Webinar Aqueous and Gaseous Phase Characterization of Catalysts for the CO2 Hydration Reaction

Great. Okay, so like John mentioned, I'm going to talk about the use of grammetry vapors option to characterize the catalysts. In particular one which I use for CO2 hydration reaction. Before I start, I would like to thank you all for dining in today. We appreciate very much your time giving us so. Also I also would like to acknowledge my collaborators Khalil Hassan and Lydia Schiller from School of Engineering at University of Newcastle. These are the people who actually provide this sample and help these work to happen. So let's dive in. Okay. As you all know, one of the most discussed topic nowadays, except the coronavirus is. Is probably the rise of carbon dioxide in atmosphere. Which is actually one of the major actors responsible for increase of global surface temperature. As you can see from this plot here, the amount of carbon dioxide in atmosphere has been steadily increasing from 1950s. And projectory trajectory shows that it will carry on increasing unless we are going to stop it. Hence multinational agreements. So the Paris agreements have been made to control carbon dioxide emissions and limit rise of global temperature by 2 degrees. There are several sources of carbon dioxides which are listed shown on the slides here. So we have the energy sector, as you mentioned many the fossil fuels, oil refineries, semen industry, iron industry. Now there are two main. There are two main capture metals. One of is the carbon capture utilization. And the other one. The other one is carbon capture storage to reduce the CO2 in atmosphere. Today we are going to focus mainly on carbon capture storage and in particular on mineral carbonation, which was very important. Mineral carbonation for instance, geological storage in all the other storage options less than geological storage. So the mineral carbonation process for carbon sequestration. So first let's define what the carbon sequestration, which refers to sequences of source carbon dioxide in day, soils, oceans or in geological formation. So mineral carbonation involves reacting carbon dioxide with metal oxides such as magnesium oxide, calcium oxide to form magnesium carbonate or calcium carbonate. Here we see the actual typical reaction. The first step. There are three steps for mineral carbonation. The first is carbonation. Basically this is a process of carbon dioxide dissolving a liquid. For example, carbon dioxide is a little water under pressure to make it easy drink. The second step is reaction of aqueous carbon dioxide with water or catalyst to form carbonic acid. This is reversible reaction. Each carbonic acid can be transferred back to bicarbonate. This reaction can be actually controlled, accelerated by catalysts. So in this case we can use either carbonic anhydrides, hydrochloric acid or Boric acid, the typical catalyst. But the aim of this work today is actually to replace this catalyst using the nickel nanowires or nickel nanoparticle catalyst. The reaction rate or extent of the calibration process is influenced mainly by the particle size so surface area, ph of steering rate and temperature pressure. So the main goal of this work is to study actually these nickel nanowires and nickel nanoparticles in silica aerogel scatter and compare the performance between each other for the carbon dioxide hydration reaction as I mentioned. So this is materials which are employed as a catalyst for silica aerogel. So nickel nanobias and nickel nanoparticles for heat tracing design by following solar thermo process. I'm not going to into details. That was by chain and nickel nanowires. Nickel nanoparticles on silicon alley gels were synthesized following the sol gel process. As you can see on the left hand side we have the TEM image of nickel nanowires which showing the wavy's structure. And on the right hand side we look at each other silica aerogels and the size particles. Now we look at the this material, this catalyst went to the characterization traditional characterization processes like semxrd. So we're going to go through these now. So now we're going to look at the scanning electron microscope images at different magnifications of nickel nanowires catalysts also googles so SEM images of nickel nanowires composites composite confirms the mesopotam nature of the support estimation of the pore diameter promise images allows shows that maturity of these pores is in the range between 20 to 4 nanometer. As you can see, this is clearly shown for 400 ppnowice and 500 ppn wires. If you look at the 700 pp nanowires we can all we can see except of the mesoporals. We see also some macroporons because you can observe the pores which are larger than 50nm in this case here. Now the other characterization of fingerprint techniques which is generally used to current material is x ray diffraction. So here we look at the x ray diffraction of silica gel. Silica gel nickel nanowires. So previously it is Broad Peak around 25 theta which can be applied to amorphous silica. And then you have 1, 1, 1 which can be accessed to nickel nanoparticles. So nickel nanowires excel diffraction potential. At the bottom here is a nickel nanowire extra reflection of insulin energy. So we just copying the correct phase of the material, the catalyst, was the characterization. As I mentioned earlier, we're going to look at the aqueous and gaseous characterization. So we start from this aqueous characterization. So it is liquid phase characterization where we're looking at the ph changes during the bubbling of carbon dioxide to deionized water at atmospheric pressure and room temperature. So do you see here on x axis we have the time. In second mobile axis we have the ph perhaps. What we see here is the fact that the silica aerogel, which is this light in blue, shows no activity for CO2 hydration, CO2 hydration reaction at all. The strongest activity for CO2 hydration reaction shows pure nickel nanowires, which is can be seen by this solid black line here. Now when we look at the different composition of nickel nanowires in silica energy, what we observe as the loading of the silica or nickel nanowires is increased, let's say from 500, from 400, 500 to 700, the catalytic activity for CO2 hydration reaction is increased. So the conclusion is more silicon, more nickel wires is doped into the silicon allergic catalase, better catalyst, better catalytic performance. A be getting in Aquarius characterization. Now we're going to move to the main part of the talk which is about the gazelle's characterization. And Gazelle's characterization is basically refers to the vapor of gas phase characterization. And this is going to be described by physiosorption process. So if you look at the scheme, a typical physics option process where you can vapor or gas molecule reacts with a solid surface of a material. And these this can form adsorbed layer and some of the molecule might diffuse into the bulk of the solid. As the pressure is increased or lattice pressure humidity increases, more molecule get absorbed into the molecule. And as you can see, the rest of the molecule does not get into contact with a solid material. They just coming out of the system. So it is the typical physics option process a thermodynamic equilibrium where heat absorption is equal to heat evaporation at each isotherm point. Now this physorption process can be described by adsorption isotherm. So the adsorption isotope is a relationship between the amount of gas for vapor absorber against the equilibrium relative pressure. As you can see on this picture down here, the relative pressure is shown on x axis. The demand adsorbed is shown on the Y axis. Now what is important exercise is we have the ratio p over p 0. What it means is the pressure divided by saturation pressure of pure adsorptive at the experimental temperature. Now, during this adsorption process. So in this case we look at the water absorption of carbon. Several phenomena can occur. First one, you have the monolithic. We can have monoloid absorption, multilayer adsorption, condensation to pores, bulksorption and hydration reaction. Here we look at the type 4 adsorption isotopes. Now this is two cycles. What you see, the light green and red is the adsorption branch for this sample. So the adsorption branch is a characteristic by stepping up the relative pressure from 0 to 90%. And as a result the sample mass or amount of absorption is going up. The adsorption branch can be explained by this reducing the relative pressure from 92 back to 0 as a result, whereas the amount of sample, the amount of astrophysical job is decreasing. So this is typical adsorption resorption isotope. And the gap between adsorption and dissoption is called hysteresis. Now the adsorption isotopes were actually classified into the very grouped and we look at the new classification on the right and old classification here on the left. So we're going to go briefly to the world when you have the 6 type of adsorption isotopes. So we can have micropodals which are typical tile1isotherms. So they are typical for micropore solids having relatively small external surfaces. And the limiting uptake is governed by the accessible micropore volume rather than binding surface area. Then we have the non porous type 2 isotames. So it is reversible isotam representing monolay molecule adsorption for non porous materials. Type 3 is for big substrates with unlimited multilayer formation process. Type 4 and 5 is interesting for us. So this is typical for adsorption of mesoporous solids processed by multi layer adsorption followed by capillary condensation resulting in type 4 or type 5 isotherms. Characteristic features of these type 4 and type 4 isotherms. It's other hysteresis loops which are associated with capillary condensation taking place in mesoporos and the limiting uptake of a range of high pop node. Okay, so now we've done this theory for adsorption size. So now how can we obtain diffuse absorption data that can be used actually to characterize the catalysis? So there are two measures, two main techniques to characterize the catalyst. One I collect the fusorption data. One is volumetric gas adsorption apparatus which is typically used for BET or porosity measurements. The second one is gravimetric with gas vapor absorption. I mean the main difference between these two in volumetric we're looking at the we measure the pressure changes. So once you draw the gas of interest like nitrogen, you wait for pressure to equilibrate. And in the case of gravimetric we actually continuously weight the sample during the during changes in concentration of gas or vapor zero sample. So I'm going to mainly focus on the rest of the talk on talking about the gravimetric vapor gasorption analyzer in this case DVS vacuum. So the DVS vacuum measures the uptakes and loss of vapor by material using balance at constant temperature and variable pressures up 2000 TOR allowing option behavior to accurately determine. Now what you're looking at here, on the right hand side we have a picture of the devious vacuum analyzer. On the left hand side is just scheme of devious vacuum. So let's go briefly. So what do you have the devious. One of the key benefits of these galamimetric vapors option or gas option studies is that everything is under thermodynamic equilibrium which is achieved by the temperature enclosure or incubator operating in the range 20 to 70. So this is typical range. We can generate full PVP knowledge for organic solvents and water vapor also to the pumps. Now when you look at the more in detail here, what we have here, the other striking difference is that this system does not require carrier gas for its operation. So we use the vacuum as driving force for the molecules to travel across the sample. So what it means in this case we will look at the water CO2 so we can connect water flow fielding we can call it flask fluid with water to MFC1 and MFC to its connected glass. Now the vapors are generated by liquid itself a thermodynamic equilibrium. So in a typical experiment we pull the headspace of the liquid over the sample and we measure the amount or absorbed or dissolved depending whether we stepping up or stepping down the pressure. Now under the dome here we have ultra balance. From the balance we have to spend time down wires. On the left hand side we have the sample side. Right hand side is left hand side is the symmetrical balance. And as you can see there's also symmetrical flow coming over the sample. Now around the sample side we have high temperature preheater which allows to heat up the samples up to 400 degrees. And high vacuum reference side is used just to count the balance. When we go over the mass is over 150 milligrams because the balance is capable of lifting up to one gram of sample muscles. Now the system measures the absolute pressure using two transducers. And our exit serve here, the butterfly wall. And outside of the chamber, as you can see here you have the turbo molecular pump and rotary pump here another pressure gauge. So this is a typical system which is used to collect dynamic or static gravimetric vapor absorption measurements. So in typical experiments, below the sample and we measure and we float the gaseous vapors over the sample while we maintain the pressure constant using the butterfly valve, which continuously receives closed loop feedback from the paratrons. And depending on the pressure, set pressure, it tries to maintain the set pressure by opening or closing of the valve, which actually regulates the amount of the sorbet molecule inside the chamber. Now look at the inside of the instrument, which is actually quite important. So now to load the sample, you just under these two clamps dissolves down and you get access to the sample like in tga. Now so you have just this bathroom. But what is important here I want to show you. So this is the solvent reservoir, this is the water which is connected directly to the mass flow controller. And the second reference is connected to the CO2. So this is very important that we're using the vacuum to take the hex bed which is flow over the sample. So this is solely water vapor adsorption. Now this setup is also important, which we're going to discuss later. When you're going to show the coadsorption data. Then you have one connected to water, one CO2. And we're going to mix these two streams, gas streams together in different flow ratio and collect the isotherms, look at the absorption to look at the behavior of the catalyst during the CO2 hydration reactions. Now so how this DBS works. So initially, as I said, we load the sample. Once we load the sample into the metal fan, we pull high vacuum, high temperature. We outgusting the material completely. We completely clean the surface of the sample and empty the pores. And when we do that, what we observe. So here we have a solid red line which represents the mass data. As a result, during this outgassing stage or drying state, we observe the mass flows. Now once the sample is cool to absorption temperature, let's say we go from 400 to 25 degrees, we introduce the water vapor. So the water vapor pressure is shown by solid blue line. And the way we do it, so we go from 0%, let's say to 0.1%. As we do that, downstream will be closed. We Open the muscle controller to fill up the chamber with amount of water vapor. And once we reach the set pressure, the both upstream and downstreams are open. So we're going to get continuously flow of water molecules over the sample while we continuously recall the changes in the mass. So as you can see this is very important because in traditionally involometric system this is done in the static method. When you just inject molecules elevate for equilibrium using the boundary motion as here is the flux of the molecule. As we do this, we continuously flow the molecules over the sample. What we observe as we go from zero to let's say 0.1% ra, we observed mass gain as a result of the sample taking up the water molecule or absorbing. And this mass gain is clearly visible here by the solid red line here. Now as we step up the concentration of molecules or adsorptive molecules, the mass of the sample going up all the way up to 90%. Now from this, so as we go up, so this is called adsorption. When we step down the concentration or the pressure is called adsorption. Now from these mass equilibrium points at each relative pressure we can construct the isotherms. What we can clearly see here is absorption variant branch and then you have the small hysteresis gap. Now the equilibrium points at different pressure steps can be reached in time mode or mass equilibrium DMDT mode. So most of the time we can't collect these data in DMDT mode and we set certain equilibrium threshold value. When this threshold value is met, software automatically go to the next stage. The systems allows you to collect very important in situ drinkers which can be obtained or outgassing curve. Our real time adsorption is option kinetics as shown before. Adsorption resorption isotope. So from the kinetics data from mass equilibrium points and different mass equilibrium different relative pressure steps, we calculate the isotopes. We can also collect the adsorptiondisorption isobar. What it means we keep the temperature, we vary the temperature, but we keep the pressure constant. And from the isotames we can collect the three different temperatures. We can calculate heat of absorption and from the kinetic diffusion coefficients. Now so that's this characterization. So let's first discuss the volumetric data. So here look at the nitrogen adsorption adsorption isotams on the left hand side of pure silica aerogels and different loadings of nickel nanoparticles into silic aerogels. So both nickel nanobioids isotopes show style 4 isotames and hysteresis loop H1. So the isotame, the type 4 isotope indicates Mesopotam structure and hysteresis loops indicates that catalyst has narrow range of uniform mesopotams. And this is also in agreement with SEM images which you show early. So SEM images shows a very dead movable materials called actually mesoporous supports. In the table here you look at the surface area of all these catalysts, pore volume and average diameter. So now let's move to the gases characterization using gravimetric vapor sorption technique. So here we're going to look first the weight absorption data. So on the top line here shows the kinetics. So what we see here, solid red line is changes in the mass change and solid blue line shows the changes in the relative pressure. So what we see here in all three cases we step up the relative pressure from 0 to 90% and back to 0. So we don't do full adsorption resorption cycles. What we can see at the bottom line shows the respective adsorption desorption isotons which we calculated from the kinetic data above. So all vapor sorption isotherms indicates higher interaction between water vapor molecules and catalys. So the adsorption process can be described by water adsorption on surface functional groups followed by the formation of cluster water molecules on existing water molecules and pore filling around 50% pop node. So when the pressure is high enough at the post accomplish field, a plateau is aged. We also observe formation of hysteresis loops for all three samples because of capillary coordination and formation of irreversible hydrates. Now let's look at now the carbon dioxide studies at 25 degrees. Again top row shows the kinetics for carbon dioxide adsorption up to one bar. And the plot below shows the adsorption resorption isotherms. So what we can see here again the absorption and desorption curves are almost identical. The process is reversible. So the adsorption calculation to the same point at the start of the analysis there is no hysteresis loop observed indicating no tensile strength applies to the pores. So they are. And what you can see, the pure silica gels shows the actually the highest adsorption capacity for carbon dioxide followed by the nickel nanowires particles and then several hydroponic ionoparticles and nickel nano particle and nickel nanowires. Now we're going to move to the coadsorption studies when we wanted to see actually the behavior or the Performance of the catalyst in the presence of the water and CO2. So first observation what we can see that the adsorption desorption behavior is very similar to the watersorption isotrans. So the all isotans have open loopy stasis. As you can see for both silica aerogels and silica non mechanoparticles, silicon aerial gels, nickel nanowires and all of the samples. Basically they suggest that all samples are in the water. And one thing is nickel nanowires actually retain the water the strongest as you can see from the hysteresis loops because on the dissoption bond because on this option branch the curve didn't return to the same point of the analysis. Nickel nanowires, any nickel nanoparticles shows the high absorption capacity compared to silica aerogel. We can also conclude that the catalyst activity is strongest for nickel nanoparticles followed by nickel nanowires and silica aerogels. And this is determining by looking at the changes in slow body isotam isotopes. Now this is also the analysis so let's move to the conclusions. So we can conclude that we successfully synthesized misoporrose silica gel Dolby's nickel nanowires. The also the hydration test or IQuea's characterization revealed that nickel nanowires slit aerogels catalyzes CO2 hydration reaction which was demonstrated here. So with the highest loading of nickelweiss for this strongest catalytic reaction and DBS analysis confirmed the nickel nanowire show enhancing of the catalytic activity for carbon dioxide hydration reaction when compared to nickel nanoparticles which is demonstrated by this board here. Now just again to acknowledge my colleagues at Measurement Systems, my collaborators at Newcastle University and we also would like to EPSRC for a financial supporting grant. Now I would like all thank you for your attention and floor is open to any question you might have.

Yes, we now invite the audience any questions they may have for the doctor in the panel to their right please if I could just get the ball rolling. Vladimir, could I ask if there's any particular need or query that caused you to explore this topic in the first place?

Oh, that is. Well, I think one of the main needs was to explore to actually improve the catalytic performance of the existing catalysts and also the abilities actually to use employee readily available silicon aerogels for this kind of reaction. So we just want to use more natural materials. Right?

We have a question from Claudia Arnold. She asks how large can the sample be? Can technical granules be tested as they are.

In terms of the sample sizes is actually if you look at the. So we typically use about 30 milligrams of sample for this kind of the tests. We can use the pellets, you can see here. We can load all the pellets as you see here, or hold the beads. So there is no really limitations of the sample sizes. The sample size is mainly limited by the opening of sample chamber. So if you don't work with the powder pellets we can use also we can load all film or whole composite and hang it directly. So the main criteria is actually the size of the base of the sample. So typically 30 milligrams for measurements.

A question from. Excuse me, A question from Dr. Remy Gillet Nukalas here. He says thank you for a nice presentation. And he asks, you showed a few open isotherms and I don't think it is related with a real hysteresis, but rather an equilibrium effect. How do you make sure the data is properly equilibrated?

Oh, thank you very much for a very good question. I mean I am via the equilibrium, since this is gravimetric vapors option collections. So we use. We can actually see the equilibrium. We can visualize the equilibrium points. And the equilibrium points was determined by the threshold values for the measurements. So these threshold values is typically determined by the user or by the samples. And I agree in this case we use the equilibrium point that if the change in the mass is below 0.003% per minute for duration of the 10 minutes, the software automatically goes to the next stage. So this is the equilibrium criteria used for this experiment. Now if this equilibrium criteria was not good enough, we can lower the equilibrium time while threshold or we can increase the time for stability duration. So I agree that if you don't have the equilibrium good equilibrium points, then you would get the larger hysteresis. But in this case we also, because we also form the hydrates as a result of formation of hydrates, you get a bit of the hysteresis. So one of the benefits of the gravimetric system is that you can visualize the kinetic which shows the equilibrium points and you can also see whether you are in equilibrium. And as we shown previously in the kinetic data, most of the data were in equilibrium. But bear in mind, maybe because of the way it is plotted, doesn't seem as an equilibrium. But in terms of the threshold, what we said we met the threshold. If there is need to increase the threshold, that's not the problem. And we can use even more rigid Equilibrium criteria. Thank you.

Another question here from Claudia Arnold. She asks during coadsorption can you distinguish between the adsorbents absorbates.

In dynamic mode it's very difficult to distinguish between amount of absorbed water and CO2. The reason is because we measure total uptake by sample and the total uptake contains contribution from both carbon dioxide and water. In order to distinguish amount absorbed from CO2 and water, we need another measuring device which can tell us how much of which is absorbed. Now there is the other way to look at it. There was no purpose of this because you want to do it in the flow system. The other way to look at the CO absorption is that you can put in the starting mode that you actually preload. You equilibriate the sample with certain concentration of the water vapor. Then you bring CO2 on top of it. If you have the right type of the materials. In this way we can determine the amount of CO2 absorbed at a constant loading of the water vapor. I agree there is a few assumptions to be made, but this is the most straightforward is easiest way to to see the performance of the materials when we perform the CO adsorption measurement. Because one thing I recently added to data actually not necessary. When you preload the sample, let's say with 1% RH and then you bring this bring the CO2 point up to one bar. It does not necessarily mean that your mass going to go up when you bring the T when you increase the pressure. What I observed actually the mass was going down. So if you have the chemist option, some reaction takes place. You can actually determine from these static measurements whether you actually have the physics option, chemis option processes or whether we're actually adsorbing the CO2 or not. So if you are really interested in determining the amount of each adsorpt, you have to go to use either static method or the other option is to use for dynamic method is to employ the ideal adsorption theory simulations where we're going to use pure adsorption isotherm of water and CO2 and then they are composites and then the mixtures and these isotherms are then used to feed the data in order to predict the amount of each other. And then the mixture of water CO2 experimental data then compared with the simulated data. That's the only way to do it. Another option, what you're looking at now at the moment is whether we could actually use XDRI or other techniques to actually do it simultaneously in order to determine water CO2 and amount of water CO2 at the same time.

Question here from Visam Fortas. They ask to what degree can carbon dioxide increase the temperature?

I'm not sure I understand the questions. I mean.

Perhaps we give Vissam the opportunity to unmute his mic and ask and pose a question himself. He may be able to pose a better than me. If you would like to unmute yourself and ask the question directly to Dr. Vladimir, please do so. So the question is typed as to what degree can carbon dioxide increase the temperature?

I'm not entirely sure I understand the question. So in our system we can work gas adsorption isotopes only up to one bar in the temperature range to 20 to 400 degrees.

Okay, we have another question from Dr. Remy. He asks can you use aggressive gases in the instrument such as hydrogen sulfide and how many vapor sources can we use simultaneously?

So first answer to the first question. Yes, we can use the hydrogen sulfide and let's say so two as well, or ammonia. So we can use most of the aggressive gases in the system, as you saw. So we have the two muscle controllers. So you can use the two vapors at the same time. So you can have the water and exylenes or water or benzene or any vapors, or you can have two gases. Now you can also do three components that you could have basically CO2H2S mixed with nitrogen and on the other MSC you can have these solvents of your choice. So at the moment you are limited two or three composition maximums to measure the vapors option or gas adsorption isotherms.

Great, thank you. And Nisham has resubmitted his question. Now he's reposed that as to what degree can the carbon dioxide increase the temperature of the samples.

Oh, so it's really. We haven't observed any increase of the sample temperature in this experiment. But when you did in the past, I saw some of the experiments, some sample could be increased. Sample temperature, especially when you work with the water, could be increased by 2 or 3 degrees. In the case of carbon dioxide, we can see any temperature changes during the measurements.

Okay, great. I think that is all the questions we have for today. But if anyone does have any further questions for Dr. Martis, please do feel free to send them through to marketingurfacemeasurementsystems.com oh, oh, Remy's had one final question. Do you have time for this, Vladimir? We'll get this in.

Yeah, sure, yeah, yeah, Perfect, perfect.

He says, you know, he says SMS has a history of allowing IR probes to be coupled with DVS instruments. Is this a potential option for the DVS vacuum?

Not at the moment. I mean, if you want to measure just the temperature of the sample in situ, that's possible to couple. But if you wanted to measure infrared. Yeah, at the moment we cannot use the. We can only measure the temperature using the infrared, but we cannot measure actually infrared data in dvs. It's only option at the moment. Also note, you won't be able to use a preheater if you're going to go for ir. So this will actually limit your operating temperature down to 50 degrees.

Right. And a final question from Vissa. He's asked, is DBS analysis more important or valuable than DSC analysis?

I think this is very good question and the answer is both. Analysis are very important, but the DBS analysis is driven by the applications and use of the material. So if you work in a field which requires to understand adsorption behavior of the material, or you try to use a material in distillation columns, or you try to determine the, or you design a new chemical plant and you want to know how much it is released, I would agree DBS analysis will be more important. So as I said, this all depends on the application, what you're trying to understand. And DBS is usually one of the main application or characterization tools when you want to understand the behavior of the material in realistic conditions. Because we never would. So yeah, I think the answer is basically it all depends on the application and what you're trying to do. So yeah, if it's really related to absorption science, yes, I would say the DBS is more important than dsc. And also if the water plays an important role in your applications and it's got a huge, it can have huge effect on performance of the material, performance of the system. Yes, DVS will be more important than dfc. Great.

Well, I think we'll close things off there. Thank you again. Dr. Martis, do you have anything final to add for our audience?

I just would like to thank you for all participants and if you have any further questions, please don't hesitate to get in touch with us. So I'm happy to answer all your remaining questions.

Thank you. And I'm sure all our audience will join me in thanking you once again, Vladimir, for taking the time to give this presentation. Today we once again invite everyone to submit any further queries or questions they have about this topic or instruments to marketingurfacemeasurementsystems.com we have a few upcoming webinar sessions which we think you might be interested in. We are taking part in the Bio Innovative Cluster Innovation Coffee Series that we will have a session covering characterization of synthetic and bio based composites on the 11th of November. And from our North American office, Dr. Daniel J. Burnett will be giving a follow up webinar to his poster session at the AAPS Pharmaci event. So please go to our website www.surfacemeasurementsystems.com to find out more about those upcoming educational content and we hope to see you all there. Thank you all again very much for joining us today and I wish you an enjoyable rest of your day. Thank you.

Thank you.