Tuesday, December 29, 2009

Open Access Journals

I've always been envious of the progress that biologists have made in providing free access journals. The Public Library of Science (PLoS) is the most visible example, but there are others. Chemistry has lagged quite far behind, but I was glad to discover this exeption: Polymers. This is a new free-access journal that is just taking its first steps.

I can't say that the name impresses me much. It's not the name per se that it the problem, it's that the name is so similar to the journal entitled Polymer. I can certainly see it being an ongoing source of confusion.

I wish the new journal well. The "Special Issues" list looks nice. I wish the "Click Chemistry" issue had a later deadline than January 31, as I would have a good paper to submit if given a few more months. The publisher is MPDI, and they already have 27 other open access journals going, so I think things should go well.

Monday, December 28, 2009

How to Improve Margins on Polypropylene

Having any sort of margin at all in resin production is tougher than usual these days, especially for commodity polymers such as polypropylene [1]. Adding something to the polymer, such as glass fibers (either long or short), colorants, is a standard manner to increase the price per pound and hopefully the profit margins, but here is something that I never thought of adding: cocaine. 750 kg of cocaine were mixed in with 25 tons of PP resin. I do not have any experience with this, but I would think that this was just a physical blend and that the cocaine was not compounded into the PP [2]. Recovering the drug a would be so much easier, as it would just be a filtering step, although I imagine that a not inconsiderable amount of powder would stay statically attached to the beads.

Let's run some math: At $100/g[3], the coke was worth $75,000,000. 25 tons of PP at $1/lb. is $50,000 (assuming this is the normal English (short) ton). The combined cocaine/PP blend is worth $75,050,000, with a combined mass of 51650 lbs. This works out to $1453/lb. Quite a markup; not something to blow your nose at (sorry, couldn't help it).

[1] The performance of PP is constantly improving, so much so that some people consider PP an "engineering" resin, but in terms of volume and closeness of the polymer's price to the price of a barrel of oil, it will always be a commodity resin in my mind.
[2] Just looking at the structure of cocaine suggests that it has way too much polarity to dissolve in a low polar thermoplastic.
[3] Again, I've never worked with the stuff, so I'm forced to use highly reputable sources.

Monday, December 21, 2009

Required Reading

xkcd is right on the mark today. If only this could somehow become permanently implanted into everyone's brains, the world would indeed be a better place. Think of all the endless hype, the mindless news stories, the misplaced research dollars that would be saved.

Friday, December 18, 2009

Some subtle, subtle surfaces

There's a new report (free access!) out about how something as simple as glass (you know, that inert material that is always the same once it's been cleaned) can cause problems with sample prep. In this case, microscope slides were silanized to allow for adhesion of some biomolecules. This is a simple, standard reaction, but one that many researchers were suddenly having problems with. After looking at every possible alternative, they had to look at the glass itself and found that its composition had recently changed (despite claims from the supplier that it hadn't). The point here isn't to blame the manufacturer, but to highlight that you shouldn't assume that "inert" surfaces aren't reeking havoc on your chemistry.

This is one of those examples that should be required reading for everyone early on in their careers. There are other examples in a similar vein where clean surfaces will start adsorbing anything they can from solution. Others have discussed this, and it's certainly well known (I hope?!) that cleanliness is essential in capillary viscometry (Ostwald-Fenske, Ubbelohde...). If you are working on very low concentrations, the bulk concentration will begin to noticeably drop. Or if you are working with polymers in small spaces, the adsorbed macromolecules will reach out quite far from the surface and entangle others in their vicinity.

It shouldn't be the first option to troubleshoot, but never rule out that the inert, unchanging surfaces in your equipment might not be so kind.

Monday, December 14, 2009

Thermal Hystersis

Pretty much as long as synthetic polymers have been known, it's also been known that the crystalline polymers don't melt and crystallize at the same temperature. This doesn't violate thermodynamics as thermodynamics requires equilibrium and what is observed here is a matter of kinetics - the polymer is cooled too quickly to crystallize at the melting temperature. Going the other direction - from crystal to melt, the system is able to take in energy, rearrange itself (annealing) and then melt at or just below the equilibrium melting temperature. That is why it is common to run two melting passes on the DSC of a polymer. The first heating pass is the result of the most recent thermal history of the sample, while the second (run after slow cooling) will better define the true melting temperature of the sample.

As Uncle Al has observed, "Thermodynamics propose, kinetics disposes".
"Man Propose, God Disposes" by Sir. Edwin Landseer, depicting the fate of some early artic explorers.

I've never had a nifty handle for this behavior, but now, courtesy of biologists, I do: thermal hysteresis. A good name: succinct but able to communicate what the item is. As I mentioned, biologist are all over this term: All the "anti-freeze" proteins exhibit this behavior, as well as the newly discovered protein-free anti-freeze glycogen.

LyondellBasell to go East?

LyondellBasell is currently the worlds largest producer of polyolefins. They [1,2] have certainly seen their better days [3] as they are now in bankruptcy. The company is private and headquarted in the Netherlands.

Now comes Reliance Industries of India, the largest private company in India to try and acquire them on friendly terms. Reports are in the range of $6 - $12 billion, quite a big chunk of change. If this deal goes through, it will be another large plastics supplier that is now owned by a non-"Western" company (GE Plastics, now SABIC is another example). I don't have any opinion one way or the other, just noticing the trend, one that will surely continue over time.

[1] Lyondell was bought by Basell a few years ago, being formed from parts of ARCO (formerly known as the Atlantic Richfield Company).
[2] Basell was formed from parts of BASF and Shell (hence the name), with those parts having previously belong to Himont (which was a joint venture of Hercules and Montedison) and others.
[3] With all this mergermania, privatization, sell-offs and IPOs, someone is making money, but I don't think it is coming from margins on the resins.

Wednesday, November 18, 2009

Perfect Fluidity

I ran across an eye-opening report this week, "Nearly perfect fluidity: from cold atomic gases to hot quark gluon plasmas". Not exactly the area that I normally work in although I have mentioned before that subatomic physics can contribute to polymer science. Instead it the abstract that got me to start reading the article.

Liquid viscosity drops with increasing temperature, while gas viscosity increases with temperature. This means that for a fluid, there is a minimum viscosity, probably in a supercritical region. One way to scale viscosity across fluids is with the kinematic viscosity (h/n, h is the viscosity, n is the density) but density is hard to measure/define for the quark gluon plasmas (I'll just have to take the authors word on it) so a better option is divide by the entropy, s. And then using string theory (which we all know is better called "the string hypothesis" since its never been tested), it's proposed that h/s >= h-bar/(4pkb), (kb is Boltzmann's constant). So there we have it - an absolute lower limit for viscosity.

Water at 226 bar and 650 K is still well above the limit, but that doesn't surprise me given the strongly associative nature of H2O molecules. 4He gets much closer at 2.2 bars and 5.1 K, but the champ is the quark gluon plasma at conditions of 880 x 1032 bar and 2 x 1012 K. The rest of the article is mostly in the realm of exotic physics, at which point I returned to my regularly scheduled reading. I'm not going to run a those conditions in any extruders.

Monday, November 16, 2009

It's Monday. I need a good laugh...

and found it here:

"One of my favorite thinkers, Will McDonough, is the leading thinker of ecological architecture. Among other achievements, he rebuilt the famed River Rouge plant of Ford, the very model of a modern major assembly line, into a sustainable model with pavers instead of asphalt, natural lighting, and grass on the roof. He is urging a technology cycle similar to a biological cycle, where manufactured products can reduce back into the ecosystem. An example is to redo plastics based on organic carbon, not petrochemicals. These plastics look and feel like petro-plastics, and yet dissolve when thrown away.The whole plastics industry can transform itself into a new range of products." (Emphasis added.)

Wow!! Organic plastics! What a concept.

Another wow!! They "dissolve". They just go away. All the mass is just gone. It's not like they would "dissolve" into CO2 or anything. And somehow they know when they've been thrown away. Too smart for me.

Monday, November 09, 2009

How NOT to Introduce a Product

Scrolling through the chemical headlines, a ran across one in Chemical Week which mentions that Total has a new metallocene catalyst available. The article is pay-access only (as is most often the case with Chemical Week, that's fine, I don't have a problem with that). Being that metallocene catalysts are a only a curiosity for me and not something that I actively work with (except for whatever scraps are stuck in the PE that we process), I'm not going to buy this one, but I could read enough to know that they are calling the catalyst Lumicene. Googling "Lumicene PE" gets 21 hits total, only 2 of which are relevant, and guess what site they are on??

Chemical Week.

So Total is introducing a new product, but the only way to find out about it is to have to pay money to a third party. Doesn't this strike you as...........wrong?

Bilski is on the SCOTUS docket today

As mentioned previously, Bilski will be heard by the Supreme Court. Today is the the day, but the decision won't come down for months.

The case concerns an issued patent over a business method (regarding the use of hedges) and whether it is patentable matter. In the narrowest sense, the case is rather boring. I think the patent claims are poorly written and should be rejected, but the real question that isn't written on any brief before the court, is how widely the court will expand their decision. Many contend that it could be so expansive as to be the death knell for all software patents. I can't see it going that far as Congress has already clearly stated that they would like as many things patentable as possible.

Right now the Court of Appeals has establish a "bright line" rule that all patents must show a physical or machine transformation, and they like the test as it is cut and dry - no judgment is needed. This was also the case a couple of years ago when the KSR case came up on deciding what is (non)obvious - that unless there was specific written words describing or predicting what was in the application, it was considered nonobvious. Also a bright line test, but one that was thrown out. I suspect the same will happen here - the bright line test will be tossed and judgment will be needed.

The issue is (somewhat) personal to me as I did in the past apply for such a patent (WO/2001/092840), although it was dropped after my employer killed the program, so it never issued.

No matter what the outcome, the lawyers (even the one unhappy with the decision) will be happy as there will be lots more to argue about in the future. (Something that you and I know very well, something that they know very well, but not something that they know that we know very well.)

Tier 1 Auto Suppliers are doing o.k. enough

Lear is coming out of bankruptcy, rather quickly, as are a lot of other supplies. The link has some good stats about the health of the auto supply industry in general. Very few Chapter 7 filings (going out of business) and lots of Chapter 11 filings (reorganization of debt). There is still plenty of pain and job losses, but it could be worse for an industry totally ignored by a government that was willing to do anything to keep the Big 3 going, a government totally unaware that the manufacturers do high level assembly of systems and subsystems built by others. I expected worse.

Maybe they were hoping for a trickle down effect - the opposite of what they were hoping in the housing market with a "first time buyer" tax credit, which now has been broadened to anyone moving up in the market. Not enough trickle, I guess, and certainly car sales have slumped since the cash-for clunkers program expired.

Friday, November 06, 2009

This could get ugly

According to Plastics News (11/2/09), ASTM is looking to change the SPI recycling codes that appear on many plastics parts, such as:

Possible candidates for getting their own identify are polycarbonate (why bother if the BPA scare is going to put this plastic away?) polylactic acid (since all the PET recyclers hate the mixed streams), and LLDPE. They are also thinking of tightening up the definitions for each resin so that only a certain % of a coating can be on the bottle.

I certainly do understand that these polymers need to be kept separate. They are thoroughly incompatible with each other not only thermodynamically, but also in processing temperatures, drying requirements, screw design, die design... The only way to avoid those issues is to incinerate them all. The flames don't care. They are an equal opportunity oxidizer.

But this could rapidly go the way of stainless steel, aluminum and other metals. For steels, you have the 300 series, the 400 series, etc. Even with something like 316 SS, you can also have 316L (low carbon) and 316 LS (surgical grade), and of course other numbering schemes exist.

Sorting 11 or more grades of plastic would be overwhelming as it would require 11 separate bins, and could easily result in more people not even attempting to keep up with it and just chucking it all, which would defeat the whole purpose, wouldn't it?

Thursday, November 05, 2009

Another part of my childhood - gone!

It's so nice to see polymer technology being used to produce such useful items, such as spitballs.

Isn't it enough that us old timers have to lecture young people about how we use to have to get up to change the TV channel? How we would actually go to this place called a library if we needed to do research for a school project? How we would have to buy a whole album of music by one artist even if we only wanted one song?

Now we can add to the list the tales of how we would make spitballs by chewing on paper or tissues, how getting the right amount of saliva and paper was essential (see, we were budding rheologists and didn't even know it!). Now that is all done for them. Oh the loss.

Times move on.

Thursday, October 29, 2009

UV Scale-Up

This past summer I spent a huge amount of time developing a UV-cured coating. Now that the lab work is done, we've started scaling it up.

You might initially think that the scale-up should be easy since there are none of the nasty surface/volume ratio scaling that normally occurs in reactors and all the implied heat/mass transfer/buildup issues that go with it. This is simple exposing a thin wet coating to a UV lamp for a short period of time.

But even in something as simple as this, there are a mess of potential problems. First off, the curing lamps are not even the same. Different manufacturers, different bulbs (and output spectra), different wattages and therefore different heat outputs. UV curing is more than just absorption of a UV photon. That is merely the initiation step. The remaining polymerization, crosslinking and termination steps are all subject to temperature conditions that (generally) do not plague the photoinitiation.

The coating methods are not the same either - in the lab I used a notched bar, but the pilot line has a type of roll coater. The low viscosity of the formulation that worked so well in the lab became problematic for the coater, so all the plans of looking at different coat weights ended up as something for the next round. We took what we could get.

Nonetheless, it appears that the formulation cured quite well, quite a bit faster than in the lab, although it does have a gamut of testing to run. Thank goodness we didn't have to look into other curing options: multiple exposures, different reflectors, bulb distance,...

Friday, October 23, 2009

Polymeric Auto Glass

Certainly this is a trend that is a long time coming, but the recent increase in the MPG targets are a de facto requirement for polycarbonate glazings. As much as PC will reduce car weight, it will also free up design. Look at the Qarmac concept car:
Those C-shaped windows just can't be done in glass. How much innovative design is being stifled because the glazings are still glass? Outside of the weight considerations, how much does that hurt aerodynamics?

Naturally, Bayer and SABIC, the two biggest manufacturers of PC are in the game, but in slightly different ways, although both are operating subsidiaries (BMS and Exatec respectively) which provide the materials. PC can't be used straight as it doesn't have the scratch resistance or weatherability (it will oxidize and turn yellow courtesy of the photo-Fries rearrangement) without a coating. BMS is going with a wet coat while Exatec is going with a plasma coating.

Sun/moon roofs are already being made so obviously the UV protection is solved to some degree. Given the repeated rubbings and abuse that windshields take, I would expect that application to be the last to go, but the sidelights should provide lots of fun in the meantime.

Tuesday, October 20, 2009

Patent Quality and Value

For reasons that I don't understand [*], assessing patents is a hot topic this week. Two new companies are out with assessment tools: Patent Site and Patent Board.

Assessing patent quality is much like assessing the quality of research articles - any logical approach is fraught with loopholes and errors. The most common basis for the analysis is to look at the citations of other patents, as these citations establish links to other relevant work. The more times a patent is cited, the better it must be (which implicitly assumes that all patent examiners cite all the relevant patents and no irrelevant ones). Certainly this is true for breakthrough patents, but for other patents that represent smaller increments of improvement, that would not be the case. And with patents, far more than with research reports, there is an economic aspect that outweighs all other aspects. Patents for blockbuster drugs are not cited nearly as much as their economic impact on the company would suggest.

An additional challenge that is becoming more important all the time is that patents can be assigned to others (exclusively or not). Patent Site claims to address this, but I don't see how that can be done given that most of these agreements are not public.

Lastly, I'm not surprised at all that these two companies come up with different results. Patent Site lists the top ten chemical companies as

2) Bayer
3) DuPont
4) Dow
5) Sumitomo
6) Mitsubishi
7) DSM
8) Solvay
9) Syngenta
10) AkzoNobel

while Patent Boards list is

1) DuPont
3) Dow
4) Honeywell
5) Nitto Denko
7) 3M
8) PPG
9) Chisso
10) Air Products

DuPont, Dow and BASF are near the top of both lists, but the other 7 candidates aren't even the same! Obviously, there field still needs additional work.

[*] I'd would guess that companies probably will use this as a PR tool to push the value of their portfolios, and since this analysis is so much more sophisticated than just counting up patents, it can used that much more so.

Monday, October 19, 2009


The number of rheology blogs is doubling everytime I look! At this rate we going to be outnumber the political blogs by Christmas.

The new guy on the web: The Rheol World.

Tuesday, October 13, 2009

Diodes, Diodes Everywhere

This is the week of the diode. Not the standard electrical diode that only lets current flow in one direction. Those exist everywhere - your computer is loaded with them and you can't recharge your cell phone without one. Instead, this is about rectifying other actions that are much more difficult to control.

Take heat for instance. In standard conduction patterns, it flows from hot to cold. But now if can be made to flow in one direction based on geometry, not temperature. By using two components, one with good conductivity at high temperatures but not low, and the other component with the opposite properties, the magic occurs.

A similar result (at a gross level) was found with a photonic crystal that directs microwaves in only one direction.

Since this is a rheology blog, proposing a flow rectifier would be appropriate. Check valves already exist (first in cardiac organs, then in human creations). A way to control reptation would be neat, and could certainly lead to some unusual rheology - it would take much longer for a given stress to relax. I'm sure the "much" longer could be quickly quantified, but I'm not the greatest at reptation theory and way to busy in the lab to hash through it today.

Tuesday, October 06, 2009

The Dog and Pony Show

You don't have to work (or be in grad school) for too long before you start getting asked to help with a dog-and-pony show. Being a service organization, we tend to more than most. That doesn't necessarily follow, does it? Let me try and clarify. Most of our work is short term (3 months or less) projects. Some of the projects will immediately lead to another, but most often not. Instead, there is a future project down the road. So we need to keep ourselves in their minds, and also look for new clients. The economic downturn has decreased the size of the projects and upped the time between.

Today's presentation was a doosey. Four of us gave 30 minutes background talks, followed by four 30 minute hands-on working sessions. Thank goodness I can just type this and not have to talk anymore. My voice is gone, my introversion character is rapidly rebelling and I need time to myself to decompress. Thank goodness the Twins game (#163 out of 162) is on in an hour. That and a beer or two.

I always have mixed emotions talking about rheology. I absolutely love the subject and can go on way too long, but the problem is that it is a very complicated and difficult subject. I keep thinking of that Einstein quote, about how if you can't explain it simply, you don't understand it. Some aspects of rheology can be explained simply, but a lot can't. And I don't think it's just me. I've yet to see an sub-undergraduate level explanation of time-temperature superposition.

Regardless, the day was certainly worthwhile - most people do not think of rheology, only gettin as far as viscosity. Looking behind the first curtain to see the storage and loss modulus is so informative (but for eternal enlightment, one must go the through the wall and seek the relaxation spectra!) Lots of good questions, which caused the schedule to lapse. Not a problem and that clearly showed we were getting somewhere. That doesn't pay the bills however, so we will soon see if we really hit the target.

Monday, October 05, 2009

Public to Private and Back Again

The motions of the business world never seem to stop, and so to the amusement. It's fun to watch a public company go private only to become public later. Kraton Polymers is the latest example. Originally part of Shell Chemical, they were spun off, bought out by a private group, and now are going public again with a $230 Million IPO.

The deal that still amuses me is KKR, the giant private equity firm. After spending it's entire corporate life inleverage buyouts and taking companies private, they announced an IPO themselves back in 2007, (although it never came go fruition).

Duplicity and Siloxanes

Finally got around to seeing the film "Duplicity". I liked it, but I've yet to see a film starring Clive Owen that I didn't like. Many reviews have said that the movie is confusing, but I think that is mainly due to the non-sequential order in which the story is told.

The film is about 2 former government spies (Clive Owen and Julia Roberts) who work for the corporate intelligence units of 2 competing companies. One of the companies has a huge new product coming out; the other is trying to find out what it is and then steal it. The spies are in cohoots with the idea of trying to cash in themselves.


I'm not going to tell you how it all ends, but I am going to talk just a bit about what the secret product is. Even knowing what the product is isn't really going to ruin the movie.

What impressed me most is that they actually got the chemistry right, but you don't initially realize that (the movie isn't called "Duplicity" for no good reason). The product is claimed to grow hair and cure baldness, and in what I initally thought was a mistake, the kind that Hollywood routinely makes, the formula is shown on a piece of paper to be a cyclic polysiloxane, although no professional chemist would bother to explicitly draw all the hydrogens and carbons.

I was laughing that they would try and pass off such a simple molecule as a drug, but that was actually the point. The whole "new product" never existed -it was just a bait to get the competitor to expose himself. In the end, the molecule is described as a lotion, although actually it might be a part of a lotion, but would never be a lotion itself - a small point.

A larger point that actually could have helped the competitor realize that the product was a fraud was that there were no clinical evaluations going on. Nobody can introduce a new drug without first registering it with the FDA and going through 3 phases of clinical evaluations - all of which are very public. Everyone knows what is in the pipeline of all the pharmaceuticals.

Monday, September 28, 2009

Marketing that anyone can love

Sure, I work in the lab so marketers drive me up the wall and vice versa. Nothing new, and I don't intend to draw new blood here today. Instead, I am LOL with this new product and product name - Vampirella.

"Blood-sucking meat trays to go global"
"The technology behind Vampirella expanded polystyrene (EPS) meat trays is now available for licensing globally. The single-layer trays feature a closed-cell surface structure and an open cell core layer that absorbs the blood excreted from meat through needle punched holes in the surface layer, thereby presenting a cleaner appearance to the consumer."

As someone who was once told during a performance review "that I was intimidating the marketers", I do have to tip my hat to the people behind this one. I love it.

Friday, September 25, 2009


This map comes from the Weather Sealed blog. Each dot is a McDonalds.
The analysis in the blog is raises a good question: what point in the lower 48 is most distant from a McDonalds?

The answer is in that small black spot in North Dakota, somewhere between Meadow and Glad Valley. It's a 145 mile drive to get your fix on fries.

Thinking of Thomas Friedman's "Golden Arches of Global Conflict Prevention" Does this mean North Dakota is the state most likely to declare war on Canada?

Wednesday, September 23, 2009

How to Not Reach a Global Optimum

It certainly is not anything new, but you don't reach a global optimum by optimizing individual variables [1][2]. That's what consistently irks me about single-interest activists of all creeds. They are simply interested in optimizing one variable and assuming that the global situation will therefore follow.

The new Plastics Scoreboard by Clean Production Action is one such example. You can guess what the targets are (chlorine, bromine, petroleum based monomers) and what the solutions are - agricultural based sources. And all the usual arguments against going to bio-sources polymers can be made here (destroying food, the non-sustainability of these practices...) but in keeping with the introduction above, this effort is taking a multivariable optimization and worrying about just one part of it.

Weighting this one variable above all others [3] is where the arguing should begin. I'm certainly not against considering such a reduction, but the case hasn't even been made that the one variable here is of such importance. But as is usually the case (I can't think of even one counter example), the single interest groups start out with the weighting in place and go from there. Without even attempting to convince anyone of the initial assumption, they argue for the outcome.

[1] As a simple example, consider trying to find the latitude (the x variable) and longitude (the y variable) for the highest point in the continental US. The correct answer is 36 N, 118 W - Mt. Whitney in California. Starting at St. Paul Minnesota, 45 N,93 W, I can try and find the maximum elevation along the 93 W line, which would be somewhere in northern Minnesota, call it 47 N. Then keeping that constant, I would look for the highest elevation along the 47 N line, which would be somewhere in the western Montana about 112 W, quite a ways from California. If I would try and maximize the variables in the other order, I would get a different result. The maximum altitude along the 45 N line is somewhere along the Montana/Wyoming border, about 110W. The maximum elevation along that longitude line is pretty much right at 45 N or a little south. So in the first case, I found 47 N, 112 W, in the second case, I found 45N, 110 W. Two different results and neither one is correct. And in addition, different starting points will yield different results as well.

[2] Yes, it could happen that you do reach the global optimum that way, but the odds of that occurring are very slim, and decrease as the number of variables increase. Obviously for a one-variable problem, one or more of the local optimums will be the global optimum. For a two variable situation, you can already be in trouble, as you can see above.

[3] If certain variables are weighed considerably higher than others the complexity can be reduced. We've all met people - make that children (regardless of age) who weight their happiness above all others. They have managed to take a multivariable problem and reduce it to a single variable.

Tuesday, September 22, 2009

Self-Healing Polymers

They are in the news once again. (Here is a free access summary.) I have had time to read the article just yet, but this research seems to be taking a slightly different tack, namely using two different sizes of polymers which favorably interact through pi-pi bonds. In essence, one is plasticizing the other.

I've mentioned this category of materials in the past(1 and 2) and have always been underwhelmed. I don't see this being much different.

"Heat and heal" is a common characteristic of most thermoplastics, as heating allows for flow - interpenetration of the two surfaces. HDPE pipe is joined like that, potato chip bags are sealed like that... It's not wonderful new technology.

Friday, September 18, 2009

Peer Review

Courtesy of the RSC (an organization that I do a fair amount of peer-review for) comes a preview of a survey on peer review. Having not taken part in the survey, I'll comment on parts of it that I find interesting.

"The survey found that respondents were divided over potential incentives for taking part in peer review. Over half felt payment in kind (e.g. journal subscription, waiver of their own publishing costs) would make them more likely to review, 41 per cent said cash payment would be their preferred reward (though this drops to 2.5 per cent if the author has to cover the cost), while 39 per cent favoured published acknowledgement in return for their services."

I'd be all in favor of any journal subscription, but I can easily see that that would mean zilch to someone who already has such access through their institution. Since most publishing is now electronic to some degree, providing access can be done at no direct cost to the publisher, although at the potential loss of paid access. Cash outlays on the other hand, are a tangible cost that would require increases in access fees to compensate for it. (I find it laughable that 41% would take the cash, unless they knew the author was paying for it. Is this another case of how isolated that ivory tower is from reality? Do they really think that the publishers (many of which are non-profit societies) are just going take the hit themselves? Somehow the logic of all this isn't very clear to me.)

"A further finding was that although reviewers see detecting plagiarism as a noble aim, it is not practical within the current peer review framework."

This got my eyebrows hunched. Given the easy access to searching tools, it's pretty darn easy to at least perform a cursory look for palgarism: just enter a few phrases from the paper and see if anything matches it. It's a technique that school teachers use, and though it is not a guarentee as it is only a statistical approach, it still can work amazingly well. Additionally, the evidence is almost irrefutible.

Lastly, "While there are undeniable gripes about the peer review system in its current form, no viable alternatives have yet presented themselves that could drastically improve the way research papers are reviewed and published - a fact echoed by the reviewers who took part in the survey."

That does sum it up quite well.

Tuesday, September 15, 2009

Tires for the moon (and beyond)

So when it comes to picking tires for a moon car, a standard set of Firestones or even a premium set of Michelins just aren't going to cut it. Even the designs from 40 years ago won't work as the expectations and demands on the new rovers will be higher IF we (meaning the US) ever return to the moon.

Goodyear has been on the case and has developed new tires that are also thought to be Martian worthy, not just lunar worthy.

The design spec for these tires must be truely mindblowing. Think not only about the temperature extremes (often with the high and low occuring on different sections of the tires at the same time) but also the massive radiation fluxes (no ozone to cut off anything below 320 nm) which would chop up all the organics like a Benihana chef goes through vegetables. Just even trying to test the materials in a meaningful way would be a huge undertaking.

I really found all of this impressive.

Monday, September 14, 2009

It's an attack on Organikers, I tell you

I can't imagine how they removed all the carbon, especially profitably since carbon is 12/30's = 40% of the mass of the purified sugar. Mining operations can make a profit, but that is for minerals and elements that are sold for hundreds/thousands of $/lb, not a food source for people on a caviar-free budget. Besides, if this technology spreads, it there will be no chemistry left for organikers.

Monday, August 24, 2009

BASF as a hostile takeover target?

To have BASF as a takeover candidate certainly surprised me, but then I suppose nothing should anymore. (Maybe it's a sign that I'm not really that old after all. Maybe not.)

This would be a huge entity to acquire, run and try and improve upon. € 62 billion in annual sales is quite an bit of change, and while the profits, € 2.9 billion, are modest even by chemical industry standards, I think anyone hoping to scoop it up, make cuts (they always make cuts, don't they?) and improve on the picture is a pretty good candidate for the loony bin despite the size of their wallets. Money can't buy happiness and it can't by sanity or good business sense.

Friday, August 21, 2009

Polymers: Meet High Energy Physics

Ever get the feeling that physicists get to work on all the really cool equipment smashing atoms together and working with subatomic particles, while us polymer people have to work with mundane plastics and rubbers? Well now you can do both. "Muon-fluorine entanglements in fluoropolymers" (J. Phys.: Condens. Matter 21 (2009) 346004 - doi:10.1088/0953*8984/21/34/346004 ) Muons are the first subatomic particle discovered[1] beyond that three (proton, neutron, electron) that chemists generally limit their concern to, having a mass 200 times greater than an electron but the same charge.

I admit I know nearly nothing of subatmoic physics, so it may not be surprising that I'm not sure that I actually took much away from the article. The conclusions seem to be saying that this technique can be used to probe the environment near the fluorine atoms, but there doesn't seem to be any expression of what was learned. But it is another example of how subatomic particles can be put to use for applications other than just keeping a bunch of physicists employed. (Yes, I am well aware of PET scans - with PET standing for positron emission tomography instead of polyethylene terephthalate as might be expected in a polymer blog.)

[1] The Nobel Laureate I.I. Rabi, when told of the discovery stated: "Who ordered that?"

Thursday, August 20, 2009


1) We had strange weather here in the Twin Cities yesterday - tornadoes.

Now tornadoes in August are not unusual at all. They are not uncommon in April through September, and on rare occasions can extend that range a month in each direction, but in most cases, they happen on hot humid days. If you live here for even a few years, you quickly can recognize the days that can breed them just by stepping outdoors and looking at the haze in the sky.

Yesterday was not one of those days. It was cold and rainy the entire day. Suddenly just after 2 there were tornadoes dropping out of the sky all over the metro - downtown Minneapolis and both north and south of there. I think with the cooler weather that they were not as powerful as they normally are, but it was still a very strange day for anything like this.

2) I've always had some unresolved issues regarding the role of the conductor in classical music. Here's some of the situations that I've seen:

a) I've seen guest conductors come in and lead the Minnesota Orchestra and the sound is noticeably better, despite the orchestra being the same as the week before. Clearly a case where the conductor does have a major role. (I've also seen the same level of improvement when there is a guest soloist. Go see Yo Yo Ma perform before you die. He is incredible and he brings out the best of any orchestra.)

b) I've seen conductors lead orchestras from the keyboard during a piano concerto or similar such piece. They start the orchestra and continue to conduct it during times when the piano is not being used. That this can be done suggests that the conductor has only a minor role.

c) I've seen conductors start the piece (usually a jazz piece) and then just walk off the stage, only to come back at the end. Obviously the conductor has no role here.

Wednesday, August 19, 2009

What I did for my summer vacation

Well it certainly wasn't a summer vacation, but it has been an extremely busy but productive one. One major project is winding down and there have been others at the same time, always with their most inappropriate timing for meetings and updates.

This is nothing new, but formulation work is long, difficult and full of failure. Every single formulation that fails is a kick in the teeth, since you obviously thought it would have worked or you wouldn't have tried it in the first place. (The exception is when management said to try it, but that's a whole other issue...) But this just makes success all that much sweeter.

While there still is room for improvement, we know so much more about chemistry and have much greater analytical techniques that 100 years ago when many of the foundations were being laid down. I always wonder how those pioneers did it, as they were half-blind at best. But they certainly did not see it that way, and 100 years from now, we will look similarly ancient and quaint.

As you can gather, I can't tell you exactly what I was working on. To paraphrase the overworked line, "I could tell you, but then you'd have to start working here". But hopefully the excessive work load is past and I can find a few minutes here and their to regularly blog.

Thursday, August 13, 2009

More fun from the New England Journal of Medicine

The Supidity! It Burns!

Everybody join me: "I know an old lady who swallowed a fly..."

Update, 8/13/2014: I fixed the link

Friday, July 31, 2009

"It's all about the Entanglements"

If you need a crash course in polymer rheology, the tag line above is a great way to sound like an expert.

This plot is iconic: it's something that everyone in polymer science is exposed to. Viscosity increase linearly with molecular weight until a certain critical value is reached, after which entanglements dominate and the viscosity increases with molecular weight to the 3.4 power. Not the third power, but the 3.4 power. Since the molecular weights to reach these entangled states are pretty low, most commercial polymers are entangled when molten. Hence the title of the post.

That difference of 3 vs. 3.4 may seem pretty small, but it is substantial. An early result in the development of reptation theory predicted the value 3, not 3.4. Since everyone knew about the 3.4 value, this was initially seen as a huge problem. Certainly it was a case where close didn't really count. My research advisor completely wrote off the theory as a result and never exposed our group to at all. I once attended a lecture by Sam Edwards, a co-developer of the theory and it was fun seeing him try to soft-shoe his way around the issue. I'm not sure how the dispute has ended up. Reptation - the idea that polymers can basically only move in the direction of the chain in the same way that snakes and other reptiles do (hence the term "reptation") - has been observed in neutron scattering experiments so there is a reality behind all this.

This post has been all about molten polymers. But entanglements also play a huge role in the solid state too. That will be in an upcoming post.

Thursday, July 30, 2009

Class Action Junk

So now the class action lawsuits that only succeed in winning money for the lawyers representing the class have gone commercial.

You've no doubt received letters in the mail saying that you are a member of a class action suit, that a tentative settlement has been reached and that unless you do something, the whole thing will be settled and you will receive your compensation which is always a minuscule amount. As an example, my wife and I received such a letter because we had bought some "dot.com" stocks back in boom days and that the stocks had been overhyped by analysts and therefore we paid too much. As compensation, we were going to receive $0.002 per share. The ridiculous part of this is that if stock were overhyped, it was certainly by more than $0.002 per share. The shameful part of this is that the lawyers involved are receiving millions. This is not speculation; it is clearly stated in the letter that they will receive millions. We've also had similar cases for computer monitors and software and baby formula and ... and I can't remember all the cases. But it's been with consumers as the class.

Until now. A full page ad in Plastics News (summarized in Plastics Today) tells of the settlement in a class action suit against four PMMA manufacturers. The manufacturers have agreed to put ~ $15,000,000 in a pot to be divied up by anyone who bought PMMA from the defendants over a 9 year period.

So let's speculate here. $15 million divided by the hundreds of millions of pounds produced annually times the numbers of years means that you will get millipennies per pound. Unless you nearly cornered the market on PMMA, you'll be lucky to get a check with more than 3 digits on it.

If there really was antitrust collusion here, the defendants were horrible at it if they only have $15 million in gains over 9 years to show for it. I just see this suit as another way for attorneys to get rich while claiming to defend a higher cause.

Friday, July 24, 2009

Coming Back

Hard to believe it's been nearly a month since the last post, althought I am not alone in being inactive.

Is there a universal chemical industry conspiracy that has ever blogger keeping their belly to the bench? Fortunately, there is light at the end of the tunnel, so there will be more soon.

Tuesday, June 30, 2009

The Credibility of Science

As happy as I was with the Melendez-Dias decision, I am also bothered by some longer term implications for science, namely its credibility.

Being a scientist, I am fully aware of all its flaws and shortcomings. I know what they are and how to best deal with them. The general public is not. The most common perception, which is desirable to me, is that they look upon science as providing factual answers that are generally not be questioned. With every passing scandal however, this perception fades. The decision mentioned above adds to this. While I certainly have no problem with people understanding that science is not perfect, the attitude that is arising seems to be that science is just an opinion, and since it is an opinion, anyone can hold their own and they are all equally valid. (This is analogous to the people that downplay evolutionary theory by stating it is "just a theory", although that argument is fatally flawed for reasons that I won't get into here.)

"Voting" in science certainly doesn't help, such as when the IAU voted that Pluto was not a planet or when 1500 scientists formed a 'consensus' opinion on global warming. This continues to give the general public the perception that science is an opinion.

Add to that the endless "health" stories about how eating ___________(insert the food the day here) is prevents __________________ (insert the illness of the day here) only to be contradicted by a report next week that the same food actually causes that same disease and you have the makings of a immensely poor perception of that factuality of science.

I'm not sure what can be done. Education is desirable, but won't work. Newly minted scientists have a very poor understanding of the inner workings of science including the flaws that I alluded to above. It takes more than a few years to really see the true picture - some never do. There is no way we can expect better of the general public given that most of them thought their science classes were dreadful.

I wish I could think of something.

We don't do logos

I often accompany our sales people on initial sales calls. Explaining what our company does is somewhat difficult, a challenge that I will leave for another post, but clearly we work in most areas of materials science. What I really enjoy is when the clients ask what we don’t do. If the atmosphere is light enough and I’m quick enough, I can interject: “We don’t do logos”. It always gets a good laugh.

Certainly we needed a new logo a few years ago, as our previous logo was clearly dated.
Can anyone guess what that large central section of the leaf is a portion of? (Answer at the bottom of this post). Hint: you need to be at least 30 years old or if not that, had access to a computer that’s at least 15 years or so. I don’t know why that was part of the logo, as we certainly didn’t develop computer software either.

We can’t do anything that looks like an aspen leaf, as the Aspen Medical Group in town already has a logo like that and our lawyer just doesn’t want to go anywhere close to that.
Being no longer closely linked with any piece of human construction, our new logo clearly will not become dated as technology advances, but we (i.e., most of my colleagues) still don’t like it. It’s not that we’re opposed to pentavalent compounds, as they clearly exist: PF5 and ClF5 to name a couple. It’s just the cartoonish nature of the logo, the green and the black, the distorted perspective. One former manager called it a squished turtle.

Answer: it’s part of a 5 ¼” floppy drive.

Friday, June 26, 2009

Melendez-Dias v. Massachusetts - More Commentary

The Melendez-Dias v. Massachusetts case was decided. The heart of the issue before the Supreme Court was that whether or not the defendant had the right to cross-examine the analyst who had prepared a report identifying some drugs. The Sixth amendment states that defendant have the right to cross-examine their accusers. The issue was whether or not the report, and thereby the analyst was an accuser. The Court, by a 5-4 margin decided that indeed the analyst can be cross-examined in court. (It was an unusual split, with Scalia writing the decision and joined by Thomas, Stevens, Souter(!) and Ginsberg (!!))

My (non-legal) opinion of the matter is that being a chemist, I am too well aware that scientific measurements are not the objective and neutral procedure that nonscientific people think them to be. The neutrality is somewhat harder to argue against, but arguing against objectiveness is much easier. There are simply too many things that can go wrong with modern instrumentation to not question there results. I do that everyday here at Aspen Research. Not that we do poor work, but the question always arises “What are we really measuring?” Answering this makes our work that much better for the clients we serve. And as I’ve pointed our before, there is a huge gap between data and conclusion, one that requires human intervention. Given all of this, I do think there is sufficient doubt on any analytical test report that it should not just be taken as a matter of fact.

Many documents used as evidence in court are clearly not accusatory and that should not change. The most common example is bookkeeping records used in accounting cases. The difference here is that the bookkeeping records do not reach a conclusion – both sides are able to argue the evidence to support whatever conclusion they desire. In contrast, a lab report has already reached a conclusion,

I love reading Scalia's opinions as he has no problem with directly addressing what specifically is written in the dissenting opinion. (He was particularly vitriolic when he wrote the opinion on the recent 2nd amendment case.) This one wasn’t quite as pointed, but there are a few gems such as this:

“Dispensing with confrontation because testimony is obviously reliable is akin to dispensing with jury trial because a defendant is obviously guilty. This is not what the Sixth Amendment prescribes.” (page 12)

This comment from page 14 particularly struck me hard:

“This case is illustrative. The affidavits submitted by the analysts contained only the bare-bones statement that “[t]he substance was found to contain: Cocaine.”... At the time of trial, petitioner did not know what tests the analysts performed, whether those tests were routine, and whether interpreting their results required the exercise of judgment or the use of skills that the analysts may not have possessed. While we still do not know the precise tests used by the analysts, we are told that the laboratories use “methodology recommended by the Scientific Working Group for the Analysis of Seized Drugs…At least some of that methodology requires the exercise of judgment and presents a risk of error that might be explored on cross-examination.”

A one line report with no basis for reaching the conclusion? Unbelievable.

My argument above is based on issues in the real world, but at least restrained by pursuing the “truth”. However, real world practicalities that do show up on page 20 are maddening:

”Perhaps the best indication that the sky will not fall after today’s decision is that it has not done so already. Many States have already adopted the constitutional rule we announce today, while many others permit the defendant to assert (or forfeit by silence) his Confrontation Clause right after receiving notice of the prosecution’s intent to use a forensic analyst’s report… Despite these widespread practices, there is no evidence that the criminal justice system has ground to a halt in the States that, one way or another, empower a defendant to insist upon the analyst’s appearance at trial.”

The dissenting opinion is loaded with even more “real world” practicalities. Since when do these matter in a legal decision on the Bill-of-Rights? All of the Bill-of-Rights makes life more difficult for the government. That should never be an issue.

I’m happy for this decision, as I think it is a right one, but that it wasn’t made for all the right reasons. There is that old saying that “Law are like sausages; people should not see them being made”, which I always thought applied to the legislative process. Now I see that it can apply to the judicial process as well.

Thursday, June 25, 2009

Melendez-Dias v. Massachusetts is overturned

A decision was finally reached, and it does appear that a written lab report is considered "testimonial" evidence, so that the person preparing can be brought to court to be questioned.

I'm short on time today, but will write more tomorrow. I agree with the decision, but am disappointed that it was only 5-4. Dissent is good, but this is too close for comfort.

Formulations, insomnia and career paths

I'm finally getting to work on that UV-cured material after endless delays from the front office. It is a new area that doesn't seem to have any previous work done, so I'm flying by the seat of my pants, using only my intuition and experience. This is no time for a designed formulation scheme spit out blindly by a canned program devised by a mathematician (or worse yet, a statistician!). This is the time to take big broad swatches of color and go for it, guaranteeing equally big failures and maybe, just maybe, a spark of success that can be slowly fanned and improved to reach the ultimate success.

The first days are the worst as there are too many functional groups to look at (including the various remnants binding them together), too many photoinitiators, and too many other additives to include. My mind was non-functional yesterday after massing out all the ingredients. Letting things sit overnight, I can already see that there are issues of solubility between the components to address, premature reactions and a host of other problems to solve.

This is fun. These problems will keep me awake at night, but I'm energized in the morning about the new ideas to try. Had I'd gone to the dark side (management), I'd be awake at night too with problems in my head, but that would be a worry-induced insomnia, the kind that would leave me exhausted in the morning from a sleepless night. I've chosen my career path correctly.

Tuesday, June 23, 2009

If anybody dares quote Paul Simon...

...I'll instantly delete their comment. It's just too easy a target, given that Kodak is stopping production of Kodachrome.

I certainly appreciate digital photography - I wish I would have had it around when I was learning the art. It's so much easier to show someone the benefit of bracketing exposures (i.e., taking a series at different shutter speeds or f-stops so as to get a better picture than what the dummy automatic settings choose) as you get instant feedback at virtually no cost. And it's so easy to delete the bad exposures instantly to not fill up the memory.

Using film in the same manner was a time-extensive and expensive. Even if you developed the film yourself, it still was a good hour or more between pressing the shutter and looking at the proofs. It also explains why skilled photographers were happy to get 2 good shots from a roll of film. But because of the irreversible nature of film, all the shots had to be developed.

I've also always been impressed with the technology of photography, particularly color. Being a chemist, I understand the technology, but I still am awed that this was created decades ago. It's a pretty precise technology and it performs beautifully.

Monday, June 22, 2009

It's finally time for bifocals

I've been fighting it too long, but this will most likely put me over the edge: The ACS is now rotating and condensing it's journals. The rotate I can maybe live with. Certainly it may appear at a distant that I would be looking at a solicitous image ("getta load of those hydrocarbons"), but that's o.k. It's the "condensing" that will cause me to concede defeat.

I certainly understand the move, although I had to smile at this comment in the announcement: "At ACS, demand for our print-based offerings has declined significantly—down over 50% in the last 2 years. Ironically, despite pre-emptive moves to digital presses, this has had the impact of increasing ACS’ own print-cost per copy, given the economies of scale in printing process." I'm sure other publishers will follow as well.

A transition to online is inevitable for all these publications. The issue I find with online access is that it is only temporary access, and when the fees are no longer paid, all access is lost even during the periods when full access was available. Meanwhile printed journals are permanent.

Friday, June 19, 2009

Buckyball polymers

This one has me a little bit puzzled in a number of ways. A paper at the physics arxiv discusses the polymerization of buckyballs (fullerenes)using 1,2,4-trimethyl benzene (TMB) as a comonomer. The resulting polymer then was an alternating copolymer.

From page 9:"However, the solubility of the material was found to change with time. Unlike raw C60 powder, well known to be highly soluble in aromatic solvents, the as-made nanowires were only partially soluble in these solvents, and this solubility decreased further with time." This is doubly puzzling, not only because of the change over time in solubility, but also because I would expect the TMB to have only a minor change on the over interactions between solute and solvent. There are 60/9 more carbon-solvent interactions with the buckyballs than with the bridge.

All of the easy explanations are not available: "We noted that the resulting nanowires were highly stable, as indicated by the fact that there was no detectable alteration in either their crystalline morphology, crystal color, or sample weight as a function of time." It's problem that will have to wait for someone else to solve.

Wednesday, June 17, 2009

At least here the Editor loses his job

Following up on last week's post about the nonsensical research article that was accepted in an open access journal after being "peer-reviewed", the editor of the journal has resigned his position.

What really gets me is the gaul of the publisher to state "In a statement, Mahmood Alam, director of publications at Bentham Science Publishing, told Nature in an e-mail that "submission of fake manuscripts is a totally unethical activity and must be condemned.""

But it appears that I am too quick to judge. Alam was actually the good guy here, actively purusing the criminals: "Alam claims that those behind the fake paper "had also tried to do this earlier [sic] in a different journal, but failed in their attempt due to our peer review system. Our suspicions were aroused this time and in an effort to unmask their identities the normal publication process was carried out on the second fake article. When they received repeated requests from us for more information and their credit card and other payment details they withdrew this paper.""

Way to go! A publisher trying to out the fakes, tracking them by their credit cards numbers. Too bad that the general public doesn't know about this stuff; I'd love to see the talk show hosts get some mileage out of this situation (and Conan needs a lot of mileage).

Tuesday, June 16, 2009

A sign of economic turnaround?

Being the economic forecaster par excellence that I am, please be assured that you can invest your entire life savings on the following sign of the imminent economic turnaround: next year's K-show is already sold out. This years NPE has been hurting in every possible way - attendance by both exhibitors and attendees is off.

The K-show is the Kunststoff show which is held every three years, Kunststoff being the German world for plastics. I used to think that "Kunststoff" was an inferior word to use, as the origin of "plastic" to describe polymers arose from the plastic deformation that they commonly underwent. But given that most people aren't aware of what "plastic deformation" is (i.e., they think that any deformation (including an elastic strain) of a plastic is a plastic deformation), maybe it is a better term after all.

Friday, June 12, 2009

Front row seat to a horse race

Just in my RSS feeds, I ran across two papers (1, 2) that made me think "deja vu" until I realized that no, these were two nearly identical papers. Both were using azobenzene derivatives, which have been known for decades to undergo a reversible cis/trans transformation under UV light, and both groups have now been able to demonstrate reversible bending of thin polymer films as a result of this. The first paper listed above was done by the Koshima group at Ehime University, while the second above was done by researchers at in the Yu group at Fudan University and others at the Tokyo Institute of Technology. Both groups have videos of the results. The JACS publication was received December 22 of last year, while the other paper was received March 11 of this year. That doesn't really clarify who was the originator though. Lastly, the JACS paper does cite earlier work of the Chinese, but the Chinese don't mention the work of the other group.

Coincidence? Academic spying? Is Hollywood calling for the movie rights?

Guar Gum - It's not just a thickener anymore

This research has it all: ionic liquids, unusual thermorheological behavior, and is based on renewable resources. How cool is that?

Ionic liquids are a rather sexy research area these days. These materials are simply salts that are liquid at or near room temperature. Unlike the more common salts made from column 1 and 2 cations and column 7 anions which have very high melting points, both of the ions in ionic liquids are made of numerous atoms, often organic, and are able to spread the electric charge around rather than concentrating it on a single atom. This dispersion results in a weaker ionic bond which can then "melt" at lower temperatures. Most commonly, the vapor pressure of the liquids is quite low.

The researchers used an ionic liquid to dissolve guar gum and make a film that is conductive (no surprise there) but also hardens when heated and softens when cooled. All told, that is quite a package of unique properties to have.

Thursday, June 11, 2009

Mendable polymers

A few months back I was discussing (unhappily) self-repairing polymers, the problems with them and my general dislike of their future. Compare that with this paper on "mendable" polymers. Not a subtle semantic difference, but a totally difference approach - working with (thermally) reversible reactions, either in the polymerization and/or the crosslinking. They are largely relying on the Diels-Alder (DA) reaction, but also other reactions such as disulfide bridges and photodimerization to a lesser extent. When the material needs repair, the reaction is reversed to the monomers, and then re-initiated. Instead of a two-component system in the "self healing" polymers, there's only one component.

The problem here is the limited number of polymer systems that can be easily reversed. You're not going to get too far with plain vanilla polyethylene. Certainly that is a real concern with the monomers, but with the crosslinkers it is a much less concern, as you can have the crosslinking groups as moieties hanging off the backbone. The challenge then becomes a numbers game. There have to be sufficient number of each group so that they can find each other without relying on extensive reptation.

One possible advantage of the DA reaction is that it require two different reactants, the diene and the dienophile. If half of the polyXXX backbone is modified with the diene and the other half of the polyXXX is modified with the the dieneophile, then the reaction within the blend is assured to be intermolecular, not intramolecular. That would not necessarily be assured with the disulfide bridges or photodimerization.

Certainly these are not perfect systems, as they require a separate processing step. The "self-healing" materials do just that - they heal themselves. I doubt that this will be a winner-take-all contest (very little is). I'm just glad there is a second horse in the race.

Wednesday, June 10, 2009

Another Journal Scandal

Yet another tip of the hat to "The Scientist" for reporting this: a completely faked paper of utter gibberish generated by software was accepted by an open access journal (as long as they paid the fees) telling the authors that the article had been peer reviewed. It's pretty clear what the dynamics here are: the publisher was looking to raise revenue, so they took anything the could get. And to speed the process along, they didn't bother with a lengthy review process.

I'be been a big fan of open access for a number of reasons, but this hurts. Not that this couldn't happen in academic journals that are truely peer reveiwed, but the motivation is clearly not there for the publisher, as retractions rflect pooly on them.

What most disturbs me is that publishing scandals of all sorts are occuring with ever greater frequency. That's trouble for other researchers relying on the publications, but also it diminishes the sterling solid perspective that the public has of science.

You may recall that "The Scientist" broke the news on the Merck/Elsevier fake journal catastrophe. They are really on top of this arena. Thank you.

Monday, June 08, 2009

Memory Foam

This is another case of making up a new name that isn't necessary. Also making lemons from lemonade.

"Memory foam" is the hot seller in the matress market, but in my mind, it is merely a compression settable foam. Put a compression on it for a while, and when the foam doesn't bounce back, it's called compression set. This is generally an undesirable property of a material. The Wikipedia article adds nothing to combat this. "it is firmer in cool temperatures and softer when warm." Now that's unusual thermomechanical behavior, isn't it?

Friday, June 05, 2009

GPC- Quantitation that's qualitative

GPC (gel permeation chromatography a.k.a. SEC (size-exclusion chromatography)) is a fairly common technique for measuring the molecular weight distribution of a polymer. A colleague had some results yesterday and in discussing them, it hit me that despite the technique producing quantitative results, I always look at the results qualitatively.

Here's why: the report we were discussing gave several measure of the molecular weight distribution - Mn, Mw and Mz. The first two have a physical;y intuitive meaning, while the last one doesn't. I've seen other reports that even include Mz + 1, also not a physical quantity. The string of all four of these are simple the first through the fourth moments of the distribution.

So the report had a nice set of numbers for all these moments, calculated out to 3 or 4 significant figures and my colleague was trying to make sense of the numbers. That's when it hit me. I only look at the numbers in a "relative" sense (there are two meanings to that phrase - see below). I seldom care about what the exact number of the molecular weight is, only what the changes are between one sample and the next. Yes, the polydispersity index (Mn/Mw) is a helpful as a measure of the distribution's width, but still, I'm only looking for qualitative changes in the distribution, not exact numbers that I can run calculations with. My colleague seemed a little disappointed with this, as certainly we all take strength from numbers, but to me, the numbers do not add anything.

Back to my double entendre on the "relative" results. The paragraph above gave one meaning, but even the quantitative values are relative in that the instrument is calibrated with polystyrene standards and so the results are always relative to this. (Polystyrene can be easily polymerized anionically, so that the molecular weight distribution is tightly controlled.) There are ways to make the measurements absolute (Wyatt's light scattering technique is prominently advertised), but that is still not something I've ever felt the need for.

In this case, we had samples which we were examining for UV degradation and the associated drop in molecular weight. We found this (qualitatively) so we didn't go any further.

And that's unusual for me. One skill that I learned from my advisor during grad school was to get as much information as possible from each experiment and measurement. It's a skill that I now greatly cherish, although I certainly didn't when I was trying to finish up and he kept wanting me to get more info out of my data! It's a skill that my clients always value, but this is one case where just I don't go any further.

Thursday, June 04, 2009

The Queen is Dead. Long Live the Queen

I am greatly saddened with the passing of Koko Taylor, the "Queen of Blues". I thought of her as inseparable from the vibrant Chicago blues scene. Other blues artists roam the world without a hometown, but Koko and Chicago were one and the same. I never did see her perform - I kept hoping that with my son going off to school in Chicago next fall that I could catch her when I went out to visit, but that will never happen. Her last album, "Old School" came out in 2007 and at 78, she still was powerful and aggressive with an in-your-face style. You'd think she would sing forever. She certainly won't be in heaven singing in a choir of angels, but will be over in some small smoky corner doing it her own funky way. God bless.

Tuesday, June 02, 2009

Cap-and-Trade and the Chemical Industry

A new report out looks at the estimated costs of a cap-and-trade program for CO2 emissions, and as you would expect, it doesn't look pretty for the chemical industry. Given that they are up against service industry businesses, this is to be expected.

"For over 80% of the companies in the S&P 500, the majority of greenhouse gas emissions are from indirect sources associated with their business activities. Examples include companies such as clothing retailers which predominantly outsource the production of goods and services, and financial institutions. Many of the S&P 500 companies are service-based and the majority of their emissions result from electricity use in buildings, as well as business travel."

Yet at the same time, "More than half of the greenhouse gases emitted by companies in the S&P 500 are direct from operations", meaning that if you're bad, you're really bad. Depending on which chart you look at, the chemical industry is in the top 3 to 5 worst offenders. Air Products in particular is singled out as the worst offender in the chemical industry (CO2/Revenue) because of the high energy associated with air separation.

This is hardly unexpected. Most chemical of interest have some energy stored into them which is then leveraged later during the reaction, and creating those energetic states requires energy input. Additionally, the increase entropy in ALL purification processes also requires energy input. It's all simple thermodynamics, which the service industry is not constrained with.

Without trying to push a particular political viewpoint or agenda, this report makes it really difficult to see that cap-and-trade would do any other than supply additional support for for exportation of manufacturing elsewhere in the world, while the US becomes more and more of a service industry base. It is doubtful that this would result in the desired CO2 reductions on a worldwide scale, and given the global nature of the atmosphere, the emissions would not drop as expect. The US could feel good however, because "we did our part to cut emissions."

More drugs from Botulism Toxin

You can't get past the first page of any toxicology text without reading Paracelsus's decree: "The dose makes the poison" and that is certainly never more true than with Botox. One of the most toxic poisons, far more deadly than any synthetic toxicant, properly diluted has numerous benefits, with additional uses now being reported.

So how come microbiologists seem immune to the decree? They love to report that there is e.coli/salmonella/campylobacter... in food and that you therefore should trust them when they say don't eat it and thank them when they save your life. Doesn't the concept of an LD50 exist in their profession? Or is it really all about fearmongering?

The Car Industry after GM's Bankruptcy

I've nothing to add to all the commentary about GM. I'm looking at the bigger picture.

As I've mentioned before, this could be real trouble for multiple suppliers to GM, as the court could easily void existing contracts, negate payments and debts and create general havoc on an industry that is already in tremendous stress.

Longer term, I would expect a nice uptick in plastic usage in cars, given the Government's tremendous ownership share of the industry (Do you really believe that no government official is not going to use their influence?? They just can't help themselves, it's what they do, it's their inherent nature) as well as the higher mileage targets. Replacing steels and other metals will plastics/composites will reduce weight, although the real increases are in rolling resistance and drag, not weight.

Monday, June 01, 2009

Supreme Court grants cert for Bilski

The US Supreme Court has granted certiorari for Bilski v. Doll, of great interest to the patent community. The question here is whether or not a claimed invention needs to be tied to a particular machine, article or transformation. At issue here are many of the "business method" patents that popped up after the State Street Bank decision, as well as other more nebulous inventions of intangible items such as computer programs and algorithms, encoded EM waves... The SCOTUS Blog does a nice job of covering the issues, but the legal issues and jargon can be difficult to the uninitiated. Regardless of the outcome (the oral arguments won't occur until next Fall and the decision will be ???), the lawyers will be busy with lots of new fodder to argue about, interpret, reinterpret and so forth until they need another new ruling from on high. (Job security!)

I personally expect that the decision will provide strong clarification on many issues, but will leave other issues untouched. That seems to be the trend with the current court. Oh, oh...let me be trendy and mention that Sonia Sotomayor is clearly for/against this issue because she is__________________which makes her under/over/properly qualified for the SCOTUS.

I'm also still waiting for the resolution of Melendez-Dias v. Massachusetts. It can't be too much longer as the term is nearly over.

And speaking of Supreme Courts, the Minnesota Supreme Court heard arguments this morning over which former New Yorker will be my Junior Senator from Minnesota. I can't say that my state has been hurt in the last 8 months having just one senator; can we continue the experiment a little bit longer? We'd be the envy of the nation as we would have to listen to Senate political TV ads only once every 6 years.

Tuesday, May 26, 2009

Harry Gray

He's won the Welch award to go alongside numerous other awards such as the Priestley Medal and the Wolf Prize.

Being a polymer chemist/chemical engineer, I've never really dealt with any of his research. I only mention this because of a memory tucked in the distance recesses of my mind. Back in early 1985, I was a freshman at the U. (Which U you ask? Why Minnesota. Everyone calls it "the U". I'm not sure why that doesn't happen in other areas. It wasn't like that in Urbana, even though UIUC dominates the town so much more that the U dominates the Twin Cities.) The professor mentioned at the end of one of the lectures that one of the authors of our textbook (Harry) was going to be giving a seminar later that afternoon and that we could certainly stop by and listen even if it was going to be way over our heads. So three of us did go and yes I can't tell any technical aspects of the work at all. I do remember a few other things though. He had a great happy personality (I don't think I would recognize him if I ever saw a picture of him without a huge smile on his face), he kept joking that he hoped
all his efforts would someday amount to something worthwhile (we all do, but how few of us openly talk about it) and he walked into the talk with a can of beer (there had been a reception before the talk, and he (and others) had kept some refreshments with them as they left the reception and went to the lecture hall. How times have changed.)

No long term lessons here, just some reflections.

Tuesday, May 19, 2009

Accelerated aging gets even faster

How 63x for an acceleration factor? My first thought was that the material would cook 63 times faster (i.e., ALL thermoplastics including the highest temperature polyimides that only exist in the patent world would be reduced to a ball of charred goo comparable to a roasted Peep) , but given that the mirrors avoid reflecting IR and longer visible wavelengths, maybe not. I've talked in the past of the dangers of over-acceleration and if that isn't a real possibility to you here, then it never will be. But this still could be a useful test. I'd just be sure to runs some slower accelerations at the same time to be sure that there is a correlation to point to.

Thursday, May 14, 2009

This worked real well

From Medical Device and Diagnostic Industry , May 2009, p. 22:

"On March 13, FDA's then-acting commissioner Frank Torti issued a memo warning staff about leaking confidential information. Three day later, a copy of his memo surfaced on the In Vivo blog."

Thursday, May 07, 2009

I guess this is the week for "Peer Review"

So it was more than just the Australasian Journal of Bone and Joint Medicine. The Scientist is now reporting that a total of 7 different such "journals" existed in the early part of this decade, all sponsored by corporate entities, all starting with "Austalasian...". The sponsors are not named, but I suspect that it won't take much detective work to ferret them out. After all, the point of these articles is to use them as a reference, so I'm sure somebody has a copy or two hanging around their office.

What are the long-term ramifications of this? What can be done to prevent this in the future? I wish I knew. I gave the FDA a brow beating the other day for their minimal standards in the use of publication as sales literature, but they certainly set the bar high enough to not allow this stuff through. A boycott of the publisher would be of dubious value.

A letter to the editor? Their website has a feedback option. Take advantage of it. In a time when the line between news/entertainment/opinion is being blurred in the popular media, having a scandal like this in scientific media is horrific.

Wednesday, May 06, 2009

Peer Review (Again!!)

Sense About Science has a nice website. It's a pop-science debunking site, but I was really taken in by the tab on "Peer Review". It's aimed at students, but makes the point that the general public is really in the dark about the process - that it exists at all and what it entails. This link will take you to the pdf.

A few of the points I take issue with, such as 1) you can tell a result is peer reviewed when it has some obscure reference with unintelligible abbreviations, and 2) the statement "Scientist never draw firm conclusions from just one paper or set of results", which is quite laughable. To try and capture all the details and subtleties of peer-review would be impossible, and making general statements is always a balance between keeping some significance to the statement and making it meaninglessly vague.

Monday, May 04, 2009

Rheological Math

The math in rheology gets to be really hairy at times, largely because of the constituitive equation. The basic equation is t = m dg/dt, which is deceptively simple. Both the stress, t, and the strain g are 3 x 3 tensors, and m, well m can be just about anything you can imagine as long as your imagination is limited to nightmares. Keep in mind that rheological fluids of interest have a memory of what has just happened to them, a fading memory, but a memory nonetheless, and that this memory needs to be incorporated into the relationship. The only successful efforts are limited to simple flow patterns that allow for simplifications, the creation of linearities and other limitations. In most cases, the equations still can't be solved analytically (in closed form) but need numerical analysis.

Tensors are more than just matrices in the same way that vectors are more than just a row or column of numbers. They are objective quantities, meaning that the relationship between them needs to be valid in all references frames, not just an arbitrary one. A really common example in rheology textbooks is to show that if you study simple pipe flow on a rotating turntable, then with non-objective equations, the viscosity can depend on the rotational speed.

Rumor has it[1] that Einstein, who's first major result was the Stokes-Einstein equation, gave up on the field of rheology as it was too difficult. He went on to something considerably easier - relativity, an area of physics which required the development of new mathematics - objective tensors.

[1] ...which means that I've heard it said, but despite looking everywhere, can't verify it. The facts are true, it's just the motivations that are questionable.

Friday, May 01, 2009

Chrysler's Bankruptcy - The First Domino?

I'm more concerned about Chrysler's bankruptcy than most commentators seem to be. Compare the noise to that made about the Porky-the-Pig Plague, which has killed only a few hundred when all flu combined kill tens of thousands each year.

The Big Three have been in trouble for years, and unfortunately they are not alone. Many of the Tier 1 suppliers (those that supplied finished assemblies to the automakers) have had the screws tightened during the decline leaving them in horrible shape as well. Look at the bankruptcies of Meridian, Tower Automotive...

Even when Chrysler is the smallest manufacturer, it could be enough to set off a whole chain of additional defaults, much like what happened in the insurance and banking industry. Chrysler goes under, one or more suppliers go under, making it difficult/impossible to supply Ford and/or GM, further compounding their problems. Keep in mind that there are also Tier 2 suppliers, mold makers, service providers...that will all be directly affected as well.

People love to beat up on the automakers for being out-of-touch with their massive designs and poor quality - "just let them fail" - but it's more than just the Big Three at issue here. There are hundreds of thousands of additional people supporting this industry. The exodus from Michigan is already estimated at one family every 12 minutes, and this can only increase it, raising the cliche question:

Will the last person leaving Detroit please shut off the lights?

Thursday, April 30, 2009

This isn't even peer-reviewed

While my post from this morning wasn't the most flattering of peer-reviewed research, it sure beats this: Merck published a fake journal with some help from Elsevier (link to The Scientist - free registration required). The "journal" was not surprisingly loaded with articles supportive of Merck's products. Activities like these keep making it more difficult for the pharma industry to be seen in any positive light whatsoever.

Updated 5/5: Both the Excimer (Carbon Based Curiosities) and the Chemistry Blog have more details on the matter.

Skip the ER for potential heart attacks and find a spectroscopist instead

This is a neat and unusal use for mid-IR spectrscopy: differentiation between heart attacks and simple chest pain. Given the ubiquity of IR machines and the ease with which anyone can run one, this could be an important new find.

Now if I can just get the IR guys at work here to start running this test, we could be billing the insurance companies for some big bucks!

Wednesday, April 29, 2009

It's "Peer Reviewed", so It's gotta be right.

The FDA has always taken the attitude of regulating drugs and devices and not the practice of medicine - i.e., doctors can do whatever they want with the controlled materials, even if the product is intended in other ways. I believe cosmetic botox injections started this way. They were originally intended for use in stilling muscles during surgery, but someone got the bright idea that it would be great for removing wrinkles in the face. The drug was not labeled by the manufacturer for this application and it was not legal for the manufacturer to sell it for cosmetic application - the doctor assumed all the risk. This is known as "off-label" useage. That has now changed as the FDA has approved this use of the toxin as well.

But now the regulations in the area are starting to change. It's now permissible for companies to pass out reprints of research articles that studied off-label uses of drugs.

From the FDA document: "A scientific or medical journal article that is distributed should:
  • be published by an organization that has an editorial board that uses experts who have demonstrated expertise in the subject of the article under review by the organization and who are independent of the organization to review and objectively select, reject, or provide comments about proposed articles; and that has a publicly stated policy, to which the organization adheres, of full disclosure of any conflict of interest or biases for all authors, contributors, or editors associated with the journal or organization;

  • be peer-reviewed and published in accordance with the peer-review procedures of the organization; and

  • not be in the form of a special supplement or publication that has been funded in whole or in part by one or more of the manufacturers of the product that is the subject of the article"

So now the FDA is making the assumption that if it is peer-reviewed, it's correct. As if peer-reviewers are short on time (I'm always pressed for time when asked to complete a review, they never seem to come during slow times), ever wrong (I don't think I am, but fortunately I'm not making life-and-death decisions to approve a polymer chemistry paper), or politically connected (I'm too much of a loner for that game). Sure, the papers are already out there, but to use them for promotion is not the original intent of the article (or maybe it is depending on who funded it) but there is no obligation to not cherry pick the articles and only pass out the good results.