## Tuesday, August 30, 2016

### Slide Rule Giggles

I've always loved slide rules. As soon as I learned in 8th grade about logarithms and how they formed the basis for a slide rule, I was hooked. Just like 2 rulers can be used to do addition and subtraction, so can 2 rulers, logarithmically scaled, be used for multiplication and division. That you have to keep your wits about you for locating the decimal is what separates the experts from the wannabes. 13 x 5.4 looks the same as 135,000 * 54. The significant figures were somewhat limited to 2-and-a-half or so, particularly as the value of the leading digit increased from 1 to 9. (The span between 1 and 2 takes up about 30% of the slide rule, while the distance between 8 and 9 is just 5%.)
Even with this, they were (and still can be) powerful calculation devices. Keep in mind that the atomic bomb was developed using just slide rules and that Apollo astronauts had slide rules in their capsule during their flights to the moon. No worries about power outages or dead batteries, they were consistent and reliable.

My wife and I both have slide rules that were passed on to us (mine from my grandfather, hers from her father) and they will never be tossed in the trash until you pry them from our cold, dead hands. They are not super fancy or collector's grade, but they are a way to still be in touch with these people, knowing that their fingers handled (and their brains engaged) the same instruments in the same way.

A recent alumni newsletter from Minnesota had a article on slide rules and it included anecdotes from various engineers who used them to get through engineering classes and even the early years of their jobs until electronic calculators came along. My favorite was this from a Hungarian emigrant:
"During his time in graduate school, [Erwin] Kelen served as a teaching assistant and decided he would have a little slide rule fun with his class.

'I was at the blackboard in front of my class, solving a problem, and I was reading the results off my slide rule. Four decimals first, then squinting, two more' he said. 'Imagine, six digit accuracy from a pocket slide rule!'

After class, all the students crowded around him, wanting to know how he could read this from a tool that basically had two decimal capability. At first, he was coy in telling them that it was a special secret that enabled him to calculate with such accuracy. Surprised, they insisted he tell them his secret.

'I 'fessed up that the last four decimals of the six were purely invention on my part and we all had a good laugh' Kelen said"
The fun of this is that the students themselves would have been limited to calculating just 2 or maybe 3 significant digits, and would have no way to prove that the last 3 (or 4) digits were wrong. I imagine having a Hungarian accent helped to give a further illusion of authority.

Here's the rest of the comments.

## Wednesday, August 24, 2016

### Theology, Rheology and some freaky strange search results

Dan Lowry (@DrFriction) tweeted last night "Whenever life seems devoid of meaning or humor, just do a web search on 'theological properties'" (referring to the fact that spellcheckers typically attempt to change "rheological" into "theological"). So I did just that.

Wow. Wow. Wow. Look at this screenshot:
The spellcheckers are winning far more often than I would have ever imagined.

But a little bit of digging suggests that there may be a far more sinister plot, one of revisionist history. I clicked on the first link and found this:
while at the bottom of the page there was this:
So what gives? Was the title later fixed? (That doesn't seem possible as it looks like an image capture, but I'm no expert in these areas.)

But weirder yet is what I found at the fourth hit:
Clearly an image of an original document, with a correct title. But that is not the weird part. It's when I searched the rest of the document for "theol" with the crtl-F key. Every single return (31 total) pointed to a word correctly spelled as rheol...For instance:

What is going on? I know and expect that Google would return a search for most people "rheology" (no quotes) as "theology", but for a word finder in a .pdf document to do that?

Again, I am swimming in the deep end. Any insight that someone could offer would be most helpful as there things here that are disturbing. I know my google search results are not neutral and haven't been for years, but for the text search in a pdf to be like that is not good.

## Tuesday, August 23, 2016

### Polyiodide

The number of elements that are capable of forming a polymer just by themselves and without the assistance of other elements is very small. A large part of this is due to most of the periodic table being made of metals, elements that not capable of forming polymers (at least as far as we currently understand). Throw out the noble gases and you only have a very tiny wedge of the table for consideration, consisting of the metalloids, the nonmetals and the halogens - a total of 16 out of the 92 naturally occurring elements.

Boron, carbon, silicon and germanium are all known to form covalent network solids, which I would consider to be polymers (although others certainly would be entitled to disagree). Sulfur can polymerize under high pressure, but that is it. 5 elements.

Now a new report (Open Access) has found that iodine can polymerize. Not as polyiodine, but as polyiodide (the anion). Oligomeric forms of iodide are already known. I mentioned I3- (triiodide) many times in my general chemistry class last year (it's a good one for drawing a Lewis structure) and higher iodides such as I5- and I7- are known to exist, but now comes proof of In-.

The unusual aspect of the polymer is that it doesn't exist by itself, but instead is supported by a pyrroloperylene crystal structure, with the entire iodide-pyrroloperylene complex being crystalline as well. That crystallinity is what made it possible to clearly identify the polymeric nature of the iodide. (Ferreting out the structure of an amorphous polymer is a whole new level of hurt.)

While the iodide-pyrroloperylene complex is of interest to the researchers because of its electrical conductivity, they also realize that polyiodide may finally crack a chemical mystery that is nearly 200 years old: the nature of iodine in the blue solution that form when iodine is added to starch (an elementary school favorite). Polyiodide has been suggested as a possible form, but without any proof (the iodine-starch complex is amorphous...), it was just a suggestion. This new research doesn't prove that the of iodine in a starch complex is polyiodide, but it does provide support for what could only be previously considered as just a hypothesis.

And it gives us a 6th polymeric element.

## Friday, August 19, 2016

### The plastics revolution: we already had it

A news feature article in this week's Nature entitled "The plastics revolution: how chemists are pushing polymers to new limits" is more of the same old, same old. And it doesn't help that it's from the same old researchers contributing to this nonsense.

The same old researchers being Lodge and Hillmeyer of Minnesota and the Center for Sustainable Polymers in particular, (They seem to be everywhere these days, even on the local news a few weeks back). And the same old hype is that we are about to enter a fantastic new future where bio-sourced polymers will magically appear and be so much better than the polymers we have now.

As I've discussed many times in the past, the future of polymers is already here. Polyethylene? It's currently derived from petroleum, but it is already established that it can be made from bio-based feedstocks such as corn, beets and sugar cane. Ferment the sugars to ethanol and then dehydrate it (remove H2O) and you have ethylene. That ethylene can then be a true, drop-in replacement for the petroleum-sourced ethylene to make polyethylene (PE).

This process will overwhelmingly crush any other options for making a bio-based polymer that is functionally equivalent to PE because it takes advantage of the existing capital equipment. To make the (mythical) alternative polymer, new capital investments will have to be made and there will be plenty of risks with that path.

And so it goes with the other Big 6 polymers (polypropylene, polystyrene, vinyl and polyester). Processes are being developed to create biobased versions of the petroleum-based monomers so that existing equipment can be used to polymerize them. Yet somehow researchers keep thinking that they can create some miraculous new polymer to displace them. Sure, right, good luck with that.

The plastics revolution is not in the future, it was in the past when plastics began to become an essential part of modern life. Changing to alternative feedstocks will undoubtedly create new polymers, but those polymers will only be successful when they fulfill the requirements of a new product, not the requirements of an existing product. And that is not a revolutionary thought. Not at all.

## Thursday, August 18, 2016

### Trash Talking Translational Research

A new editorial (open access and less than a page long) in ACS Chemical Neuroscience takes a few swings at all the emphasis being placed on translational research and proposes that more of it should go back into basic research, particularly in synthetic chemistry. And of course, there are testimonials from famous synthetic chemists to support this view (surprising, huh?) The editorial is being praised around the internet (Ash Jogalekar, Chemjobber and Tehshik Yoon, and I'm sure there are more to follow.)

I don't agree, or perhaps more accurately, I think that the value of translational and applied research are greatly overlooked. Not because of their focus on a defined endpoint, but because of the unpredictable results that can arise from it. In some cases, the results are basic science. Consider these examples:
• Louis Pasteur was trying to determine what caused wine to turn to vinegar, and ended up creating the field of microbiology.
• While attempting to reduce noise in a communication signal, Arno Penzias and Robert Wilson discovered the cosmic microwave background radiation, the residual heat of the Big Bang.
• Roy Plunkett was working was trying to improve the coolant gases used in refrigerators and discovered Teflon
• Viagra was originally developed to help with angina pectoris (chest pains). It didn't do so well at that, but the researchers discovered an unexpected side effect.
Research is research is research, basic, applied or translational. It can (and should) lead to unexpected results. The old clichés are "If we knew what we were doing, it wouldn't be called research" and "Chance favors the prepared mind". True clichés, but completely spot on in this case. Put them two together and good things will happen, including the discovery of fundamental science, intentional or not.

## Tuesday, August 16, 2016

### Is there a retraction ahead for the microplastics and fish larvae research?

Retraction Watch is reporting that a recent article in Science regarding microplastic pollution is undergoing a thorough re-examination. The article claims (in part) that the particles reduce hatching rates and are preferably eaten by hatchlings over their normal food.

I was immediately critical of the whole publication as were others. It'd be nice to think that my comments played a role in this investigation, but if they did, they would be just a small part of the picture. There are other fish to fry here. Eyewitnesses of the testing have reported
"...there is a significant mismatch between what is described in the paper and how the experiments were actually performed. Examples include:
• The exposure times of eggs and larvae reported in the paper are longer than the actual duration of the experiment at the Ar research station in Gotland, Sweden.
• The actual number of replicate tanks and fish is lower than what is stated in the paper.
• Aquaria maintenance and monitoring were not conducted as described in the paper"
Yikes! If verified, it looks like this paper is head for Davey Jones' Locker.

## Monday, August 15, 2016

### Behold the lowly syllabus...

One of the unexpected surprises of starting a teaching career is the syllabus. I don't remember much detail about how they were when I was in school some 30+ years ago, although I know that they would have office hours, exam dates, how grades were determined (% from quizzes, % from homework...) and that is about it. Maybe there was more, but that would have been all that I cared about - and I can't imagine it being different for other students both then and now.

Unfortunately, administrators have a different outlook. The lowly syllabus has now become a document of great significance, almost a legal document, with more and more burdens placed on it. "Course objectives" are now a major concern for accreditation and attempting to change them requires approval from above. "Competencies" must be present as well. Policy statements about academic honesty, disabilities, attendance, harassment and more are required. What should be a simple 1 - 2 page handout becomes a 10-page (or more) monstrosity. The schoolwide policies are repeated verbatim on every syllabus for every class and so I am not surprised in the least that students don't put the effort into reading it. (Or they read it and forget it.)

And it's only going to get worse - we've already been given a heads-up for changes coming next semester.

I would love to split the syllabus into two parts, but that's too large a Gordonian knot for me to slice.

## Friday, August 12, 2016

### How to NOT Write a Patent Claim for Plastic Films

One of the stranger patent claims that I have ever encountered is this one:
” 1. A multi-layer, thermoplastic stretch wrap film containing seven polymeric layers, comprising:

(a) two outer layers, at least one of which having a cling performance of at least 100 grams/inch, said outer layer being selected from the group consisting of linear low density polyethylene, very low density polyethylene, and ultra low density polyethylene resins, said resins being homopolymers, copolymers, or terpolymers, of ethylene and alpha-olefins; and

(b) five inner layers, with each layer being selected from the group consisting of linear low density polyethylene, very low density polyethylene, ultra low density polyethylene, and metallocene-catalyzed linear low density polyethylene resins; said resins are homopolymers, copolymers, or terpolymers, of ethylene and C3 to C20 alpha-olefins.”
(US 6, 265, 055)
What is so strange about it? It’s not the overall claim. What the inventors are describing at a high-level is just a 7-layer plastic film. And both paragraphs (a) and (b) are pretty clear for the most part; the end of Paragraph (b) is what is known as a Markush claim, where some key elements of the composition are described (in this case, that the resins are homo-, co- or ter-polymers) and non-key elements are left vague (the ethylenically unsaturated C2 to C20 monomers).

What is so strange about this claim is it’s inconsistent use of the words “comprising (of)” and “consisting of”. To me and most people, we wouldn’t think twice about using either phrase and would be likely even less concerned that both phrases were used in the same sentence. But to an attorney, especially a patent attorney, the usage is mindboggling.

It is well established in US patent law that when identifying a group of something (polymers in this case), “consisting of” means that the group is exactly what is listed – and nothing more. “Comprising of” means that the group is representative, but that other entities can belong to the group as well.

So know you can see why this is such a weirdly written claim. First you have the use of “comprising of” (the initial paragraph), and then you have two uses of “consisting of” (paragraphs (a) and (b)) and then you finish up with a Markush claim. The use of “comprising” and a Markush claim is expansive, and attempts to broaden the claim, while the use of “consisting of” is restrictive and narrows the claim. So we have expansive → restrictive → restrictive → expansive. (Mindboggling indeed. Particle-wave duality, you’ve met your match!)

None of this is a concern for receiving the patent in the first place, but only for attempting to enforce the patent. Unfortunately for the patent owners, that is now a reality. Another firm began making 7-layer film that is very similar to what was claimed above, so close that they ended up being sued. But were they infringing or not? Does the expansiveness of the Markush claim trump the restrictiveness of the “consisting of” phrase? What exactly does this claim cover?

A recent Federal Appeals Court decision said that the “consisting” restriction wins out over the Markush and given the facts of the case, there is no infringement. Let that be a lesson for us all. Consistently use the phrase “comprising of” in your patents.

Why the attorneys who filed this patent decided to risk anything by going with the wording “consisting of” is beyond me. I hope they have good malpractice insurance – I think they are going to need it.

## Monday, August 08, 2016

### The Fettuccine Approach to Vinyl Siding

It's an interesting question: "Stone, concrete, wood, metal and glass all have inherent qualities that can be celebrated. What inherent qualities come to mind for vinyl in any of its forms?"

This question was raised on a recent blog post by Catherine Kavanaugh last week at Plastics News. It highlights my longstanding feelings about plastic (or any other material) being used as a substitute for another material, namely that there are.
"...two diverging paths for the industry. One would be to build a system of components that are so good that they’re indiscernible from wood siding and trim at arm’s length. The other is to build a system of cladding that makes no attempt to fake wood, but rather celebrates the fact that it is vinyl."

I've always felt this way about other products, such as vegetarian food. Many omnivores (including me) look askance at something that is a vegetarian knockoff of a meat-containing dish. Yet dishes that don't contain meat and don't pretend to be meat are commonly consumed without question. Nobody complains that fettuccine Alfredo is vegetarian, and that is because it doesn't pretend to be a meat-substitute. But vegetarian hot dogs? Not a chance. The fettuccine celebrates the inherent qualities of being vegetarian while the mock hot dog only mocks it.

So what are the inherent properties of vinyl that we can celebrate? (Unfortunately, Catherine's blog has not yet had a single comment). To me, one of the key characteristics of vinyl or (any other plastic) is that it is plastic in the traditional definition, meaning moldable. Plastic can be easily formed into three dimensional shapes that wood, stone and brick can't. Take advantage of that and do so in a way that allows it to excel in any of the demands placed on siding (weatherability, water/hail/snow-repellency, insulation, visual appeal).

I don't have any specific proposals, but that would be how I would tackle the problem. Call it the fettuccine approach. The vegie dog approach has already been tried and we know the results. Not good (or we wouldn't be having this conversation).

## Friday, August 05, 2016

### An Unexpectedly Quick Ending to my Summer

It’s been a pretty crazy summer for me, and it just got shortened tremendously: I landed a fulltime teaching job at a local college. Yep, no more adjunct hell.

My wife and I just would have liked to know that this was coming, as I was in the midst of a very large project at home, painting the kitchen cabinets. While I/we did know and plan for other project this summer, neither my wife nor I had any idea that we would be painting the cabinets too. It was a terrible accident. It had all started innocently enough when we decided to replace the cooktop in the kitchen island. It was original to the house and needed to go. We also realized that it would be a good time to update the surface on the island from vinyl to a “solid surface” (i.e, a quartz/polymer composite).

We picked out the new appliance and surface and had it installed. It was then that we realized that we had a major problem. The wood cabinets, which I previously liked, suddenly looked awful. My wife had wanted to paint them for the past year and I had always disagreed, but I couldn’t any longer. They had to be painted.

The painting has turned into a nightmare however. The water-based primer we applied wasn’t blocking the tannins(?) from bleeding through and so we had to switch to an oil-based primer. I’ve very limited experience with oil-based paints, and I now realize what a blessing a good water-based paint is.

In oil-based paints, the polymer is dissolved in solvent. The solvent evaporates and the unsaturated segments of the polymer eventually oxidize and crosslink (cure), leaving a good tough coating. While both solvent (in a solvent-based primer) and water (in a water-based primer) start evaporating the moment you start painting, it seems like the oil-based paint's viscosity increases much more rapidly. This makes it difficult for the paint to level (i.e., for the brush or roller marks to disappear). You need to work quickly, get an even coating and then leave it alone. Water-based paints are entirely different. They are far more forgiving, better at leveling and can be easily touched up.

Painting the cabinets themselves is no small job. First, all the the doors and drawer faces come off. One side is primed and allowed to dry, then the other side is primed and allowed to dry. Then comes the paint, first on side, followed by drying time, then the other side is painted and allowed to dry. If needed, an additional coat of paint on one of more sides is needed to coat spots that were missed or dewetted. All this is done on some 8-feet long 2-by-4’s that are supported by sawhorses, meaning we were limited to about 8 linear feet of doors per batch, which isn’t very much. It was a long, project, but I was home most of the time so I was able to make steady progress.

So you can imagine the panic when I was offered the new position and a quick start date. Our kitchen looked like this:
and still looks like that - halfway to nowhere. Instead of being able to paint during the week, I am now only to paint on weekends, and we already had other plans too for that time slot. The slow process has gotten even slower. Maybe I’ll be done by September, just maybe.

About the new job: it’s at Dunwoody College of Technology. The position was listed for a math/chemistry instructor (you mean a chemical engineer, such as moi?). The school is expanding and starting a bachelor's of mechanical engineering program. As part of that, they need to establish a chemistry program. And that is a big part of my new position – building a chemistry program from scratch, both course and lab.

I have prior experience in building a lab from thin air, so I’m not overly concerned, but teaching fulltime will be a new experience, guaranteed to keep me plenty busy. New classes which I’ve not taught before so I’m preparing multiple lecture notes and gathering new materials. Classes don't start until the 22nd, so thankfully I have time to get even further prepared. And thank goodness I taught last year. I have a much better feel for how much I can cover in each class period and how to keep students engaged.