Hands-on at the PAINERA Powder Diffraction Beamline at Sirius

Thank you Graciela and we are ready for the final presentation of this final session the week we are very glad to welcome Dr. Cristian Codela welcome. Cristian Cristiani is offering usage hands on the action be at series in Brazil. So Christiani let me introduce you Christiani is a senior researcher at the at the Brazilian Center of Research and energy and materials where the fourth generation synchronization facility serious is located. She is also the coordinator of the power ray distraction beam line at series named beam line and group leader of the XPD group that includes painera and the distribution analysis beam called Jatoba please apolog me Graciela I missed your presentation let me just remind the audience Graciela studied at the university of Losantes in Venezuela and her PhD chemistry at Brandes University Massachusetts in USA. She has been a chair of the crystalography laboratory chair of the interdisciplinary graduate program in applied chemistry and director of graduate studies at the faculty of science. She is a member of the American crystallography association, the international center for detection data of the American Chemical Society and a founding member of the Venezuelan Society of Crystalography of the Latin American Crystalographic Association. Please let me know how the presentation will go. You will be presenting in Brazil, at LNS, and at the National Center for Research in Energy and Materials. Dr. Cristian Rodela, we are very glad to have you with us and please bring us with your nice presentation. The floor is yours. So can you hear me and see my presentation? Yeah, we can hear you very well. See your camera and your presentation. Great. Thank you Carolina for the introduction and first I' like to thank the organizer of this very prestigious school for giving me this opportunity to show the be line that I'm the coordinator at Sirius a Brazilian Synchron facility. So to start I'll just give you a brief overview of the series. And so here is just to specify where Sirius is located. So it is in Brazil and in São Paulo state in a city named Campinas. Campinas is 80 km from São Paulo Capital. So, but Campinas has an international airport relatively easy to come from abroad and to arrive in Campinas to go to use the synchron facility here. in campus a lot of national laboratories all of them are open facilities and they are supported by this the ministry of science technology and innovation so in this campus we have the serus sycra sych facility we had another one that was called uvx this was a second generation synchronous facility and it was deactivated in 2019 and in the same year serius started operating that time was we had just one line. and two facilities are part of the LNLS and you have more a Brazilian biorene national laboratory that works with green fs and methodologies to obtain these green fields. We also have the national bioscience laboratories that study neglect diseases and proteins and things related to the living matter. We have an engineer group that gives support for all national laboratories here. We also have nanotechnology laboratory where we have the most advanced Brazilian microscopes. And also we have a quality that's called and is to how can I say create scientists that can work in all these laboratories. here a diagram of how the be lines are distributed inside the laboratory and we have finished the one project that it was determined in the past of the laboratory it was to finish 2015 with 14 lines running Sirius and we are almost there. In fact, operationally we have up to now 11 lights but we already have that are in blue sorry in yellow here. And we have more we have already started the phase two project that where lines are predicted and at the same time we are building lines that will be connected to a biosfety level laboratory innovative is anything like this in place details of all the lines that we have here but especially in the phase one because you can get information in our website but we cover from infrared to heart xrays and we have powder diffraction facility are techniques that used image tomography and image using different chemical contrast Paneira to powder xray fraction analysis. So to start like to talk about the advantages of using a synchron light as the xray source for a powder fraction being line to study polycrystalline materials. presented for the way that not if the case that you are seeing what I want to discuss here as a second time is good to emphasize because at some point in a synchron proposal to use n to write a proposal to use a synchronome facility you have to justify the need facility to compare what synchron brings in as adv in the powder fraction compared to a bent stop deatometer i listed some items. The first one is intensity. Using asynchronous facility, you have much more intensity than using an x-ray tube and this is connected to a large number of samples that can be studied using a synchronal facility. And I'm going to show you that at paine binline this is possible. Another advantage is to study samples in a kinnetic situation. What I want to mean here is when the sle sorry the sample so when the sample transforms the structure according to the sample environment that's connect to the first lecture that we had in this morning in fact is afternoon for you and in a synchronal facility usually have very fast detectors that will take your XRD pattern in a matter of seconds or minutes and this will be important to study transitions in this kinetic experiment or stable phases but you have another advantage that's high resolution And with this possibility of using high resolution methodology, we can identify and separate crystalline phases that in your defractogram are overlapping and we have an accurate determination of peak position, peak profile that will be very important to quantitative structure. refinement synchron we offer a much better signal to noise r and with this we can identify a crystaline that in minor quantity in your sample and with the energy stability we can change the bin line energy methodology resonance so all just another message because you have to use a bent top deatomy and probably it's easy to get access to this equipment and sometimes it's very important first to screen your samples that you have prepared in your laboratory for your scientific case. in some cases a stopatometer can solve the scientific answer that you have when you are characterizing the structure of your material but when this is not enough or you need one of this parameter or more than one of these it's when you need to apply a proposal to go toch facility and paina can be one of the alternatives. So Painera is named after a very Brazilian tree that I'm showing here this figure. But just for curiosity if you all the lines at Sirius facility they have treats or animals name. The connect the name of the tree and animal with the technique that the bean line bruns but particular I think that sometimes it doesn't match very well. I prefer just saying that it is a tree or it is a bird and if you have the opportunity of visiting series you see that we put stamps the be line with the tree flowers and animals relates to the name of the be very colorful experimental hall. So in the case of PER is a dedicated facility for high resolution and fast XRD exists to study polycrystal materials. can determine and quantify crystaline phases and you can study micro and nano characteristics of your crystal such as defects, dislocations, strain and determine the crystal size. can study the sample under opera experiment this encompasses the kinetic experiment that I mentioned in the slide before and it's when used the sample environment that it was shown in the first lecture today and we also offer a gu analysis for your sample so you can spectrometer or microc det how this gas fluid has changed after going through your sample. So when you design pain be and you knew that would be a state of artder being or in fact to have a state of artder line we decided to work in a transmission geometry that you see in my slide and We design keep in mind that we like to operate the B line in a hydrop mode and you see a video that I put here in my presentation and it achieves one of the the advantages of synchront that we can measure very quickly. So we can the user can bring a large number of the samples to be studied there. Another system that we are implementing is the Maywin system. So for scientific cases that you can work in this hydrop mode. In fact the user is not necessary that the user comes to the laboratory to run the experiment. We the user send the proposal and this call will be open for the entire year and once the proposal is approved because it has some it shows that using a synchronous facility will be important for the scientific goal of the user. So we approve and we send the sample holders to the university of the user with a manual how to prepare your samples and the user prepare your samples register in an online form and send your back and we receive put in in the experimental hut and run the experiment for the user and after that you just send the have module to control operface for the user operate the line and software for the data visualization in the same time that you are you are acquiring your XRD pattern and in a couple of seconds you see your XRD pattern on the screen and even if interact with this data as I'm going to show you. So we like showing this type of diagram here and especially I decide to put in this school because you have the opportunity to know how the optical elements are placed and importance of in synchronal facility. So here I'm showing the you can find in most of the bean lines here at serius so our bean lines that have size of micr and like 30 nanometers and very divergence so everything was optimizing the optics to have a very good powder defraction be line. Here is a slide that shows the experimental hut of paineira and is where the user the sample. So is where the user interacts with the bean line and we have these big three circles fratometer working in transmission or the by shader or capillary geometry. that put in the mirror fixed in the tita circle and we have here the high resolution detector that one that can go to this resolution and it travels on the top of the diratometer. I put it here just a scheme of the x rates that come in this direction the same be here in the middle of the theatometer and the bonds will be created depends on the crystalinity in specific angles and we take specific intensity and it's a 3D con so we detector that travels on the top of the atom and another one that travels on the bottom of the diffractomer. The one that travels on the top is the high resolution detector and the one that travels on the bottom is our high or fast detector. So we cannot work with both at the same time other they will collide here in the zero of the XRD pattern. So our option is always first acquire XRID pattern with this one that takes seconds and depends on the scientific case or yeah if the user knows that it's necessary to use the high resolution detector so you put it in the safety position and start working with this one that goes from zero to almost 145 degrees. El be magazine samples so used number of samples we work in the may system we have two robotic arms the the the small one that based on the be geometry that's the sharer we name this robotic arm of the buy and disorder of share so the buy takes the sample from the magazine identify the sample and put in the mirror of the diffractometer this automatically you see in my video and shader the job of shader is to take our temperature source that we offer two one is a it's here is the cryet when it's necessary to decrease temperature up to 8 eh kelvin or increase temperature up to 400 kelvin when only high temperature is necessary sh can take the the hotter blower that's placed here and with this The temperature in the experiment can vary from 300 Kelv to 100 about 100 Kelv. So and you offer different sample holders eh talking about a specified hydroput experiment we offer this two type of eh sample holders. One is a capiton capillary. Capton is a polymeric material and almost transparent to the X-rays. So the user can feel this tube is like a straw a very tiny straw. So f this tube with the sample and connecting this magnetic pin and on the bottom of the magnetic pin we have a QR code and talking about the user that receives this set to prepare the sample at your university system we only work with the sample variation from 8 kelvin up to 573 kelvin otherwise this polymeric sample holder will melt and another sample holder that we have is to inder formets films or rigid samples and you have is less our pin has this neck and we on the bottom have the identification system so the sample is placed here and connect with the sample holder comes from the back of the sle holder to this point here and where xray interacts with the sle now to show how system in video that I hope it works. I saw a way here but now let me see. Oh my god. I think that I need to change. No. Ah, start running. I'm sorry. So it shows the experimental hutch of pineira and after receiving the samples from users and in this case going to show you samples in a powder forming all the systems that we Now it starts working the taking the sample that was previously prepared and identified it takes it goes to a sensor to connect to the table that it was online. by the user and in this table is the same composition but also how is going to be measured using the high resolution detector or fast detector at room temperature or varying temperature. Shad that first take our blower. So here's to show that the sample is spinning and the hotter blower is hitting in the same position that the beam will touch the sample. And here is just the detector going fast because in fact this detector has a high resolution but it doesn't measure very fast because a punctual detector. to acquire whole pattern it takes depends on the sample it can take two hours but it won it will be impossible to have this type of detector in a bent top deatometer So this automatic system is something that you have seen in some presentations here because very handful for us at the and the user It optimizes our the time for us and for the user is a trend you see in a lot of synchrontones and another thing is because a bean time and it takes 24 hours. and you have been during the weekends during holidays. So what I say to my team this is something our dream comes through this year because we have everything implemented and it's working very well. So now we can put the samples in the magazine and keep system running during weekends at night and holidays and machine to work for us and during the day or at least in the week weekly days we work with experiments much more complex and we need to be there just So it doesn't run so slowly as I'm showing here. Just what you see in slow motion. So when the measurement finishes sh takes the pin I mention magnetic pin because in the middle of the atom we have another magnetic system thats So you finish here XRD pattern in high resolution. So I'm going back to my slides here. Okay. So after finishing that hydrop system of measurement we can have a high resolution pattern. So in here showing one that we have just to guide us that the be functional and working very well is6 standard that we buy from NIS and with this we do the RF refinement and we give to the user the experimental Wength and everything contributing to the broadening that belongs to the instrumentation. So we give this parameters to the user and the user after measuring a sample using the high resolution detector and to do ref analysis we need this parameters in the refinement and for us from time to time we run this standard just to check that the bean line is working perfectly and I'd like to show some examples. solve scientific case here is a ceramic a mixture of alumina zirconia and they put raffine in the ceramic composition just to increase hardness oxide zircon sorry here the zircon oxide what type of cstaline it was forming cubic it's me that made a mistake thera is cubic or tetragonal and graffini they know if graffini ceramic if they cr the sample to create a powder it won represent the way that ceramic would be used so they in a solid system and here holder andowing here important we start working with the sample without spinning and we got this very noise fraction peak and when we implemented the rotation it was essential to obtain a more defined and high quality pick and quantity of graphine so they could small amount of graphine signature that they saw here meaning that at least partial of the the grain was precipitated in identifying and distinguishing crystaline face I'll go to another example it didn't come from paineira in fact I took it from the literature is a very famous researcher who runs this company and specialist in pharmaceutical samples and XRD analysis and synchronization. So she used a synchronal facility to determine the lowest quantity of a polymorph of a pharmaceutical compound could be identified in the sample. Graci and could identify just 0.05% of this face mixture in the pharmaceutical sample because there she could work in a high resolution. She had a better signal to noise signal ratio and the signal has improved. So it's just to show the powder the power of using a synchronal facility to determine to study this pharmaceutical sample and the previous experiment with a ceramic to another one it came from a user of pinea bean line the group is studying this type of perov skart material and they are doping ir and the doping was exchange titanium s so if it was they would have three crystaline picks here but using a a regulareter they just obtained this large peck so it wasn't substitution of the simple composition or not. So they sent a proposal to line and got the XRD pattern. got separate define very well the confirmation that the substitution has created a different structure of the material another thing that offers de pain bin and this is for incite experiment is a system that the user can Mass flow meter to flow a gas phase, a liquid phase or a vapor phase. possible to work at high pressure to so this system here that showing from in the back side is installed here the bean line as close as possible of our diratometer and it controls aor operand experiment so this is very handful and apart from linesyncr because using capillary cell in here we are not working with a capital capillary or a polymeric capillary here we are working with a quartz capillary because quartz is is a morphose almost transparent to Xray and you can increase temperature up to 1000 kelvin the sample is in the middle and we have quartz w just to hold the sample and keep it here in this place and using this cell we can flow fluids through the sample and work with the hotter blow example work environment pressure glue the capillary with the cell in two points and we seal the cell but when pressure is required in the experiment the glue who wants to hold the pressure. So we have a more sophisticated system. It's a very similar cell reactor, but what changes eh especially is the way that we seal the capillary cell just to support pressure and here is the system inside that you have to install here to maintain the pressure during the experiment. It's and I can tell you that it's a much more sophisticated system to prepare the sample to keep this the sample here and increase temperature. Sure increase temperature and increase pressure. Here me showing the first cell reactor capillary cell reactor the simple one for ambient pressure installed at the be in the tita circle of the diffractomer. So the gas is this tube is connect to the that great eh great system that I showed where you have the the the mus flow meters and so on. So the gas flows from this tube go inside the capillary cell and in the outlet we can install a gas a micro DC or a mass spectrometer to do the gas analysis. And here on the bottom is our fast detector that we be able to acquire the XRD pattern. The Xray comes in this direction and we have a bean stopper installed here just so the direct bean doesn't touch the X-ray. As I told you, we can work with liquid face and for this instead of flowing gas we flow we have this liquid injection to flow. And here me showing our heat source that goes very close to the sample to increase the temperature during the measurement. And as I mention at the beginning we spent a lot of time and effort developing interfaces that believe to be a userfendly. interfaces to the user during the experiment just press buttons and put in numbers and control an entire experiment in a how can I say in a comfortable way because it has a lot of parameters to take care during a synchrono experiment and if you are working with the number of parameters experiment of interface to make us life easier and give a couple of examples very quickly. Here is one that my student prepared a sample oil titanium oxide that he put iron and he wanted that the iron would go to the vacancies of the brut and created this iron and titanium oxide face but he was about not substituting entire brut face and some brutile will remain the structure and we went to the piner line and this is the screen that you see during experiment where you are XRD patters that in this case were acquired in 20 seconds been here and you all the experiment all the the structure variation during your experiment when you finish you can plot in this way or this way to do your structural analysis another example that I'm going to show here and I'll go yeah it was just a very complex material a high entropy material and the idea was force to The doping of material formed a new structure and the experiment was performed at pinea and here all theatograms that it was obtained during the experiment and by doing a zoom the user could see all this formation that crystal face and here possible to know when it starts forming a new face in terms of temperature or in terms of time or depends on the gas that is flowing through the sample is another picture because after preparing that sample creating new crystaline face it was applied to a catalytic reaction so and here is just falling the way necessary to activate the catalys and after the during the catalytic reaction how the crystaline structure remains during this experiment offer user the user can take one of this here and plot three things that can vary during the experiment one is the pick position another is and the third one is integrated area that will give more information about structure so with this possible to infer about the cell parameter variation or macro strain with this result how the crystal size or strain or disorders are working at the material and here the face abundance atomic positions experience possible for a lot of results during the time and we are also developing cells for batteries one that holds a coin cell battery and another one that's a flow cell battery. So if this change I hope that convinces you that Pira being line is a very robust and good being l to have a high resolution and high quality XRD patter. It has infrastructure to run in experiments there and it's a user friendly be line. So here is my team because everything that was done at Pira in fact much more bigger than this because engineers and a lot of people that work in them are there for us and here is my contact. Because if you decide or you want to know more about serious facility, you can contact me and put in contact with my collees that work on different lines. But at Paineira, I'll be there your messages. And thank you very much for your attention. Thank you so much chrti for convincing presentation about it andal research energy materials laboratory national de and other national centers inside infrastructure in latin american the carb is a unique place in the world i have a couple of questions in the chat let me start So a little bit I can tell you little bit because not my scientific case in fact it belongs to another researcher that she works with me and if you want much more details, you can send me a message and a forward to Flávia but as far as I prepare a mixture of composition alumina and zirconia to and he could prove that could graphine the hard increases it in ceramic what is not something that I would say without proving engineer measurements and see how much graphine needed to increase this hardness or if put more than how can I say quantity specific quantity what is going to happen and how the crystalline structure at least partially and he did the ref and he knows that part of graphfine is structure and part is is precipitated in a very small quantity it's all that I know thank you good that you love your contact I draw list of questions as well and two questions from saying can you explain how you switch between the detector and high resolution detector and how do you put each detector in the xray path after the fraction he is asking for something additional let me see if you can answer jointly he saying does this uh x or dractimeter only works on powder samples what about analysis eh so answer if forgive something you let me know. So the diratometer we have those three circles and they move independently. So in the mirr is where you put our sample holder or the capillary cell and it holds the second one we fix it our high resolution detector and it moves. And the third one that's delta we fix it our fast detector and it moves. So to change from one detector to the other is just to keep the sample holder, right? If you are working with the capit sample holder, we keep it there just spinning and we move the two theta circle when you want to take the XRD pattern in a high resolution. But when you finish or high resolution is not necessary, you just move it as far as possible from the direct being. It goes to a safety position and you can take the fast detector linked to another circle and you move it to get the XRD pattern. In this we have a control in the in the operations room. The user can do this and we put some safe system to let the user move both together. It's possible when they are very close a system breaks the electrical energy and everything stops before crushing the detectors. What else? I think that I forgot the additional question that could repeat the additional we can come back we have several messages also greeting your excellent presentation and telling me this exordeter only works onwder what analysis Yeah, we can have a solid sample as I showed. So the majority of the sample are in a powder form but when the user has a film or a pet or a solid sample we work with the other eh sample holder. And this two the other one that has a hole on the bottom and two sample holders we can put in the high system so a lot of samples and just keep the robots working. commission that in sy a commission a way of working in brag bran geometry because theatometer is it was made to transmission mode powder samples or when the s are very th working with the solid sample sneering ones is it possible to use with broad instead of this method yeah I'm not sure if yeah when you for exil minerals overlap so we go to high resolution because because your background you be almost zero and of things that are not scattering doesn't correspond to the brag law so your background will be very flat you have you can work with a step size very very small and and in this situation we also have our best how can i say the instrumental interference the instrumental parameters separate when possible because sometimes if work with not well crystaline face and thection prck is broad it doesn't matter if you are working a high resolution or low resolution your sample is not so crystaline it structural information when a very well crystaline sample uses high resolution that will help you a bri way of fantastic thank you for this brilliant way of closing s everybody having wishing a nice weekend to us all so thank you very much for participating thank you very much for the active participation of the audience as well as with questions and we are very much looking forward to seeing you in the next week of uh this symposium thank you Christiani for your contribution and hope to see you soon Goodbye.