Monday, November 25, 2013

Whistleblowing - Some Thoughts

Dr. Fredrik von Kieseritzky, aka Dr. Freddy, the author of the Synthetic Remarks blog has stated that he is willing to be the "whistle blower" for anyone that knows of corruption within the world of chemistry. While I admire his ambitions and his objective, ("sunshine is the best disinfectant"), this is effort may come with a heavy price for anyone involved in it.

1) While Dr. Freddy thinks he has the law on his side to protect your anonymity, I would seriously recommend that any potential whistle blower think again. All he can supply for support is a link to a Wikipedia page. Very seldom is the law ever clear. Even something as simple as a point of the US Constitution has volumes of case law that are necessary to interpret a simple sentence, and that case law is often not static but changes over time. The fact that Sergeant Bradley Manning is spending 35 years in a military prison while Julian Assange is free says that you need to think long and hard about what it means to be a whistleblower. Swedish law will protect you while you are in Sweden and will not protect you anywhere else. Hire a Swedish lawyer before you proceed so you can go in with your eyes wide open.

2) While Dr. Freddy has suggestions about how to avoid detection (all of which seems pretty good), I would still emphasize caution. As the recent episodes with Mr. Snowden showed, the reach of the NSA or other agencies is far greater than we can possibly imagine. The fact that the Russian President Mr. Putin is using typewriters strongly suggests that the NSA is not gathering information by hacking PGP keys or other security features, but may in fact have the ultimate backdoor via firmware. If they want access to your computer, they will get it and short of disconnecting it from any network, you probably can't stop it.

3) Institutions with damaging information intentionally limit access to it, not only so that it is less likely to be leaked, but also so that they can quickly identify possible leakers. If you know damaging information and leak it, don't think that you won't be under suspicion, especially if you have history of stating your dissatisfaction.

As for Dr. Freddy, I need to caution him as well. Consider the case of a Mr. Dan Rather, who used to be the lead reporter for the US's CBS News. Back in 2004 when President George W. Bush was up for reelection, Dan got a copy of letters that showed that Bush was disobeying orders while in the Air Guard back in the 70's. Dan and all the resources at CBS agreed that the letter was in fact authentic and so they ran the story. As soon as release it, it became clear that the documents could not have been prepared on a typewriter for that that time period. Dan had been duped by a liberal/Democratic operative that didn't want to see George Bush reelected. Firings and lawsuits soon followed. The person that gave Dan the letters was left unharmed.

I can't imagine that Dr. Freddy has better resources to authenticate documents. Further, I'm not sure what the Swedish laws are regarding libel and other defamatory remarks are, but I can't imagine that they take to kindly to publishing damaging words that are untrue.

A whistleblowing site is quite different than finding fraudulent published papers such as has been done by Paul Bracher, Stuart Cantrill and others. In these cases, the authentication of the papers is never an issue - they are accessible from the publishers website. Paul, Stuart and others are pointing out items within the papers that look suspicious.

Again, I understand what Dr. Freddy is trying to accomplish and I support his actions. But I would strongly advise caution for him and any potential whistleblowers. I think the issues that I've raised here are serious enough that it should give pause to both sides. People not involved in this may be cheering the whistleblowing on (who doesn't love to see a trainwreck), but since they have nothing to lose, it's easy support to give. That support won't be there when trouble arises. The people will, watching excitedly the next phase of the trainwreck, but their support won't.

Friday, November 22, 2013

Talking Turkey (Netting, that is)

I expect readership to be down next week with the Thanksgiving Holiday, so today will be the day to talk turkey. More specifically, the netting that surrounds the turkey when you buy it at the store. Unless you have worked in the manufacturing of plastic netting [1], you WILL take that netting for granted. Don't. It is far more sophisticated than you realize. Take a look at the netting closely. It is a continuous tube, and there are two layers of strands in the netting. It stretches in both the x- and y-directions and is perfect for conforming to the odd shape of a cleaned, plastic-wrapped turkey and most importantly, it forms a nice handle so that you don't have to bearhug the thing with both arms.

The process for making diamond netting is known as the Netlon process. According to one source, it is only the ninth basic textile process since the dawn of civilization. The inventor, Frank Mercer, became not only a Fellow of the Royal Society, but was also OBE and won numerous other awards from Her Majesty for this revolutionary process.

The Netlon process is fun to watch in action, and really pretty simple, although much more difficult to describe. (Sadly, I can't find an online video showing the process.) Let me describe it this way. Much like pushing Play-Doh through the Play-Doh Fun Factory to make Play-Doh worms, molten plastic is extruded through 2 slotted dies which produce continuous strands of the plastic. The slots are located in a circular pattern around the dies, and most importantly, one die is located within the other one and along the same axis. This is what produces the 2-layers of the net. However, what I've described so far would only produce long strands of fiber and not netting. The netting is made by taking the dies and counter-rotating them. The plastic is molten enough that the two strands meld together where they cross. If both dies rotate at the same speed, a tube of netting with the lovely diamond pattern is produced. This diamond pattern is what gives the netting its biaxial deformability even when the plastic itself is not stretchy.

This is not the only process for making plastic netting. There are others, but the netting they produce are not as appropriate for wrapping a turkey. They generally don't deform as well (unless made of fundamentally elastic material) and are seldom made in a tubular form. They are another subject for another day. As for today, I hope you have a better appreciation for that little bit of netting that's around the turkey. It's also likely around the onions that were used in the stuffing [2], and caramelized for the haricot verts salad [3] and the gravy and the...

[1] I have.

[2] Of course we stuff our bird even as the TV news always tells us not to. Why don't the same TV news crews do live shots from outside a hospital on the day after telling us how many people were treated for food poisoning that came about because they stuffed their bird? Because there aren't any.

[3] The only way I will eat green beans is in my wife's haricot verts salad. Caramelized onions, beans, toasted pine nuts and a spoonful of creme fraiche. Simply incredible and it pairs so well with turkey and chicken.

Tuesday, November 19, 2013

Your Plastic Waste is Valuable

I've been saying for nearly two years now that 'your plastic waste is valuable and the plastics industry wants it'. The local newspaper supports this idea in an article published yesterday showing that the state of Minnesota alone (with just just 1.7 of the US's population) tossed more than $217 million dollars worth of recyclable materials away as trash. And 42% of that value - $93 million - is attributable to plastics:
" $500 per ton, what now goes into trash cans would be worth $93 million to manufacturers."
If Minnesota is representative of the whole US, then nationwide there is more than $5.4 billion dollars of recyclable plastic that is waste. Minnesota is actually a bad example of the potential, since across the state, recycling rates are already high:
"Minnesota’s average recycling rate is higher than that of most states — and it has stayed high, just under 50 percent of what gets thrown away..."
which means that nationwide figure would be even higher. Any company spending $5+ billion on raw materials is pretty good sized, so you can see the potential.

Repeat after me: Your plastic waste is valuable and the plastics industry wants it.

Monday, November 18, 2013

73 Quarters of Losses - And Still in Business

Amerityre Corporation makes polyurethane foam tires and not much else. Certainly not money. Last week, the company announced their latest quarterly results and were pleased that they had cut their loss to $174,566 from $277,889 a year ago. While companies can loose money a quarter or more and still be in business, to have this quarter be the company's 73rd consecutive quarterly loss and still remain in business is quite surprising, at least for an established company that is making something as mundane as tires. The last line of the press release is particularly jawdropping: "The fiscal 2014 first quarter loss brings the company's cumulative loss over 18 years to $63.3 million."

Startups will often report long strings of quarterly losses, but that is often expected, particularly for innovative companies that are developing new-to-the-world products or medical devices that have long approval times. Amerityre is none of these. They have been in business since 1995 and while it can be argued that their technology is innovative, their last claimed innovation, polyurethane elastomer tires, came back in 2003, all of 10 years ago.

The tire business is very cutthroat because of the many competitors fighting over the very small margins available. There was hope that run-flat tires would have changed that and allow for higher margins, but the tires never became as accepted as the businesses hoped [1], and so nothing has changed. And that is what Amerityre is competing against. There will be niches that they can do well in, but that's all. $63 millions dollars is not a niche business.

I'm amazed that someone keeps bankrolling the company, and that that someone is stockholders. "Amerityre is asking shareholders at its upcoming annual meeting on Dec. 4 to approve increasing the number of authorized common shares to 75 million from 55 million to help raise $2 million to $3 million to help 'meet…current obligations and grow revenues...' " The thinly traded stock is available for less than a dime if anyone out there is interested. [2] I wish them luck. They must have a very compelling story if they think they can raise another $2 - $3 million in the open market, but I just don't see it.

[1] Personally speaking, my wife had a set on one of her cars. Besides being noisier than other tires, the tires didn't last very long. When it was time to replace them, we either had to continue with run-flats or buy standard tires and new rims since the two tires were incompatible with each other. Never again.

[2] I probably should include one of those disclosures that states that I do not, never have and do not intend to own any stock in Amerityre. I'm the last guy in the world you want stock tips from.

Friday, November 15, 2013

The Stick-Slip Mystery Deepens

Every once in a while, I run across a journal article where the title completely underwhelms me. Such as this one: "Strong dynamical effects during stick-slip adhesive peeling".

If you know what stick-slip adhesive peeling is (and as you'll see in a moment, you already do know), then you know it is a highly dynamical phenomena. Stick-slip peeling is what happens when you pull a piece of pressure-sensitive adhesive off the roll and it makes a loud noise. Here in the US, regular old-fashioned Scotch Magic tape (the one used around the home and office, and also for wrapping Xmas gifts) is pretty quiet, but compare that to the clear tape used to tape up boxes for shipping. That noise is at most a minor inconvenience at home, but imagine that you have a factory full of automated box taping machines that are all running and making that stick-slip noise. Now you have have an environmental hazard where workers need hearing protection. All because the tape won't peel off smoothly, but instead behaves in a highly-dynamic fashion of peeling for a little bit, then stopping, then starting again, then stopping...

So to say that there are "strong dynamical effects during stick-slip adhesive peeling" is stating the obvious. The research results, however are not.

Using a high speed camera, the researchers [*] built on existing research, redocumenting a number of well established phenomenon, such as that amplitude of the stick-slip length increases with the pulling speed and that the stick-slip cycle time decreases with the same. But what they also unexpectedly found was that the time for the stick phase (Tstick) and the time for the slip phase (Tslip) varied independently of each other. (Tss is the total cycle time = Tstick + Tslip.) Depending on the peel speed, either phase could dominate the total cycle time, which makes it all the more challenging to attempt a reduction in this phenomena. This discovery is way beyond current theory.

Earlier in my career, I spent a lot of time on adhesive development which can be plenty challenging in its own right. I knew of "issues" in stick-slip, but never worried about it as long as my new rolls of tape could be unrolled. But clearly the whole arena of stick-slip is a fascinating area to research. Many people already know about the triboluminescence that can be seen from peeling Scotch tape from the roll quickly (do it in a dark room with your eyes well adjusted to the darkness), but you may also recall that half a dozen years ago, researchers found that the stick-slip phenomenon can lead to the generation of x-rays.

If I ever get back into adhesive research, I think I might spend a little time poking around in stick-slip behavior. There is undoubtedly much more to be discovered.

[*] Marie-Julie Dalbe, Stephane Santucci, Pierre-Philippe Cortetc and Loïc Vanel

Tuesday, November 12, 2013

Carbon Dioxide as a Strong Viscosity Modifier

It's well known that adding "stuff" to polymer solutions alters the viscosity. Whether that "stuff" is inert fillers (spherical, rodlike or othewise), (co)solvent(s), or anything else, the viscosity of the modified solution will change to some degree. But keep in mind that this "stuff" that I'm referring to are what physicists call condensed matter - solid, liquids and anything else in between. Anything but gases.

A new paper in Polymer Chemistry changes that. Canadian researchers have developed an aqueous polymer with a viscosity that is strongly modified after dissolution of CO2 in the water. [*] The top row on the right hand figure (along with the decoder ring at the bottom) shows the chemical makeup of the polymer and how the polymer-polymer interactions are affected by the CO2. Recall that dissolved CO2 in water acidifies it via the formation of carbonic acid (H2CO3). The acid then interacts with the basic, tertiary amine. Not surprisingly, salts (NaCl in this case) also cause havoc at the same sites, either amplifying or further reducing the effective interactions.

The impact of changing these polymer-polymer interactions on the Brookfield viscosity is quite large as this next figure shows. In the absence of salt, the dissolved CO2 knocks the viscosity down by a factor of 100, and the addition of salt takes it down by almost another factor of 100. (For reference, water has a viscosity of about 1 mPa s, while honey would be on the order of 10,000 mPa s.)

The paper has more details about concentration affects (for both the CO2 and salt), and also shows that these changes are repeatedly reversible as sparging the solution with nitrogen brings back the original viscosity. While this polymer was specifically designed to maximize the impact of the carbonic acid on the viscosity, it wouldn't surprise me to learn that other aqueous, ionic systems could also be similarly affected, although most likely to a much smaller degree.

[*] To be clear, this paper is not proclaiming the initial discovery of gases strongly modifying viscosity. Previous research exists, but this is the first time I've become aware of it.

Friday, November 08, 2013

Comments on "Are We Refereeing Ourselves to Death"?

Angewandte Chemie has an open access editorial regarding how the refereeing system is being increasingly overburdened as the number of submitted manuscripts increases without limit. While the author has a number of helpful suggestions such as increasing the number of referees from China and other countries that are increasing their submissions, and also asking authors to show some self-control by not just automatically submitting to Nature/Science and then working on down the line until a paper is accepted. There are other good suggestions as well, but sadly, the author misses out on a huge opportunity that could drastically increase the number of referees available.

**Use industrial scientists.**

I don't have exact figures, but industrial scientists outnumber professors by what, 20x? 40x? Maybe even more? Whatever the number, all that manpower is available and yet it is seldom tapped. I am a outlier in that I referee for the Royal Society of Chemistry (RSC) but I have never encountered any other industrial scientists who referee papers at all for any publisher. Why is that? Cynical thoughts would be that academia doesn't want to dirty itself by working with "prostitutes of science", people who weren't "good enough" to make it as professors, or people who wouldn't be interested in research that doesn't have immediate economic applications. Or is the thought that because industrial scientists don't publish much compared to their academic counterparts, they aren't interested in what's in the literature or making sure that it is kept to high standards? Most assuredly, they are very interested. Some industrial scientists will say no, but that also happens with professors that are asked.

If I were working for journal and needed to find referees, I would start trying to tap this potential workforce now. Start with the few people you do know that are in industry and ask them who else they can recommend. And ask those recommendations for additional recommendations. And then do something with them. Start sending them manuscripts, even if you already have your 3 reviewers lined up. Take these new reviewers out for a test spin and see how they stake up to the regular reviewers. Once you have confidence in them, then start using them and give your regular reviewers a bit of a break. And by lining these new reviewers up early and using them, you are more likely to have their loyalty down the road when other publishers approach them.

When the RSC first approached me to referee about 10 years ago, I was honored by the request and have been happily helping them out. I contacted the American Chemical Society (ACS) shortly thereafter to volunteer my help. They said they would be in touch but have never yet sent a manuscript to me. So if the RSC and the ACS were to both approach me for refereeing and I only have time for one, who do you think I'm going to help?

Monday, November 04, 2013

Who's Been Eating My Ocean Plastic?

Reports (1 and 2) came out last week of a newly discovered "sink" for much of the plastic floating in the Pacific Ocean gyre - fish, and lanternfish in particular are eating it.
NOT Ocean Plastic
Sadly, the research was only presented in a seminar and so no formal paper (let alone peer-reviewed) paper has been issued yet, and so much of what has been published on the interlinks all comes down to the same PR release being recycled over and over (even more sadly with yet another misleading picture about what plastic in the gyres looks like). But the initial reports indicate that researchers found far less plastic in the gyres than they expected [1], and after ruling out UV and microbial degradation [2], they were able to conclude that lanternfish were eating the plastic [3]. Lanternfish are small fish that live in the day in relatively deep waters to escape predators and then rise to the ocean top at night to feed, apparently mistaking plastic particles for more nourishing victuals. And since lanternfish make up 65% of all deep sea fish biomass, they can have quite an impact.

(Through my footnotes I am raising a lot of questions which I realize will eventually be answered when the results are properly published. I'll wait patiently until then and then have another say on the matter.)

So is this good news? I don't see it as such. Consumption of plastics by any stomach-containing animal removes the plastic from the larger environment, but always temporarily rather than permanently. Plastic are not digestible and so the plastic is only temporarily stored within the animal swallowing it. Whether the pieces quickly pass through the animal's digestive track or remain trapped within the animal until the animal dies and decomposes, the particles are not permanently removed from the environment. And since lanternfish make up such a large niche in the open water ocean, they are a food source for a number of other species, listed in the Wikipedia article as "whales and dolphins; large pelagic fish such as salmon, tuna and sharks; grenadiers and other deep-sea fish (including other lanternfish); pinnipeds; sea birds, notably penguins; and large squid such as the jumbo squid..." All of this further supports that the sink is temporary, not permanent.

Plastic waste has no business being in the ocean, and lanternfish eating up large quantities of it does nothing to change this perspective.

[1] How did the researchers arrive at their expected value of plastic waste? Since the waste has been extensively measured elsewhere, why did they feed a need to derive a new value?

[2] How was this ruled out? Recent research suggests that microbial degradation is more significant than initially thought.

[3] How? Did they actually see lanternfish eating plastic?