Holy Grail Projects

My work here at Aspen Research involves solving problems for clients. Sometimes they are simple analytical requests, sometimes they are failure analysis, sometimes they are product development, but one class of projects stands alone. These are what we call "Holy Grail Projects". These projects always seems to come from a new client, and they throw at us some problem that is industry wide and plague everyone in it, something along the lines of "make it twice as good at half the price without making any capital investments". They can even involve something that borders on being physically impossible or unreal.

(We certainly don't have a corner on the market for these projects. I've run into similar requests at previous employments with the requests usually coming from the marketing department.)

There are always lots of snarky comments that can be made ("Once we do that, you'll save even more money by eliminating your sales force and having my 7-year son sell it") but I've always had the good sense to force those ideas from my head and focus on the problem at hand.

Clearly the problems can never be solved as proposed. Everyone's been looking at it for years or decades and tried all the obvious solutions. So then it's a matter of redefining the problem. My usual approach is along the lines of something attributed to President Eisenhower: "Whenever I run into a problem I can't solve, I always make it bigger. I can never solve it by trying to make it smaller, but if I make it big enough, I can begin to see the outlines of a solution." That doesn't always work, but it certainly is a great way to start.

Phosgene Death

I mentioned earlier this month that phosgene is the real concern in manufacturing polycarbonate, not the BPA comonomer. Unfortunately, a DuPont worker was killed this weekend from phosgene exposure.

I ran across this first at the Chem Blog. There is a very strange image on the page - what appears to be an old poster with an elephant (!?) - also warning of phosgene's dangers.

Math According to the Chief Justice

CHIEF JUSTICE ROBERTS: “2 plus 2 is somewhere between 3 and 5, right?” (Page 6, lines 24-25)

I suppose that for sufficiently vague values of 2 it is.

Patent Searches and Prior Art

The IP Watchdog has a nice entry today about patent searches.

Some of the points that he makes are nothing new, but I've never before thought of or heard of them applied to patent searches, such as the idea that as the certainty of the result increases, the expense in getting there does too. This is a standard idea from statistics, but then this leads to some interesting outcomes. If you are just applying for a patent, there is not as strong of a need to be 100% certain that there is no prior art as that would be too expensive at the application stage. At later stages (i.e., entering production), the need to reduce risk increases, so there is stronger justification for spending more on a more detailed search.

One line from the blog may raise your eyebrows: "In patent litigation it is not uncommon for defendants to spend upwards of $1 million looking for prior art, sometimes substantially more." The million dollar figure would only apply to the biggest of infringement cases, but considering some of the sums that Article One Partners is willing to lay out for just one good bit of prior art, I can easily see a million dollars being spent.

In this day of trivial internet searching, it is easy to get complacent and assume that everything of importance is on line. Book are a huge exception, although that is slowly changing, but the difficulty is that they have to be manually searched (after being manually located!).

A patent examiner is a lone individual looking for prior art, so it can be safely assumed that they will occasionally miss something. But when a patent is issued, the whole world can suddenly be looking for prior art, sometimes forcing the whole novelty story on a patent to quickly change.

Getting a patent is easy, keeping it is difficult.

What's In My Inbox

In my current job, we get clients from a very wide range of industries. While we try to solve their problems by focusing on the scientific fundamentals (those elements that cut across all industries) it still helps to know what some of the issues (and even the terminology) are in specific industries. So we get a lot of trade journals. Here is a short list of what I have on my desk at the moment. Some of them may seem like obvious entries, others may not.

• Plastic News
• Modern Plastics Worldwide
• Injection Molding
• Coatings World

(so far, so good - polymers are my specialty)

• LC/CG
• American Lab
• Spectrscopy

(o.k., I work in a lab and have lots of analytical work done for me by coworkers)

• NASA Tech Briefs
• R & D

(who doesn't get these?)

• Glass
• Window and Door

(we are owned by Andersen Windows, and we do do some work for them)

• Photonics Spectra
• Biophotonics
• Laser Focus World
• Nature Photonics

• Medical Devices
• Medical Product Manufacturing News
• Drug Discovery News
• Biopharm

(The Twin Cities has a huge number of medical companies, so we do a lot of work in this area)

• The Scientist
• Genetic Engineering News
• Nature Methods
• Biotechniques

(These are starting to wonder a little too far from home, but are still relevent)

• Stone World
• Hydrocarbon Processing
• World Oil
• Space News

(These are the result of work in the past).

And lastly, ones that I have no idea why I'm getting them and yet can't seem to get them to stop showing up

• Consulting (we are not consultants - we work for living!)
• Infoweek
• Microwave World
• ECN
• CRN

I don't even know what the acronym in the last two are! There are certainly plenty of others out there that I could get, but you get the point - we really do work broadly and do not specialize in any industry.

Yesterday was a goverment holiday (Martin Luther King, Jr.), so it was a day without mail - welcomed relief and a chance to spend more time on the technical literature. I won't even begin to tell you how may table-of-contents I scan in that area...

From Large to Small

Elkhart Indiana, for reasons that I cannot gather, has always been the capital of the RV industry. That Detroit is the capital of the auto industry is less of a mystery, but Elkhart is a pretty small town - not the sort of place in which you would imagine half the RV's in this country are made.

Having done some work here a few years back for one of the RV manufacturers, I've paid far more attention to the industry than I normally would. (My idea of camping is to "get away from it all", not "take it all with me", but to each his own.)They've been hit hard, what with the price of gas hitting record levels in 2008 and the general malaise in the economy, and so it has been trying times for Elkhart.

It is rather ironic that Think, a Norwegian maker of electric cars is looking to expand into an Elkhart Indiana facility. Going from one of the largest vehicles to one of the smallest. It certainly seems like a good move for both the company (the reasons are outlined in the link) and for Elkhart, as diversity is never a bad thing. (I'm not going to forcase the demise of the RV industry, as that will depend strongly on the price of oil, and if I could forecast that, I would be blogging in my pajamas from a cabana in St. Kitts. Any reader who thinks they can predict the price of oil is encouraged to invest their money appropriately and see how well they really can predict it.)

A Viscoelastic Surface for People, too!

Following up on the rubberized race track surfaces from yesterday, Bayer has announced that they have developed a viscoelastic carpeting. It's going to be commercialized by an outside partner (good move) but could be fun.

I wonder how the beater brush on vacuum cleaners will react?

Recycling Plastics

A big problem with recycling polymers, (overlooking all the other problems such as obtaining a feedstock of high quality in large enough quantities at a good price, and also having a market for the output) is that they degrade. This is not unique to the recycling process: any thermomechanical processing of polymers will result in some degradation. The resulting polymer is not as strong as the virgin material from which it was made.

One option to offset this is to rebuild the polymer. DSM has a chain extender available (with more in the pipeline). The chain extenders are bifunctional materials that react with the endgroups of the polymer. If both groups can react with a polymer chain, then a new longer chain is formed. Getting two engroups to react is always a challenge of a statistical nature. The chain extender is a small molecule so it can diffuse relatively quickly and find an endgroup to react with. But that is the easy step. Finding a second endgroup is the issue. Since polymers can't move quickly, it takes quite some time for another endgroup to diffuse and find the chain extender that is already bonded to the end of a chain.

An additional challenge can be posed by the actual chemistry of the polymer.

As expected, the chain extender has to be matched appropriately to the base polymer and more specifically to the endgroups of the chain. Even that may not be as easy as you would expect. PET is most often made by copolymerizing ethylene glycol and tererphthalic acid, resulting in -OH groups on both ends of the polymer (albeit in one case as part of a carboxylic acid group). However, DuPont also has a process that copolyermizes dimethyl terephthalate and ethylene glycol, in which case there is a methyl endgroup on one end of the polymer chain. That methyl group certainly won't react with a chain extender, or much of anything else for that matter. This then means that only half the chain endgroups can react with the chain extender - a real challenge.

PET and nylons are good candidates for this because of the potentially reactive engroups. Other condensation polymers, such as urethane and ureas would be candidates, but given the diversity of urethane chemistry that exists along the chain between the urethane groups, recycling urethanes will likely never happen.

Race Horses and Rheology

Tip of the hat to the Plastics Blog for pointing out this joke. I certainly didn't get it at first and I doubt many readers here will either. I'm don't follow horse racing (although I loved the movie "Seabiscuit" for the racing scenes. It greatly reminded me of when I use to race bicycles - everyone packed close together, a little gentile pushing and shoving, trying to get some space to make a move, but knowing that a crash or fall is disaster because everyone else will just pile right over you.) But also surprisingly, I've been exposed in my current job to some running horse and the physiology of them. They are fascinating in that regard, but that is for another day.

I didn't know that such "plastic" surfaces exist.Finding out more about the surface is a bit of a challenge. The Pro-Ride Racing website is awful on the eyes and lacking in information. I couldn't find any US issued patents or applications with an assignee of Pro-Ride, but a search of "horse track surface polymer" provided a few hits, with the application US 2008/0017826 (available at FreePatentsOnline with registration or elsewhere) looking particularly relevant (the inventor is an Aussie). Real simply, a binder composition of some oils and elastomers (EPM or SBS block copolymer) are mixed with a sieved mix of sand. The oil swollen elastomer will stick to the sand some and provide a springiness to the surface.

So that is one tie-in to rheology. But I can also find a larger analogy when looking at what was at the root of the joke.

Certainly if I had a million dollar race horse, I'd extremely cautious about even letting it go for a walk in the garden pasture and nibble on flowers, let alone run on a "new" surface. New? Sure, it's been used for a few years, but look at this from the perspective of the Deborah number, where you compare the relaxation time of the polymer to the observation time. Horses have been bred for thousands of years to run on natural surfaces, while this new track has only been available for a short time. In this case, you have a very high "Horse-Development Deborah Number", suggesting that the horse is not going to change quickly to the new surface, that it might break rather than adapt.

You can see this analogy in other areas of breeding and evolution. We've been able to get pure sugar from plants far faster than our bodies have been able to evolve to the change in diet. Same for other food products that are of dubious nutritional value. The same is true for chemicals that we're exposed to in the environment.

Jim Cramer is Hot on Plastics

As the title states, Jim Cramer is quite bullish on plastics in the immediate future (PolyOne in particular).

For those who don't know who Jim Cramer is, he's a US-based business commentator that is extremely extroverted and opinionated. To me, he's more entertainer than serious commentator or analyst - I feel the same way about the chef Emeril Legasse - but he does have a large following and people do listen to what he says. And just as Emeril says "Bam" to suggest excitement, Cramer also has a one-word phrase to really suggest excitement: "Booyah".

The problem I have with "Booyah" is that it is a word used (and used for far longer than Jim's been using it) in the upper Midwest for a stew. A restaurant that is real close to here advertises for a couple of week ahead of time when they are making it (often with jokes such as "No roadkill this year! We Promise!), and they basically clean out the freezer of leftovers and throw whatever else they think they need to make it taste great. People will line up, toting gallon buckets to bring some home and freeze.

So if Jim Cramer thinks that yelling "Stew!" is going to get people fired up to buy a stock, good for him. I'll eat it instead.

Time to Close Up Shop

This week's Plastics News (Jan. 4, 2010, pg. 7) has an interesting opinion piece. It states that "it took GE 15 years and $50 million to make Ultem (polyetherimide) profitable", but then contrast that situation with what has happened since.

1. Shell developed Carilon, a aliphatic polyketone amide by copolymerizing ethylene and carbon monoxide, but discontinued it in less than 1 year.
2. Basell stopped Hivalloy polypropylene 6 years after introducing it.
3. Dow killed Index ethylene-styrene copolymer after 4 years and Questra, syndiotactic polystyrene after 6 years.

Certainly developing a new large scale polymer is a risky proposition: not only do you have to figure out how to make the material on a large scale, but you also have to do so with only rough goalposts. The new material will not be a drop in replacement for any other material, so your customers are either going to be looking for new applications (which take a long time to develop) or take their own risks by using your new material in an existing application that was already doing well enough. (Maybe not great, but well enough). In either case, it makes it extremely difficult to know how the new polymer should be made, so certainly one can't expect all new polymer introductions to succeed. It's just that the case of Ultem certain makes a strong argument that it won't happen quickly.

What really had me laughing (although also embarrassed (see below))was this quote:

"Banholzer (Dow's Chief Technology Officer) went on to say that he didn’t think any new polymers would be discovered, since chemists already had done a thorough job in finding ways to link carbon, oxygen, hydrogen, nitrogen and sulfur atoms."

Now I can remember think that 20 years ago when I was winding up grad school - that all polymers had been invented and that the world was going to need us engineers to do all we could with them. 5 years on the job and I could see already by then that I was wrong. Seriously wrong. Thank goodness I never published those thoughts anywhere. I still cringe thinking about it.

But for a senior technology officer to say those things is unthinkable. More and more organic chemistry articles are written each year, with new and improved reactions for "link[ing] carbon, oxygen, hydrogen, nitrogen and sulfur atoms". All the reactions are not discovered, anymore than all the drugs, using those same links have been discovered. Given Banholzer's logic, there is hardly a need for chemists any more.

Certainly there will never be another polyethylene, just as there will never be another steel despite thousands of years of research, but here's a big hint - you don't want to be in that business anyway. The profit margins are razor thin if they exist at all in the volatile marketplace where prices jump around with oil futures. You want to be an small market with nice or even huge margins (think medical polymers that sell for thousands/kg). There are endless possibilities for new polymers there (I know, I've developed some myself). It's not areas that large corporations get into, as these comments clearly show.

Polymer Production Volumes

Yesterday's post mentioned the most downloaded data sheets in 2009 from IDES database. While I did mention that Lexan held the number one position, I should have also noted that Makrlon (BASF's polycarbonate) was #7 on the list. Also, Cycoloy, the PC/ABS blend from Sabic is at #5.

I'm not sure that I understand why PC is so high on the list, as it is certainly not the largest volume for polymers - PE, PP, PVC, PET, PS. So why so much interest in PC? #2 on the list is Zytel, a nylon 6,6 from Dupont, also not a really large resin.

You can get the complete report and scroll down to the bottom (63 pages) where 16 different resins were all accessed just 1 time. Tisarbon caught my eye as a fun name, and quite surprisingly, it's a PC as well. Another one hanging-on at the bottom of the list is FPD Blue, a fluoroelastomer for use in flat-panel displays (hence the name). That this is here is not surprising as fluoropolymers are definitely low volume.

Both of these polymers are already off to a good start for next year - the fact that I accessed them means they have already been accessed as much this year as last year. 1 more access from a dear reader and they will be up 100% for the year.

Polycarbonate (and BPA and Phosgene)

Polycarbonate is in the news quite a bit and even bigger in the blogosphere, so it might be worth a bit of effort to look at it a bit closer look.

Strictly speaking, polycarbonate is not just one type of polymer but is a whole family of them. The name simply indicates that the monomers that reacted to form the polymer did so by forming carbonate groups:
The R₁ and R₂ are generic and can be just about anything. That's why polycarbonate can refer to family of polymers. A common example is CR-39.

But in most cases, "polycarbonate" refers to a specific polymer that is typically made by reacting two monomers - bisphenol A (BPA) and phosgene. A given molecule of BPA will react with two molecules of phosgene on opposite ends of the BPA. Each of the reacted phosgene molecules will then add on another BPA molecule, which then react with more phosgene...alternating back and forth between BPA and phosgene. (The reaction is a little more complicated, in that there by products formed, and even the BPA needs to be modified initially in order to react with the phosgene. But since no one is going to be trying this on their own, I'll gloss over that.)

The resulting structure has none of the chemical properties of either BPA or phosgene, which is a good thing: as bad as BPA seems to be, phosgene is far worse. It's a gas that was used in World War I as a chemical weapon. So why the concern about BPA in polycarbonate, and why not phosgene? No matter how carefully a polymerization reaction is carried out, some monomer remains unreacted. The polymer can only react with monomers at the ends of the chains and there are very few of them making it difficult for the monomers to find them and react. BPA is a solid at room temperature, so the unreact portion stays in the plastic only to come leaching out later. Phosgene, on the other hand, is a gas, so any unreacted portions are able to quickly volatilize especially with a little heat to help.

The most common tradename for polycarbonate is Lexan. In my mind, it's becoming a generic term much like Plexiglas is for polymethyl methacrylate. This might have contributed to "Lexan" being the most searched plastics on the IDES database in 2009. Or maybe it was because of the BPA scare.

But let's be perfectly clear on one thing here: BPA is not a plastic, it is not even added to plastic. It is used to make a plastic.

Amusing Names for Rheology Models

Physicists have always found a good way to get the general public interested in some of their most arcane research - by using amusing names for things. Subatomic particles have "flavor" and "charm" and "color", words chosen strictly for their general appeal, as no one ever has and ever will lick a quark to see what their flavor is like. In the same vein, color is meaningless in the subatomic world where the wavelengths of light are far too massive to interact with a quark. We can't "see" them with visible light, so they certainly don't come in red, blue or green.

Chemists have not found this pathway - we speak in jargon that only other chemists can hope to understand. But for some strange reason, there are more and more rheological models of polymers and other long molecules that have amusing names. It's long overdue. Look at the history of rheology modeling. There are such beautiful names as the 8-constant Oldroyd model and the Zaremba-Fromm-DeWitt model (ZFD for short), all of which are good for commemerating the discoverers but not for exciting anyone about the model at all. The first big break came from Doi-Edwards - the reptation model, although you would have to know that "reptation" refers to the crawling motion that reptiles make. Things have progressed from there. Larson developed the Pom-Pom model, and now there is the Rolie-Poly model from Likhtman. The problem with this last one is that Rolie-Poly is an acronym for ROuse LInear Entangled POLYmer. But since there is already an extended reptation theory and an extended Pom-Pom theory (plus a modified extended Pom-Pom theory too!), even the best of names don't last long.

A new year, a change to the comments

Unbeknowst to most of you, there is a huge ongoing comment war on a old post. I love the multilingualriy of the rivalry with one side pushing "Viagara" and other pushing "Cialis".  You can see where this will end up.

I've made adjustments so that all comments on posts more than 30 days old will need my approval.  Further changes may need to be made in the future.