Title:

Brenan Wodrig at NPE 2024 | Shell Polymers

Duration:

14:53 minutes

Description:

Meet Brennan Wodrig, Technical Service Engineer at Shell Polymers.

Brennan spoke to us at NPE 2024 about Polymer Processing Aid (PPA).

PPAs are typically used to reduce the melt fracture and improve processability of high molecular weight materials.

Watch this video to find out more about PPA trial design, the PPA study itself, compatibility study, optical results and sealability.

Transcript:

00:00

Music.

00:09

Good afternoon, everybody. Welcome to our Innovation Center here at the shell booth, I would like to introduce to you Brennan Woodrig, who will be going over a PPA case study. Brennan,

00:20

great.

00:20

Thank you again. My name is Brennan Woodrig, technical service engineer here with Shell polymers. And today I'm going to be going over the PPA case study. So I'll be going over today's background, PPA overview, trial design, the PPA study itself, compatibility study, optic, optical results, sealability, and the conclusion of this. So first, I want to give you a background about uh, Flora polymer, the processing a that's a traditional PPA. They've been around an industry for quite some time, uh, since the early 60s. If you were here for Dan Moldovans uh presentation, he talked a little bit about that, but many of these contain per in polyfluorokill substances known as PFAs, and are currently undergoing regulatory restrictions due to potential harmful effects to people and the environment. These restrictions are driving converters and film producers to search for potential PFAs, free PPAs, which would be the next generation PPAs and their replacements. But this presentation, I will not be identifying each specific commercial PPA during these trials. So first, we'll start off. Why does industry use a PPA? Well, PPAs are typically used to reduce that mal fracture and improve process stability of those high molecular weight materials. You might ask yourself, what is melt fracture? Melt fracture is a pipe of flow instability that begins as a roughening of the surface and can create imperfections in your film, as you see here on the picture. On the left hand side, you would see a nice, clear image in the background of a house, and to the right side, you would see that shark skin. So some of you may have already heard of some traditional PPAs out there, like 3n dynamar, Chemours, Phyton and Arkema Kynar, but these have been around since the 60s. Like I said earlier, but they have been perfected to reduce motor load, lower extrusion melt pressure, and minimize and eliminate melt fracture at those higher outputs and to reduce the Dilip buildup. I So the goal of the trial was to compare the efficacy of PFOs free PPAs with an industry standard floral polymer. So we had started off with a barefoot material, or the control material. And when I say barefoot, I'm talking about a material that does not have any processing aid into it. So as the line is smoothed out, we would calculate that as 100% melt fracture, and that would be a zero minute time stamp. From then on, we would introduce the PPA into the extrusion system, and with that, we would measure criteria like extruder RPM, motor load, metal temperature gage, variation and time to clear of that metal fracture. So that's every 10 minutes for 90 minutes, or until it completely cleared melt fracture. Just wanted to note too here too after it's done and we would move on to another PPA, we would make sure we'd purge out the system and also change out the screen pack so we make sure there's no cross contamination. So the equipment that was used for this is an industrial size here at our facility in Monaco, Pennsylvania, a monolayer blown film, 250 millimeter dye diameter, with a screw of 75 with an L over D, 30 to one, a dual lip airing, IBC, two millimeter dipen screen pack. Same screen pack configuration was used for all of them. And also we have a four component vibratory blender. This is the equipment that was used. So if you guys would use, utilize the PPAs that we look through, you may get a little bit different results. What we need to look at is, this is a newer type of machine. You're looking at different dye designs, different screw designs, and how old or how wore your equipment is. So some of the evaluations that were completed was completed in multiple next generation PPAs for time to clear and the processing parameters against the traditional PPA, but that traditional PPA was three M's, FX, 592, 9m, studies were going. From blending the fully compounding, blending two part component, blending in to the extruder, blowing up the film fully compounded would be the two part component going to a twister extruder, making one single pellet, and then going back into the blown film process and blowing that up. So therefore, there's another heat history involved in that completed lower and higher parts per million limits and also completed extended run checkings for Dilip buildup or anything that's on the machine after extended amount of time. The two control materials was a linear, low density hexene zegonata One mount, and also a metallocene hexene, 1.3 mount. You'll notice that the output on here on the metallocene is a little bit less than the zygonata that was due to the bubble stability. But during that time, there was equal to enough melt fracture of each of those during those studies. So some select PPAs, during the initial introduction of it, we had an increase in extruder output on some select also deviation and melt temperature, which then created peaky frost lines, Port lines, but over time, it would stabilize closer to levels of that control. We did notice some buildup on die surfaces and on the blowfilm equipment, but luckily, most of these PPAs did decrease motor load, did decrease in melt temperature, and also did clear melt fracture. So these did work with the zygoma nada the metallocenes worked well with Master batch. Worked well with the Nate form material and compounded forms as well. So here is a graph of time to clear the so the melt fracture study. So you can see on the bottom the next time, zero to 90 minutes, and on the Y percent mal fracture, zero to 100 you can see on here, we're looking at the traditional fluorinated which is the dotted line that's going down, trying to find something that's either similar or better for the considerations. But that's not the only consideration to look for when you're looking at different PPAs, you need to be looking at cost, compatibility, loading and printability. So one may say B right here, cleared within 30 minutes. But there's other considerations out there that they'll be looking at each individual PPA. So now I'm going to be talking a little bit about a compatibility study that we did. The purpose of the study is to identify any compatibility concerns between different PFAs, free, commercially available PPAs. And the three criteria that we looked at was milk fracture processing conditions the same, and also looking at optical insealability on that. So I kind of have these categorized with sloxane based PPAs, and the next slide will be non sloxane based PPAs. So this is here. We are looking at a as being one PPA and a being another PPA, and the 5050, is mixing those two together. So for example, I'll say a we loaded it at maybe 2000 parts per million, and E was 1000 parts per million to get the time to clear graphs of themselves. When we mixed it 5050 we went ahead and reduced a down 50% so it would be 1000 parts per million, and then it would be like 500 like I said 1000 parts per million in the beginning for E so then we went down to like 500 so we were looking at these, and both of these slots in base PPAs are antagonistic. So what does that mean with being antagonistic means the time to clear took longer in the 5050 trial than each of the other respective trials. So here are some non siloxane based PPAs. You can see a and d here was synergistic. So time to clear took less time in the 5550 to 50 trial than the other. We have C here that's compatible being in the middle between the two, and then all in the far right, A and B was slightly antagonistic, where you can see at the end, it took a little bit longer to clear than itself.

09:33

So looking at that 5050, mix of compatibility, looking at some processing conditions, here we observed, we were observing output, bubble stability, melt pressure and motor load. So if you look here A and C, even though it was compatible, we had output, a decrease in output. You can see we had visible port lines, and we had slight variation in that bubble. So why? Did we decide to look at 5050, mixes? Well, we have not been able to find a PPA, PPA out there to really suit everybody's need. So at your facility, you may have multiple PPAs out there. So what's going to happen in your guys's process if you go from one PPA to another? So we're here to help and look at those things. So we can give you some clarity on that. So optical, we're looking at haze and gloss. Here's the control. Here the control, no PPA involved in it. When we went to E, you can see that haze increased and gloss decreased. S, we had a decrease in haze and also a really good increase in gloss on the non selection based PPAs the control, again, we had a decrease in both, very similar haze results on B, very similar gloss results as well on B and C, very similar haze, reduction in gloss, and also D here, very similar haze and a little bit loss of gloss, so unassalability. So here was a hot tack study that we were looking at. So this is ASTM, f1, 921, so hot tack, we're going ahead and clamping it down at certain temperatures here and pulling immediately. So where it seals, you still have a little bit of temperature. You have that hot temperature, so the pull onto that for the force. So here's our control for barefoot on sloxing based e you can see a little bit of Spike, but nothing too crazy. F, very similar to E, hot tack for non slocing Beast control. Here you can kind of see a shift, maybe about three to four degrees shift for A, B, very similar, but still a little bit of a shift, C, pretty much close to the control and D, very close to the control. So on these two, I just wanted to state that these were done with about 40 hours of conditioning time and running these. We have other studies out there that are looking at the film samples that will be done months in advance to make sure that nothing is blooming to the surface. So this is just the first initial results. Seal initiation, temperatures, ASTM, F, 88 once again, the siloxane base. There's the control, there's E, very similar. F, a little bit of improvement. Nonslocking the control. A, once again, like we saw a before, a little bit of a shift downward. B, very close C and D. So in the first initial results, I'm looking at the sealability and hot tack. Nothing really sticks out to us right away about any issues with them. So in conclusion, most of the next generation PPAs cleared melt fracture faster than the traditional PPAs, but it took less time to purge in the extrusion system. So some possible limitations you could have out there could be extruder output with some of these PPAs could be melt, temperature, pressure deviations, extruder stability and surface build up, although several next generation PPAs were identified as functional, there are still further studies ongoing. The test for the criteria, any questions,

13:49

not there at all, compared to lock same bait and not lock same base

13:55

you have. Where are you guys at as far as that concern? So as I can repeat your question again, just so looking at sloxing base versus non fluxing base, how I did that? So you're kind of asking, Which one are we kind of looking at more likely? So since sloxing base or could be with d4 d5 d6, are on substances, I'm very high concern. In the Europe, we are kind of concerned about that here, because in five years down the road, what happens if they're on substances of very high concern here, and we don't want to go ahead and reevaluate all these PPAs again, to have more restrictions. So for us, we're trying to look at something that is a non SLOC chain based PPA I EPA, all right, thank you. Applause.

Title:

Dan Falla at NPE 2024 | Shell Polymers

Duration:

23:59 minutes

Description:

Meet Dan Falla, from our Technical Service Polyethylene and Advance Recycling team at Shell Polymers.

Dan spoke to us at NPE 2024 about monolayer coextrusion in packaging.

Watch this video to learn more about how the industry has changed and where it's going in the future with a focus on multilayer extrusion.

Transcript:

00:00

Dan, good afternoon. Welcome to NPE. Our next speaker is Mr. Dan Falla from our Technical Services team, and he is taking us behind the scenes of going from monolayer to co extrusion and packaging. Dan that said she treating me better than she said she was going to, she had this long list of things that she was going to disclose, and she didn't do it. Oh, thank you. Well, thank you very much for everybody attending. And what I'd like to do is to talk with you about the train the changes in the industry today. So there's been really no new polymers introduced since the early 90s, when metallocene and single site technology came about. Where the changes have happened out in the marketplace has been primarily with the equipment. The equipment has gone from the old monolayer lines that would run 10, 15% gage variation to now today, with the new nine layer and five layer co extrusion, we're down as low as 2% gage variation. I know what the equipment that we have installed in our laboratory in Pennsylvania, we routinely get 2% gage variation. So what I want to do is just go through and show you a little bit of how the industry has changed, and a look as to where it's going in the future with a real focus on multi layer, co extrusion, some packaging statistics, and everybody's seen these that are out there. We the big change is towards flexible packaging, Gage reduction, source reduction, and just even taking a look at heavy duty shipping sack bags, the down gaging of those, and I'll show you later on, going from eight mil down to four mil in thickness, an entire truck full of jugs can be replaced by part of a role of film and being able to produce a flexible pouch. So big changes. So why is that happening? Well, for a number of different reasons. So you look at variation in unique properties, lower cost, improve productivity, and you can engineer that film to do what you want it to do. And here's a picture of what our line looks like in Manaka. And it's a this particular one's a five layer co extrusion, and each layer is unique. And I'll show you a little bit more about that little later. So why co extrusion, you combine the best attributes of the individual resins. You can combine them together and take advantage of them. And as I said, you can engineer it, produce a multi layer blown film sheet impart unique properties. So you can take the advantage of each one of the individual layers. And I'll show you some tricks later on. If you do some funky things with it, you can come up with some very unique properties. Reduces the need for lamination. And before to get certain properties, you could produce a stiff film, but you'd have to laminate it with a sealant web in order to have sealing properties to it. Well, now you can do all that in CO extrusion. It uses less expensive materials in a five layer co extrusion, you can put the more expensive layers filled with all the additives on the outside, and put some filler materials and stiffening materials more towards the inside core. It it took me a while to figure that one out. I like little unique things, so that little works out well. So it's a balancing act. You got to balance labor costs, energy costs, equipment, materials and output rates with all the other physical attributes that you want that film to do. So looking at the market itself, there's between four and 6000 blown film lines still in existence in North America. Many of those films are monolayer, old, antiquated, analog control types of films. But the change in the industry is towards more multi layer, blown film, computer controlled, direct, direct control from temperatures, etc, like that. So the trend in the industry is, if you're going to go seven layer, you might as well go a nine layer in a barrier application, three layer blown film lines are the predominant lines that are being produced and used in North America, and the old monolayer lines, as they slowly become more antiquated, broken down, are being replaced by the three layer and five layer lines. So let's take a look at how the industry is actually changing. This is the number of lines by a percentage. What was interesting is this slide was actually put together based on a collaboration with macro, Brampton engineering, rifenhauser, W and H Alpine, all of the major manufacturers were able to get together to predict what the CO extrusion technology is coming in North America. This is actually more globally as well. So nine layer line, if you're going to do a barrier film, seven layer Yeah, it started off with five layer you put EVO h into the core. Really expensive to have a five layer EVO H line. But. The technology evolved to seven layer, and where it is today is now nine and even 11 layer blown film lines for barrier applications. So just think of it. You can have a 2% or a 5% EVO H layer. You can have two of those, an 11 layer line, and you can get that additive effect, plus in terms of barrier properties. So then looking at five layer and three layer technology monolayer lines. There are some in specialty applications that are out in the marketplace, but we're seeing a much more prevalence of going towards five layer co extrusion. So if you come back tomorrow, I'm doing another presentation looking at the economics, and economically, why does that make sense to go from a monolayer to a three layer, and even why a five layer is economically better than going with a three layer blown film line. Here's a picture, a schematic of what our five layer looks like that we have in Manaka, Pennsylvania, so that's just northwest of Pittsburgh. It's an small, industrial sized line. It's a commercial line with a lay flat that customers can take that film, take it out to as a pilot film to their customers and do qualification work on it. Up at the top, we have oscillating haul off with an annealing station so we can do the run flat. That's the 2% gage variation that I talked about. And the old industry was nine, 10% was considered acceptable. Well, that's wasted resin when you're up there and you're just reprocessing it, but that's kind of how the line looks. So some of the film structures and applications, I want to go through examples of where the technology has gone. That's another fun that took me a while to figure that one out. So we'll go through each one of these layers into into why they go into a film. We'll start off with the optics. So people purchase stuff on a store shelf based on how it looks, and most times, in fact, almost all the times, unless it's lacquer coated. That's a reverse printed structure, reverse printed, P, E, T or reverse printed opp. You have to reverse print it in order to protect that surface from scratch and mark. Then you want to a tie layer. So if you have EVO H or nylon in there, it doesn't stick to polyethylene. So you have to have something to function as an adhesive to tie them together. And that's the materials. You pick which one you like, and you see if it sticks to the other one. Nylon is going to stick to EVO H, but it's not going to stick to polyethylene. Commonly, molec anhydride is used as that common that tie layer to go between them. Barrier improved shelf life. By far. The best barrier that's out there in the industry is aluminum foil, but unfortunately, when you use that, it makes it extremely difficult to recycle. Now, if you pick your favorite resins on here, you can see which ones act as a pretty good barrier. One of the most recent introductions to the market is the barrier, high density material, and it's done a pretty good job. And there's, there's a number of producers out there with it. You'll probably see in the not too distant future, something that we could do in that market segment with a with a barrier, high density, but the lowest in terms of water vapor transmission, is nylon. And the lowest for oxygen is Ionomer, as I said at the very top, is, is foil. You need a barrier for certain applications, abuse, resistance. Do you want puncture, tear, scratch resistance? This shows an example of a dunnage bag in which you want that dunnage bag to survive. You pack it in between skids and crates and stuff like that to keep it, keep it safe. Sealant, web, well, you have the film now you got to stick it to something be able to stick together. I'm not talking about peelable seals here. I'm talking specifically about heat seal kind of products. But having say, said that ionomers, there is a certain grade of Ionomer that works extremely well for peel seal applications. Some of the key things with seal ability you want low seal initiation, temperature, low hot tack initiation, high seal strength, high hot tack. And what I mean by hot tack is when that seal is still molten, you can put a force or stress on it, and that seal will still stay together. Picture packaging potato chips, and you put the material into that seal before it's had a chance to set that bag could open and you'd have potato chips all over the place. That could be fun, but not in a packaging application. The most fun I had with that was was milk packaging milk in Canada, they tend to buy milk and pouches in Mexico and elsewhere in the world. So for that application, you needed very high hot tag strength. So before that seal has had a chance to cool, it has to have enough strength to keep that pouch together.

09:46

So when I talked about being able to do some funky things by taking advantages of different parts of a film, and I'll use this one as an example. So this is a three layer co extrusion. You have metallocene in the sealant layer. High density polyethylene as a stiffening layer, and you have linear low density polyethylene in the other side. So the goal with this study was to try to keep the same oxygen transmission rate, keep the same water vapor transmission rate and the secant modulus, and keep the tear. We wanted to keep all of those consistent. But what I was really trying to look at was what happens when you separate up that high density layer as far as possible. Call that the I beam effect. Thus the little schematic over in the far corner. So by just separating up that high density layer closer to the skins, you've taken that stiffness from five newtons all the way up to 7.7 so what that allows you to do is to down gage that film, keep that same stiffness, and run that packaging machine a lot faster. So it's an overall source reduction and overall improvement in physical properties and performance. Now another evolution in the marketplace, chicken package. The chicken package back in the 1990s would have been primarily an octane, linear, low density polyethylene come along to the 90s, when metallocene technology first came out, we're able to reduce the thickness from four mils down to three mils. And today, back in the 2023 kind of time frame. We're looking at 2.75 mils in thickness, incorporating a high density barrier layer in there to keep the moisture where it's at, as well as a more of a filler, kind of linear, low density metallocene skins. Because you're using that concept of the I beam effect and the overall performance coming from that sealant layer, you're able to improve the overall performance, and you can see the change in cost. That's cents per 1000 square inches. A lot of people sell film out in the marketplace in dollars per pound. That's kind of the old way of doing it. As we're doing more source reduction, we have to focus on how many impressions or how many bags that you can get for the same kind of product. So that's why I'm using per 1000 square inches now, getting a little bit further along into more complicated structures, a barrier film incorporating EVO H and a tie layer in order to get the barrier properties you're going to get from nylon from, or, sorry, from, from EVO H, talking about the the the oxygen barrier, back in when five layer co extrusion first came out, and again, typos in here per million, that'd be 15.9 cents per 1000 square inches. And how much that can dramatically change by going to a five layer co extrusion, reducing down the amount of EVA wage, because this is, this was definitely overkill for the application that it was going for. Okay, typical film structures. So now I showed you the general trend. Now I want to show you some examples of films that are out there and some of the residents that could be used from shell that could be used to make those structures. So blown film, co extrusion, trash bags, that's a good example. The big trend right now is incorporate PCR into it, and that can be very easily done in this kind of film structure, stretch films. Stretch films today a typical example of what could be used for a five layer blown film for for stretch applications. And then the three layer, they're kind of kind of common films that are being used out there. And this isn't intended to tell you how to make a film, just examples of materials that you could potentially see in the marketplace. Collation shrink is now the state of the art. Is going five layer blown film for collation shrink. You see a lot of low density in there, because that's where the physical properties come from. For the shrinkage itself, you need the low density in order to get it. It's not easy replaceable because of the geometry of the highly branched low density heavy duty shipping sack. So there's some interesting parts with heavy duty shipping sack. You need a high density in there, or a higher density material. And the main reason for that, I call it a dimple effect. If you're packaging resin or you're packaging rocks, something for nurseries or agriculture, the high density functions to stop the dents that happen, and retards the the ability for that to happen. So you get the stiffness coming from the high density for faster packaging speeds, and you get the dimple resistance that comes with it. So that's a big advantage of going with a five layer co extrusion. You can put kind of a filler material in the core. You can put metallocene in there for higher puncture resistance. Or you can go with the metallocene on the skins. Or you could do both, in order to get the better the better physical properties out of the film. And depending on what you're going you tend to have the agricultural soil package tends to be a lot thinner than what, say, a resin bag or a bag of cement, something that. Packaging, 50 pounds, that sort of thing. Cereal liner. Cereal liners have really changed in the last number of years. If you remember back probably about 10 years ago, you try to open up a bag of cereal, so you pull on it, and it would blow up, and you end up with cereal all over the floor. We don't see that anymore. So the where the changes happen is primarily in the peel seal layer. I mentioned the Ionomer early on. There's a number of technologies out there that are very good from a peel seal perspective, you also see that the optics of that film has changed quite a bit. So the barrier high densities are very good for that. They have extremely high moisture transmission properties in terms of stopping it migrating through to extend the shelf life of that cereal as much as possible. And the way you tell that that material is in there is by the optics, for some strange reason that high density has very good optics to it. Well, the main reason is because of the nucleating agent that's used to to make it ends up producing very small sphere lights and and the lamella is very small, so you tend to have much better optics to it. And then, as I mentioned, separating up that high density, you get the you get the I beam effect. So you can make it a lot thinner. You have the moisture transmission rate properties that come with it, and a better overall performing product, cereal bags, or, sorry, not cereal bags, but when we get into retail salad bags, when you buy your salad, do many of you just take that salad and take it out and put it into another container or another bag and throw that, that bag away? Well, you shouldn't try to put it back into that original bag, because that bag is designed for the respiration rate of each of the living materials that are in there. That salad, that lettuce, is still alive. So are those carrots? So is that broccoli? So you have to design the film for the migration of oxygen and and carbon dioxide with that film. So put it back in probably one of the best case scenarios. When you put the salad back in that bag, you know, those CO two spritzer things you can make the seltzer with. You could even use that just put a little bit of carbon dioxide in there, and that would even extend the shelf life a lot further frozen vegetables. They've changed a lot too. So in this particular case, this is a microwavable bag. You have really good surface gloss and optics to it. It's usually reverse printed oriented polypropylene to a tie layer using an adhesive, and then you have the filler laminate web that would be under that so you want a very low seal initiation, temperature, high graphics, and it has to be microwavable. And in this particular case, that's how that structure would work. So really, the use of the butene resin in the core helps to reduce the overall cost of that film and still have the functionality that comes with it. Barrier for meat and cheese kind of applications. Again, you have the barrier high density. And the function of the barrier high density is EVO H is destroyed by water. If water is present, it drops off that oxygen. Barrier property significantly. So the barrier high density stops the moisture from migrating through and contaminating that EVO H, and you can see the general, overall, nine layer structure that goes with it. And that's why I've offset the barrier high density with the butene resin. It's on the wet side. Then you get into some more items out there that you just don't realize how many layers are there, like that salad bag I presented before, it could be 11 layers. And if you look at this particular these are two different webs. You got a top sealant web and you got a bottom one. The top one is a little bit thermal form, so its composition is a little bit different. Again, each of the layers are designed for specific things, going from mono layer to multi layer, co extrusion, you engineer it for the performance attributes that you're looking for, and just other general applications out there. And you probably didn't realize that in some of these cases, for agricultural films, they're barrier films. They have EVO h in the core, because when they do a fumigation of the fields, they want to keep that fumigant inside and not migrate out, keep it in there for as long as possible. Plus you also have regular polyethylene, like a butene or a hexene, linear, low density. But I found it interesting, the amount that's used EVO H is used in that kind of market segment. Yeah. Well, thank you very much. Any questions. I

19:43

Oh, all right, sure. So Dan, really interesting presentation. Thanks. One of the things I'm interesting, particularly with the push to sustainability, is two things. One, to what extent is that trend in down gaging still continuing? And two, to what extent is that. Compromised by sustainability, where people want to put more recycled resin in that might not have the properties that a virgin resin will have, so you'll make the overall structure thicker. How are those two things playing out?

20:13

Okay, so with regard to the addition of of the recycle content, so I'm assuming that you're referring to mechanical recycling versus chemical recycled. They both present their challenges to each other. Mechanical is obviously the best choice. It's the easiest thing to do after you clean the material, and it's great to have it in there. There are large trends, and it is being legislated in various geographic locations, and we're seeing that legislation continuing to expand, and we we fully support it, and we're trying to help out as much as possible. In fact, when we designed our resins for the film applications, we've designed them for recyclability, so we have the most up to date, the most advanced catalyst kill technology, as well as the antioxidant package in there to maximize the number of times that you can recycle it. Does that answer your question? The down, oh, yeah, yeah. So as the multi layer co extrusion technology continues to evolve, as there are more and more five layer lines out there, then the I beam effect can be really taken advantage of, and at that point, the down gaging can happen more, because you can make the films a lot thinner, but still keep the same bending stiffness to it, not the modulus, but the bending stiffness. And we have to separate those out so I can see it. So to continue the other latest trend is that the latest word that I've heard in the last number of months is mono material. So we're now seeing that's the Omega trend, is mono material. And what we mean by a mono material is it's the same polymer. It's a polyethylene. It could be many different kinds of polyethylenes together, but it's a mono material. We're going to see more of that, a lot of MDO machine direction oriented materials coming out into the marketplace.

22:09

So is these materials you're showing in the trends. What is the outlet for recycling these? Are you going to make them into bricks and build houses out of them? Or what I mean, you can't reuse them in the same method they were originally intended to

22:27

so what I hear you saying is, the outlet for mechanical recycling can be somewhat of a challenge. Yes, it can be. There is, I know there's a lot of mechanical recyclers out there that are using advanced cleaning technologies to try to get the materials as clean as possible, and adding it back into the Virgin resins and using it. It's also being legislated, like California has 30% that's required for grocery sack applications, and we're seeing trends with garbage bags and being used in that application. There's some things that you have to get out, like fibers, and unless you unless it goes to an application where fibers and gels are not quite as bad, the concern is FDA compliancy, so for direct food contact applications, but with the proper tracing and tracking, they're able to get that then the complementary side of that would be chemical or advanced recycling, or molecular recycling, how you call it. And in that particular case, you break it down to the molecule, and then we can advance recycle and and using ISCC plus mass balance systems, recycle the polymer that way. So there are two complementary systems i

23:44

Okay, no other questions. Well, thank you very much. I appreciate it. You.

Title:

Dan Moldovan at NPE 2024 | Shell Polymers

Duration:

18:52 minutes

Description:

Meet Dan Moldovan, Technical Service Manager at Shell Polymers.

Dan spoke to us at NPE 2024 about the history of Polymer Processing Aid (PPAs).

Watch this video to learn more about how the PPA industry has changed and where it's going in the future with a focus on multilayer extrusion.

Transcript:

00:00

Dan. Good morning, everybody. Thank you for joining us here at our innovation center. This morning, we have Dan Moldovan, who will be giving us a history of PPA.

00:22

Good afternoon or good morning. Everyone this morning, I'm going to talk about the second part of a three part series we're putting on about PFAs. So the major, the biggest thing that's going on in the flexible packaging is basically replacing the traditional PPA with PFAs. As you heard, we had a talk on the first day, and it talked about the regulations affecting, you know, the PFAs in not only blown film, but the whole area getting into the water, the drinking water, etc. And so there's been a big push to remove PFAs from all the film products. We initially had the PFAs or PPA to be put into our product when we initially designed the grade slate, but about two years ago, we decided moving forward, we would not have PFAs in our products. So at that time, we started a study looking to find replacements. So we finally came upon a replacement. It took us about a year and a half, and as you'll see in my presentation, the traditional PPA took 30 years to really develop, and so we were able to do that development in less than two years. So just want to go over the history so you understand all the criteria for a good PPA, first thing is important to understand. There's lots of additives that go into polyethylene, blown film. And you start with the basically antioxidants. You gotta have antioxidants. You put a lot of shear and a lot of heat into mania, make blown film. And then you have the acid Scavenger, because of the catalyst, you have basically free chlorine that gets into the system. And so you got to somehow capture that, because you're running through stainless steel equipment, and you don't want it to corrode or decay. And so then you have acid scavengers. And one of those acid scavengers is calcium stearate. During my career, we went through two or three different acid scavengers at Dow, which I was part of for 30 years, and continued to try to find the best and greatest but we're back to basically calcium stearate, which we started from. They also have zinc oxide, which, again, can be used as a acid Scavenger. We have, then the anti blocks are used in the film business, and one of them is silica oxide. The other things we're looking at now is UV stabilizers for ag film, et cetera. So this is put into the film also. And then you have anti stats, so you get the rule, and you don't want static build up. And so now we're adding anti stance to the film, and then the big anti block is talc. Talc is the cheapest and so that's what most folks are using today. We also have corrosion inhibitors. We have zinc stearate. Zinc stearate X is a process aid so it can be used. And some of the newer PFOs free products are using zinc stearate as part of their new PPA structure. It's one of many components that are used in that. And then the big thing is we have the folks from Milliken here is nucleator. So we developed the nucleator for polyethylene. It helps with the barrier, and it's now used in a lot of the food packaging applications. So it continues to evolve the additives that are being used in blown film. And then today, I'm going to focus on PPA, and the traditional PPA, which is a floral polymer. Well, it was first patented in 1961 so almost you know, you're looking at 60 years ago, PPA was patented. It was patented by DuPont. DuPont basically kept it under wraps until the patent expired. But what they filed in their patent is it allowed for increased output at without increasing melt temperature. So usually increase the output, you're going to increase the melt temperature of the product, and then if you increase the melt temperature of the product, then you increase the chance of degradation, so more additives. The other thing it did is you begin to run the film faster and faster. You begin to have. Melt fracture. So back then we had much wider dye gaps. So the wider the dye gap than the less melt fracture. The other thing you had back then, mostly all the film, was either high density or low density, linear low really wasn't invented or developed until later. And I'll show that. The other thing is, with all these additives in the material, they tend to come out of the film at the dye, so then you have this brown stuff coming out on the dye. And so with the floral polymers, you didn't have that dye build up. And again, as I mentioned, then we wanted to use narrower dye gaps, because with using narrow dye gaps, it's higher output, and it really started to take off. The history is when you know we have a unipolar process that we make our blown film on. Well, the first unipolar process, plant to make linear low started up in 1977 so 1977 was really the advent of linear low. Dow soon followed with their Daleks plan in the early 80s. So with the advent of linear low you had to then optimize the PPA, and so then the equipment. Again, like I said, was getting narrower dye gaps, faster line speeds. And so in order to do that, you had to optimize. You can see right here, this is what shark skin looks like. So it's basically the roughing of the film surface as it comes out of the dye. The process and the rate you had to try to optimize. Because, again, to make a PPA that would optimize these higher temperatures and higher run rates and the melt index of resins. Now we went from low density, which was a two melt, had the melt strength you were going to one melts or lower. So because of that, the viscosity of that is much higher than the low density. And then we added metallocene. Metallocene even is higher viscosity or higher shear than linear low so again, a great need. You can't run metallocene without a PPA. You're going to get melt fracture. And these additives are all used in the film process. And again, they were optimized to build for the linear low, then optimized for metallicy, and then they were optimized by the particle size and distribution. So again, these are the features. Again, the PPAs allowed you to reduce the pressure significantly. So if you increase the output, the pressure went down. And so as we're looking at the new PFAs free products, that's the thing we're always looking at, what does it do? We drop the new PFAs free in? It's got to match, or similar to the incumbent. And that's the issue. Some of them drop tremendously. Some don't drop. And Brennan will talk today about that in more detail and go into those but those are the things we're trying to match. So if you understand the history, this is what all our film converters are used to having this type of function that reduces the dye temperature. So you add the PPA in, and the dye temperature drops. Well, some of the ones that we're looking at do, some of them don't. So again, we want to try to match those, or that's what our the companies that are trying to develop a P phosphory are trying to match these same characteristics, and again, you can see the motor load. So we drop the PFOs free in and we just sometimes see a huge drop in motor load. Sometimes it's bad because it slips, because they have too much PFOs free in there. You don't give that where, with the traditional PPA, it drops the motor load, but you still are able to extrude and maintain output. And again, the one thing good about the traditional PPA is you want to have uniform dye thickness, so you have the dye and you run in a one mil structure. You want to have one mil around there, plus or minus 2% that's a good process. Well, with these stuff that we've been looking at the PFAs free, we've had variations up to five 6% on some of them. And so our customers are not going to want a product that doesn't have this. And really, our customers, when we deliver a product with a PFAs free PPA are going to want to have these same type of characteristics, because they've had those for 30 years.

09:52

So a little bit of chemistry here. So I'm a chemist, so these, this is the traditional fluorine molecule. And again, by. Definition of PFAs is any fluorine to carbon bond. So anything with a fluorine to carbon bond is considered a PFAs. So that's what's causing all the trouble. And so really for us, the PPA is composed of these two fluorine molecules. So what they do is put those they've developed these, and the companies like 3m schemors have developed this where they put those in the ratio of one to two to the carbon ratio. And so in that development, they also realized that they need a partitioning agent. So a partitioning agent sort of separates those into discrete particles. And what they found is microtalk does a good job of that. But then how do you get these molecules to the surface? So you have to get it to the film surface when you're extruding. So what they then decided is you can put it in polyglycol that helps to carry it to the surface. So they always say the model for traditional PPA is an egg. So the microtalk is the shell, the glycol is the white, and the fluorine is the yolk. So that allows it to get to the surface. The egg breaks, and then you come to the surface. So basically, again, there's a lot of science over here, but basically the PPAs. The other nice thing about PPAs, remember, I showed you all the additives that go in, so you'd want a PPA that uses a lower level of PPA, because then you have less interaction with the others and more issues coming to the surface. So you can see traditional PPAs, you could run up to only 200 ppm. Most folks were running for blown film, right around 500 to 600 which is still low. Well, some of the new PFAs free products, they're up in the neighborhood of 1500 to 2000 to 2200 so much higher loading. Now some of the other ones are coming in with lower loadings, but again, whenever you had the higher loading, there's a potential. So what happens is, when this droplet comes to the surface, it coats the metal. So it sort of puts a coating on the metal. So it takes a while. And what folks usually do, they add a high concentration of the traditional PPA to coat all the metal to get it started. Because the film producer doesn't want to spend a lot of time getting on spec. Just like with our plant, we want to get on spec, and so the faster they can coat it, the faster they can get rid of Mal fracture, the new PFAs products we found. None of them seem to work that way. They hit the dye and they immediately work. There is no coating time, and Brennan will talk more about it, but that's a new thing that customers say, Hey, should I dose it? We say no. Most of the time there's no dosing needed. So once you coat this surf, and it's sort of so you have the surface coated, then the other PPA that comes to the surface, it sort of is like an interaction. It's a negative interaction. And so you have this flux effect, which is like a magnet. So when you put a positive and negative magnet together, they repel each other. So that's why this PPA was so nice, because it never really came in contact with the surface and had any interaction or any buildup, it sort of just deflected. And so it didn't really come in contact, to give you the MAL fracture. And they were able to do that by depositing by varying the particle size. So it wasn't one uniform particle size of these fluorine molecules. It was variation so that you had to fill in all the holes. And it was nice too, that all the excess that was in the PPA, if you had to put excess in, it didn't coat, or didn't have any dye build up. It just went out with the polymer in the film. So, and this is basically how it works, it coats the screw, it must be in contact, and it happens autocatalytic. So it was a really nice product that they developed, and they continued to develop it in, you know, both three amps, Chamorros, Arkema had developed a really good product, and then all of a sudden it's like, okay, the government says you can't use it anymore. And again, the one thing about it too, is, remember, I said, How does it reduce the amps, and how does it get you to nice temperature? What it does is, basically you have, in typical materials, you have a shear on the wall face, and as you have more shear, then you don't get plugged flow. So you don't have plug flow. Then you have more degradation, but you can see that drag flow is less with their traditional PPA, so you get more of a plug flow coming out of the die. So that means then your consistent temperature is going to be same consistent back flow. And again, your variability around the output is in a consistent at less than 2% because of this phenomenon of the plug flow. And again, this is just some chemistry here, but again, this is what I mentioned on the first slide. You have all these other molecules competing for this space and coming to the surface. And so that's why, after a while the efficiency of the PPA becomes a little less because you have all these antioxidants, you have degradation processes taking place because of the high temperatures and the shear that's going in through there. And so then occasionally, with the old type of PPA, with the fluorine, you have to clean the dye, occasionally to continue to keep that surface clean, because if the surface is clean, then it reacts. It acts it with the metal, forms that bond, and then repels it. If it's dirty, then it can't get on there, and then you will start to get some melt fracture.

16:17

So again, these products have around since 1960 they've around, you know, almost 40 years, and all of a sudden now we're told to, in a matter of a year, two years, develop something that's took 40 years to develop. And so we have lots of suppliers, lots of master batch guys are working to develop it. We're continuously looking at those new products. We've looked at least over 1617, different products from different manufacturers, different compounders. We're continuing to look at new products, because it seems like every month, somebody's coming up with an improved variation of the additive, and so we're always looking at those. We want to make sure what's in our polymer is the state of the art and the best technology. And again, it allowed this lower back pressure, lower ramp. So these are the things that when we're testing for our PFAs free. We're trying to match these. So we have our blown film line. It's a monoline that we're using. It's industrial line. We're running around 450 pounds per hour out of that die. And we're trying to mimic what our customers in the sea. So when they get our product, they have pretty confidence that this product will work as a fluor elastomer replacement. And again, less downtime. Again, there's no dye buildup, so the customer, if you don't have that, then they're gonna have to shut down and clean their dye more often. So again, these are important things for us to look at. And again, what we have here is, I'll give you a little clue, but this is what Brandon's going to focus on coming up. And hope you'll come back. But this is the time to clear. The time to clear is what we always looked at for PPAs. And so what we've done is looked at all the different materials, and we look at time to clear and so but again, it's not only time to clear that just gives you, but as you see, there's a lot of other properties that are needed of the PPA that we're trying to match. So again, Brennan's in a talk today at three o'clock. I hope you can come back. It'll be the conclusion of our series on PPAs. Thank you. You.

Title:

Francisco Alvarez at NPE 2024 | Shell Polymers

Duration:

20:14 minutes

Description:

Meet Francisco Alvarez, Senior Technical Service Engineer at Shell Polymers.

Francisco spoke at NPE 2024 about Shell Polymer’s injection moulding grades and our internal qualification process.

Watch this video to learn more about how we turn concepts into reality.

Transcript:

00:10

Good morning. Welcome to NPE. Day two here at the shell polymers booth, our first speaker this morning is from our own technical services team, Mr. Francisco Alvarez. He will be discussing, from initial concepts to internal qualifications the shell process.

00:27

Yes, thank you. So thanks for coming to this talk. What I wanted to share with you is all the work that we have been doing to be able to bring our injection molded resins to the market. So that's why we call it from concept to reality, right? So, and this is the different topics that I'm going to talk about, I hope that we have an opportunity to show you our injection multi capabilities. That's the main thing that I want to share with you, but also to share we have been talking with all our customers about all the different things that we were doing. And you know, we have a really robust internal qualification process. And this is really what I want to share a little more in detail, what we have been doing, especially related to our injection molding rates. So this is our plant that, you know, it's located in Pittsburgh, like 30 minutes from Pittsburgh, in manaca, Pennsylvania. It's a really beautiful plant. Everything is brand new shining, you know. And the best thing is that we've already been producing resins for a couple of years now, and I am very proud and excited to tell you that we have been able to produce all our high density polyethylene injection molding resins. So I'm one of the lucky ones that our process has been able to produce all different types of injection molding resins, which you can see here in this slide. And the best part is that not only have we been able to produce them, but we have also been able to complete all our internal qualifications. So all our resins have been internally qualified, and then that has allowed us to come to the market, bringing to our customers. And most of our residents have already been customer qualified, and a lot of them are in the process of also being qualified. So where do we start? You know, once we start producing the pellets, you know, the the quality lab is going to be measuring the density, the melt index. We're going to be checking for all the different quality controls for the production plant. But besides that, we have to make a very detailed resin characterization right to understand the molecular weight distribution of a resin, the mechanical properties. So for that, we have really nice state of the art lab equipment. I'm showing you here are compression molders, and we have also all the different sets of compression molding molds to produce the specimens for mechanical properties testing. We follow the ASTM standards, and then our testing capabilities are also state of the art. So you know, we have our materials testing lab, where we can do GPC, DSC, all the other intensive properties, mechanical properties. And besides that, we have an applications testing lab. And what we do with that is we have an applications hole, where we have capability of producing three dimensional parts, let's call it that So, real parts that similar to what our customers are using, and then we have the capabilities to do the testing, which is what I'm going to be talking about, in particular about the injection molding side. So yes, yes, yes. You. Okay, so we can talk a little about that. Yeah. So all the testing that we do for for the compression molding, we have been following the ASTM standards, and that's what we use to produce all the technical data sheets. So as you can see now, as I mentioned before, since we have been able to complete our different qualifications, we have all the technical data sheets for our products, which include also the environmental stress, crack resistance and and all of these different testing the interesting part for injection molding is that besides all the meeting all the ASTM standards, we also have capability of testing our injection molding resins in the actual process where they are going to be used. So for example, we have these cross modify, edit on injection molding machine. It has really nice characteristics, as you can see, and we have a really nice hexagon mold. So you know, it's one of these modular systems that allow us to do a quick change to make different test specimens and different types of parts, as you can see, that we can, we can produce according to the ASTM standards. Now, besides having the capability of changing the doing. A Quick mode change to produce the parts. The back plate has a really nice mirror polish, so that also helps us to, for example, check optical properties and make good quality parts. And the other thing that is very interesting in the back plate is that we have capability of measuring using different sensors. We use Kistler sensors to make sure that the parts are being produced in good quality and repeatable. So I invite you to come to the talk of my colleague, Matt feldbauer. He's going to talk a little more in detail about how we use the Kistler sensors to make the parts that his talk is going to be tomorrow. I'm not going to spend more time talking about this, because I want to talk about the other part of the of the testing. But if you can come tomorrow, it's going to be a really interesting talk. So why is it important to test the injection the injection molding resins using injection molded parameters? Right? If you read the ASTM standards, you know, the one that we use to prepare the technical data sheets, it goes very clearly that we need to use compression molded specimens. So you know, if the ASTM started and is calling for for compression molding, why would we want to do injection molding right if we already meet the requirements complying with these methods. So I want to explain a little bit more about the differences between compression molded specimen and injection molded specimen. So assume this test specimen, and I'm going to make like zoom in into the thickness of of this part. So when you do the compression molding test, this is a micrograph of the thickness of the part. You can see that there is a little bit of darker area here. That's where the part is being cooled down into in contact with the platens of the of the mold. But if you see the internal part, everything looks very even, right? So, polyethylene is a semi crystalline material. So what it does when it starts cooling down, it starts forming crystals. And you can see that the formation is pretty, pretty even. So what we have is a really homogeneous area. That is because during the testing, if you follow the ASTM standards. You know, you need to heat it up at a certain heating rate, and then the cooling rate is really slow, so that allows for the part to relax. And you know, you have a really nice good formation, the creation of spherulites, which is what we form for the crystals, right? And the reason for for the ASTM standard to use this is because you eliminate any variability, right? What you are really checking is the properties of the resin. So the way that the resin is cooling is not going to affect the actual properties of the resin. So that's why ASTM says use compression molded parts. What happens when we do injection molding, when there are a series of very interesting phenomena that happens. So you can see also the dark part is the the surface of the part that is a part that is immediately cooled down into in contact with the mold, right? But here you can see that there are different faces in in the internal part. So remember, this is the plug thickness, and you can see that there are two very discrete areas. This is what we call the frozen plastic. So as the material starts flowing inside the mold, as soon as it touches the mold that is cooled down, it freezes immediately. And then what happens next is that you have this area that is a little bit darker you can see it well, I mean, with this resolution, I don't know you can see it, but there is a lot of orientation. So you can see that the first, let's call it the crust, it's already frozen, but then hot plastic is still flowing and it's touching now the frozen plastic, and that generates a lot of orientation and a lot of stresses in that part. And then in the middle, we have a similar situation than what we had with a compression multiplier. But now remember that the cooling is going to be different, because now we have kind of an isolator, right? You know that plastics are really good insulation materials, so now this insulation is going to change the way in which the cooling is going to happen in the middle. So the things to remember is we have frozen on the crust, then we have higher intention that is touching the crust, and the hot material that is still filling in, this material is going to stay hotter for a little longer time. And then the insulation that we have here with the plastic that is frozen is also going to change the way that the plastic is going to cool down so many times what we what we have with this is

09:49

this Inc layer is going to change depending on the injection molding conditions. It reduces the cooling rate because, as I told you, there is that insulation that we have generated with the plastics and. In this part, we have longer relaxation than what we have in these areas. So because of all of these, ASTM does not like to use injection molded specimens, right? Because they say, okay, depending on how you mold the parts, you may change the mechanical properties of the material. That's why they want to use the compression molding plant, because that way shell or any of our competitors, we know that we are all producing the plugs the same way, right? Because I could use this and change my conditions, and hey, look, my resin is having better properties than my competition, right? So that's, that's the reason why, why ASTM requires to use compression molding. But again, these are injection molding resins, right? So we really want to know how they are going to behave under the injection molding conditions. That's why we wanted to be able to do all of these testing. Yeah, so this is just to summarize. Now the test specimens fabricated by compression molding are less sensitive to the processing conditions. We are allowing the resin to relax. We have a really nice crystal growth. Everything is very well controlled. And injection molding part. We have the differences in thickness. We have different processes happening. You know, higher orientation, less orientation, frozen layer. So it's very different, very different components. So I wanted to show you what happens and how this theory is really true. So I'm comparing here different mechanical properties tested in compression molded parts and injection molded parts. So see in the case of the tensile impact and the ISO impact, so we can definitely see that the injection molded specimens have much better impact than the compression molded ones, right? And this is a very good sign of how the orientation is going to be affecting the the crystallization and the way that the parts are are being formed in a similar way. And you know this, right? Every time that we have better impact, what happens to the stiffness? It does go down, right? So if we compare the flexural modulus and the HDT of compression molded specimens compared to injection molded specimens, then you can see that the values go go down a little bit, right. So again, this is helping us to understand better how our resident is going to behave, beyond the ASTM and the technical data sheet information that that we are sharing with you guys. So this is one part of our internet qualification. The other part that we are doing is we have, besides our 80 ton machine, we have this 120 ton coronavi machine. I put in there all the different characteristics of this machine, and we have a really nice capsule. So for some of our resins, we can produce this 28 millimeter CSD cap. We have a four cavity mold. So Well, it's not as big as the ones that you can see here in the show, but it's a really good representation of what our customers can be producing with these caps. So some of our residents, we're going to be running in this one, for example, the 10 mi we have been testing in our CSD mold. And as what we do for the internal qualification is an extended run. So you know, we do not only check for the mechanical properties, but also the consistency of our production. So you know, when we produce the first campaign of our resins, we collected several batches throughout the campaign, and we saved them, and then when we came back on the wheel to produce for the second time the same resin, besides confirming that all mechanical properties were what we expected. We ran an extended campaign. So as you can see, we are monitoring all the processing conditions and the processing variables, and made sure that between our internal qualification one and our internal qualification two, all the mechanical all the process ability, the properties of the resin were exactly what what we expected, right? That there was minimal variation between the different the different batches. So that also gives us more confidence that we are not just meeting the mechanical properties required, but also that our resin is going to have good process ability, and that we have repeatability in our process in a similar Oh, and then, as I told you, besides the process ability, we can check the dimensions of the part. We can do torque analysis, which, in this in the in the sense for the caps and closures, that's a really important testing. We do have that capability in our applications whole. The other thing that we have is cross my GX 650 it's a 650 ton machine. This is a really nice machine that, besides having all the characteristics that you can see there, we try to make the platen so that we could share our capable. Facilities with you guys. So if our customers do not want to spend time using their lines to do testing, we could work with you to bring your molds to our facilities. And we made our plan to be capable of adapting many different types of molds. And also, I'm sorry the the daylight opening is pretty, pretty wide. So we try to make it versatile equipment, so that we could try different types of molds. We have two molds in this machine. One is the lead for a pail, for a five gallon pail. I put there the the different characteristics of the mold. It's a really nice mold. You know, top grade molds is one of our partners, besides Krause Mafi. And with this mold, what we do is produce the parts and then do mechanical properties testing. We also have the five gallon pail itself. And similarly, what I show you for the CSD caps when we produce our resins, we tested them here, we ran and extend the campaign and measured all the processing conditions, made sure that we had consistent product, consistent process ability. And then we also performed all the mechanical properties testing, right? So we have capabilities of running similar to the DoD testing for for the pails, using the leads to, and that is part of what you were asking before. So we do the ECR on on pails. So yes, as you can see again, what I wanted to show you is that we have been trying to be really thorough in all our internal qualification, we have been trying to not just comply with an ASTM standard and bring to you the technical data sheets and let you guys figure out if you can run a resin, but we try to use all our internal capabilities to do a thorough investigation make sure that the processing is going to be good, that the mechanical properties in the actual injection molding process are going to be met, and that we that we have repeatable, repeatability in our process. We have really nice testing capabilities. I just show you very quickly the the lab test, the lab pictures, but I can assure you that we have state of the art equipment to do all the testing, and I also share with you part of our applications, whole capabilities related to injection molding. My colleague Mike Misko is also going to be give a talk about our internal capabilities for blow molding. So if you are around, that will be another interesting talk to to see, because you will learn more about what we do we with our products for what. Yes, tomorrow is Mike misc, yeah. So yeah. I mean, I just wanted to finish because, you know, all of these works involves a lot of people. I wanted to have here some of the names, and, you know, I would need another 20 minutes to show all the names of the people that have been involved in this work, but at least some of them and the ones that have been really helping us and supporting all our work. So that's what I had. And then we can go to the Q and A questions, can you come back to the product? Yeah, sure. Let me see if I can go back.

18:45

Yes, if you want to, after the talk, we can go to the Product Selector, and you can also see all of these and get all the information that you want from the different grades. Already.

19:07

So we have already been testing the 52 and 10, the this resin we have been using for caps and closures and also the so the 52 and then has been more for the for the soft drinks and the 65 and eight, the HOMO polymer. This one we have been using for the larger parts, right the the ones that, for example, for hot fill applications, those, those are the ones that it this one would be better fit the 65 and eight. This is an eight MI, 965, high density, yeah and the 10, the 52 and 10 is 10 MI, 50 952, density. Yes. Do you have any other questions or comments? I. Okay, well, thank you for coming to this talk, and I hope that you learned something about our internal process. Thank.

Title:

Mike Misco at NPE 2024 | Shell Polymers

Duration:

21:42 minutes

Description:

Meet Mike Misco, Technical Service Engineer at Shell Polymers.

Mike spoke at NPE 2024 about the term ‘drop-in resin’ and how it's used in the industry.

Watch this video to learn more about blow molding, why drop-in resin is sometimes mis-used in the industry, and perspectives of a resin producer versus a converter.

Transcript:

00:09

Good morning. Everybody. Just wanted to introduce our next speaker. This is Mike Misco, and he will be debunking the term drop in resins.

00:20

Thank you. So yeah, thanks for introducing me. Thanks for attending. My name is Mike Misco, tech service engineer for Shell polymers. Been here for just over six years prior to joining shell, I spent eight years of my career on the converter side of the industry and with a large blow molding converter. So today I'm going to be taking you through a presentation where we look at the term drop in resin and how it's used in the industry, accurately or inaccurately. We'll save that for later, so we'll jump into it so we have the kind of what we're going to talk about today. Start off, quick introduction into some of the below morning capabilities we have at Shell polymers in our applications Hall. You heard from Dan, you heard from Francisco, injection molding blow or blowing film capabilities. So I'll touch on the below morning. Then we're going to set the stage for the presentation and kind of give a quick overview of why I think drop in resins is misused in the industry, and provide some backing to that. Then we're going to share the various perspectives of a resin producer versus a converter and what all really needs to align to mean you actually have a true drop in resin, and what those different layers are to contribute towards that. Then we'll go to a case study that was performed in the Applications Hall to support some of this content, and then we'll wrap up with a Q and A Okay, so some of the capabilities on the blow morning side, we have two blow morning machines. First one being a unilo. You are 70. This is a reciprocating screw machine. Can see some of the details on the machine were roughly 575 pounds per hour, two stations, two flow head. We have the options of two molds, half gallon dairy bottle, one gallon dairy bottle. The case study was completed on this machine, so we'll have a little bit more data on this in the future. Slides. The other blow morning machine is a Cal text, KBB 400 s. This is a all electric continuous extrusion shuttle machine. This machine was uniquely designed with interchangeable flow heads, so we want to be able to mimic multi layer blow molding. So we have a W Mueller Coex six flow head. You can see the two molds that we have selected for this. This flow head are a 28 ounce cylindrical bottle, which we have the product drawing here. And then we have just your standard one liter motor oil bottle, rough output of 22 to 90 pounds per hour. Then we have a Cal text mono layer flow head that allows us to simulate larger part below molding, where we have a 20 liter jerry can to support that flow head upwards of 350 pounds per hour, kind of like Francisco mentioned yesterday with the GX 650 his injection molding machine. This machine was designed with a plant that will accommodate customer molds. So we encourage customers bring their molds, their toying to our facility, rather than shutting down your your production line and using up your your time. Okay, so let's jump into the main content here. So drop in resin, in my opinion, is a term that is very, very loosely thrown around the industry. When referencing a transition from one resin to another, you'll have definitions of a customer wants a resin where they drop it in and there's no changes, no processing adjustments needed. Now I'm going to kind of show you why that's theoretically impossible. There's always going to be some changes necessary from output, differences in output, how it flows, differences in dye, swell, et cetera. So in the remainder of this presentation, we're going to explore some of those variables that will discredit or desponk How this term is inaccurately used in the industry. All right, so what we have here, and I thought it was important to show kind of the various, I guess, segments or levels from the resin supplier to the converter, and how that impacts how that resin will perform in the hands of the consumer, as well as a converter. So we have on the left side, and I also use inverted pyramids. I think it's a good visual of any discrepancy in any layer will cause that pyramid to kind of lose its balance on the point. And the point in this this case, is the resin performance as it relates to a true drop in drop in resin. So at the top of both resin supplier and converter, we have people. I mean, this is in every industry. As far as what's your turnover rate, what's the skill level. So do you have employees who've been there for many, many years that can troubleshoot essentially everything, or do you just hire somebody off the street that's from a completely different. Industry and is green, and you're training them culture in that plant, is it poor in that they are fighting machine issue, quality issue, etc, day in, day out. That's going to impact how the attention that they give to those processes. Now we're going to focus on resin supplier. Next on the list is catalyst. So catalyst is paramount in how that resin is going to perform, how it's going to process and then in the hands of your consumer. So two things, how it's activated is going to affect the reactor productivity. That will impact the ends, the end product. Also a catalyst that has a broader molecular weight distribution versus narrower, where habits pros and cons and each will process differently. Next is feedstock. Feedstock is typically, you won't see many issues as long as it's within that purity spec, but once you get outside of that purity specification, that's going to adjust and impact your reactor productivity, and that will, in turn change your resin performance. And then additives. Each resin supplier formulates and designs its own additive package based on what they feel the industry needs. So, different types, different loadings. So if we look at antioxidants, if you have a lower loading that's going to cause significant degradation in heat through heat histories. So that's going to affect all of your mechanical properties, your color, even odor, to some point. So on the resin supplier side, to have a consistent, true drop in resin, batch after batch, those all have to stay the same. Okay. Now we'll jump over to converter, jump down to the second level process, material handling, as it relates specifically to blow molding. The process that's simple could be extrusion blow molding. It could be injection blow molding. Material handling, I've seen first hand where this is critical in how that bottle performs and how it processes. So in terms of most below molding has closed loop regrind process. So what's the level of that regrind? What's the quality of that regrind? Is a consistent flake size. I've had a example from my past life. We were fighting a new product startup, new mold, startup. We were seeing significant pressure surging in that extruder for days. We couldn't figure it out. We did all of the common troubleshooting, where we bridging, where we haven't blockage was there we went purging. Is our heaters on our extruder? Heater bands bad? Or is it reading correctly? Then we started looking at the regrind. It was a closed loop system. So you grind the bottles, you grind the scrap, reintroduce it back into the hopper, goes back into your bottle. What we saw is that the temporary workers, they were responsible for grinding these bottles all the all the flash that goes with it. They would take one entire bin of just just the scrap, so your tails, your handle, slugs, your flash. Then they would grind a tire bin of just the bottles, no scrap, and then flash, then bottles. So you have layered different bulk densities of material that's going right back into that process. That's going to make it literally impossible to complete that process and set it up. Next level down, we have equipment, or the motor. So equipment, blow molding is unique in that there are so many different types of extrusion blow molding equipment. You could have a reciprocating screw, accumulator head, continuous extrusion, Rotary wheel. We can have Paris and vertically extruded, upwards, sideways, vertically down, fighting gravity. So all of those kind of have a fair share in their own, their own pros and cons. More importantly, what's the condition of that equipment? So is it properly maintained? It is the screw. It's appropriate. Where on that screw is the are the heaters appropriately functioning? Is the air system? Is that giving you consistent, repeatable air to that blow motor, all those factors, and any discrepancy in that will change that process. And I keep, I know I'm going on and on about this, but this all kind of goes and contributes towards that drop in resin, and how that repeatability is from resin to resin. Next we move down to environment. So this is, is the plant climate controlled. I've been in plants southern Florida, Summer, 130 degrees F, and then you have a water cooled mold, 43 degrees F. Those don't really, those don't mesh very well, so you're constantly fighting the condensation build up on that mold. And you're never you're never going to be able to achieve a good process. So as you can see, all of these in order to support a true drop in resin where you're transitioning from one resin to another, no changes are needed. These all have to be the same, day in, day out. And quite frank. Really, I mean, going through all this, it's really kind of impossible.

10:06

Okay, so now we're going to shift a little bit. I'm going to talk about tech data sheets, and caution the use of those for for actual comparative, comparative data. So what we're looking at here is for homo polymer, food and beverage type resins for extrusion, blow mowing processes, looking at the melt index. So let me back up. So Tech Data Sheets is typically used as a comparison side by side. Let's see how the melt index adds up. Let's see how the density adds up and some of those other properties. And that's used to make a lot of decisions in the industry. And I want to iterate that Tech Data Sheets is very much so a snapshot in time, very tiny snapshot of how that resin is processed, how that resin is made, et cetera. It doesn't account for your spec limits. It doesn't account for any of that stuff. So while it's good for a high level comparison, I'm going to get into a little bit later here the need and the priority in asking questions and truly understanding how that resin characteristics play side by side with each other. So if we're looking at Tech Data Sheets, let's look at meta index. You'd expect resin A, B, C, they'll flow pretty similarly. Resin B might be a little bit different, but then you look at resin D, you could probably easily, easily predict that that's going to have a little bit lower melt strength. You're going to have to make adjustments for bottle weight whenever you're transitioning to or from that resin. Now we'll look at density, all pretty similar. So you'd expect mechanical properties would be probably pretty similar as density is that key driver, tensile strength. I mean, they're all all within 300 psi of each other, so you'd expect this very same performance, then flexural modulus or stiffness. This is kind of, in my opinion, a useless call out on Tech Data Sheets, in the fact that the resin supplier can choose what test method they use to populate on these tech data sheets. So you're looking here, across these four you have 1% secant, you have tangent. There's also 2% secant that you can populate these tech data sheets on so trying to compare your stiffness from resin to resin, it's not really possible without deep, diving into that resin a little bit more. All right, to the case study. So the case study, this is kind of the premise and the structure of how we did it. So we wanted to first analytically understand those resins. So we did competitive benchmarking for this. So first, based on that Tech Data sheet that we just looked at, we wanted to verify those melt index values, those density values, rheologically understand that Polymer complete additives analysis, mechanical property testing, so your escr, your tensile properties, etc. Then we fabricate samples. For this case study, we use the uniloi, you are 70 machine that we that we referenced earlier on. We conducted it with a two hour run to understand any changes over time. Got that stable process, collected samples over two hours to understand how repeatable of a process and material do we have, and we chose a one gallon dairy bottle mold. We wanted to understand that differences in dye swell, and I'll kind of get into some of those dye swell results here in the coming slides. But one gallon dairy bottle is super, super sensitive to differences in dye swell. Where you have that handle on the side, it's a larger bottle, where it really any differences in that dice? Well, will cause you to either under blow that handle or flash it. Then we took those bottles. We completed all the article tests that our customers would so all your weights, your wall thickness, distribution, overflow, volume metrics, top load, drop, impact. Then all that data was used to really, truly understand why that resin performs the way it does. Why are there differences across the various resins? And then with an end goal of being able to communicate to customers, you can expect these processing changes when you're converting from resin X to resin B, that's the end goal. So referencing back to the Tech Data Sheets, and the fact that it's a snapshot, what we have in the upper right hand corner this table are those results and those values pulled from that Tech Data Sheets. These are what we measured in our lab of actual tech data sheets from that or actual mi values, I two of those four resins, and if you look, none of them are the same, and they're really not even close. Where you see resin D is a plus 10% difference from what you see on the Tech Data Sheet versus what's actually measured. So. So this just kind of supports that ask questions, and this is this will come in My conclusions, and I'll back it up, but you need to ask your resin suppliers to prove and give you true specs and true data on that resin outside of just those, just those Tech Data Sheets. Use Tech Data Sheets as a high level comparison to kind of narrow down that that choice, but then truly ask the questions to fully understand what you're getting. So now we're going to look at some of the processing conditions on the unilay. So the table we have here on the right is showing all of those different processing parameters. Top top table here we have what those measured mi values were, and then everything from cycle time, differences in shot size, melt temperature, melt pressure, etc. And I'll highlight some of those, some of those here. Okay, so we're first going to focus on the transition from resin D to resin C. So we're running resin d2 hours, transitioned, dropped in resin C no processing changes. Let's see what the differences are in the processing side. What we saw six gram increase in bottle weight, roughly 200 psi increase in melt pressure, given the melt index that probably could have been pretty easily anticipated. Of what those differences would be given that higher mi of resin D, now we shift our focus to transition that on paper might look like it would be a drop in so resin C to resin B, we have a point seven, four MI. Point seven, five MI. Those densities all measure out to be very, very similar, kind of similar situation. We saw a five gram decrease in bottle weight, and we saw a 238 psi increase in melt pressure. Remember, the study that we did, we first analytically understood that Prop, that resin, so we checked the rheology we were on, GPC. What we found the GPC and that final analysis of truly understanding why these differences are present is that resin C had a higher molecular weight than resin B, so that is driving that differences in that viscosity and how that resin flows. And with just using those Tech Data Sheets, you would have never, never predicted what those changes would be. Now we're going to shift to die swell. We created a pretty simple schematic here on the right, going from left to right. So this is showing the polymer chain orientation, where in the extruder the screw, you have pretty random orientation. Then you start tapering down into the flow head. And it's not random, it's not fully oriented, but they're starting to orient. That's called the deform stage. Once it goes down into the actual dye, that orifice is much smaller, those chains Orient. And then as it comes out of the dye into the Paracin that that, uh, that Polymer tends to coil up, those chains coil up, and then they want to relax or swell back to their original position. So that's kind of the dye swell phenomenon. Some variables that affect dye swell, melt, index, molecular weight, which we'll have an example of here in the next couple slides. Melt, temperature, flow rate, and how your dye is designed. So this was a study that we did on the unilo. So I said we used the one gallon dairy bottle mold, and we started with resin D. Resin D was that highest MI, MI resin that we had. We took that Paracin pre blow pressure as low as we could without physically under blowing that handle. It's kind of hard to see on this screen, but there is consistent handle webbing of incomplete, finished handle in this then we we dropped in resin C. Drop that rate on top gave it time to introduce into the process, and we saw that handle webbing immediately disappeared, suggesting resin C has that higher dye swell than resin D. And again, circling back to that analytical testing that we did, looking at the GPC, we see that resin C has that higher molecular weight, so you have those longer polymer chains, more entanglement, that means more higher elasticity, and that'll cause that dye swell to be greater than what we're seeing with that higher MI, lower MW resin. This is just more supporting content for dye swells. So these tails were pulled off of the bottles from the previous picture, just another illustration of the differences in dye swell. And this is kind of simulating that Paris and as it first comes out of that die, measuring the width, you can see visually the difference in that width, without making any processing adjustments

19:52

to accommodate those differences. So wrapping everything up here, we talked about a lot from. Are Tech Data Sheets? Are they valid? Should they be used? Are they overused? I think they are. They're good in a sense of initial comparative data. Don't use them as as as this. Do all sale to understand what resins you're you're buying. When we talk back to drop in resins, it's where a drop in resin being defined as no processing adjustments are needed from resin to resin. I think we can all agree now, after some of the content we look through, that that's virtually impossible. So everyone's going to continue to use the word drop in resin, but I hope you come out of here understanding that drop in resin might mean you might have to make accommodations for differences in die soil, differences in how that material flows, differences in bottle weight, etc. And based on this, what I highly, highly encourage, start asking questions. Ask, fundamentally, ask your resident suppliers to provide you the data that you need to make a successful transition, so ask them, what differences are they going to see when they transition from their incumbent to your resin? And they should be able to give you that data. Okay, communicate that knowledge to your plant team that's going to make for a much successful startup, more resin transition, less downtime, and overall, much better culture. Any questions?

21:32

Nothing, okay, thank you. Applause.