Tuesday, May 29, 2012

Playing Telephone and Patents

Scientists and engineers are well known for having years of training and education in using data to help them know what is true and what isn't. And yet there are times when most of them absolutely fail to look at the data themselves and make their own decisions, and those times involve patents. It's almost like the child's game of "telephone" where someone claims something is patented, and then the coverage of that patent is expanded by the next person in the chain and so on until pretty much all of polymer science is patented and we can only work in the realm of expired patents. The surprising part is that few people seldom look to see for themselves what is actually covered by a patent. I say "surprising" as again, we are all data driven. If I said that HDPE has a Young's modulus of 4 GPa, you can bet someone will be looking it up to verify that claim. (Please do, I just pulled that number out of thin air!) But if I said someone's work is already patented, few people will challenge me.

Patents are long (getting longer each year), pretty poorly written from a scientific communication viewpoint, and full of obscure phrases from lawyers, but making an initial decision on what a patent covers is easy - skip to the very back and read the claims, and if you really are into the TL;DR part of life (TL;DR = too long; didn't read) only read the first claim. Don't read the title of the patent, the abstract, the introduction or anything else written. The claims and only the claims define what is patented. The rest of that stuff was written when the initial application was written. Once the patent office got a hold of the application, they most likely cut the claims down in scope, but it was only the claims that were edited, not the body of the patent application - that other stuff will still remain there for all eternity even as the claims are withered down to nothing. Again, pay attention only to the claims and nothing else.

Let me give you a specific example. Here's a patent that issued last week, US 8,182,888.[*] Claim 1 states
"A packaging article, comprising: a layer of an oxygen-scavenging composition including: an oxygen-scavenging polymer that includes: a condensation backbone, and an unsaturated side chain attached to the backbone, wherein the side chain includes at least one acyclic carbon-carbon double bond that does not involve the first carbon atom of the side chain; and an oxidation catalyst; wherein the packaging article is suitable for use in packaging food or beverage products to preserve the freshness of the food or beverage products.

If that is tough to read, it should be as it violates all the good writing habits we've learned. However, it is legally necessary to write it in a style like this as all claims must be written as single sentences - hence the difficulty. If we can use multiple sentences, its much easier to get the point across. Let me show you.

The patent claims packaging materials with oxygen scavengers in them. The scavengers are made from polymers formed from a condensation reaction and they have an unsaturated side chain. The unsaturated side chain has at least one acyclic double bond, and that double bond isn't associated with the first carbon in the side chain. There is also an oxidation catalyst, and that is required since it doesn't claim that the catalyst is optional. And that's it. Nothing more, nothing less.

But lets look at the rest of the writing that's in the patent particularly what's on the first two pages. Start with the title: "Oxygen Scavenging Polymer" Does that mean it covers ALL oxygen scavenging polymers? No, having read the claims, we know better. Look at the abstract (it's right there on page 1 and it's really short and so easy to read!):
"A polymer with a backbone and an unsaturated side chain attached to the backbone. The polymer may optionally be combined with an oxidation catalyst and/or other ingredients."
Now that is very misleading, isn't it? The abstract discusses a polymer backbone, but doesn't mention that the claims limit it to a condensation backbone. The abstract also states that the catalyst is optional, even though the claims, what is actually protected by the patent, do in fact require the catalyst to be present.

Turning to page 2, the Technical Field is described as
"This invention relates to an oxygen scavenging polymer. The polymer may be applied to a package, or made into package, wrapping, and storage articles to preserve the freshness of, for example, foods and beverages."
Here is says the polymer may be made into a package, yet we know from the claims, it has to be made into one.

This post came about as a result of a remark made a colleague here - that a new invention is already covered by other patents. If you look at the body of the patents, you may be lead to believe that that is the case, but only when you look at the claims do you see that there is no overlap at all. Claims can be difficult to read because of the one-sentence requirement, but parse them just like you did sentences back in high school so you can understand them. Then you will see what is protected and what isn't and you won't be part of the telephone chain.

[*] I just picked this patent at random. I'm not working on oxygen scavengers, and I certainly am not holding this patent up as an example of a "bad" patent. It is representative of many patents where the claims can be quite different from the rest of the patent. My point here is to show clearly that the claims are what matters and that they can conflict with the balance of the publication rather badly at times.

Friday, May 25, 2012

My Favorite Toxic Chemical

Submitted to the Toxic Chemical Fair sponsored by Science Geist

I have loved reading the thoughts of others this week, but after wracking my brain for a week, I decided that I'm not sure that I have a favorite toxic chemical (and I'm comfortable with that).

But the other thoughts I had this week on the subject have largely been around this: As scientists, we are trained to accept diverse and contradictory behavior. The most famous examples are from physics, such as the Twins Paradox in Special Relativity and particle-wave duality. The general public has a hard time with this. If you want proof, just go to any physics forum where questions can be posted and discussed. You won't have to go long before you see someone posting that Einstein and/or quantum mechanics is all wrong, largely because the paradoxical behaviors that they describe don't match with everyday reality. But regardless of what these people may think, we all know that these dilemmas are factual and reproducible, so we ignore the naysayers and go on.

So is the idea that a chemical can be both good and bad just as large a dilemma as the Twins Paradox? Just because we as chemists are comfortable with it doesn't mean that everyone else is. We see the one-or-the-other-and-nothing-in-the-middle mindset in chemophobia, where people believe that all (synthetic) chemicals are bad, while all natural chemicals are good, when the actuality is that in both cases, the chemicals can be both good and bad. We as chemists know this on a factual and reproducible basis, so why do the the naysayers get to us? Should we just ignore them?

Are we expecting too much of the general public to accept this dichotomy that chemicals are both good and bad? Sadly, I think that our comfort with the dilemma blinds us so that we can't see how big a gap it is for others to bridge.

On a lighter note, I submit that there may be one group of people who should have no problem with this duality, but just not in public when the microphones are on...

Thursday, May 24, 2012

Slimy Alien Invaders in Minnesota?

When you leave the Twin Cities of Minneapolis and St. Paul start heading north and west, you end up in some beautiful areas of woods and lakes, but also an area where very strange things have been known to happen. This is after all, the region where the movie "Fargo" and its infamous woodchipper scene occurred. This last week however, something that might well have occurred in a B-grade science-fiction thriller happened in the small town of Dent, Minnesota. It was an invasion of alien slime!
The local newspaper described it as:
"Strange jelly-like blobs found on patio near Dent.
I can just imagine the scene on that fateful morning. "Dear?! There's something slimy on the front porch." "Why don't you touch it and see?" "I'm not going to touch it, you touch it." "That settles it, I'm calling 911. And the newspaper."

From the photo, you can see that the slime has been successfully captured, although probably with significant loss of life and injury to innocent civilians. The newspaper got a local chemistry professor to look at it: "I would say looking at it and feeling it [Editors note: you mean he touched it? Eeww!], it probably is just a water retention gel of some sort. A silicone polymer … maybe." I agree that it is a water-retention gel, but those are usually crosslinked polyacrylamide. The gels are definitely not a hydrophobic material like a silicone. The gels swell a tremendous amount when wet and do have a nice glistening appearance of an alien slime monster.

In closing, remember too however, that the city of Dent is very close to the lost county of Mist in which Lake Wobegon is located, so while it may well have been a quite week in Lake Wobegon, the City of Dent was invaded by aliens. And they're coming for you next.

Monday, May 21, 2012

A Monomer I Won't Work With

Derek Lowe's blog, "In the Pipeline" has an ongoing series of posts entitled "Chemicals I Won't Work With", usually something that is frightfully explosive or odoriferous. Today I'm countering with my own offering - a monomer that I won't work with. Maybe surprisingly, the monomer has a number of positive features inherent with it
  1. It is biobased, so you would think it would be rather appealing in this era of "get-us-off-of-Big-Oil".
  2. It is an oil found in the sap of various species of the genus Toxicodendron, plants which grow in the temperate zones all across the northern hemisphere, so it can be grown widely.
  3. The plants are actually considered undesirable weeds plants and are not cultivated, which is a further attraction of this plant as it will not need arable land.
But if you looked closely at the Latin genus I just listed, you will notice that it is made up of two words - toxic as in "poison" and dendron as in "tree". Put the together and you have "poison tree", as in poison ivy, poison oak and poison sumac, three popular (?) species of the genus. Having been in the Boy Scouts for 7 years, I've already "worked" with urushiols and found that they don't like working with me.

Urushiols are actually a bunch of substituted catechol molecules as this figure shows [*].
The molecule has two parts - the catechol head (the dihydoxybenzene)and the mostly unsaturated hydrocarbon tails. As far as the contact dematitis and associated itchiness, it seems to me that the catechol is the business end, as catechol itself is noted for causing contact dermatitis. (I've never done a side-by-side test of urushiol and catechol to see if the effect is similar. I would, but my calendar is booked out for the next 23 years or so...). But in terms of forming a thermoset polymer, the double bonds react with themselves and oxygen to polymerize, much like what occurs with drying oils.

Urushiols have actually been used in Asia for hundreds of years to create the beautiful lacquers that are so emblematic of their furniture and artworks. The sap is diluted down with solvents, a thin layer is applied and allowed to dry/cure. The process is repeated hundreds of times building up to incredibly beautiful finish.

[*] Source The source can be freely accessed (after a simple registration) for the remainder of 2012.

Final (?) Thoughts on a Resin Shortage

I have some (what I hope to be) final thoughts on the nylon-12 shortage, but they really are about disrupted supply chains in general rather than nylon-12 in particular. However, since nylon-12 is the subject at hand, I will be specific to that and state that the nylon 12-resin shortage will have long-term damage on all the nylon-12 suppliers. And by long-term, I mean years beyond the time that the Evonik plant is rebuilt and fully operational.

A disruption of the supply chain like this will create a good deal of self-examination for the customers. The biggest outcome will be a "never again" response - never again will they be caught needing nylon-12, unable to get it and having no alternative but to let it impact their own production (or at least potentially impact it).

While many nylon-12 customers thought they would be safe from such disruptions because several different companies sell nylon-12, they never realized that these suppliers were all so dependent on a common feedstock - cyclododecatriene - (CDT) used to make nylon-12, and that the CDT supply was so dependent on one supplier. Since the disruption in the CDT supply, that vulnerability has been made clear and few people will volunteer to get back on the horse that just threw them. All the companies feeling the pinch of the shortage will have either found an alternative material or at the very least examined other alternatives and will continue to examine those alternatives. Those that switched away from nylon-12 will not switch back just because the material will be re-available, as any switch involves a large body of work, paperwork, approvals, meetings... There may be an economic justification for switching back, but any such reversals will be done with much analysis of the risks and how to handle future disruptions and are not guaranteed in any way. Because of these switches away from nylon 12, the CDT/nylon-12 market will quickly change from being in undersupply to oversupply once manufacturing is re-established. (Ironically, that would be the best time to start using nylon-12, as there will be excess capacity.) This oversupply will eventually be sold, but it will not happen quickly as nylon-12 is a non-commodity product, not widely used. Most of the niches in which it can be used have already been found and only time and a big sales effort will establish more.

These comments are based on some personal experiences that I had while working at Hercules. (Hercules again?! It was a pretty crazy year there in Terre Haute for me, wasn't it?) This had nothing to do with the potato chip bags, but involved a customer who is best known for making caffeinated, carbonated, caramel-colored beverages. We were supposedly within 6 hours of shutting them down because of nagging production problems that gradually reduced how much material we made. The customer bought film from us and no one else (this was a time when all the business consultants were pushing "single source supply" as a way to work closely with your suppliers and to build trust). It was to the point that we would make a roll of film, immediately slit it down and ship it to the converter, who then immediately printed it and shipped it to the final customer. Even though we resolved the production problems, the customers clearly saw the risks of relying solely on us, started exploring alternatives and took advantage of those options.

So while the nylon-12 production crisis will be soon resolved, the marketplace will not soon forget the disruption that occurred.

Friday, May 18, 2012

The Impact of the Nylon-12 Shortage Grows

I've mentioned before some of the fall out from the Evonik fire/explosion in March of this year. The initial concerns were regarding the shortages of nylon-12 for the auto industry. While that situation is being addressed, a new issue has arisen in the medical device industry - the explosion is now leading to a shortage of Pebax as well.

Pebax is a polyether-block-amide copolymer, meaning that there are alternating blocks of polyethers and polyamides, with the polyamides in this case, being nylon-12 (although other nylons are used depending on the particular grade). The materials are nice soft elastomers that have lots of uses, but the most important use is as balloon catheders used in angioplasty procedures. Since the nylon-12 is only part of the polymer, the demands that Pebax production places on the supply are less, but that doesn't make life any easier for the product development engineers.

I already have spoken before about the challenges that automakers will have with "drop-in replacements", but for medical device manufacturers, there is no such thing - by law. All these devices have FDA approval, so using alternative materials would require resubmitting the whole new device for reapproval, a long and expensive option not only to get the submittal papers together (with experimental data), but also to get the FDA to respond. For now, Arkema, the manufacturer of Pebax, is triaging their clients needs and applications and has stated that they will dole out their limited supplies to "life-saving" applications (such as the balloon catheders), and everyone else will just have to make do without.

Yet another example of how important ring-opening polymerization, that oddity of polymerization mechanisms, can be.

Wednesday, May 16, 2012

Time to Test My Beliefs

I've said in the past that I don't think much of the field of "materials science" - it is simply too broad of a field for anyone to do justice to. Metals, ceramics, semiconductors and polymers? All mastered by one individual? "Jack of all trades; master of none."

So I now get to test my beliefs this summer. I'm interviewing interns on Friday. I didn't get a crush of applicants, and promptly tossed the mechanical engineers (too much chemistry for them) and the biomed engineers (too little biomed for them) and were left with 5 candidates, 4 of which were MatSci majors and only 1 ChemE (who already has accepted an internship elsewhere). I thought it was a very strange ratio until I got my University of Minnesota Alumni newsletter for the Department of Chemical Engineering and Material Science [1] last night [2]. The letter from the Department Head (Frank Bates) states that the undergraduate class in MatSci has recently double and that doubling is expect to occur again in the next few years. So that explains why there are so many MatSci applicants.

Unfortunately, Prof. Bates must have had a little bit too much space to fill, as he then tries to rationalize (?!) or at philosophize on the two areas being in the same department.
"MSE is fundamentally rooted in quantum mechanics; chemical engineering draws heavily on statistical mechanics. Traditionally, MSE has emphasized solids; chemical engineering has focused on fluids."
Not being extremely familiar with MatSci (or MSE as it was called here), I'll withhold judgment on its roots in quantum mechanics (solid state physics I can maybe see), but to say ChemEng draws heavily on stat mech is enough to get anyone laughing. The one stat mech class I had was taught in the chemistry department, not the ChemEng department. In grad school, the department head constantly gave me a hard time for having done so well on the quantum/stat mech placement test ("No ChemE does well on stat mech. What's your problem?") I loved stat mech, I'm glad I took it as it certainly explained thermodynamics better than the thermo class did, but that's it. It's not an underlying basis for chemical engineering. Now tranport phenomena - that's a whole different story. And that whole solids/fluids distinction? Can anyone say that with a straight face?

So now I get to see this summer what a MatSci person knows. I am looking forward to it, as challenging my beliefs is something I strongly believe in.

(...so does that mean I need to challenge my belief in challenging my beliefs?)

[1] The department has been that marriage of two fields for some 40 years, so it is not a johnny-come-lately, but when I was there, MatSci was clearly the second-class citizen of the department.

[2] I did my undergraduate work at the U and that is also where all the candidates are doing theirs.

Friday, May 11, 2012

What a Crappy Project

For some Friday "fun":

There are times around here when our clients give us crappy projects to work on. Rather than being flushed with excitement, these projects leave us feeling drained. One example from years ago involved improving the ability of porcelain materials to resist staining. In order to be able to differentiate between more staining and less, a reproducible soil was needed, not only in bulk composition, but also in in rheological consistency. This is where we started using the Bristol scale:
Think of the scale as being like a melt flow index - the higher the number, the more material passed through the orifice in a given moment of time. (A further rheological connection to this subject is literary - like rheology, diarrhea is another word that is based on the Greek work "rheos", meaning flow.)

Our methods for creating such matter were much less sophisticated than what Texas A & M recently devised. But at the same time, our results were proprietary, thus preventing us from being published in the Journal of Improbable Research and/or winning a highly coveted Ig Nobel Prize.

Thursday, May 10, 2012

The Technical Data Sheet for a Polymer? You Can Pretty Much Ignore Them

Any polymer resin that is commercially available has a technical data sheet with it. It is a short summary of what some of the mechanical attributes of the polymer are, such as the Young's modulus, the breaking strength, maybe the yield strength if the polymer behaves that way (glassy polymers need not apply), maybe some flexural properties, and maybe the heat deflection temperature. These are usually measured according to some ASTM or ISO standard (with modifications being made as the supplier wishes, such changes seldom being communicated).

In most cases however, I ignore this data [*].

These values are not worthless per se, as they do represent fundamental properties of a material and the values are fairly reproducible (although we all know that processing conditions can have an pretty big impact on a products properties). And the values can certainly be useful for making relative comparisons between polymers. The reason I ignore them however, is that they seldom represent how a material is used in its application. Tensile modulus is an extremely important value for ropes and anything similar that is only under unidirectional tension, but for most other situations, tensile stresses are combined with shear stresses, and if a part is being torqued or flexed at all, there would be compressive stresses too.

So when I read a statement that the Automotive Industry Action Group, in response to the Nylon-12 shortage has established "...guidelines [that] lay out specific requirements for replacements in areas such as tensile strength and elongation, chemical resistance, fuel exposure and other key performance issues", I have to laugh. Automotive parts are not under pure tension and so even if a replacement resin has the EXACT SAME tensile strength and elongation (it won't), it will still behave differently under shear and/or compression and so the products made from that material (not the material itself, but the products) will need to be requalified, which means a lot of long nights in the labs for the engineers doing this under a tremendous time crunch.

Ford Motor company however, seems to be ahead of the game. Their CFO said, "We’re pretty clean. That’s largely due to the fact that we have alternative materials that we can use. There had been some materials the team had previously tested, but didn’t use them at that time, so we had material already on the shelf that we could use." Pretty smart, huh?

[*] Much like an MSDS sheet. There very seldom is anything meaningful to me in them.

Wednesday, May 09, 2012

Peak Plastic? Not a Chance

I assuming by now that we've all heard about the concept of "peak oil", that at some point in time (past, present or future - the exact date is open to plenty of debate) a maximum rate of oil production will occur that will never be obtained again due to dwindling oil supplies in the earth. The concept has also been applied to other natural resources - "peak coal", "peak gas", "peak uranium", "peak phosphorous", "peak water", and even "peak nitrogen".

But now Prof. Debra Chachra is stating that there will be a "peak plastic" event, since after all, there will will be a peak oil event.

Oh, please.

People are so use to the concept of making petroleum into plastic and other chemicals that they don't accept what a technological miracle it really is. Think about petroleum - what it's really like. It's a nasty thick black goopy mess of stuff. It sticks and it stinks and 150 years ago people couldn't imagine it having much use at all. When you look at it, do you see the potential plastic in it? I admit, I don't. But is there really a problem that we don't see it? We can make plastic from something that isn't the least bit like plastic because of our knowledge of chemistry. A vast array of chemists and chemical engineers entered the scene and figured out how to make something useful from it.

So at some point, we will run out of oil. Which means that we can't make any more plastics from it. Does that mean we won't be able to make anymore plastic at all? That, as Dr. Chachra suggests, we will have to mine landfills for plastics to recycle? Or does that mean we might have to rely on the creativity of chemists and chemical engineers to make plastic from something else, something else that we don't see the obvious connection of raw material ---> plastic? Such as corn? Or sugarcane? Or mushrooms? Or mad cow carcasses? Or anything else that isn't quite as limited of a resource as petroleum is? If you look at a pile of corn, do you see the potential plastic in it? I don't. What about sugarcane? Or mushrooms? Or mad cow carcasses? Is there anything that you look at that immediately puts into your mind the idea "Oh, we can easily make plastic with it"? I can't imagine anything.

And yet, all those items I just listed have already been used to manufacture plastics (corn, sugarcane, mushrooms, and mad cow carcasses), and there are plenty more feedstocks that have been used too. Luc Averous and Mike Tolinksi have compiled lists on their blogs of what's been used, and my employer is actively involved in the matter and getting some exciting preliminary successes.

So why the fearmongering in creating the concept of "peak plastic"? It just ain't going to happen.

Tuesday, May 08, 2012

At Least I Didn't Invent Clamshell Packaging

My post last week about the seals on potato chip bags had an overwhelming response [1] around the world (The US, Spain, and Australia for starters). I'm surprised, as I wrote it mainly to talk about heat sealing of polymer films, but everyone seems to have liked the idea of having someone to hate for the difficulty in opening the bags, and so...I'm infamous.

Peter Farquhar of news.com.au in Australia did a email Q & A with me, which he then turned into another online article [2]. And yes, I am glad I've had nothing to do with clamshell packaging, as that is on my top-10 list of worst plastic inventions ever.

[1] Over 38,000 hits on that page alone. That's as many as I had for all of last year for the entire blog.

[2] What a bad picture. I'm far older and worse looking than that nowadays.

Thursday, May 03, 2012

Wrong Kind of Nylon

The heading on the email seemed fabulous: "Offer Good Until 5/9- John, Complimentary Subscription to Nylon". Oh boy! A magazine all about polyamides, a subject that I blog about often enough.

Or maybe not. Here's what was in the email:
I certainly enjoy my wife's legs when she is wearing nylons, but I don't think I'll be subscribing.

Wednesday, May 02, 2012

I'm that guy...

I'm that guy. The guy that everyone hates. The guy who made it so difficult to open your bag of potato chips.

It was my first job right out of school. I was working for Hercules Chemical, a company that no longer exists although you have to blame that on some one else. I was in the Packaging Films Group, making multilayer polypropylene films for food packaging. The film had a heat-seal adhesive on one side of the polypropylene base. One of our larger clients used our films to make potato chip bags. The problem they had with our existing films was that the seal was too weak. The client's chip-making plants were located west of the Rocky Mountains, so when trucks would drive their chips out to California, some of the seals would open up due to the pressure difference between the high altitude air and the air sealed inside the bag. And so they needed a stronger seal from us, which was then passed down to me.

Other options besides a stronger seal are technically possible, but not economically feasible. Potato chip bags are made on a vertical form-fill-seal(VFFS) machine. The preprinted film is unrolled and shaped to form a tube. A seal is made along the tube forming the back of the bag, and a seal is also made at 90 degree to this back seal, pinching the tube and forming the bottom of the bag. The chips are then added to the bag. This is actually a very cool process that is more complicated than you might imagine. The chips are feed to a number of weigh-pans located just above the bag opening. Each pan has a fraction of the total weight to be added, say 1/8th. A computer then decides which combination of 8 pans are to be dumped into the bag so as to most closely match the desired value. While it would be much cheaper to have a single pan machine, having the additional pans very quickly pay for themselves. All of this is done at high speed. I would love to post a video of a VFFS machine, but I've not ever found one that really shows the process very well to someone who's not seen one.

The point here is that while technical options exist to prevent premature opening of the bag, such as reducing the initial air pressure in the bag, attempting to add this to the existing processing equipment would be a nightmare. So it was necessary to increase the seal strength.

In a heat seal, you are attempting to melt the adhesive polymer and get it to flow into the other layer. Upon cooling, the two layers are now entangled and show adhesion. The strength of a heat-seal depends on three and only three variables: time, temperature and pressure. Increasing any one of these will increase the strength of the bond, but most manufacturing engineers are really only open to increasing pressure. Increasing sealing time slows the entire process, and increase the sealing temperature also slows the process since it takes longer to heat the adhesives to the higher temperature; that adds to the time as well. The best option was to develop an adhesive that sealed at a lower temperature, something that was successfully accomplished, or so I'm led to believe from all the complaints that colleagues pile on me now that they know I'm that guy.

Update September 18, 2012: I'm getting a lot of traffic today from one of the Motley
Fool discussion boards, one that unfortunately I can't access. Anybody feel like cluing me in about what is being said? Either add a comment or email me directly at john dot spevacek at aspenresearch dot com. Thanks

Tuesday, May 01, 2012

I Hate Scale-Up

I hate scale-up. Going from the lab, where temperature is controlled with the twist of a wrist or a few clicks on the keyboard to big hunking pieces of metal, where calling for a temperature change in the equipment is no more difficult than in the lab, but the time to enact that change to occur is now an different matter, one that is a negotiation between the thermal capacities and diffusivities of the heating equipment and also with some convective heat transfer coefficients thrown in for good measure. There is lots of standing around and waiting (and little time for blogging).

Of course, scale-up is necessary as it is the knothole through which entry into all-hallowed production is ultimately achieved with its potential for making the company money. And it also is an source of internal happiness as it means that the bench efforts were successful enough to merit further effort. But I still hate it.