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And, of course, Donegal's start to the season. I'm going to catch up with him. Of course, we talked many of the questions that you have from, you know, around GA at the minute. And it's different from his previous tenure with Donegal. And, of course, the year ahead. And his trip around the world, of course, and soccer. And everything that he's brought back now to Donegal. A fascinating chat. I hope you're going to enjoy it as much as I did. I'm here, of course, with Joe Dex producing as ever. He's back again. Good man, Joe. And, of course, he had his board, Ash and Kelly. I want to thank, of course, Sister Sarah's, Karen Brogan and all the crew down there for their ongoing support and everybody who unputs the show. We're going to have a few different guests on this year. Change the format up slightly at times. And that's all coming in the next couple of weeks. I want to say, first of all, well done to John McNulty and the Donegal ladies and their league opener in division two, Wade Elise, a comfortable victory for them in hard fought conditions. Well done to John and the girls. We'll get more updates from the ladies as the few weeks go on from the legs of John and from Maureen O'Donnell. I'd also like to congratulate the Wadi Grahams of Glen. I'm sure you all seen it there yesterday. That was an epic victory. You really took the game. Talk about the jaws of defeat. You know, finals, everyone had backed them to the hull thinking it was a straightforward victory. And, of course, finals rarely are, but they looked down and out and it was an amazing last couple of minutes there to come back and snatch victory. As I say, Jordan is an author and a man that lives up in the area. Michael McMullen will be live from the centre of Mahara later in the show to discuss the game itself and, of course, the bulls around the town. But now, as I said, I went to the lovely town of Chrysler earlier today and I caught up with the man himself, Jim McGinnis. Here's what I have to say. Jim, are you as happy to be back for your second tenure as us Donegal fans are to have you back? What's the feeling? I am. I'm happy, Brendan. Obviously, this week, anyway, started the National League looking forward to it. There's a good old campaign there in terms of the pre-season. I suppose when you're going back in, you know, you're always trying to get to the bottom of a lot of questions, you know, energy levels and, you know, what's in the group and how much do they want it and all that type of thing. And in fairness to the lads, they've been excellent. They've worked really, really hard. We've obviously thrown the net fairly wide in terms of looking for new players and young players and players for the future and players for the present, if you like. And that's been a great success, I think, in terms of looking at the squad and what the squad could be now and what it could be in the future. So very happy with their work rate and their endeavour up to this point. We had a good McKenna Cup campaign. Disappointed in the second half, particularly, I think apart from that, it was quite a good performance in the first half against a very stiff breeze. So, no, we take a lot of positives from that, certainly a lot of positives from the pre-season in general. And we're looking forward now to the start of the National League and this is where, in many respects, where it really, really starts to kick in, you know. Jim, your first tenure in charge of Donegal, 2011, phenomenal four years, you know, the three also championships, the All-Ireland, the second All-Ireland final, that epic semi-final one against Dublin, you know, it was history making stuff. I'm just wondering, from your introduction in 2011, are there any similarities between the start of that tenure on this one or has football completely changed now? I think so, Bren. I think, I suppose, expectation would be one word that would come into my mind. You know, the expectation level at that stage was very low and obviously we're on the back of a very tough run and Donegal at the minute and I suppose the expectation level would be in a similar place or was in a similar place. I think the job is quite similar in that regard. We have to try and find a way, I suppose, to find new players and to bring new people into the fold, build a team, build a style of play and obviously the most important thing is build that confidence that will come with that and hopefully then get to a point, you know, in the not too distant future that we were very, very competitive like I've said many, many times before. You know, there's no guarantees in football, no guarantees in life and if you're in really good shape and you're really tuned in and you're training really hard the only thing that that gives you is the opportunity to be competitive and then you've got to get into an environment where there's a lot of other teams out there that are looking to do all of the same things. So the challenges are the same but I suppose in terms of your question, like my belief system in terms of coming back would have been the same then and that is we always have good football players and sometimes, you know, the key is trying to get the best out of them and I think that is probably one of the most important jobs over the next number of weeks and months is to find a way for them to sort of grow together and the team to grow together, you know, and get scores on the board and be competitive and put ourselves in a position where we're going to Celtic Park in the summer that we can give a good account of ourselves. And it was interesting to, people I think are over-analyzing maybe there's a cup final a bit because if you look back from your last tenure there, there was so much happening, I know the tactic that Donegal brought and in many ways caught a lot of teams out and a lot of teams murdered and copied it years after but there was so many players increased their own abilities substantially, you know, became the very best of what they are and as people look, people are trying to match us up but I think individually and then collectively, you know, you'll bring a huge lift to these guys and on the earth a few new players, I suppose that's the plan. That is, I think the two things run side by side.  I'm going to say the group I'm talking about because there's a lot of people now that sort of impact you know, on the players that are on the pitch and everybody you know, I always try to have people in and around it that have a very clear specific job in terms of supporting the team and then obviously trying to get them to be in the best position possible to go and do that as you're talking about, go and express themselves and a big part of that is the game plan as well having clarity around things, knowing what your job is knowing what the opposition want to do and how you can impact that and so you know, I think you're probably right there was a lot made of the mechanic up like you know, previously we wouldn't have put the same emphasis on it at all but I think one of the reasons for that was we were very very focused at that time and just working on our fitness because we knew that whenever the league finished we would still have time to get a lot of stuff done whereas this time around because of the split season and the fact that you know, the mechanic up runs into the league and the league runs straight into the championship you know, you have to use that really as a springboard you know, to get your fitness levels up and to get your game plan up because like even going back to them years you were speaking about Brenton you could have had a situation where we say we played Kevin or Derry or whatever it was in the first round of the championship and you might have had one or two fellas maybe a grade one hamstring and a tight hamstring and everything them fellas are probably gone now they're not going to play in the next game whereas previously it was a three week or a four week turnaround to the next game so you could have had you know, your squad and you could have had your team and then chances are you know, bar something pretty you know, on the more serious side they were going to be available for the next game but that's gone and that's why I said you know, you have to cast the net you know, wide you have to try and find as many players as possible you have to try and find as much cover as possible but we're not at that point yet because we're still trying to find out who's the best player for the position but you need two people for every position you really do like and not sort of you know, token you know, tokenism if you like they have to be fellas that can actually step in and play because you know, those turnarounds are much, much less than they were previously and just on that you know, on the last ten you spoke a lot about the journey what a journey you've been on yourself, you know when you left on a goal last, you went to Celtic performance coach you did your coaching badges, you then we got to use your head in the Beijing as assistant coach then you become head coach at Charlotte you know, what a trip you've been on yourself Jim I suppose everybody's wondering how has that impacted your overall coaching now and the trip you're on and what you've learned and how you've grown in terms of now coming back to J That's a good question Brendan because like obviously when I made that decision you know, I knew the road that was ahead of me and it's a very, very long road because all of the things that we would take for granted in a GAA context are things you're learning for the first time so that imposter syndrome is very, very, very high when you're trying to find your feet you're trying to understand the game you're trying to understand how you could train it you're trying to understand tactics you know, all of those things are building and developing over years it does take years and then when you're in like four years, five years, six years you know, and that sort of is your life and it's kind of full time and it's 24 hours a day you know, there is this kind of crossover between your Gaelic back and your soccer background and then there was this kind of sense of everything merging at some stage and then you move across the divide almost you know and then you're always so initially your impulses are so strong towards the GAA because that's all you know and so that part of it has been interesting but coming back has been very easy because them instincts are still there but I do believe there is a lot of things from the soccer point of view as well that now are embedded, if you like, in your thinking so the journey continues in that regard another book? I don't know about another book there will be no book, not now as there's results that's for sure and that's what we want out of this journey we want, you know, like the bottom line is we want to try and put Dunny Gull in a better place and we want to try and strive to move up the ladder and make ourselves competitive again again, sorry, in the provincial championship and then go from there and that's really all we're focused on at the winner, Brendan it's an absolutely phenomenal, fascinating story I don't know many people could take on what you did in that time I think a lot of that is down to not just your coaching your ad-libs but your personality I remember when you first had come up about the Dunny Gull job and people were talking to me and I only knew a bit about your tactical and putt in terms of your philosophy obviously you kept on me at Dunny Gull and you know we had some good times together but personally in a group you're always a great man and I thought then that was going to help you so much and it probably helped you a lot on that journey that you're on but even though you were obviously going there I mean China, the language barrier and how all that worked and then of course Charlotte coming late in and the players and that was a very, very difficult outcome but you just meant about being back here and I just noticed from you when I talked to you after Ross Common how kind of content you were in terms of I'm back now and ready to give Dunny Gull I could see it from you, you're very comfortable in terms of applying again your principles back in the Dunny Gull and I suppose that's the big thing now Jim everybody now after last year's situation we've not been able to find a manager we're very, very lucky to have you back in in terms of what you can bring to Dunny Gull and I think after your next tenure there might be some of those players that you coach in 2012 ready but just at this point there wasn't anybody ready so between the timing of that being right for us in you Jim was it something you always thought you would come back in terms of taking Dunny Gull? Well you know it was one of those ones sort of I suppose just in the comment you made there about sort of seeing that in me in Balyshan of the Ross Common game I firmly believe that if you're going to do something you have to fully, fully focus on it and that's what I am doing now I'm fully focused on this job and fully focused on trying to make it the best possible version of itself and trying to get the most out of them fellas I think that's the only way that's the only way anything can work you know before taking the job and where Dunny Gull where and how I ended up taking it based on where they were you know I just finished me pro license you know so I want to go back there someday too you know and I do want to go back there someday in the future and nobody knows what the future holds obviously and how you might feel you know further on in your life but that's something definitely that I want to revisit sometime in the future and that will be a full focus then and you know and so for now we're here and Dunny Gull are where they are and I now just have to give it absolutely everything and focus every single day in terms of the team and what the team needs and trying like you asked the question earlier there about sort of the similarities the similarities are very similar Brendan there's a lot of gaps and there's a gaps that have to be closed and you have to fill those gaps and sometimes that's about fitness sometimes it's about tactics sometimes it's about culture sometimes it's about you know kick outs whatever it is but there's gaps appear in all the time and the secret is to identify them as quickly as possible and come up with a solution for them and fill that gap and you know we played Derry the last night and you know they looked a million dollars in the second half there but you know they're four years system and style of play and it was nice to be there nice to be on the sideline and see it that close from my own point of view and they're really good at what they do and that's a byproduct of the work that they're doing consistently night after night season after season now and so we're just climbing that ladder now and that's good and we're road testing things as well and there's an unpredictability to some of the things that we're doing at the minute which is fine as well and you know our job is to sort of settle on things you know midway through this league the end of this league and then sort of come up with a plan hopefully that can be impactful in the provincial championship in the summer Tim you just mentioned the start of the league now where we joke about it Ross Commonize says it's a priority to go up uses it if we do go up it was it, if we don't it wasn't but Tim is it important in the evolution of the team in terms of you did it the last time in 2011 we were on about those similarities in terms of coming up to be back in the top flight we've seen the area of course they did a second go at it Division 2 nothing could be taken for granted and so it's going to be a tough league campaign as you're saying Jim I think probably different from last number of years as the top divisions got better it's pushed Division 2 to be better as well and as you said there's a lot of percentages where everybody's trying to gear in that extra yard which maybe years before teams at the top teams have been down from Division 1 generally come up and it too often was a few years calving in Ross Common you'll you'll do that so you had the top six, seven core teams that really didn't go down if they did they come straight up but I think that landscape's changing now particularly the likes of Galway coming back in they had Armagh coming back in it now Derry's back in it so it's really made the top 1 and 2 a lot more competitive than they were going back a number of years ago No I totally agree like I mean we've gone back to Dunny Gall and Sunday and you know they are a team you know probably they're not as far on as Derry but they're definitely a team that has been together for a couple of years now and they're moving up they're moving up the ladder and they showed that last summer in terms of in terms of the performances they put in so that's going to be a very tough not to crack for us you know Armagh is in the division they were in the Ulster final last year you know took the game to penalties against Derry you know you've got me there you've got Kildare there you know so there's there's a lot of really good teams there that we're going to have to contend with but that's good like that's where we want to be you know it's very very important from my own point of view anyway you know that we try to do our absolute best for the people in Dunny Gall particularly them games that are at home we need to make sure that we're on it as best we can on Sunday and put our best foot forward and take the game to Cork and ask as many questions as possible hopefully that's enough to get two points on the board on the first day because it is your first game is a very important game it gives you that platform for the rest of the season and if you can get a positive result in your first day you know your momentum is already building so Cork will be looking at that the exact same way you know they will feel probably coming to Dunny Gall if they can get a good result that that will set them up as well for the next six games so yeah we understand where we're at and we understand that this is a really big game for us and we have to prepare accordingly Jim see the overall philosophy you know you look at everybody now do you got a feeling everybody's playing something similar type game you know they packed their defence, they break at pace, there's a lot of work and kick outs is it something now you see every side kind of has in the round a similar tactic so then it really comes down to like fitness strength composure on the ball and really I suppose maybe then those players that have that real ability maybe they open up the play or they have an out and out talent for scoring they then make the difference between the teams yeah listen I think that that has always been the case in many respects like you know going back you know through decades the team that won the All Ireland you know that was what most people coached the following year you know you're looking at the best product that's out there in that current year people will always look at what they're doing they'll always try to sort of bring those elements into their own group and into their own environment you know the big difference from the last time I was there was the game now is very much about possession and it's hard to get the ball off players now players skill level on the ball you've seen that yourself on Saturday evening with the Dairy lads you know they can take a lot of heat on the ball and still manage to retain it and solo and solo out of situations that wouldn't have been the case 10 years ago, 15 years ago players would probably have coughed that ball up so people are the skill levels in terms of retaining the possession at an individual level have gone higher and then tactics then are impacting as well you know you talk a lot about sort of defensive teams and defensive structures but if you can get your short kick outs away and a lot of teams are doing this Roscommon do it, Dairy do it Dublin do it, once they get that ball in their hand and they're looking for that overload with the goalkeeper in the first third the rest of them are flushing on through and if you don't track them players then you're going to be in a very difficult situation and if you do track them you're in a low block so it's not, I don't actually believe that everybody wants to be in a low block all the time I actually would really disagree with that but tactics, offensive tactics are moving the dial in terms of defensive tactics and I think maybe ten years ago defensive tactics were moving the dial in terms of offensive tactics, people were asking questions and running into difficulties and now people understand the game much better both sides of it and so it's going to take it's going to take shifts in the game again to move that before people start following that again Brent and it will be my take on it and that's why we will always keep an open mind in terms of all that and for me personally like the finger print of our team previously was transitional football and that for me will always be the case and I just love that energy and intensity and that doesn't necessarily come from the defensive structure anymore but most of that transitional football now comes from the opposition's kickouts or your own kickouts and that's why teams are working so hard to make things happen in those two phases of play because it's the moment when the ball is in contest if you decide to make it a contest because sometimes we'll decide we don't want to make it a contest we'll let them have it and they're going to build the play but then you're into the scenario where they've got the ball and if they're good on the ball and they know what they're doing on the ball forward then you're going to be in a difficult spot the whole day so all of them things I think tie into each other in relation to how you want to control the game allowing the opposition to control the game and that's coming down to possession at the minute and that's why we've gone the way we've gone in the early stages of the season so far we've been asking questions of teams to see how we can navigate that not just how you can navigate it but also what's the impact of that is it successful or unsuccessful worth holding on to and I've always believed that you have to have an idea or ideas like previously in the McKenna Cup even 12, 13 and 14 we would always have road tested about five or six concepts from the year previous and maybe one or two of them would stick so we've done the exact same thing this time around but probably with more concepts because you're coming in after a long period of not being there and you need a lot of answers to a lot of questions there'll be less next year but I think it's important to ask those questions I think it's important as a coach as well to be thinking about those things because if you run from 24 to 25 to 26 to 27 it's the same thing you were doing last year you're going to go stale and your players are going to go stale and try to find ways to innovate your own game plan and the last time around our game plan innovated the game that was outside of our control and it's impossible to create the carbon copy anyway it's just impossible not unless you're coaching the exact same way as has been coached it's not going to be the same thing and I think it's going to be a defensive intensity and a transitional game and if you look to what came after that with county teams and club teams I would say it's defensive shape and not defensive intensity and a lack of transitional like when Donegal won the ball last year I would say there was an 80% chance that ball was going to go lateral instead of forward so you get all the bodies back and you aren't in the world but as soon as you win that ball and you go lateral you're allowing the team to go back anyway and that's where I say it's all about your own belief system and how that ties in with the players you have and so yeah all of those types of things are things that are swirling around in your head constantly as you're trying to piece this thing together you know when you have to take the rough with the smooth during that period you know like we had some very good outings in the mechanic cup without overreacting the mechanic cup and then sort of a dose of reality on Saturday evening and that's all good we probably learned more in the second half on Saturday evening than we did in the previous three and a half games very interesting Jim and I think you're responding to some of the criticisms around Donegal and people mirroring them the difference is the transition and as we've seen, we haven't seen graphs where the Dublin team, that brilliant Dublin team were highlighted, basically they're a full team and say the 40, let's say but the transition meant that you didn't notice it because when they broke, they broke with pace like Donegal did and I think that's the difference they've just mirrored the defensive shape without having the attack so soon as they want it they give it to the safe option which was a simple hand pass back or lateral as you said and when what that did allowed the other team to drop in so what you had was two teams that you thought were playing blank at defense but without the quick transition or an attempt to go forward or kick pass the ball you had a real steel mate and then that was thrown back to Donegal, not saying you're copying Donegal but as you said it wasn't a complete copy but yeah, but I think as well Brendan you have to understand who you are yourself you know and if you go back to when we played and historically before that and since that and now, like if you think about Donegal and who Donegal are you know we're probably a top 8 team you know, when we're going well we're a top 4 team when we're not going well, we are where we are now and that's in division 2 and you'd be expected to be maybe in the top 2 and you know in division 2 so you're a top 10, top 8 top 4 when you go that's what we are and so you know there's always those star studded teams that are going to be up there from a Donegal perspective historically the whole way through our history and so we have to understand that we are a team that's fighting that adversity and fighting that challenge and that was the reason we did what we did we had to climb that ladder and we're in the exact same situation now we have to climb that ladder and for Donegal success in the long term would be that sort of consistency of top 4 or top 3 or top 2 but that's history has shown us that's almost impossible that's almost impossible because of the carries and so forth of this world so we have to understand where we are and that then filters into what you need to do you know the teams at the bottom of the Premier League play Man City and Liverpool and these teams differently than they play each other that's the reality because they know who they are and equally Man City make 800 passes in a game because they know who they are they know they're the best with the best players and the best structure and the best support systems and the most money so they play the game a different way and they see the game a different way and those other lads at the bottom if they don't do what they do they don't win and the interesting thing in the last 10 years is the things that we were doing 10 years ago are the things that the top teams do now because they have to win because they have to win and so now it's up to the bottom tier and like there's a top tier in my opinion at the minute and you could put dairy and Dublin and Kerry into that and there's another tier then your Mayows and your Galways and so on and so forth and then there's another tier and we're in that third tier at the minute so we have to find a way to get from tier 3 to tier 2 before we can start thinking about tier 1 and that is the reality and I think too much is made about sort of the impact the reason I think Donegal had such an impact on the game the last time around was there was like a light bulb moment that well if they can do it and there historically that top 8, top 10 team then maybe we can do it as well and that's why so many people latched onto it and so that doesn't change anything from our point of view we are still historically we are where we are and at the minute it's not tier 2, it's tier 3 to find a way to come again build a team and build a group and try to climb that ladder and that's not going to be easy because the dial has moved and you know so much has gone into every single aspect and so many teams now are so tactically savvy it's not going to be an easy task and that's what you get up in the morning for that's what's enjoyable about it just you mentioned there previous about players fitness and keeping everybody how do you juggle the whole season now because it's different from the last time you're here particularly with the group stage as a championship and my question is 2 fold you have McKenna copy of the league, you have Ulster and then you have the group stage as a championship is in many ways the group stage the championship in terms of success is does Ulster handicap the Ulster teams can handle it and how do you keep the Donegal side between that extra training you want to put in and the freshness and the whole season in general yeah listen Ulster has always been handicapped you know that's the reality like you know you have other counties in other provinces that just slide straight into a provincial final and then that sets them up you know for the next big that has always been the case but equally you know those counties don't celebrate a provincial championship the way we do and that's the trade off and so yeah like it'll never ever change for me Brendan you know spent my whole life trying to won a provincial championship you know and so did you and lots of others that never managed it still haunts me yeah exactly you know and loads more and brilliant teams and the reason for that was it was so bloody hard to won it that's the reason for it and so you know from our point of view you can sort of have a moan about that it doesn't impact anything you know there's always going to be two championships in my opinion you know we've cast the net wide in the mechanic up and we've looked at lots of things and lots of people only with the view of trying to narrow things down and get more focused in the national league and that will only be used to narrow it down even more and the lead into that dairy game and then the number one thing for us is Celtic Park because it will never ever change my thought process you know I remember us playing in a mechanic cup game, a railway cup game and playing in railway cup games previous to that with you know with Noel Higgard and Mark McHugh and Yedantley Toll and Henry Downey and James McCartney and all these lads like and there were brilliant games and brilliant players like and that competition was talked down by every single person that had a microphone that competition was talked down into oblivion and there's a lot of people in the GEA that are hell bent and talking down the provincial championships even though the provincial championship in Ulster there's no change on it still the exact same thing that it always was but people's perception of it and people not taking it seriously and people focusing on the All Ireland and you absolute nonsense you know a paper doesn't sort of reneg ink and conversations you know in podcasts but the bottom line is for us it will always be the number one competition and whenever we're out of that competition the next one will be the number one competition there's two competitions every single year in terms of championship football and you focus on the first one first and you focus on the second one second and that is absolutely it and so for us everything from the very first training session to that ball being thrown in in Celtic Park is focused on that moment nothing else nothing else and we will obviously be going out to one as many games as we can in Division 2 and you're trying to get promotion and you're trying to keep the wheel turning and build the positivity and get up and play at a higher level the next year but the only reason you're trying to do that is to be in a better place to be playing better teams so you're better positioned for the Ulster championship you know so you have to have that context all the time you know when you're making decisions at this time of the year what works and what doesn't work and who's available and who's not and who's fit enough and who's not and sometimes fellas have to play to put them in the right spot for that game down the thing and today or Sunday could be impacted but you're not thinking about that you're thinking about that sunny day when the referee reaches for the ball and throws it up into this guy that's all you're thinking about and I know you're going to revel in this deri game Jim and finally question this and the insights have been phenomenal they really really enjoyed it Jim in terms of success going in this season I know it's year one there's so many things to be done you have the mechanic copy of the league I'm just gauging from talking to you there you're not thinking about the group stage of the championship at all you're thinking about Ulster and whatever happens after that happens but your total focus is on getting through the league now in terms of if we come up hopefully we do but again getting players and getting players' mindset right getting your tactics in place and then it's all about Celtic Park in the start of the championship yeah the group stage is the All Ireland league so you don't even know who you're playing do you know what I mean you can't be there anybody to be disrespectful to the other competition so we will work hard in the national league to make sure we're putting ourselves in the best spot possible we also know after Saturday night seeing Deri up close and personal that that's going to be a huge task they are you know a finely tuned machine at the minute with huge belief in themselves and that's a really good combination you know and that's what we want to strive for and we have to close that gap as much as we can between now and then to make that game as competitive as possible and if we were somehow managed to get over that game then you know who you're going to get in the next one so that's all it is Brinn it's just that full focus on today with that picture in the back of your mind that we need all of these guys to be in the right spot as it may be 12 or 13 weeks this weekend you know Jimmy McGinnis thanks very much for joining us in the day of debate always a pleasure thank you Brinnis stop from Jimmy McGinnis really enjoyed that take some great insights and I'm sure as the season goes on we'll get some more words from Jim it was brilliant to get down there and chat with him today really enjoyed it I think you know he really opened up in terms of what he thinks football is at now and I think the difference in the way sides are well in the play and it was I suppose it was pointing the way Derry you know we're looking at a side like Derry back to back also champions but they're still well in the play that really rigid percentage game and he's talking about climbing up the ladder and how difficult that is now and you can tell from how he's talking there the hours and hours the input the analysis, the planning the tactics to get the Dunnegal to climb this ladder but certainly we look forward now to this week and it's Cork and McCool Park hopefully the one settles a bit get everybody out there in support it matters so much to the team the big Dunnegal support and we've already seen it in the McKenna Cup so far so that's Jim McGinnis's tale Michael McMullan who is live at Mahara and all the celebrations that are going on there we'll be speaking to Michael just after this break the DL debate with sister Sarah's letter Kenny serving food you'll love till 9pm daily in Sarah's kitchen and there's free admission entertainment every weekend Hi folks, Paul McDevitt here inviting to join myself and Jimmy Stafford this Monday night for another edition of the Monday Night Sessions on the show this week the annual anniversary show in the Ballard Theatre we welcome the legendary Mainbenders letter Kenny and district pipe band will also be joining us to tell us all about their upcoming Morn's Night celebrations and of course playing a few tunes 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Check out ShaneconnellyCars.com or call into us at Shane Connelly Cars from London Road, Donegal Town The DL Debate with sister Sarah's letter Kenny serving food you'll love till 9pm daily in Sarah's kitchen and there's free admission entertainment every weekend What a story indeed from the weekend we had all Ireland club finals the whatty grams of Glen went in search after their heart breaking defeat last season to kill McCulloch Croakes in a bit of controversy they already accounted for them in the semi-final and a little bit of them were expecting a straight forward victory I wouldn't say straight forward but they were huge favourites getting into the game I have a man up here now that knows a bit about them and the area and he's going to talk to us live from Mahara Michael McMullen, how are you sir? Brendan, the forum is very good Mahara is absolutely buzzing two degrees the famous Monday club band that everybody in Ireland knows about are playing and the homecoming has been in gone on the back of a lorry James McFerrin, Andy Merrigan and John McDoughlin and playing our champion Big Night Three big names there are three big trophies indeed what a few years I texted earlier and you said I'm going to be in the middle of town and I said that's great because it gives you a bit of atmosphere and a bit of hype for what's happening there what a few years people talking about some of the powerhouses of Ulster and coming through and how long it takes in that from Glen there, from the phenomenal on the Rage and the breakthroughs and now to be at the pinnacle of club football have you ever seen a story like that in all your time? Well it's definitely a fast growth sprint in like 2013 they were relegated they didn't win the intermediate championship they obviously dominated minor football and actually in the middle of the naughties there was a couple of years where they couldn't actually feel the minor team I was told last night so that's where they came from it makes a story even more seismic than it actually is but to have won three Dairy Championships to Ulster Donald Ireland was Kylku after extra time who won the All-Ireland and Kilmakod obviously in the final are the only two teams to have beaten them under Malachy's tenure in championship that's an amazing statistic that's amazing consistency and I suppose there's no coincidence that Andy Merrigan cups in the hall behind me here Yes, yes indeed and Michael, good on the game of course you know after the victory over Kilmakod you've seen Malachy Road getting the players a little quick and being very conscious of getting the head down and getting ready for the final of course Brigid's coming over Castle Haven not playing well in the second half and almost everybody Malachy thought that over the course of the game that Glen would have more firepower be better just all round team and they would kind of I'm not saying comfortable of course a final but they thought they would in some way control the game enough to see it out and the game was anything like that I mean you had to be impressed by what Brigid's brought to the game Definitely I'm and Brendan if you're talking about Glen it was probably the most on Glen like performance like chatting to some of the fans on the Apple Green on the way down and even in around Mars they were so so nervous Brendan because they were favourites you could sense that they were nervous but I would sort of say to them look use our team that are good at playing with the ball regardless of the conditions like it was difficult but they were the exact opposite they were giving the ball away they were kicking it over the side lane and when it was coming back Ben O'Carroll had an acre of room to do damage and it was worrying for them and the problem, the other problem was at any time when up the pitch they were much firing and it's not a it's not a good combination Yes, yes, you always felt there was passages of play though Michael where Glen really controlled the ball but as you say they were snatching the chances and hitting from long range and you know some subs were coming on having a goal probably at the wrong time particularly when they needed to eat under that four point deficit and the camera span around to Maliki Rourke a few times and I thought God it just doesn't seem to be happening you know in the pivotal moments then we had a course well the glass come with the air come with the man scenario but what you're feeling on that goal in terms of the keeper coming out the positioning obviously lost his bearings and a lot of things led there but certainly glass kept house cool and that that I think there was never I don't think points were going to be enough possibly you could say they may have got to a draw point but even it looked difficult and unlikely but certainly a goal was needed and glass conjured up a wonder goal They definitely weren't going up one up without that goal you know and as we saw in the minutes after that sure it was a last-minute free it was missed so they needed that goal and as you say the goal he was out of position and he just went for it he actually said in his interview that he just had to go for it like this time last year he had a snapshot Connor first saves it and it's kill McCoddy you're all there in champions and I was interviewed here in Flanagan afterwards and he actually said he was behind glass when he took the shot and he sort of thought look there's only one place this is going here and but you know it just capped off everything that he did like whenever they were struggling in the first half he made three interceptions that unseen work that he does and probably a lot of people don't actually see it he scored a point with his left foot when they needed to score he went for absolutely everything in the middle he slammed over a 45 and then as you say that goal what a performance you know there's absolutely nothing else he could have done in his whole area yesterday there would have been probably a ten performance of such a thing well I suppose you looked at the first half there was a couple of really last ditch blocks you always get to feel in a cool park it is a forwards type pitch I mean you've played like Ben O'Carlin nipping round changing runs I was really impressed with some of the movement of Bridgets but again for every movement there seemed to be a last minute a ditch block there was some phenomenal blocking by Glane right up until the end of the game remember I think it was O'Carlin as well there was a brilliant block down you know there was some heroic efforts from their defence to I suppose that made up for a lot of the misses from the forwards yeah that one you're talking about well turning funding had been one and the one you're talking about Brenton it was Cattleman Holland who had spent ten minutes in the send-in probably you can imagine his whole career was probably going through his head in those ten minutes about have a miss my chance and when he went on I think correct me if I'm wrong here it may have been level or Glane may have been one of I can't remember but you know that block was another dose of energy and another thing that sort of sticks out with me when you're talking about those chances was after Glane's goal he's already took possession and where most of the game he's bottled up he just seemed to have a completely different level of energy after the goal and he just got that feeling even from that run that there's only going to be one winner I felt that run alone typified it I thought and just at that point with the black yard and the four points up on that and we see this all the time was it Glane was enforcing them so because I thought they were anyway and Bridges look to sit and probably thought to tag on one or two it's just when they broke forward and they seem to be very isolated and it seemed that Glamour just building up this head of steam you know they were they couldn't get the scores that they needed to pull it back and points up in the glasses goal but you really sent I think they really feel a champions maybe maybe the Bridges didn't have in that vital moment to maybe get possession and work it up the pitch it seemed to be very much a breakout on their own along the line they would turn over possession and Glamour would build again that's probably bang on it would be interesting to ask Bridges their view on that because as you say it was isolated and when it went up Ryan Duggan put in an unbelievable second half performance on O'Carroll he made a turn over he used that word isolated he used it he made a turn over onto the scoreboard and you know one of those ones where you roar and fist pump when you do it we're looking up at the scoreboard and thinking there's still time and some Bridges haven't pulled away yet so and Glam seem to be happy enough to think we're going to put Duggan back on O'Carroll and we're chasing this game it's up to every other person to just go for it you know is there any point in being beat by four points of me as well we beat the 44 as opposed to not go for yeah listen Mal what a story and I think the whole country is captured and I suppose the drama then that led there particularly after the defeat last year third year in a row a team has come back from losing the final to won it I suppose Bridges can take that as a as a consolation we mainly see what they come with next year but Mal listen just from all us here in Dunnegoges when it wishes well done you have a great night up there in Mahara and make sure you don't have to work early the morning never miss a day's work Brent never haha my man for plenty of your legend Mal listen thanks so much for that update this evening and as I say enjoy the celebrations thanks Brent as ever great man up in Mahara folks that's the end of the show hope you enjoyed it Jimmy's interview true to exposition here of course Michael McMallan you just heard there head of sport Oshin Killian as I say sister Sharers and everyone for support in the show we're playing Cork next week we'll be back to review it and all the other GA news of the week we'll talk to them and we'll debate with sister Sharers Lether County


In the last lecture, we looked at the importance of precursor method. As I emphasized in the last lecture, precursors are a very convenient route and wet chemical route to prepare complex metal oxides. So, you start in solution, but you end up with a crystalline solid where the atoms and the anions take their position in the right symmetry. So, this involves both kinematic approach as well as thermodynamic approach. In precursor method, I distinguish between solid solution precursors and simple precursors. Today, before I discuss more with the simple precursors, I just want to touch one more example to refresh our idea about solid solution precursor. Just to recap what is the importance of it and then we will look more into the simple precursor routes. And this is the precursor wheel as I put it in simple form. A lot of precursors can be used to bring about the metal oxide formation, but one route is solid solution precursor route, another route is simple precursor route. So, just one more example on solid solution precursors, we can think about zinc magnesium oxygen system using the same concept of isostructural cunnoline complexes. In the last lecture, I emphasized about the importance of structural similarity and once you pack all the corresponding atoms into that crystal, then when you decompose it, the corresponding metal oxide that you get will also have the finer and atomic level doping can be achieved using such a principle. Now, this cartoon shows how the x-ray similar patterns can be exploited for making solid solutions. As you see here, this is zinc Q2 and zinc Q2 is nearly cubic in its x-ray pattern because you have only three obvious or major peaks and they are nearly equidistant. So, just by looking at the precursor x-ray, one can guess what sort of crystal symmetry it can have and in this case, because of equidistant peaks, you can easily map it to be a cubic because of higher symmetry, you get very less peaks whereas, when it is more complex, you get more peaks. .. So, if you look at magnesium Q2, if you take magnesium Q2, again there is a similarity between Zn Q2 and magnesium Q2 and therefore, this gives us a privilege to dope magnesium and zinc together. So, the next three solid solutions are with varying percentage of magnesium from 5 to 15 percent. So, you can keep varying it and as you see here, all these precursors are having this low degree reflections or low reflections at around 7 degrees. So, once you ensure that such a solid solution precursor is made, then you can try to look at the possibility of converting this into the corresponding oxide. The values, the major peaks are all listed here. As you can see, they are all closely matching. Therefore, we can say that they resemble the same crystal symmetry and if you take the precursor itself, they are highly photo luminescence, especially zinc Q2. Therefore, when you put magnesium Q2, you can try to see whether there is any systematicity with the doping concentration of magnesium and as you would see here very clearly, this is the expanded version of this region. Just to highlight that as you dope magnesium in zinc Q2, you can see the peak maxima is shifting towards the blue region which you would expect because magnesium has a different size and it is also showing emission near to blueish green. So, you can take clue from PL that magnesium is indeed getting dope. That is why you see the peak shift and if you look at the thermogravimetry, it gives you idea about how you can translate this quinoline true oxide by taking magnesium Q2 and zinc Q2. If you look at the thermogravimetry, zinc Q2 is decomposing somewhere around 450 degree C, whereas magnesium Q2 is decomposing around 550 degree C. So, you need to have some idea about how the precursors decompose on their own. By just having an idea of zinc Q2, suppose you are decomposing the precursors at 500, what it means is you are you are going to have a incomplete decomposition. Therefore, analysis of thermogravimetric traces is very important and as you would see here the DAC plot is clearly showing the dehydration step and the decomposition step and melting before the composition all are prominent and this gives an idea how we can translate it into the oxide and this particular x-ray diffractogram shows how zinc oxide with magnesium oxide can be ably substituted and as you would see here up to 15 percent there are no traces of any peak of magnesium that is coming here which means absolutely magnesium is going into the zinc lattice zinc oxide lattice. Therefore, you can say that magnesium is getting substituted and it is not a phase separation. So, this is a very useful way that you can try to dope magnesium into zinc oxide and the absorbance spectra also clearly shows that there is a blue shifted absorbance and as you would see zinc oxide is absorbing which is denoted by this curve and there is a shift towards the blue with the periodic doping of magnesium and since magnesium oxide is a high band gap material magnesium oxide itself would come somewhere around here and therefore, progressively you can see the bandage is shifting towards the blue region, but what we have to understand the PL emission does not seem to really give the necessary feature that we look for for example, zinc oxide is showing this band emission which is very useful and which is very conclusive of zinc oxide particles they show a very small gap small peak and then a very broad peak around 500 this is due to defect chemistry and as a result we can see irrespective of magnesium oxide doping that defect induced emission is much more compared to band to band emission. So, we may be able to prepare at low temperature we may be able to prepare the same thing using a novel method, but what is important to understand is how we can get this surface free defects and that is very critical. So, just a mere consolation of a low temperature synthesis or a solid solution approach does not guarantee the end product what you desire it may be compositionally good, but then there are defects which are intricate with the precursor model. So, this we need to bear in mind and when we come to simple precursors we are now going to talk about several combinations. We can talk about nitrates, hydroxides, acetates or even chlorides all substituent metals for example, if I take metal 1 and metal 2 corresponding nitrates I expect those two blend together. So, that I can get the resulting oxide by decomposing it, but there are some nitrates which have a very clear crystal symmetry therefore, one can go for such match also and these are more or less hygroscopic that is why I grouped these together hygroscopic and because nitrates hydroxides and acetates sometimes are hygroscopic even chlorides we can add here and because of that the use of a nitrate precursor or chloride precursors are very much restricted because if you are going to bring two metal salts then hygroscopic ones will react as a result you would not get a perfect control over the stoichiometry. Whereas, carbonates and oxalates are mostly they are air stable and as a result it is better for us to use oxalates or carbonates as precursors because even when you try to weigh those starting materials you can precisely weigh that therefore, the error involved in your stoichiometry will be very less and thirdly the most used among precursors is solgile precursors. I will come to this shortly from now solgile precursors are mostly alkoxides when you treat any metal with alcohol then you can get metal alkoxide and therefore, that is largely used but as the name itself suggests there is a phase which where you get a salt phase and then you progressively take it to a gel phase and then it brings about a metal oxygen framework which will serve as a good precursor for getting metal oxide. So, I am going to take you through all these three examples with several approaches. So, in the next few slides I will give a representative idea of how this simple precursors can be used. Next one as an example I want to quote how zinc oxide can be made zinc oxide is not only used in classical electrical conductivity or sensor applications of UV radiation it is also used in variety of other application. Therefore, there are for some applications you need a very stringent control on the stoichiometry or purity there are certain applications where you really do not need such phase purity. For example, if you are looking at fastening the color for any equipments sports application zinc oxide is used because in all these polymers you need to put the zinc oxide to filter or to absorb the UV radiation. So, that the coatings or the coloring agents that are added are not degraded. So, to fasten the color zinc oxide is used pigment in cosmetics it is used as a base because you can make very fine zinc oxide and it is non toxic and in ceramics you can use it it is also used to bring a good blend between brass and rubber. Therefore, zinc oxide comes as a very good one, but zinc oxide is not just used as a additive, but zinc oxide also has a very peculiar application as a surge arrester for high voltage applications zinc oxide is a very potential one. Now, zinc oxide is a white powder and you know there are many ways we can prepare that I will just show you how simple precursors can be used and how it can transform distinctly. This particular cartoon tells us that zinc oxide thin films can be made by merely spin coating or spray coating zinc nitrate solution zinc acetate and zinc chloride solutions. So, you can just spray it and then decompose that into a film and as you would see here in this left cartoon this is the region where you need to get all the reflections in the right intensity and as you would see here the chloride precursors are very poorly represented and then the acetate precursors, but what you see here as a good crystalline phase is coming from nitrate. So, among nitrate chloride and acetate it gives us a very clear clue that nitrates can be considered as a very useful one because it gives a crystalline phase and corresponding thin film also you can see the morphology completely changes in case of chloride because the chlorates do escape during the heating process they give discontinuous grain growth. Therefore, you do not see any grain growth which is continuous and although the morphology looks attractive, but electrical continuity is missing between the grains and therefore this particular film might lack percolation and in the case of chloride based ones you see lot of segregations or larger particles which are crystallizing. So, this is not a smooth growth comparatively nitrate appears to be much better, but then there are also lot of voids and the films are not very smooth. So, precursors can be used, but then we should have in mind the limitation that comes along with every precursor, but all these precursors can be decomposed in less than 300 degrees centigrade. And if you look at these films there are transmittance technically the transmittance has to be somewhere around 90 percent. So, you would expect a fall like this for your absorbent spectra or in most cases using PLD or MBE method you can get a transmittance up to 80 percent, but using this precursors you can see that the transmittance is going down very abruptly and therefore the quality of this films are not very resolved as in the case of PLD. However, when you look at the band gap band gap clearly shows that it corresponds to 3.3. So, for electrical resistivity purpose all the films seem to match with the desired values whereas the for photonic application or for other applications which are critical with the microstructure we seem to see a very inferior film. .. Let us take another example of garnets. Garnets are those which have A3 B5 O12 sort of stoichiometry and these are all garnet crystals naturally occurring. For example, this is nothing but YIG crystals which occur in nature and to make such crystals or powders it is very very difficult because it involves very stringent thermodynamic requirements. So, how do we achieve that? For example, case of YIG which is iron garnet this has very wide range of applications including microwave, optical, magnet optical applications and also in non-linear optic applications it has been used. Now, how do we do that? One example is using a citrate nitrate gel because when you try to deposit such layered structure with complex stoichiometry it is always important to go for a slower method rather than a rapid method because you can get a much more stoichiometrically stringent or controlled stoichiometry in the final oxide. So, citrate nitrate gel is one of the best methods why we can use citrate nitrate gel is they almost behave like a combustion mixture because citrate forms the fuel part nitrate forms the oxidizer part but the best part here is instead of keeping it in solution you can isolate that as a solid as a result it is possible to isolate a solid which can act as a precursor to give the corresponding oxide and this is the difference between the regular combustion process which I discussed in one of the earlier lectures and the combustion that comes out of a citrate nitrate gel. So, if we do a thermal decomposition you would see exothermic peak coming and that is mainly because of the reaction between the fuel and the oxidizer in the gel. Now, as an example quoted by this person we can actually use a yttrium aluminum garnet or we can also make yttrium iron garnet. So, we can make this precursor using citrate nitrate gel and then as you would see in the room temperature mostly they will remain amorphous because they actually undergo a sol-gel reaction where a disordered metal oxygen bonds are made. So, in your order to crystallize this you have to heat and this is a usual protocol in the sol-gel chemistry. Therefore, if you keep heating it you can get very good phase or a single phase compound, but sufficiently at lower temperatures. So, this is one approach by which one can make complex oxides. I will come to the chemistry of this sol-gel in the later slides in this lecture. Dentate is very useful mainly because if you look at the structure of citric acid you have a carboxylic group here, you have a carboxylic group here and then there is another carboxylic group also here. When metals are brought in closer proximity these two carboxylic groups can actually bind like a dentate. So, it is a mostly a bidentate therefore it can easily cleave to the metal ion and as you would see here for iron tridentate iron 2 citrate you can see a complexation of this form and on oxidation it transforms to ion 3 center and this sort of citrate complexes usually brings about a three dimensional network. So, when you have the this sort of complexation in three dimensional picture once you start heating it all these organics will start leaving away and therefore you are essentially leaving a metal oxygen network which is more reactive to form the corresponding oxide. So, that is the philosophy of using citrate ligand because the binding capacity is very high and therefore you can build a three dimensional network of these complexes. . Another example is spinal oxides that is gamma Fe 2 O 3 which is a very popular oxide and usually it is reddish brown in color and gamma Fe 2 O 3 is magnetic although another phase is also magnetic that is magnetite phase that is Fe 3 O 4. Gamma ion oxide is particularly important for recording purposes as you would see here making this sort of needle shape or acicular shaped ion oxide is very very difficult. Therefore, if you are successful then this can find applications in magnetic recording industry. There are other applications of ion oxide apart from the magnetism that it holds it is used in several industries mostly a pigment also, but I will just highlight how simple precursor root can be used for making this compounds. For example, a series of compounds have been reported by Vernacher group and this one is ferrous fumarito hydrogenate in other words use fumaric acid and make complex which will readily form and you can remove the water of crystallization with the hydrogen of crystallization and that is what you call it as ferrous fumarito hydrogenate and similarly you can use succinic acid or malic acid and you can form a series of hydrazine precursors. What is the use these precursors as you would see here the final decomposition temperature is somewhere around 300 that means you can make all this ion oxide precursor below 300 and when you do that the best part is you can stabilize gamma ion oxide and gamma ion oxide incidentally is a low temperature phase and it is a ferromagnetic phase when you try to heat this ion oxide to very high temperature you lose the magnetism therefore gamma ion oxide transforms into a alpha phase and as a result you lose the magnetic property. So, to stabilize this gamma ion oxide you need a chemical root which will stabilize only the low temperature phase. As you see here gamma ion oxide the reported value is very peculiar where you get two X-ray diffraction peaks at 2.95 and 2.78. It can also be in cubic phase where it is again 2.95 and 2.78, but a closely related ion oxide peak is nothing but Fe 3 O 4, but Fe 3 O 4 almost has the same reflection as that of gamma Fe 2 O 3 only thing one peak would miss here and this is the only peak that distinguishes between Fe 3 O 4 and gamma Fe 2 O 3 why it is important because both are magnetic. However, Fe 3 O 4 is actually a black compound so it is easy for us to guess whether it is a Fe 3 O 4 or Fe 2 O 3, but X-ray can be very deceptive. Therefore, the only clue that you get here is this one. So, knowing this particular phase if you follow all the precursors fumaric succinate or malic based precursors you would see here almost all the precursors are showing only selectively gamma Fe 2 O 3 phase. So, this is a very highly selective precursor that can be used for stabilizing only the low temperature phase. If you need high temperature phase then you need to use a different precursor all together. One more thing we need to understand if you are transforming this to a very high temperature then you are actually going to lose the property and alpha Fe 2 O 3 will come and the best way to distinguish alpha Fe 2 O 3 is you will get a peak at 3.66. So, once you know that then you can understand that part of your gamma Fe 2 O 3 has transformed into alpha. So, here is an example where we see a phase can be stabilized only at low temperature and for which you need to take a corresponding precursor. All precursors does not necessarily give the high temperature phase. So, you need to have a mechanism by which you can control the exothermicity. Another example of a perovskite compound as you see here is a metal ion which is actually in the A site and another metal ion is there B these are the dark blue ones which are nothing but your B cation and these are your oxygens in the corners of the octahedra. So, making this compound again is a big challenge I will just leave one example to show how simple precursor can be used for this is a very old paper published in 70s by Bell Labs by Gallagher. I presume that he passed away in the last decade, but one of the finest metal scientists who really worked on a variety of metal oxide systems. One of his paper shows how we can make rare earth ferrite and rare earth cobaltates. This is rare earth ferrite and rare earth cobaltates both have ABO 3 sort of structure and as you will see here they have used cyanate precursors. Take for example, case A is here and this is lanthanum ion hexasino precursors and this precursor seemingly has a correlation to lanthanum cobaltate because they almost are x-ray similar only thing the major peaks in this case in the case of cobalt is split almost all the peaks that you see is split. Therefore, what you assume there is from orthorhombic it is getting transformed to rhombohedral if you have 200 percent peak which is your largest peak that is usually resembling rhombohedral whereas, this is your orthorhombic or tetragonal symmetry. So, you can index this, but what you see here in all these cases you can get x-ray isomorphous pattern. Therefore, you can even make changes between L A F E 1 minus x cobalt X C N 6. This set of mixtures can also be made because you have x-ray similarity. Nevertheless the point I want to make here is even cyanate based precursors can become useful as you would see here that the decomposition is almost over well below 400 degree C and there are no reports where you can find making ABO 3 structures with such fairly low temperatures. So, low temperature process gives you advantage to get finely reactive powders which can be sintered to theoretical density. So, that is the advantage of using low temperature precursors to get this oxides. Some more examples on complex oxides and I will give you some example of how nitrates or hydroxides can be used as a precursor. For example, you take the case of barium B A P B O 3. This is nothing but ABO 3 type of oxide and we can actually build upon this using Rudelson-Pauper series. Rudelson-Pauper series says that with every addition of another barium you go from B A P B O 3 to B A 2 P B O 4 and we can further keep going adding stackings of the A site cation based oxides as inter layers. So, we can build on this sort of systems for example, strontium lead oxide then you can go for another homologous series that is S R 2 P B O 4 and so on. Now, if we know this X-ray similarity of this precursors then you can even make a mixed metal precursor for example, if you look at B A P B O 3, this is your nitrate precursor which is 7.99 and the strontium is 7.824. So, they are having close structural dimension as a result we can use this as a precursor for making the compounds. Only thing is when you use simple precursor sometimes you may not be able to bring down the calcination temperature in that case you have to go for very high temperatures. As you see in this case you have to play around between 700 to 900 degree C to achieve this perovskate compounds. Vidya Sagar and co-workers as early as 84 they have used hydroxides, cyanides and nitrates as precursors to prepare complex metal oxides. I will give you some more example on that for instance if you look at lanthanum hydroxide lanthanum hydroxide and lanthanum hydroxide both are showing same X-ray isomorphous nature and as a result you can try to make lanthanum aluminates. Similarly lanthanum nickel hydroxide lanthanum cobalt hydroxide they all seem to have the same crystal symmetry and this can be usefully transformed into the corresponding perovskates and here again as I showed to you in the view graph of this X-ray data's you can see the nitrate precursors all having same X-ray morphology and as a result a variety of solid solutions can be made mixed metal oxides. I will come to the last example that of solgile chemistry of all the precursors solgile chemistry is still thriving mainly because the although the cost and the stringent requirements for solgile processing is not that simple and it often involves expensive starting materials yet solgile precursors give a lot of advantage. What is the advantage number one it can be used for not just making metal powders but it can be used for making metal oxide films also. So the same precursor in solution form can be decomposed to get powders or it can be decomposed to make films therefore in thin film approach one of the very well studied method from chemical processing is solgile method therefore it is better to understand little bit on how the solgile processing works. Let us look at the definition of what it is an increasingly popular method for producing ceramic powders is solgile processing stable dispersions or salts of small particles are formed from precursor chemicals such as metal alkoxides or other metal organics by partial evaporation of the liquid or addition of a suitable initiator a polymer like three dimensional bonding takes place within the salt to form a gelatinous network or gel and the gel can be dehydrated and calcium to get a intimately mixed ceramic powder so this is nearly a three step process where you have salt formation then you gel it and the gel builds up a three dimensional network on decomposition gives a metal oxide. Solgile route usually can be scalable we can go for bulk quantities as a result this particular cartoon shows how even in a factory or R and D center you can do the scale up and as you see here these are all the setup for solgile process and it is possible for us to get even kilogram quantities. So lab scale process but it can be translated into a log of industrial scalable process the step that is involved in solgile processing as I told you it says three step process first is taking the corresponding metal oxide in a solvent and hydrolyzing this metal alkoxide to get metal hydroxide and this metal hydroxide actually will be a gelatinous precipitate which has to be gelated which means by careful removing of this water molecules it is possible for us to gel it and this gelation sometimes can take even days and therefore you got to be very patient with this gelation process and when the gelation occurs there is a network that is getting formed which is usually a three dimensional network and on carefully removing the solvent then you can actually get the hydroxide particles and heating that further you will get nano crystalline oxides. So if you are looking for very finely divided oxides and of controlled morphology then solgile process is a very good approach. In the next few slides we will see some examples of how we can make such solgile derived powders and films. So in the next slide we see several products can be made metal oxides like zirconia, copper oxide, titanium and as you see here a range of compounds can be made and one of the specialities of this compound is compounds are you can actually control the size such a way to make circular disc for other applications can also be worked out. Therefore it is very important when we try to transcend from a powder to other forms we need to know whether we have a final control on the size dispersion. One of the chief advantage of solgile process is you can control the size so much so that they will be nearly mono sized and as a result sintering of this kind of compounds to make as disc for other applications becomes very useful. In the other precursor cases sometimes the size distribution of the metal oxide particles are very very less and as a result it is not easy to make such compacts and therefore solgile is still being used in industries to make targets these are targets could be used for sputtering or for pulse laser deposition or for MBE sort of applications and solgile is still considered to be the most popular method by which mono sized oxide particles can be made. So with this reference to its application let us see some examples of non aqueous roots to metal oxide nanoparticles using solgile. Why we are talking about non aqueous because once you do it in solution root which involves water then sometimes the end product can have influence because of the water content. Therefore if you can totally make it organic it is much more refined technique than using aqueous root to get this powders. So aqueous solgile chemistry is usually making a molecular precursor and then you try to use reagents to polymerize it and then get the metal oxide network and molecular precursors are mainly metal organic compounds or they are inorganic salts and polymerization as I told you in the previous slide it involves two main process one is hydrolysis and the other one is condensation process. So in the case of hydrolysis you take alkoxide and you hydrolyse you get metal hydroxide metal hydroxide and condensation actually it involves a elimination of a water molecule therefore you will get a metal oxygen framework and that you can build it for making it into a bulk form. Why non aqueous reagents or reaction is advantageous because in the case of aqueous solgile procedures you have problem with fast hydrolysis and sometimes they are very much dependent on pH and the rate of oxidation concentration of anions all this matters in aqueous chemistry. Therefore if you use a non aqueous method for solgile preparation it will be much more viable and last of it as I mentioned you earlier surface adsorbed water has a significant role on the oxide properties therefore it is better to deal with a non aqueous protocol. Non aqueous solgile procedures they can actually overcome several of these disadvantages. For example what set of techniques can be used or combinations we can use we can actually use a metal alkoxide and think of a ether elimination if we can do a ether elimination then we can build a metal oxygen framework or we can try to look for a ester elimination and in such a case you can actually get a metal oxygen framework of this kind or we can go for metal oxide and metal halide under alkyl halide elimination so we can try to distinctly eliminate this again get the metal oxygen framework. So without water we can without hydraulic system we can go for this elimination reactions and we can still bring about the same final product. Halide was actually reported very early as early as 1951 and where they have used silicon tetrachloride and treated with the phenyl ethanol you can get the silica framework. This was one of the best examples of solgile process which was reported and this was picked up in late 70s and 80s solgile became a very good method for making metal oxygen framework or porous metal oxides. This was the first report of a silica gel formation and then we can actually think of making several nano particles with different approaches. One is titanium nano particles as you would see here the nano particles are nearly mono dispersed and of very fine structure and you can also see the lattice fringes of each titanium particle and the broadening of this x-ray clearly shows that they are nano sized in nature. How do we do that? Take titanium chloride it is very important these are very reactive therefore it has to be done in inert atmosphere if you just expose titanium chloride in air it will immediately convert into titanium salt. So, titanium tetrachloride and titanium propoxide if you try to do that then you can get a alkyl halide elimination all you get straight away is titanium and those are very finely divided. So, this is one way that we can prepare a titanium nano particle using a non aqueous solgile route similarly we can actually take other organic compounds like metal copheron complexes of iron, copper and manganese and then try to do a solgile approach you can see here cuprous oxides can be made manganese Mn3O4, gamma Fe2O3 all this can be made but in this case we are not actually using ROH. So, solgile method does not necessarily demand a metal alkoxide you can also start with any other organic precursor zinc oxide nano particles can also be made using solgile route and in this case you can actually take diethyl zinc this is ZnEt2 and try to react it with topo which is a solvent and then one can get zinc oxide nano particles with very good crystallinity. So, this is another approach by which zinc oxide can be made again zirconia this is a very useful high temperature material. How do we make zirconia take zirconial isopropoxide and zirconial chloride if we try to add this again you get the alkyl halate elimination and straight away you can make zirconia. As you would see here each of this is a zirconial particle and they are almost a mono size. So, if you look at the histogram of this you would see a very narrow distribution of the particle size. So, in a very selective way circular with circular morphology you can get zirconia nano particle and not only that you if you look carefully at the x-ray zirconia shows a cubic phase. It is very important to stabilize a cubic phase zirconia under this conditions. Therefore, this is one of a very proven method by which you can make zirconia nano particles, but only thing the handling becomes a problem as I told you all these are very expensive precursors, but if you are looking for mono size dispersions then you have to use costly chemicals. So, that is the stringent requirement in solgill root again titanium nano particles the methodology is the same use titanium chloride and titanium isopropoxide you can see this sort of rod shape nano particles are formed and these are actually formed with the different temperature and the gelation. The gelling time is a kinematic growth approach and therefore, you can actually restrict the gel formation over a period of time and depending on the gel formation you can actually determine the length and breadth of your nano rods. Therefore, this aging gel aging is very important while you transform it into an oxide. So, synthesis of perovskites and related materials in general the synthesis protocol is all procedures are to be carried out in glove box. So, this is one stringent problem and we can actually try to make other combinations like making lithium oxides and lithium oxide or other perovskites we can follow a general protocol where we can mix metal with benzyl alcohol and then react it with this sort of propoxides to get mixed metal oxides and how do we do that if you are wanting to control the size and shape of this crystals general procedure that is suggested is to put it in an autoclave and heat it. I will show you one or two examples of how such mixed metal oxides can be made specially for oxides like perovskites. Take for example, barium is a metal and it is very reactive. Therefore, you need to keep it in a glove box and dissolve it with the benzyl alcohol and once you do that then you can dissolve barium into benzyl alcohol as a clear solution and then you can mix it with titanium propoxide all this has to be done inside the glove box. Otherwise, the exposure of barium to air it will catch fire and titanium will go into T I O 2 missed. Therefore, it has to be handled with care and this is how it will look like barium dissolved in benzyl alcohol initially it looks like this and then it dissolves into a clear solution and this solution has to be mixed with the titanium isopropoxide and this is your autoclave and you can maintain this in a with a pretreatment at 200 degree C you will get a white powder of barium titanate and this is the general protocol that is followed. So, barium titanate if you want start with barium metal mix it with benzyl alcohol and add it to titanium propoxide heat it in an autoclave at 200 degree C you get barium titanate, but the advantage of using this in an alcohol in an autoclave is that you are not only generating a high pressure, but you are also lowering the temperature. So, at high pressure you are able to stabilize all these high temperature phases. So, this is one way a modified high pressure route I will talk to you about the hydrothermal process in the later lectures. Similarly, if you want strontium titanate you have to start with strontium and barium strontium mix it mix it titanates you can do that and again lithium niobate then you start with lithium and you can try to take the corresponding alkoxide. So, this is one way you can try to make this compounds as you would see here lithium niobate shows a very nice crystalline one. Whereas, in the case of titanates these are phase pure, but the broadening X-ray broadening shows that they are really in a nano size and these are all some of the view graphs that I wanted to show just to say what sort of particles that we can get and whether they are crystalline all this can be mapped with the TEM pictures these are the TEM morphology of the particles and in this case lithium niobate gives a polycrystalline ring pattern whereas, barium titanate gives a polycrystalline ring pattern, but not with this dots this shows that the order or the symmetry is distorted little bit whereas, in this case you can see that the powders are nearly amorphous they have just started crystallizing. So, all these information you can get from the TEM picture and we can also make simple oxides take benzyl alcohol and put vanadyl isopropoxide in an autoclave then you can get vanadium oxide, niobium oxide, tarantula moxide, indium oxide all this can be done with the precise control on the geometry and shape of these particles as you would see the X-rays are very clearly showing that and you can also find out at low temperature when you heat the samples they are amorphous in nature, but they crystallize when you take it to high temperature. These are the TEM characterization results which shows that sol-gel process has a size and shape control therefore, you can see tantalum oxides very nice lattice fringes of this is seen and you know almost all cases you would see a polycrystalline feature and here you can see square or rod ship particles here again V2O3 particles are agglomerated and similarly we can show tin oxide, tin indium oxide and nice indium oxide particles can be formed using TEM. So, in brief sol-gel process can be a very useful method for precursors these systems bear a very high potential for making high purity metal oxides via soft chemistry route and therefore, among the precursor roots sol-gel precursor route is one of the very coveted and more used method. The reactions are simple easy to scale up and they form highly crystalline nano powders, nano particles in form of powders are highly decided for applications as a result sol-gel can be used for scaling up operations. To sum up on these two lectures on precursors I just want to make two comments one is precursor roots therefore, range from simple to complex mechanism and procedures. So, as you saw examples of simple precursors like nitrates, hydroxides something some of these can have x-ray similarity we can widen the scope of solid solutions, but usually they are cheaper and therefore, you can try to make the corresponding oxides at a fairly low temperature, but when you look for high purity and mono size and lot of others stringent requirement on your final products you need to go for sophisticated methods, but there are given taking in each approach. So, there are certain things that the sol-gel chemistry approach lacks which you can take it from simple precursor roots and as I told you solid solution precursor root is one of the other approach which really stands up, but then there again there may be compromise in the issue of the final properties. So, precursor roots can give us a lot of dimension to making new metal oxides there may be some phases which may not be known, but precursor roots can help us understand and help us synthesize such new stratometries or new phases mainly because what is achieved at high temperature can be realized at low temperature as a result it provides a new pathway to stabilize metastable phases also. So, we need to take all these issues into consideration when we try to look at making new stratometries and new metal oxide combinations.


What's going on, everyone? Sam here with late sports cards, ripping 2022 Panini Clearly, Don Russ Football Hobby, 8-Box, half case break, number 8, Picker Team Style, read off Elizabeth Names and her teams, Anthony P, Chargers and Commanders, Brandon V. Bills, Bryce B. Ravens, Chris C. Dolphins, Dallas P, Broncos Saints, Evan R. Titans, Fidel G. Bears, Garrett C. Browns, Henrik J. Raiders, Jason W. Falcons, Jeffrey D. Cardinals, John B. Panthers, Jonathan M. with the Colts, Jorge R. Steelers, Niners, Justin F. Cowboys, Kahunke Chiefs, Levi R. Lyons, Manny V. Seahawks, Mark S. Texans, Matt Z. Vikings, Matt S. with the Patriots, Matthew S. Bangles, Maximilian H. Jax, got Paul L. Jets, Scott T. Bucks, Sonny N. with the Giants, Stephen W. Rams, Stephen H. Eagles, and Zac S. with the Packers. So good luck here, guys. Let's do it. You can play and not get paid. Like, hell, I'm gonna do that. Oh, yeah, my favorite player of all time for sure, Mark. By far my favorite player of all time. Big fan. Yeah, I got a handful of Ray Lewis, pretty big pieces. Yeah, a little bit of everything. Christian McCaffrey, color match to 49 for the Niners. Wow. Night moves. Matt Stafford, fourth case hit in this case, dude. Fourth case hit. Going to the Rams. That's Stephen W. on a $20 spot. Case hit, Stafford. Let's go. Nice one there. I'll be just microfiber a little on the bottom right there. Looks like it'll come off. Good lord. Sauce Gardener and James Cook. This is, this is silly, silly redemption. Arone is Drake London on the Orange to 75. There you go, Falcons. There you go, Falcons. There's going in 10. Grats Falcons. Traylon Burks, Tyler Algier. No way, there's a downtown now, too. Joe Burrow, downtown. Good lord, dude. Was that in the same box, too? Yeah. Same box, two case hits in the same box, dude. Oh my god. Unbelievable. Unbelievable. Joe Burrow, case hit downtown. Wow, dude. Again, little bit of damage on the top there. We'll send an empty box and wrap it. Drake London, Sona Askins. Five case hits in this one case, dude. Five case hits. Or five short prints, I should say. Crystal Lavey, Goldfoil Rookie, Desmond Ritter, and Tray McBride, including two in one box. Two in one box. Good god, dude. Insanity. Crazy case. Crazy case. Purple Jalen Tolbert to 175. Jermaine Johnson, Chris O'Lavey. Who had the bangles, by the way, since Matthew S. Calling another downtown. It's downtown in every box now. K-Von Tibidot to 175 for the Giants. Trust me, that's okay with me, Jason. That's more than okay with me. More than okay. Champions, Tom Brady for the Patriots. Nice one there. Congrats on that, Matt. Pierre Strong, Jr. and Skymore. It's pretty solid, Ashley. Those are relatively short printed as well. The champions. Rock Purdy, Goldfoil. Nice one there for the Niners, Calvin Austin, and Christian Watson. Terry McLauren to 175. Nice one there for the Commanders, Kway, and Jahan Dodson. That chat was dope. There's nice for the Titans. Asan Haskins to 25. Grats on that, Tennessee. Nice one. Titans. Who had the Titans in this one? Evan. There you go, Evan R. Sean White, Sam Howell. Stefan Diggs. Throwback. We've got Kyle Hamilton, Trey Mono Walker. Nothing in that one. Danny Gray and Wanda Robinson. Let's go, Matt. No problem, dude. Blue, Austin Eckler to 99 for the Chargers. Drake London on the Tracks, on Haskins. Trey Lon Berks. That is Purple Auto to 175 for the Titans again. Sort of machine broke. Tensman Ritter and Trey McBride probably would not shock me, Manny. There's Eckler on the 92 throwback. Taekwon Thornton, David Bell, Justin Jefferson, Goldfoil base, Mechie, and Ryan Robinson. Good God, dude. The amount of involvement spots coming in is ungodly. Ungodly. They forgot the canine autos. Yeah, they knew you had the Seahawks in this break, Manny. They were like, absolutely not. Again, guys, just the Panthers left, I think. Let me double check that really quick. Yep, just the Panthers left at $30 in the next break. Obviously, Corral's the guy you're looking at. Who knows? Might get traded. Might start somewhere. The Ravens might trade for him at this point. Purple, Alec Pierce to 175. Radar Rookie for the Colts. Danny Gray, Juan Dale. Danny Gray for the Niners to 49. 20 of 49 on the Radar Rookie Auto. Congrats, 49ers. Coltomash there. Sauce Gardener, James Cook. Micah Parsons, 92. Donner's. Traylon Brooks, Tyler Algier-Rookies. Titans and Foutons. Let me see one more case of it. Get greedy. Matt Corral, Goldfoil. Drake London and Hassan Haskins. I mean, we don't know enough about it yet because apparently, like, I'm sure the reason why some of them got suspended, so the law is, like, the rule in the NFL for gambling is, what's up, chicken? What's up, escalated? What, like, the rule in the NFL is you can bet on other sports, like MLB, NBA, NHL, UFC, so on and so forth, but you can't do it, like, at an NFL establishment. So, like, my guess is what Jameson Williams did because he didn't get banned for a year. Has he bet on other sports while he was at the Lions facility? Yeah, see, there you go. Two bet on college from their facility and the three other bad NFL games. That's what I thought it was going to be. Yep, exactly, exactly, exactly. So, like, what Williams did wasn't really that bad. Like, I understand not wanting to bet in an NFL facility because it's probably, like, I don't think any, well, you probably could if you're in the stands and it's legal in that state, but, yeah, the three, like, betting on NFL games, you, that's a no-no, like, you can't do that. There's Derek Henry to 175 for the Titans. Desmond Ritter and Trey McBride, like, whether or not it's your team or any other team like that, you cannot do. Tyler Algier, that is for the Falcons. Really, another teammate ratted them out. Wow, Thorin and David Bell. Wow, that hits, like, actual media. That's wild. Randy Moss, O2 throwback. John Mechie and Brian Robinson. Here's Goldfoyle, Zach Wilson, Chris Olave. There's Blue of Josh Allen to 99. David Bell. Now, Hamilton, Rookie Otto for the Ravens. Nice one there, Baltimore. Ravens. And guys, just the Panthers available in the next one. Mechie and Robinson. Champions of Emmett Smith for the Cowboys. Jermaine Johnson, Chris Olave. There's Romeo Dobbs. Nice one there on the Rookie Logo, Holofoil. It's been pretty good. Pretty good, Joshua. In this case, between break seven and eight, which came from the same case, we've had five case hits. Two night moves, two gridiron marvels, and a downtown in this one full case. So two case hits in this break and three in the last one, which is insanity. Yeah, those foils are cool. I like those rated rookie foils, especially on the autos. They look really good. But yeah, clearly it's been fantastic, man. I've had no, no complaints on clearly whatsoever. Purple, Brian Robinson, Jr. Two, one, 75. Sniping certain teams in Boehmann Briggs. Yeah, I saw you pick up a bunch of teams in Boehmann. Air sauce. Her sauce of the day. Sauce Gardner, Rated Rookie Auto for the Jets. Saucer. Trayvon Walker and Juan Dale is Thrill Davis for the Broncos. Sauce Gardner, James Cook, and last back, Rated Rookie Foil, John Mechie for the Texans. Short print, Trayvon Briggs and Tyler Algier. Still a quick recap here, everybody. Another fantastic break that is Sauce Gardner, Kyle Hamilton, Tyler Algier, Trayvon Briggs, Kavon Tibido, Danny Gray, Hassan Haskins, Drake London. We've got a night moves of Matt Stafford and Joe Burrow on the downtown for the Bengals. We'll do it for the break, guys. Thanks again for the fill. Let's get a panther sold out on number nine.