mutual friend's birthday party. She soon introduced him to Townsend, of Tustin, whom she had met through a man she dated, and the three sat down to brainstorm ideas for a show.
The ultimate topic for "The Sweet Spot" arose from that conversation, according to Russell.
"The girls spent so much time talking about their dates or husbands or experiences with guys that it was just kind of a natural, organic fit for them to be hosting on that subject," he said. "So it sort of came together. We sat down for like an hour, and they gave me some girl advice, I think."
So what was the advice?
"I can't remember what it was that day," Russell said. "They give me some every time I see them, I feel like."
Advice is Reinhardt and Townsend's metier. Every Sunday at 9 p.m., the two go on the air to talk about the ins and outs of relationships: friendship, romance, family and more. Their first show in January outlined love-life resolutions for the new year; a recent episode invited callers to debate the reasons men cheat on their partners.
Though the hosts consider their personalities different — Townsend harder and more outspoken, Reinhardt calmer and sweeter — they didn't begin the show as Siskel and Ebert-style adversaries. The two have been close friends for more than five years, and Reinhardt served as maid of honor at Townsend's wedding.
"We're living two completely separate lives, but we have very similar morals and values, and we both are very business-oriented and very business-minded," Reinhardt said. "We connect on that level."
That bond grows even tighter when Reinhardt and Townsend have a foil on the air. During the cheating episode, which aired Feb. 9, the hosts discussed infidelity with a slew of males, including a guest who attributed such behavior to genetic hard-wiring and a caller from South Carolina who dismissed it as a symptom of rotten human nature.
After the last caller, the time came for closing statements.
"Oh my gosh," Townsend said. "I would — this is insane to me. Men, this is making me so sad."
"I wish we would have, like, taken a poll of how many people, like men, think it's OK to cheat if their girlfriends or wives don't find out," Reinhardt added.
"All of them are gonna say yes, except my husband," Townsend retorted. "Because he knows I know his voice."
The Sweet Spot
Format: Talk radio
Hosts: Casey Reinhardt and Mahsa Townsend
Time: 9 p.m. Sunday
Station: KX 93.5 FM


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May 2008 Issue
Complete O2 Systems: Aeromedix is Top Value
But its not quite as simple as that. We found good deals from Aerox and SkyOx, too, but features and accessories vary. Read our fine print for more.
Its no secret serious use of a personal airplane requires climbing far above pattern and practice altitudes where the air is thinner and true airspeeds peak. That, more than anything else, may explain the veritable explosion in complete, state-of-the-art portable oxygen systems and the accessories that go with them. If your airplane doesnt have built-in oxygen, and the time and money to add it isnt in the cards, youre a prime candidate for a portable system. Total cost for a two-user system? Under $500. But if you usually carry more people or need a few bells and whistles, things start getting complicated: The choices available from some vendors can be almost as dizzying as five hours in the teens without O2. In the January 2008 issue, we examined in detail new accessories such as regulators and cannulas, but we skipped discussing full systems. So in this article, were considering the whole enchilada, so to speakcomplete, in the box systems. Since we last examined this topic five years ago, the market has become more competitive and there are some excellent values out there.
To continue reading this entire article you must be a paid subscriber.
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subset: commoncrawl


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Kanye West sure did create a perfect workout song! I want more of these songs for workout in my mp3 player, I mean dude, this tune drops the beat like a motha fucka'.
The beat is strong and you can go pump up your muscles in the gym; It also has a slow part at the beginning just like that calm before the storm!
Go lift some iron bro but first of all, listen to "Blood on the leaves" from Kanye West!
Because I like you guys, here's a workout top tip:
Keep your cardio after the hardcore workout because after a research was conducted, it appears that the growth hormone is drastically reduced if you first do cardio and then lift weights at the gym. If you want more muscle gains, keep this top tip in mind !
What do you think? Is this a brilliant gym song or not?


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Are you cause driven and can embrace our mission where brain tumors are eliminated? Are you a person who can partner with the CEO to create a great workplace culture? Join us as the Senior Human Resource Manager to be a strategic partner to this important mission.
As a member of the leadership team, the Senior Human Resource Manager is responsible for the strategic planning and visioning of the organization in addition to overall management, coordination and evaluation of the human resource function. This position is responsible for developing and implementing Human Resource programs and functions while advocating positive employee relations and best practices in support of organizational growth and strategic initiatives. The American Brain Tumor Association (ABTA) (located near O'Hare) is a steadfast advocate on behalf of the brain tumor community in the U.S. where we help patients, caregivers and their loved ones navigate the brain tumor journey. Visit us at www.abta.org for more information about our mission.
Position Duties and Responsibilities of the Senior Human Resources Manager
Knowledge / Skills / Abilities
Salary is in the mid to upper $70k range.
If you share our passion for human resources and creating a world free of brain cancer, please forward your resume by clicking the continue to application button.
Equal Opportunity Employer The ABTA, inconformity with applicable laws, is an Equal Opportunity Employer and does not discriminate on the basis of race, color, sex, sexual orientation, age, religion, national origin, or disability.


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In short, the short, short story below is an account, a narrative – however brief it may be – about two forces of nature – wind and sun – at work and how in harnessing energy from such can indeed benefit humankind. I ask: Is there a better story to be told?
Chapter 1: A great disturbance in the air
Wind: Call it air with attitude. Call it ineffable. Call it tough to pin down or put a finger on. But however it's described and whatever one thinks about it, wind can be sized up thusly: One, it blows. Two, it howls. Three, it rouses. And four, it's out-of-sight, no, I'm not talking "cool" here but it could be that too.
If wind is what people are in search of, look no farther than California's San Gorgonio, Altamont or Tehachapi passes.
And, how exactly, can one tell there is wind in them thar hills? Wind turbines; the presence of wind turbines is how.
That this telltale tale is being told at all, tell me, what would any good story be without making reference to the dark side, oh, and there's a dark side all right, in this case the part where the fly-by-night, day or what-have-you wind picks up an unbecoming and unwelcome hitchhiker going by the name "air pollution" and discharges such wherever. In blowing through the Altamont for example, if any pollution is adrift in the air, more often than not, it will end up smack dab in its eastern neighbor's yard – the San Joaquin Valley, all on account of prevailing winds, that is, unless there likewise exist Valley winds to carry the pollution on past there. It is bad enough that the wind can pick up pollution, but if air currents are strong enough, dust and other debris can get kicked up as well. That's when things can get hairy and in a hurry and sometimes does. Which reminds me; once on my way through the San Gorgonio Pass, the wind there was blowing so fiercely it was all anyone could do to keep from getting blown away.
Chapter 2: Starpower
Since every picture tells a story, in order for the picture to be complete, wind cannot be mentioned without mentioning the sun. That'd be like peanut butter minus the jelly or burgers without fries. Bite my tongue!
Having said that, this is where the sun comes shining through and sunlight shows its true colors. And you can bet your bottom dollar that where the sun does shine it follows there will be solar; as in solar-collecting-stations or solar-panel-array-outfitted homes and businesses.
Now, whereas wind turbines generate electricity from mechanical energy via sufficient air currents, solar systems generate the same using light. In the case of solar collectors, heat too is produced and that, of course, can be used for heating purposes.
That the technology exists to create electricity and heat from plentiful wind and sunlight, and yet at the same time is done in sustainable fashion, it's win-win all the way.
End of story … for now, anyway.


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Northwest of Simikot, the principal airport of West Nepal, lies the remote valley of Limi (a.k.a. Takuche Khola) and its three villages: Jang, Waljie, and Til. They are Tibetan in culture, isolated in winter, but linked to China by a road over the Lapche La (ca 5,000m) for three months of the year. Northeast of Simikot lies the Chuwa Khola Valley, descending from the Changla La, an ancient traders' pass across the border. Between the two there are ca 15 summits of 6,000m or above, all virgin and most unnamed.
We wanted to visit this paradise for exploratory mountaineering, ascending the Chuwa Khola before branching left and crossing the Nying La from the east. After this we planned to climb Ashvin, one of the 6,000ers. However, heavy spring snow blocked normal access routes to Limi. Desperate to reach Waljie and its four-faced Vairocana Buddha statue, unique in Asia, we decided to go west from Simikot to Yangar, and then cross the small Phupharka Himal to the north. Reaching a base camp proved easy with mules. We then left our Nepalese staff, crossed a snowy col (Phupharka La, 5,175m), and in passing a second ridge climbed a peak we named Vendée Himal. We reached the Limi Valley with just sleeping bags in our rucksacks. We were delighted with the statue and the hospitality of local villagers, but after we returned to a high camp on the Ardang Glacier, bad weather thwarted our plans to attempt Ardang (6,034m) or Tirawa Himal (5,876m). We forced a passage across the Ardang La (5,580m) and reunited with our Nepalese team.
Ardang, either by the easier south face or more directly from the north, presents an attractive objective. It should be on the list of new peaks opened by the government in 2014. I also suggest you look at Phupharka Himal (5,630m), especially its elegant north ridge.
Paulo Grobel, France


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Free support group for caregivers of dementia sufferers
Beverly | Website
This event occurred in the past.
Map | Find Parking
Residents of Chicago's Beverly/Morgan Park neighborhood who are caregivers of older adults with Alzheimer's disease or dementia are invited to attend special programs offered by one of the area's leading life plan communities. Meetings begin at 6:30pm and topics vary each month. Call to register in advance.


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Guangzhou Autumn Fair.
The CCTV, China most popular and authoratitive TV station reported that Guangzhou Autumn Fair this year is more worse than expected. Especially the foreign customers' quantity is 10 % less than last year.
This data indicates that the economy next year will not be good, or even worse than we expect. But on the other hand, we can expect that more customers will buy from the internet which is more easier,quicker and convenient. We hope that our retail business on our sexy lingerie website, dhgate, and aliexpress next year will be better than or double this year.Because the sales trend shows that people purchasing habit changes a lot while the internet influence is everywhere.
It is bad news, but also good news. It all depends on how you read it!
Guangzhou Autumn Fair
Guangzhou Autumn Fair.


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Connect, Chat Beta Testing, and Hear from Dating Expert, Gabi Lovve
(Sponsored by Smartbeer. We'll Have Wine Too!)
RSVP HERE: updateme.eventbrite.com
We're not the only one trying to solve our frustrations with the dating space. Ray Ficken, founder of Updateme, is too!
A couple of years ago Ray was at home on a Saturday afternoon thumbing through Facebook and Plenty of Fish when the desire to post a status update on POF triggered - "Anyone wanna go for Happy Hour?"
The thought birthed Updateme, a social dating platform that allows users to broadcast status updates to initiate conversations and discover potential matches based on common interests.
Updateme is now available in the App Store but before they attract users, feedback is needed!
In the spirit of collaboration, we're helping Updateme curate men and women for Beta Testing. Sunday evening we'll connect, talk the app, and receive a few dating "tips" from Dating Expert, Gabi Lovve.
Following the event and if you then choose to Beta Test with Updateme, we'll ask that you:
- Download the app and be active on it for the 12 days following
- Join the Facebook Updateme Beta Group for communication purposes during the 12 days
- Dial into two (2) of the scheduled calls to provide feedback OR email detailed and honest thoughts / feedback as it arises
- Help Updateme create an offering that's desired!
In return for your full participation during the Beta Test Period, you'll connect deeper with each other, focus on your dating life and we'll give you $100!
Join us! You never know who you'll meet!! :)
RSVP HERE: updateme.eventbrite.com


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Often mistaken for topaz, citrine is a variety of quartz found mostly in Brazil. Its name comes from the French word for "lemon," a reference to its soft yellow to golden-brown color which is caused by ferric iron. The discovery in Brazil in 1979 of a unique deposit of citrine in conjunction with amethyst resulted in a new gemstone called ametrine. Though they are sister quartzes, the cause of their combined occurrence is still a mystery. As a healing stone, citrine is associated with relaxation of mind and body and can be helpful to the digestive system.
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In the win column: I have written blog entries since November 17. Some even pre-date that.
In the lose column: I didn't finish any of them.
So over the next week I am going to engage in some binge blogging, posted in order of origination. Brave Rudolph has offered to lead the way now that he is out of a job for the next 11 months.


text: Srbljanović, Biljana March 2011. © Струјајое Biljana Srbljanović, born in 1970 in Stockholm, has written plays since 1995 and has already had much success on the stage with Beogradska trilogija [The Belgrade Trilogy] and Porodične priče [Family Stories]. She has also been extremely successful with subsequent plays, which, in addition to numerous productions, have lead to repeated invitations to international festivals, contracts for work from well-known German theatres, and awards such as the Ernst Toller Prize and the "Europe Prize New Theatrical Realities" (Premio Europa). Her plays have now already been produced at over 100 theatres worldwide. Biljana Srbljanović lives in Belgrade and Paris. Books:Stücke aus SerbienСкакулци и други драми


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This post was for most of you is too late, but I talked to many people who are still just in social networks and try to organize all parties. If your background, eight ball, give me your tips, starter.
Firstly, you must understand how social marketing is due to the fact that I say that it is not really a commercial platform, how much you suggest. Dave Evans has written a book on "media social marketing-hours per day" and "social media contains natural, genuine conversation between something people or common interest, built of ideas and experiences of participants in the conversation". I believe that this statement completely, and this is something that you really remember when you start your social networks."Social" IT is a network cannot give rise to some things sometimes, and I hope that someone in the notification.est a chance to demonstrate their commitment to communicate with clients and with them you really work.
There are many companies that can help you with the creation of the network (including us), but a challenge really, it is not set them, follow the actual comments and interaction. People do not want to see only the posts of "Hey look at us, we offer nothing but look!"Want to try to provoke a conversation, interaction with you and your company can be special called in. and Aginský? true but with the upholstery. If you make a sale, you can block the desire and your time and effort is wasted.
When in the Office, we connect to our network and the only customers speak and try to work as possible.anniversaire, ads, or simply "Salvation" to go far in relationships online. Many network services such as Facebook to perform this type of interaction is very easy.For this reason, I recommend that you start here on Facebook.
It is literally hundreds of social networks to develop some are and some of them are really bad, but Facebook has the largest tool and the best (in my humble opinion) created at the beginning of the.do not, however, forget that Facebook is not designed for businesses of offer of personal is the interaction of any advertising to create a page for your company to some part.Dans in many cases, you can create a personal page, than the "pages" to add the site to serve as company ECE profile ' mentioned above, we can help in this process and usually free (depending on how you want to longing).
This gives you the location of the default anyway, and I hope that more tips in this section, the number of questions that we keep checking each week more updates.


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Large multi-level head offices needed plant solutions for several different areas.
In foyers we used large Dracaenas on one level & Ficus Topiary on another.
To fill a large stairwell we placed a 6m Black Bamboo, Magnolia arrangements in boardroom & in open area courtyard- Dracaena Troughs & Boxwood Topiaries.
Address: 4 / 117 Ashmore Rd, Benowa QLD , Australia 4217
Email: firstname.lastname@example.com
Google Maps: See our location online.
Toll Free: +61755278955


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Big Fat Soap
Peppermint Bar - Temporarily Out of Stock
The fresh and clean scent of peppermint can be your happy wake up call in the morning. Go ahead, shampoo with it! You'll see what we mean. But make no mistake, this one is mild enough for the most sensitive skin - even for delicate face cleansing. Take it with you in your travels to lighten the load and simplify the toiletries packing experience. Bath, shower, shave and shampoo all with one simple bar of soap? Try it, we're confident you'll love it! Like all of our handcrafted soap, the Peppermint Bar is a chunky 6 oz. hard, long-lasting bar, because we want our customers to receive the best value possible.


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Say thanks to
They came by ship - Assisted Immigrants who arrived on the John Barry in 1839Passenger lists - NSW lists as families or singles, Victoria has age of individual, or C=child, A=Adult.
Some are not on both lists, people slip between the lists - Vic includes crew and maybe the paying passengers.
John Dunmore Lang's Bounty Scheme Life was tough in the Highlands in the 1830's. Many people were living in appalling conditions; the crofts were too small to support expanding families; kelping was no longer as profitable; men were forced to travel to the Lowlands in search of seasonal work, disrupting family life and tenants were turned out to make way for sheep grazing land. Families lived in squalor in one roomed huts which they shared with their animals. The years of 1836-8 had particularly high rainfall and the peat was so saturated that it was useless as fuel and the crops failed. People were cold, starving and life was miserable.
John Dunmore Lang's Bounty Scheme (1837-1841) sought to bring out Scottish Highlanders to the Australian colonies. Lang believed that although poor, they epitomized the moral values and solid work ethic which would improve the tone of Australian society which was largely convict based in the 1830's. They were honest, God-fearing and hard-working free settlers. There were 20 ships in the original Bounty Scheme which gave assisted passage to about 4000 Scots between 1837-40 These ships were the John Barry, William Nichol, Midlothian, Brilliant, Duncan, Lady Kennaway, William Roger, St. George, Boyne, Asia, Lady McNaughton, James Moran, British King, Hero, David Clarke, George Fyfe, Henry Porcher, Glen Huntley, Dauntless and Calder.
My GGGGrandparents, James and Anne Cameron and their 5 children ( John, Jessie, Alexander, Dugald and Margaret) along with nephew James Cameron, sailed from Tobermory on the Isle of Mull, on the 28 October 1838 on the British King, a "Government Emigration ship." On board were 140 adult males, 32 children, 112 females and 43 children. Six births took place during the voyage including that of baby Jane to James and Anne Cameron. Sadly, Jane died after arrival in Port Phillip aged 7 months. James was described as a farmer and Anne a dressmaker and both came from Ardnamurchan, they were literate and belonged to the Church of Scotland. My ancestors were fortunate in their choice of ship. A school was established on board and "35 scholars attended regularly- all of whom made great progress." It was noted that, "whenever weather permitted they were made to appear on deck" and "the greatest attention was paid to cleanliness." The ship's surgeon was happy to report that "all the immigrants have arrived in the colony in a healthy state."
On 2 March 1839, the 'Sydney Gazette' reported, " The principal part of the emigrants on the British King are farm laborers and shepherds. They are a healthy and respectable sort of people. Great credit is due to the officers and surgeons on board for the cleanly state of the vessel. There were 7 deaths on board, one adult of consumption and 6 small children." Dr Donaldson had pointed out that it was not babies but small children who had just been weaned who were most likely to die.
The newly arrived immigrants were not all destined to remain in Sydney. Local settlers were not particularly interested in hiring men with large families and Governor Gipps was persuaded to send, at Government expense, 48 families from the British King on to the Port Phillip district of N.S.W. which was in great need of free settlers, as labor was scarce. The John Barry was the second vessel to bring Government immigrants to the district. The Cameron family arrived at Port Phillip on the 28 April 1839.
"When they disembarked at Williamstown, no shelter was available and they had to spend their first night in the open. William Lonsdale found 'a miserable hut' to accommodate those who had fallen ill with typhus fever and dysentery. Lonsdale pleaded with the Sydney government to make proper arrangements for the reception of any future migrants. Gipps replied that a permanent establishment must not be set up. Once again all healthy migrants managed to find work in Port Phillip without difficulty."
1837 The "John Barry" was quarantined in Sydney, and passengers helped to build the hospital.
1838 The "William Roger" was quarantined for typhoid with 295 passengers. More than 60 passengers died - 29 of them at the Quarantine Station.
John Barry520 tons, master J Robson, arrived from Sydney, 28 Apr 1839 at Port Phillip with 48 families from the British King, 199 men, women and children. All the healthy immigrants obtained work without great difficulty as labour was scarce - though 15 of the 42 listed just got day work in Melbourne. Donald McDonald 17 and the families of William Matthews, Donald McPherson and Duncan McDonald remained in the sick quarters.
From Scottish emigration, in March 1837 the first ship sailed with a full complement of emigrants from Scotland under the government-organized bounty system, as distinct from the shipping out of bounty emigrants by private individuals under licence. This was the John Barry, which sailed from Dundee to Sydney with 323 emigrants selected by Dr. Boyter, mostly from the Lowlands, and including in their number many craftsmen, especially masons and joiners, and several engineers, farmers, and shepherds.
The following excerpt from Michael Cannon's book 'Who's Master? Who's Man? Australia in the Victorian Age'. Thomas Nelson (Australia) Ltd., 1971. pages 128-129, relates the nature of sea travel to New South Wales for migrants.
"The former convict ship John Barry boasted one bath tub and two privies to cater for its normal complement of 300 felons. When it was 'converted' in 1834 to carry migrants, the facilities remained the same but more people were packed on board." Embarked 24 Mar 1837 with 87 men, 95 women, 44 children 7-14, and 97 under 7, total 323. 10 were born and 3 adults and 22 children died of 'fever' on the voyage from Dundee, in the care of Surgeon Superintendent D Thomson, arrived in Sydney on 13 Sep 1837. 12 died while in quarantine after arrival. A Quarantee facility was later built in Sydney.
The vessel arrived off Williamstown in Port Phillip on April 28th with passengers sick with typhus on board. Perhaps Jane Matthews was the unwitting carrier of the disease vector (lice) from the Quarantine Station onto the John Barry. The records have not been checked to see whether others, besides Jane, left quarantine to become a passenger on the John Barry.
Bounty passengers - each link is to notes on each family or individual, including details from the shipping lists
GP Anderson 37 with wife and son,
David Barry 28 single,
John Bowden 43 with wife aged 40, son and 5 daus,
Michael Burke 24 with wife Catherine,
James Cameron 38 with wife and 6chn,
Moses Carr 42 with wife and 7 chn,
Maurice Conner 48 with wife Ellen, 3 chn,
Patrick Conner and David Conner,
Cooper Dickson 27 single,
John Ellis 26 with wife, dau and 3 sons,
David Fitzgerald 25 single,
Mary Fitzgerald 22 single,
Michael Fitzgerald 40 came with wife Mary and 3chn,
Simon Fraser 44 widower with 6chn,
James Gamble 34 with wife, 2 sons,
Thomas Henry 23 with wife,
James Hunt 42 with wife and 4 dau,
John Hunt 46 with wife and 4chn,
William Kirkpatrick 29 with wife and 2 chn,
Margaret Madigan 50 Widow with John Madigan 28,
Ellen Madigan 18 and Mary Madigan 21 and Patrick 5,
Edward Matier 37 with wife and 4 sons,
William Matthews 41 with wife, son and 3 daus,
Alexander McDonald 30 Single,
with sister Jane McDonald and dau Mary 1,
Donald 1 McDonald 34 with wife Margaret and 6 chn,
Donald 2 McDonald 44 with wife Uphemia and 7chn,
Donald 3 McDonald 48 with wife Mary and 6 chn,
Duncan McDonald 36 with wife Mary and 4 chn,
Flora McDonald 20 single,
Hugh McDonald 30 Widower with John 3 and Mary 1,
Hugh McDonald 17 single,
James McGin 30 single,
John McKillop 56 with wife and 2 chn,
Archibald McLean 31 single,
Donald McLean 36 with wife Mary and 3 chn,
Donald McPherson 48 with wife Anne and 7 chn,
John Montgomery 22 single,
James Mullaney 31 widower with 3 chn,
James Neville 30 with wife Bridget and 3 chn,
James Parks 29 with wife and 4 chn,
Dennis Sullivan 52 with wife and 5 children,
Owen Sullivan 32 with wife Mary and 4 chn,
Robert Waugh 35 with wife 32 and 2 sons,
John Winder 43 widower with 4 chn
|Please Email me.
England - Tetbury around 1735
First site was our Anglican parish
This latest is Victoria to 1847


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Your small or medium-sized business deserves more than just an 'IT guy' for your computer services – you need a technology partner who takes the time to listen to your needs, who understands your business, and who can design and deploy solutions to your problems. Of course, you also need someone who can show you how to harness the power of technology to help grow your business too.
With Tomorrow's Technology Today as your single point of contact for all things technology, you can:
We believe that there is no point undertaking any task unless you are committed to excellence. That's why we treat your business as if it were our own. We look at the bigger picture and pay close attention to detail so that we can deliver results you can actually see. Let us help you get rid of the unreliable IT guy today.
Lisa Niekamp-Urwin,
Tomorrow's Technology Today
Thanks for all of your help with the migration. I really don't know how it could have went much smoother. I was very impressed. I know I told Lisa I felt your guy's hourly rate was high, but you have proven it is one of those things where you get what you pay for. Thank you for over delivering on my expectations.
Luke Vantilburg,
Chief Financial Officer,
Van Tilburg Farms,Inc
We appreciate the service and support we receive from Tomorrow's Tech Today and enjoy the relationships we've built with your staff. I certainly would not hesitate in recommending your company for computer maintenance / support or web site work should I encounter a situation with a company looking for a provider for these type of services.
Larry Abels,
Cy Schwieterman, Inc.
My name is Becky Dues and I work at Midwest Certified Boom Repair Services Inc. Over the years, we have worked with various IT companies and people and have decided to continue to work with TTechT because of their polite, friendly and knowledge personnel. We had a major computer crash in 2010 and TTechT helped get us back up and running and worked directly with Intuit on or QuickBooks issues. We have since utilized TTechT's Smart services for continued monitoring on our computers and are alerted if a problem arises. I would highly recommend TTechT to anyone!! Read More
Becky Dues,
Midwest Certified Boom Repair
Services Inc.
Not ready to call us just yet? That's fine! In the meantime, we'd like to help you get to know us better by sending you a copy of my book. The Hassle-Free Way to Have Tomorrow's Technology Today - The Ultimate Business Owner's Guide for finding an expert, knowledgeable, authoritative, considerate, on-time, fairly-priced, dependable, technology strategist.
This free guide arms you with the questions you should ask a computer consultant before giving them access to your company's network, database, phone systems and even your office. And if you have a sneaking suspicion that your current IT guy is not delivering the level of service and support you deserve, this book quickly helps you determine if you're correct – AND tells you what you can do about it. Best of all, the book doesn't cost a dime and comes with no strings attached.
Get your FREE copy today!
Over the past decade we have helped numerous clients in rural Ohio lower their business risks, improve efficiencies and increase profitability. Read More
Working with TTechT you can expect:


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Belfast should be an example to the world of people overcoming differences, the Queen has said.
In a landmark visit marking Northern Ireland's steady transition from a violent past to a peaceful future, a symbolic visit to the once forbidding Crumlin Road Gaol echoed in her words.
The Queen and Duke of Edinburgh toured the 19th century prison with Peter Robinson and Martin McGuinness, Stormont's First and Deputy First Ministers - two of its former inmates.
Images of the monarch and former IRA commander exchanging pleasantries and small talk as they walked slowly past gloomy cells set the mood for a packed schedule in Belfast.
Undoubtedly a highlight of the trip for Northern Ireland was showcasing to the world the HBO hit series Game of Thrones - filmed at the Titanic studios in the old shipyard.
The royals were taken on a tour of the main sets familiar to millions of fans and met six of the leading cast.
It was this new era of life in Northern Ireland that the Queen drew on in an optimistic speech to invited guests, elected representatives and dignitaries at City Hall.
"I know there are many challenges ahead and peacemaking is not always an easy task," she said.
"But you have come this far by turning the impossible into the possible; and, as you face the future and difficulties that may appear insurmountable, always remember that the thoughts and prayers of millions, including my own, are with you."
The Queen added: "The world yearns for examples of positive transformation and of people overcoming differences.
"I hope and believe that Belfast will continue to be one such living example, and I want to thank you - all of you - from every part of this city for the hard work and dedication which you and your families have given to help reshape the city of Belfast and the lives of all the people who live here."
The Queen's undiminished popularity was another image of the day.
One young lad captured it best when he came within an arm's length of a security breach as he lent in for a selfie with the Queen in George's Market.
Throughout the narrow stalls dozens of other over-excited well-wishers lined up for a snap with a sea of smart phones and tablets at the ready.
The day's events began at "the Crum", an imposing courthouse and jail used for executions, jailing terrorists and the scene of some of Northern Ireland's most high profile trials and incarcerations.
Among the cells they passed in C Wing was the room where 12 condemned prisoners were hanged.
Sinn Fein veteran Mr McGuinness was held in the prison for over a month in 1976 on a charge of IRA membership - a count that was later dropped in court.
Democratic Unionist leader Mr Robinson was detained on a number of occasions during the 1980s for his involvement in protests against the Anglo Irish Agreement.
The site is looking to the future now and becoming a popular tourist destination with a visitor centre and plans for a whiskey distillery.
Mr McGuinness described the Queen's visit to the Crumlin Road prison as another "bold step" by the monarch.
"The vast bulk of our people appreciate the effort Queen Elizabeth is making to peace and the reconciliation process and I think many people will look at the visit to the Crumlin Road prison, for example, with a degree of astonishment," Mr McGuinness said.
The former IRA chief's demeanour in the company of the Queen was scarcely imaginable up until their historic handshake at the Lyric Theatre in Belfast two years never mind the dark days of the Troubles.
Despite heavy security cordons and rolling road closures hundreds of flag waving well-wishers lined the City Hall, as well as the front of the Crumlin Road Gaol and around St George's Market.
At the end of her walkabout, chairman of the traders Pat Dyer presented the couple with a hamper packed full of locally made products.
"It was absolutely superb," Mr Dyer said of the visit.
His three-year-old grandson Jack Morgan gave the Queen a cushion with an image of a helicopter on it for the youngest royal.
"He's been practising and he said when he handed her the cushion 'this is for baby George'," said Mr Dyer.
Dozens of schoolchildren were invited on a cross community basis to greet the Queen on arrival for a banquet with city councillors and dignitaries.
She used her speech to address their future and said they would see the words of her grandfather George V fully realised.
In 1921, at an address at the City Hall, the King asked "to stretch out the hand of forbearance and conciliation".
"Much has happened since I was last in the City Hall (in 1966)," she said.
"We have learnt a lot in those years about ourselves, each other, and how societies can only grow and flourish if they are built on trust, respect, justice and inter-dependence."
The Queen wore an Angela Kelly lemon light wool tweed coat with silver and black thread running through it and a silk lemon dress with floral designs.
Her hat, also by Angela Kelly, was lemon tweed and wool adorned with petals.
Later, at a garden party in Hillsborough Castle hosted by Northern Ireland Secretary Theresa Villiers she wore a Stewart Parvin peach croque coat, matching hat by Rachel Trevor-Morgan, a silk floral dress and a Queen Mary brooch.
She met a number of police and military personnel at the event including retiring Police Service of Northern Ireland Chief Constable Matt Baggott and the Army's Brigadier Ralph Wooddisse, commanding officer of 38 (Irish) Brigade.
Ireland's deputy prime minister Tanaiste Eamon Gilmore and former US diplomat Dr Richard Haass, who last year chaired ill-fated talks on Northern Ireland's legacy issues, also attended.
The royals mingled among the 2,000 invited guests, from a cross section of the community, and the Queen planted a tree to mark the occasion.
Throughout Comber Silver Band provided an upbeat soundtrack to the afternoon tea.
The symbolic visit unfolded after the Queen last night held her first one to one meeting with Mr McGuinness, having met twice previously.
The castle plays host to the Antiques Roadshow this week and the Queen and Duke will stop by to visit them tomorrow.
Her Majesty will also attend a Royal British Legion reception in Coleraine in Co Londonderry.
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"The Multnomah County Sheriff`s Office said an 88-year-old woman fended off a naked intruder by grabbing the man`s crotch and squeezing. Deputy Paul McRedmond said the man got into the house Tuesday through a sliding door. He backed the woman into her living room and pushed her face down onto a chair.
That`s when the woman reached behind and squeezed. The man tore free and fled."
The Associated Press
If I`m confronted by a naked intruder in my home, after a couple of seconds of stunned disbelief I would reach for my shotgun. But his dear old lady didn`t blink, she grabbed the bull by the horn. She squeezed the man`s privates, and the fool ran way in pain contemplating his shortcomings.
The intruder was caught a few minutes later by the police. I guess that night he was the only naked guy running while holding his family jewels.
I hope the brave elderly lady buys some secure locks for her sliding doors, she may not be so lucky the next time.


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"Originally I'm from Lubbock, a small city in west Texas. Educationally it's a great city, but musically there wasn't much to offer which is why I moved to Houston for more opportunities. Houston's underground artists and fans are somewhat of a subculture here which is cool."
Check out the interview with Zay Vasquez exclusively on Skilly Magazine Online.
Skilly: Where did this all start? Tell us about your journey in the entertainment business.
Zay Vasquez: Music is a family thing, so honestly it's all I've known from the beginning. Growing up I remember watching my grandpa, uncles, and aunts play together in the backyard on the weekends. My cousins and I had lip syncing battles while my family members played the songs for us. I began taking all of this seriously when I was about 16. I started off writing poetry, then I ventured off into songwriting and have yet to look back.
The entertainment business for me has been a roller coaster. Most of my issues have been having to start all over a few times because life hit me too hard for one reason or another. I would have to set music aside and focus on myself before I could start my music back up again. I've always held up to my responsibilities, so it's always left an open door for me to go back.
What would be your biggest piece of advice for the young kids out there trying to do what you do?
The biggest piece of advice that I have is to believe and invest in yourself because people will take you more seriously when you do. Also, try not to keep "yes men" all around you – meaning people that are quick to tell you it sounds good just to get you out of their face or just be around you.
What are some of the hardest challenges and tasks in your position?
One of the hardest things is being my own worst critic and over critiquing my work. Another thing is it's hard to stay current with certain issues in your music due to technology advancing so quickly even though the information is at your fingertips; there's still so much going on all the time.
We all know the entertainment business is very tough, but what do you find is the best way to promote and advertise your music?
Facebook is a great tool for promotion and placement where you need it if you're doing it correctly. They have online classes or you could hire a marketing team which can be expensive. Soundcloud is another great way to be heard and pick up a following as well as promoting your music.
Tell us about your city. How are the artists and the fans?
Originally I'm from Lubbock, a small city in west Texas. Educationally it's a great city, but musically there wasn't much to offer which is why I moved to Houston for more opportunities. Houston's underground artists and fans are somewhat of a subculture here which is cool.
It was a great experience to be a part of the tours with T-Lady of The Grinding Bulliez and Tessa Allen of Boss Hall Ent. The fans here are amazing and very receptive to the vast majority styles of music. However, there is a lot of undiscovered talent here.
Where do you see yourself a year from today?
I see myself furthered in my career while still honing my craft because it's a never ending process of learning. Also, picking up a few new skills along the way.
Who and what were your biggest inspirations? Who do you look up to in today's world?
My grandfather was my biggest inspiration to do music and still is. I'm helping to continue his legacy of music that passes from generation to generation. I don't have anyone that I look up to in particular, but I do admire a couple people's strategies in their road to success.
How do you feel about the music coming out today? Do you like it?
There's a few artists that are putting out good music. As for other artists, there seems to be an epidemic of music with no substance. The message they're giving is rubbish and gives no direction. I like the production more than I like the lyrics. I'm not speaking to everybody, but if the shoe fits wear it.
Where can we contact you and find you online?
Facebook: getdoeent
Soundcloud: get-doe247
Booking: firstname.lastname@example.com


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You are here: Manchester Confidential › Food & Drink › Bars.
WHITECIRCLECREATIVE, one of the companies based at The Greenhouse, MediaCityUK, has designed and built the first outdoor bar at MediaCityUK.
Dock Bar is being managed and run by Fluid Bars and will be located on the MediaCityUK piazza besides the double-side outdoor screen. The bar will serve alcoholic and non-alcoholics drinks.
Should the sun shine then the bar can be used as a comfortable viewing area for the Olympics on the screen. There'll also be the 'Summer in the City' events on the MediaCityUK piazza to keep people entertained.
WhiteCircle has utilised two 20ft shipping containers to form the Dock Bar structure, one being the main bar and serving area, and the other behind to form a store for deckchairs which will be out in abundance on sunny days.
Oddly, the arm of WhiteCircleCreative called WhiteCrate is behind the bar. WhiteCrate has one of the weirdest niche employment sectors of all specialising in the creative conversion of shipping containers.
The Dock Bar will open early week commencing 9 July.
Like what you see? Enter your email to sign up for our newsletters which are chock-a-block with more great reviews, news, deals and savings.
Wicked! I was at Box Park (built from 60-odd shipping containers) in Shoreditch yesterday... very cool!
I used to work here too Phil was such a legend, what happened to him??Read more
No Gretch, Cllr Gillard is Withington ward, part of which is famous for student house parties.…Read more
Sure those "skanks" would say Port Street beer house was populated by bearded identikit Chorlton…Read more
Yep the world would be so much better if it was inhabited only by the middle class hey Gareth. No…Read more
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Professional journals and fairs are another good source for applicants as long as the ads are timely. Hard copy ads can take a long time to appear in print, whereas online ads can be placed the same day they are received. Many services are for a 30-day minimum, which needs to be factored into the timeframe for accepting applications. The ATS administrator will help you to create your ad and ask that you or one of your team with a membership place the order to get the membership rate.
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Leicester City forward Ahmed Musa will be returning to CSKA Moscow, according to Nigeria coach Gernot Rohr.
Musa joined the Foxes in 2016 for, at the time, a club record fee of around £16m from CSKA Moscow. He played 32 times in his first season for the club, scoring four times. But this season, he has only made two appearances for Leicester City, in cup matches, scoring a goal in both games.
Foxes manager Claude Puel admitted earlier this month that the 25-year-old could be leaving the club during the January transfer window.
Nigeria coach Gernot Rohr seemed to confirm the player's exit from the club when he revealed Musa is returning to his former club in Russia. According to Score Nigeria, Rohr said: "Ahmed Musa is going back to CSKA in Russia, that is good news, because they like him there very much and he will get to play more."
Musa enjoyed a good spell with the Russian club between 2012 and 2016, scoring 42 goals in 125 appearances for CSKA Moscow. During his time there, he won the Russian Premier League three times, while also winning the Russian Super Cup twice and the Russian Cup.
If he does go, he will be leaving a Leicester City side who are currently eighth in the Premier League table. They are three points off Burnley and eight points behind Arsenal, who fill the two places above them.
The Foxes will host Watford next in the Premier League on Saturday as they bid to climb the league table.


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Journal of Nanomaterials
Volume 2012, Article ID 130725, 10 pages
Growth Mechanism of a Hybrid Structure Consisting of a Graphite Layer on Top of Vertical Carbon Nanotubes
1imec, Kapeldreef 75, 3001 Leuven, Belgium
2Department of Electrical Engineering, K.U. Leuven, Kasteelpark Arenberg 1, 3001 Leuven, Belgium
3Oxford Instruments Plasma Technology, North End, Yatton, Bristol BS49 4AP, UK
4Department of Physics and Astronomy, K.U. Leuven, Celestijnenlaan 200D, 3001 Leuven, Belgium
5Metallurgy and Materials Engineering Department, K.U. Leuven, Kasteelpark Arenberg 44, 3001 Leuven, Belgium
6Chemistry Department, K.U. Leuven, Celestijnenlaan 200f, Bus 2404, 3001 Leuven, Belgium
7Centre for Surface Chemistry and Catalysis (COK), K.U. Leuven, Kasteelpark Arenberg 23, 3001 Leuven, Belgium
Received 14 October 2011; Accepted 3 June 2012
Academic Editor: Jianyu Huang
Copyright © 2012 Nicolo' Chiodarelli et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Graphene and carbon nanotubes (CNTs) are both carbon-based materials with remarkable optical and electronic properties which, among others, may find applications as transparent electrodes or as interconnects in microchips, respectively. This work reports on the formation of a hybrid structure composed of a graphitic carbon layer on top of vertical CNT in a single deposition process. The mechanism of deposition is explained according to the thickness of catalyst used and the atypical growth conditions. Key factors dictating the hybrid growth are the film thickness and the time dynamic through which the catalyst film dewets and transforms into nanoparticles. The results support the similarities between chemical vapor deposition processes for graphene, graphite, and CNT.
1. Introduction
Graphene and carbon nanotubes (CNTs) are carbon allotropes with similar and exceptional optical and electronic properties [1] which can find applications as electronic or optoelectronic devices such as interconnects [2, 3], transparent electrodes [4], photodiodes [5], photodetectors [6], or solar cells [7]. The similarity in their properties derives from the identical atomic structure consisting of sp2-hybridized carbon atoms arranged in a hexagonal lattice and from the fact that the band structure of CNT is derived from that of graphene simply by confining the electronic wave functions to a smaller portion of a graphene plane [8].
Moreover, their manufacturing process is similar since CNT [9–12] and graphene [13–15] can be deposited via catalytic chemical vapor deposition (CVD) by exploiting the catalyzed decomposition reaction between a carbon precursor (acetylene for example) and a catalyst of the iron group (Ni, Co, or Fe). More specifically, the catalyst provides active sites for adsorption and decomposition of the precursor molecule and a template to organize the adsorbed and/or dissolved carbon into graphitized structures. The main difference between the two processes lies in the shape of the template; that is, a nanoparticle in the case of one-dimensional CNT or carbon nanofiber and a film (infinite large particle) in the case of two-dimensional graphene.
In this work, the link between graphene and CNT is further investigated by studying and explaining the formation mechanism of a hybrid structure consisting of graphitic layers on top of CNT. This peculiar structure is receiving increasing interest in the scientific community [3, 16–18] since it basically shows that an horizontal top electrode of graphite can be deposited over vertical CNT in a single process step at low temperature whereas most of the times the two materials are deposited with independent stand-alone processes at high temperature. For instance, a horizontal top electrode in graphite could serve for interconnections [3] as a protective carbon cap for the CNT underneath or as self-formed large area electrode to contact the carbon nanotubes [18]. Clearly, the coexistence of both graphite and CNT in a unique process window would offer advantages in terms of manufacturability using a relatively inexpensive single-step process.
In this work, the key factors dictating the process window for growing the hybrid structure are identified in the film thickness, studied here in a relatively narrow range, and the time dynamic through which the catalyst film dewets and transforms into nanoparticles (also dependent, among other factors, on the film thickness). A based growth mechanism is identified for the growth of the hybrid structure on TiN as observed in [17] but not in [3]. Its formation appears catalyst independent since the hybrid structure has been observed for Co and Ni on TiN (this work and [3, 17]), Ni on Ti [16], or for Fe on SiO2 [18]. Finally, based on the observations of catalyst debris near the base or inside the CNT, we agree with the qualitative idea that the CNTs underneath the structure form as a result of a catalyst in a viscous liquid-like state of high mobility over the underlying metallic substrate [17].
2. Experimental
Nickel and cobalt films of different thicknesses were deposited on a blanket 70 nm TiN/100 nm SiO2/p-Si stack by physical vapor deposition (PVD). The amount of material deposited by PVD was first calibrated on SiO2 test wafers and measured using Rutherford backscattering (RBS). The depth of the test films measured by RBS was 1.24 1016 atoms·cm−2, 2·1016 atoms·cm−2 for nickel and 1.02·1016 atoms·cm−2, 1.75·1016 atoms·cm−2 for cobalt, respectively. These data correspond to an equivalent thickness of about 1.3 nm and 2.2 nm for nickel and 1.1 nm and 1.9 nm for cobalt, respectively. Moreover, a film with an equivalent thickness of 5 nm was also included in the set of experiments.
In a typical growth experiment, a sample of each was loaded together. Pieces of 2 by 2 cm were placed next to each other in the center of a carrier wafer and processed in a plasma-lab CVD tool from Oxford Instrument consisting of a main deposition chamber with a heating stage of graphite connected to a load lock stage by a robot. Gasses are top injected into the main chamber via showerhead gas inlets in the top electrode.
As the exact sequence of tool operations during the growth experiments is important for the interpretation of the results, the growth recipe and the tool operations will be described in detail and are schematically represented in Figure 1 for clarity. All recipes begin with a load step where the samples are automatically transferred from the load lock into the main chamber in about 30 s. As soon as the carrier wafer is in contact with the heater in the last 5 s of the load step, the sample temperature rapidly increases to approximately °C, which is the sample temperature at the chamber base pressure of 3 · 10−5 Torr.
For temperature stabilization, the samples were left for 10 s (stabilization step) in the chamber at base pressure. Then, the growth step begins and a 5/495 sccm C2H2/Ar mixture was introduced into the chamber up to the process pressure of 4.148 Torr. Helium was also present in the chamber at this stage at a partial pressure of 0.148 Torr. As a result of the pressure increase, the sample temperature rapidly increases to about °C. Note that, except for the loading and stabilization steps, no extra heat treatment or catalyst activation step was done.
For all experiments, the growth step consisted only of the operations described above, except for the fact that the growth time was varied for 2, 5, and 10 minutes. After growth, the samples were characterized by SEM and TEM. For TEM analysis samples were sonicated in isopropanol for 10 minutes and few droplets of the solution were deposited on a carbon lacey copper grid and dried. The analysis was done with a HRTEM Tecnai F30 operating at 200 kV to limit damage to the CNT during beam exposure.
3. Results
Figure 2 shows the growth results for cobalt and nickel films with increasing film thickness after 5 minutes of growth time. Dense CNT mats were obtained for layers below 1.3 nm, while no CNTs were observed for films equal to and thicker than 2.2 nm, under the presented growth conditions. For the intermediate film thickness of 1.9 nm, CNT growth was also observed but an atypical layer can be distinguished on top of the CNT (Figure 2(c)). This top layer appears to be porous and some elongated CNTs extend through the pores. For a film thickness of 1.3 nm, a peculiar tapered shape was found near the top of the CNT mat, showing a broadening towards a platform shape on top of the CNT (inset in Figure 2(b)).
To study the type of structures in more detail, TEM analysis was done on the 1.1-Co, 1.3-Ni, and 1.9-Co samples. In all cases (Figures 3 and 4), the structures consist of multiwalls CNT with diameters 10.8 ± 3.4 nm for 1.1-Co, 13.1 ± 5.1 nm for 1.3-Ni, and 12.7 ± 5.0 nm for the 1.9-Co samples as measured by SEM.
For the thinnest 1.1 nm film, cobalt nanoparticles are located mostly at the extremities of the tubes (Figure 3(a)) whereas only a few were found in the interior of the tube. Similarly, the 1.3-Ni sample had particles at the tube extremities but the amount of particles found inside the tube interior was larger in this case. Figure 3(d) shows a detail of the tapered platform-like shape which was observed with SEM at the tip of some CNT (inset of Figure 2(b)). As for the 1.9-Co sample, a crust has formed on top of the CNT but isolated to a single or a few interconnected CNT in contrast to the closed (porous) layer formed on the 1.9-Co sample in Figure 2(c).
In the 1.9-Co sample, the crusty top layer indeed connects the tips of all neighboring CNTs as confirmed by the TEM image in Figure 4(a). Underneath the crust, straight multiwall CNTs are present as shown at high magnification in Figures 4(b) and 4(c). Note that under different growth conditions, carbon nanofibers were found underneath similarly crusted top layers [19]. The fact that the CNTs are still connected to the top layer allows us to unambiguously locate the root of the tubes. From TEM, it follows that a cobalt nanoparticle sits at the base or root of the CNT. Arrows in Figure 4(a) indicate the particles in the tubes and a high-resolution image of a cobalt nanoparticle at the root of one CNT are shown in Figure 4(e).
For the 1.9-Co sample, nanoparticles are also in the core of some tubes (Figure 4(d)). In particular, comparing the inner particles among the samples, their number and size seem to increase according to the initial catalyst thickness: few and smaller nanoparticles for the 1.1-Co sample meanwhile numerous and larger nanoparticles in the 1.3-Ni and 1.9-Co samples. Note that the interior "particles" can be quite elongated to rod-like structures (see Figures 3(e) and 4(d)) and in some cases even long nanowires suggesting the formation of metal filaments during growth.
Figure 5 shows high-resolution TEM images of the top-layer for 1.9-Co samples. Multiple layers of graphene form the graphitic top layer or crust (Figures 5(a) and 5(b)). Even though the TEM shows only clearly the graphene sheets at the very surface, they appear to extend much further but their visualization is difficult because of overlapping. The global structure looks entangled without long range order (polycrystalline). Small and elongated nanoparticles are found right below the graphitic top-layer; that is, in the tapered transition region between the planar graphite layer and the vertical CNT. The tapered shape is then formed by graphitic encapsulation of these catalyst particles, some of which are trapped into this transition layer, others already in the CNT below.
Figure 6 shows the Raman spectra of the samples analyzed so far (from Figure 2 to Figure 5). The spectra are reproducible and representative since they appear identical for different spots over the same sample.
The samples with CNT only (1.1-Co) and with CNT and a graphitic layer on top (1.9-Co) exhibit identical Raman spectra. This is probably due not only to the fact that the spectra of graphite and MWCNT of large diameter have strong similarities but also depends on the penetration depth of the laser in our setup using a wavelength of 632 nm and a 1 μm laser spot. For instance, a peak for silicon at 500 cm−1 is present in the spectra of the samples without CNT (2.2 nm and 5 nm) suggesting that the probed thickness is likely in the order of a hundred of nanometers as SiO2 is separated from the samples surface by a 70 nm thick layer of TiN. The top graphite layer, instead, is expected only few nanometers thick (from TEM) so large part of the Raman signal originates from the MWCNT underneath.
In all the samples, the typical features of graphitic materials are present in the first-order Raman spectra: that is, D and G bands at ≈1350 cm−1 and ≈1580 cm−1, respectively. Considering the pronounced shoulder in the D peak at about 1100 cm−1 and the fact that the D and G bands merge in the region between 1350 cm−1, and ≈1580 cm−1 it is concluded that the samples contain some degree of disorder. In fact, the TEM images of the graphite top layer (Figure 5) revealed a polycrystalline structure made of small domains of undulated fringes continuous over a length of few nanometers only. The edges of each domain can be considered as defects which contribute to the broadening of the D and G peaks as discussed in [20]. For graphitic materials with defects, a D' peak is also expected at 1620 cm−1 but it is not distinguishable here probably because buried in the G band as also expected for nanocrystalline graphite when small grains are present [21].
Similar arguments can also be applied to the samples with MWCNT even if broad G and D peaks are more typical because of the parallel contribution of several walls with different diameters. In particular, some degree of disorder in the structure of the tubes can be inferred from the shoulder at 2950 cm−1 [22]. Moreover, we noticed that the Raman spectra here reported are similar to those in [23] which were obtained for defective MWCNT and also to the spectra measured in previous works [24] on MWCNT grown at 470°C and 400°C. In this latter case, the quality of the MWCNT was quantified by extracting the electrical resistivity. The result showed indeed that those MWCNT behaved as diffusive conductors for a length of few hundred of nanometers, namely, as a material with some degree of disorder or imperfections. The 2D peak [25] at ≈2700 cm−1 is an overtone of the D peak also present in graphite and CNT; however, for what mentioned above, it is believed not to originate from the graphite top layer.
The point of major interest for our discussion is that the D and G peaks also appear for samples without CNT (2.2-Ni and 5-Ni) and which looked inactive in the SEM of Figure 2(d) and Figure 2(e). In particular, since the G peak originates from sp2 carbon domains [23], we conclude that for these samples some graphitic carbon is deposited on the catalyst in the early stage of the growth recipe even if CNT did not form.
The CNT length and consequently the height of the graphite top-layer increase linearly with growth time as shown in Figure 7(a). From the slope, a growth rate of 136 nm/min was found. The intersection with the time axis suggests an incubation time of about 20 s before the graphite layer is lifted off by the CNT. The top-layer morphology did not change significantly with growth time as ascertained from the SEM images in Figures 7(b) and 7(c).
To assess the effect of pretreatment time [17] on thicker films, the 10 s stabilization step was extended to 2 minutes which is equivalent to a thermal pretreatment of 2 min and 10 s at 480°C in vacuum (≈10−5 Torr) before the introduction of acetylene gas for growth. The remainder of the growth recipe was kept the same. The results for the 1.9-Co and 2.2-Ni are presented in Figures 8(a) and 8(b). CNT growth was now observed in both cases without formation of any graphitic layer on top. The 5-Ni film still did not show any growth but after the thermal pretreatment was further extended to 10 minutes, CNTs under large patches of a graphitic top layer were achieved also on this sample (not shown here). Figure 8(c), instead, shows that CNT with a graphite top layer can also be grown in patterned structures using 1.3 nm of Ni and the same recipe without pretreatment used to grow the structures in Figure 2(b).
4. Discussion
The atypical structure observed in the 1.9-Co sample of Figure 4 basically consists of two components: a 2D graphitic top layer on top and a mat of 1D CNT underneath. It is here explained by the interaction between acetylene and the surface of the catalyst template which dynamically changes shape during the process; that is, from a planar film to distributed nanoparticles with possible formation of nanofilaments [28] as the first graphitic layer lifts off from the surface. Note that the term "nanoparticles" has to be seen in a broader sense in this case, namely, as a nucleation center for a CNT (e.g., extrusion in the metal film) which does not have a welldefined distribution in size and density as in the case of CNT growth with a controlled pretreatment or film dewetting step. The necessary conditions are discussed in more detail in the following.
For the decomposition reaction to occur, the catalyst template must be in its "active" state. In catalytic CVD of CNT, a pretreatment step is commonly needed to activate the nickel, cobalt, or iron catalyst. It is believed that the pure metallic form is the most active state for the decomposition of acetylene (access to the transition metal d-orbitals) [29–31]. Reactive reducing gasses like H2 or NH3 are typically used to facilitate reduction of the native oxide, especially for those catalysts whose oxides are more difficult to reduce, like iron [29–31]. However, in the case of nickel and cobalt, the oxide reduction or removal is much easier which explains their higher reactivity at lower temperature [12, 31, 32]. For example, in [31], peaks in the XPS graph corresponding to metallic nickel were found at relatively low temperatures in vacuum.
In the first series of experiments, no dedicated pretreatment step was deliberately done. As CNT growth was still observed for the 1.1-Co and 1.3-Ni samples (Figures 2(a) and 2(b)), it can be concluded that the conditions used were sufficient for the activation of the catalyst. Activation may occur either in vacuum, namely, during the sequence of load, stabilization, and purge steps (40 s at 10−5 Torr of base pressure and °C) or, more likely, during the very early seconds of the growth step where acetylene or the H2 present as a product of its thermal decomposition can both help the reduction of NiO.
Whether or not CNTs were formed (without a graphitic layer) was dependent on the pretreatment time. Indeed, it is generally accepted that catalyst nanoparticles are needed for CNT growth. Catalyst nanoparticles are typically formed by thermal [33–35] or plasma anneal [10, 36, 37] of thin catalyst films. Because of the larger energy available at high temperatures, the catalyst atoms become mobile which can lead dewetting of the film [38].
The results found here indicate that the time scale at which a film dewets and transforms into nanoparticles is strongly related to the initial film thickness. In fact, only the thinnest films (<1.3 nm) gave CNT when a short (process intrinsic) pretreatment of 40 s was done (Figures 2, 3, and 4). In the case of 1.1 nm Co, this is because either the film was thin enough to break with a 40 s pretreatment either because it was already discontinuous after deposition. The 1.3 nm Ni film, instead, showed small graphitic patches after the 40 s pretreatment. Since a graphitized top layer was observed for the same film in patterned structures (see Figure 7(c)), this film must have been initially continuous (see [26, 27] for details about the patterned structures). In this case, film breakup occurs during the 40 s pretreatment step, although partially complete.
Thicker films either gave CNT with a graphite layer on top (1.9-Co) or were inactive (2.2-Ni and 5-Ni) with only a 40s pretreatment. However, when the vacuum anneal pretreatment time was increased to 2 min also the 1.9-Co and 2.2-Ni yielded CNT without the graphitic layer indicating that the catalyst film was completely transformed into nanoparticles (Figures 8(a) and 8(b)). Even the 5 nm thick Ni film could eventually be broken into large patches after 10 min of vacuum anneal. Note that the assistance of plasma and reducing gasses may aid the dewetting of thick films [9].
Thus far, we have confirmed the notion that CNTs are formed only when nanoparticles are present before the growth step commences. Now, we will discuss the intermediate phase where the carbon precursor gas (acetylene) is introduced when the catalyst film is still, at least partly, intact. Indeed, the reshaping dynamic for films thicker than 1.3 nm occurs on a time scale of minutes. Hence, when acetylene is introduced in the chamber immediately after the load and stabilization steps, as for Figure 2, little time is left for these films to transform into nanoparticles. In the 2.2 nm and 5 nm Ni films, no growth at all was observed after 40 s of pretreatment. As the catalyst is active, though, these layers have been covered by a graphitic coating as confirmed by the presence of D and G peaks in the Raman spectra (Figure 6).
The 1.9 nm Co sample has a thickness intermediate to the extreme cases mentioned above. It is sufficiently thick to be continuous after its deposition but still sufficiently thin to fragment into nanoparticles when the pretreatment time allows for it. The incubation time of 20 s observed in Figure 7(a) indicates that CNT growth does not occur immediately after the introduction of acetylene. Hence, the film retains its 2D film-like shape during the whole load and stabilization steps and at least for the first seconds of the growth steps. Because the catalyst is active, the decomposition of acetylene can occur and a graphitic layer is formed on the surface of the film at this stage, similarly to what happens in catalyzed deposition processes of graphene [39].
At this stage, film fragmentation proceeds and after about 20 s CNT growth can start. Consequently, the top layer is lifted by the CNT structures growing underneath. Theoretical calculations showed that graphitized structures have low adhesion to nickel (100) [40] and Ni (111) [41] surfaces which supports the idea that the fragmentation of the underlying catalyst film can occur without being hampered by the graphite top layer. Note also that CNT growth might start either from nanoparticles as well as from sharp protrusions which form during the dynamic reshaping of the catalyst film under the graphite layer. In this latter case, metal filaments encapsulated in graphene sheets are observed at the bottom of the CNT like in Figure 4(a).
This seems a direct consequence of the fact that catalyst saturated with carbon appears is in a viscous semiliquid state [42, 43] suggesting facilitated reshaping. Metal atoms in this phase are much more mobile than in pure metal which leads the catalyst to easily deform into elongated shapes [28]. For example, elongation and reshaping of catalyst nanoparticles has been observed at the initial stages of CNT growth with in situ TEM [44, 45]. Hence, reshaping of the catalyst template can be facilitated by carbon; that is, after introducing acetylene in the chamber. Furthermore, the semi liquid carbon-saturated catalyst state explains how the CNTs end up partly filled with metal especially near the top layer where growth started.
A few remarks should be pointed out regarding the catalyst particles formed during this dynamic process. It is often mentioned that the CNT diameter closely matches that of the original nanoparticle. In particular, for MWCNT, a 1 : 1 correlation between particle's and CNT's diameters was observed in [46, 47] but not [48]. This rule does not apply here as the amount of catalyst found inside the CNT as debris is large and cannot originate from a single nanoparticle with the same diameter of the tube. It seems more plausible that CNTs start growing from particular nucleation points on a larger patch of catalyst. Because of its semiliquid state, the excess of metal is encapsulated in the final CNT and appears in its interior as nanoparticles. This is a major difference compared to most of reported literature data on CNT where the growth recipes had dedicated pretreatments to properly break the catalyst into well-defined nanoparticles.
As catalyst is observed at the CNT root as well as right below the top layer (Figure 5(c)), the CNT growth mechanism is not evident. Nevertheless, the fact that several elongated particles are observed at the CNT root suggests a strong catalyst substrate interaction sufficient to maintain the catalyst, or part of it, anchored to the substrate. The remaining excess of catalyst is dispersed along the entire tube's length as debris. This picture would lead us to propose a base growth mechanism as observed in literature for the Fe-TiN system [10] or for Ni-TiN systems [49–51]. The presence of pores in the top layer could suggest that these are the preferred channels through which the gas can reach the bottom substrate for feeding the catalyst reaction at the CNT base.
Our results have striking similarities with [3, 16–18]. Although the authors investigated the process window for different catalyst thickness and growth temperatures, a similar trend to that reported in Figure 2 can be deduced. In particular, a transition between CNT growth only, the growth of a graphite top layer on CNT, and no growth at all is observed when increasing catalyst thickness [16, 18]. The process window for the hybrid graphite/CNT structure strongly depends on the capability of the catalyst to retain its film shape when the gas precursor is inserted into the chamber and to dewet during the subsequent instants. Hence, at high temperature, thicker catalyst films or growth recipes without pretreatments [3, 16–18] should be used to guarantee the formation of the graphite layer before the film dewets. At lower temperature [17], instead, thinner films or mild pretreatments can be used so to increase the catalyst mobility and guarantee that after some time the film dewets yielding CNT.
5. Conclusions
The growth of an atypical structure composed of CNT with a graphite top layer has been observed and studied. To summarize, the following four conditions have to be satisfied for the formation of this type of structure.(1)The catalyst has to be active.(2)The catalyst must initially be a continuous film. (3)The carbon source has to be introduced before the catalyst has reshaped into nanoparticles.(4)The thickness of the catalyst layer and the growth conditions have to be tuned such that the catalyst film retains its 2D shape during the first seconds of the growth but then it is sufficiently mobile to dynamically evolve into distributed nanoparticles.
The first three conditions allow for the formation of a graphitic layer on top of the catalyst film in a similar way to what reported in literature for catalytic deposition processes of graphite/graphene. When also the fourth condition is satisfied, then nanoparticles or patches of catalyst can reshape underneath the graphitic top layer to initiate CNT growth. Consequently, the top layer is lifted up by the underlying CNT [17]. In this phase, excess of catalyst can break and remain in the tubes interior as particles.
Satisfying conditions 2, 3, and 4 all together is not straightforward as the dynamic a film transforms into nanoparticles was found to largely depend on the initial film thickness and temperature used. Very thin films, in fact, either are discontinuous after deposition so that condition 2 cannot be satisfied or break very quickly making condition 3 difficult to satisfy experimentally. Very thick films, instead, may not break at all making condition 4 incomplete. This explains the narrow process window for film thickness in which CNT and the graphite top layer are observed (Figure 2) under the growth conditions used: 1.9 nm for cobalt blanket films and 1.3 nm for Ni patterned samples. Note that this type of structure was observed for both nickel and cobalt but other catalysts might possibly be used probably in a different process window.
The result reported strength the clear correlation between deposition process of graphite and CNT. By improving the control on the dynamic of catalyst breakage and most likely by carefully tuning the growth conditions, it could be possible to achieve a well-defined transition between the growth of graphene or graphite on top of CNT. Such hybrid structures might be of relevant importance for electronic and optical applications such as carbon-based interconnects, field emitters, sensors, NEMs, and optical devices.
The authors would like to thank Francesca Clemente for support with Raman spectroscopy. The EU projects CARBonCHIP (NMP4-CT-2006-016475), TECHNOTUBES (NMP2-LA-2009-228579), and the METACEL project (IWT-SBO project 060031) funded by IWT-Vlaanderen are acknowledged for financial support. Nicolo' Chiodarelli has this current address (CEA LITEN/DTNM/LCRE, 17 rue des Martyrs, 38054 Grenoble, France).
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