It's the Rheo Thing

A House Built from Plastic Bottles

2017-06-23T08:53:00.001-05:00

Plastic beverage bottles are considered by many to be a bane of modern society, but their durability and strength has an appeal that some people are able to take advantage of. In Argentina, there is a house constructed from these bottles. Not just the exterior walls

but also the bed

While this may seem like a novel idea, a little digging shows that it is not. Such houses exist around the world. Just don't expect to see one in my yard soon however. I suspect that my wife, the neighbors and the City of Woodbury would disapprove.

All of this demonstrates many of the strengths (literally) of water bottles. While most people focus exclusively on what only during its brief life in the hands of the consumer, I've mentioned before just some of the many requirements that a water bottle needs to meet, many of which the consumer is not directly aware of. Having a long life before it degrades can be good or bad, all depending on the application.

These houses are new to me, although the use of plastic water bottles in construction isn't. I wrote in the past about the use of water bottles in roofs, either as a light source or as a thatching material, all of which shows further the limitless of human creativity. I doubt that this is the last new use we will see here for such bottles.

Plastic rice and other fake foods

2017-06-19T07:47:00.000-05:00

One story that seems to never die on the internet are claims of "plastic rice" (1, 2 and 3.) I find the endless claims very strange, not only because of their endlessness, but also because the whole idea of making rice from plastic in the first place is pretty idiotic for more than one reason. As was noted in the Bangalore Mirror article,

'Rice is being sold at Rs 40-Rs 50 per kg while if at all one has to make plastic rice [sic], the cost would be somewhere around Rs 200 per kg. So, I don't think there is any logic in this.'

Further, plastic rice would be immediately obvious to the consumer with the texture being extremely different from real rice, (assuming the rice was cooked even close to properly).

What really hits me as funny is all the "testing" that the articles do to ascertain if rice is plastic or not. Burn some with a match and you can easily tell the difference.

I'm old school enough to remember kits available for purchase that relied on this technique for quick-and-easy plastic identification. While the kits no longer seem available, the information still is. And anyone who has spent much time in a plastic processing plant will rapidly be able to tell what resin is being run just from the aroma in the air.

But getting back to the costing of creating fake food, rice (and eggs) and other low cost food items are worth the bother. If your are going to create fake food, go for something expensive. Fake caviar would be a good starting point. Hydrogels are readily available. and already used in bubble tea. Add a little bit of fish flavor, salt and color - voila! cheap caviar, and most people wouldn't even know the difference - PLUS, there would be much bigger profit margins available. But alas, it's already been done.

Ok, so that idea didn't work out. How about something else, like fake cheese...

From Magma to Wildebeests to Smartphone

2017-06-16T08:29:00.001-05:00

Today's post is going to cover a wide range of topics, starting with magma rheology, and connecting to that wildebeests and smartphones. It might be too much for a Friday, so if you hold off reading this until Monday, that's just fine.

This rambling journey all started a post from Atlas Obscura (a really great site for wasting huge amounts of time on fascinating, relatively unknown items from around the world). It mentions a unique volcano in northern Tanzania, Ol Doinyo Lengai, which spews carbonatite lava instead of the usual silicate magma.

Magma is still magma - hot, molten rocks, but the lack of silica in the magma is very unusual. This is the only active volcano in the world that has carbonatite magma (more on the inactive volcanoes in a minute). Silica, as you may know, is capable of forming long chains thereby increasing the viscosity of normal magma. It also increases the temperature at which the magma needs to be heated in order to flow. Carbonatite magmas cannot form such long chains, so their magmas can be of lower temperature (500 ^oC vs. 1100 ^oC) and viscosity. (At 500 ^oC, the stuff isn't even glowing red!) And it appears to freeze pretty quickly, leading to some exotic formations:

The Atlas Obscura article is pretty short, but some more digging turned up some further fascinating connections. The Wikipedia page for the volcano states that

"The carbonatite ash spread over the surrounding grasslands leads to a uniquely succulent, enriched pasture. This makes the area a vital stage on the annual wildebeest beast migration, where it becomes the nursery for the birth of several thousand calves."

And further digging led me to this article by a Dennsion University Professor. The whole basis for some volcanoes being silicic and others being carbonic is still unresolved. Weirder yet is that Ol Doinyo Lengai used to be silicic and only recently has become carbonic. And still weirder yet is that carbonic magmas are associated with deposits of rare earths elements. The largest rare earth mine in China as well as the rare earth mine in the US are both located in carbonic deposits, and rare earths are crucial components for smartphones, supermagnets and other items of modern technology.

Prior to this, I never new that there were such variations in magma, let alone that they would have such profound impacts for those of us living on the surface of the planet.

Two Worlds Collide in 1 Photo

2017-06-15T09:08:00.002-05:00

This is one strange photo:

So many questions. So many. Staged photos (and yes, this obviously is one) will often do that, but this one seems to have gone off in a third dimension.

This was on the walls last month for a 50th class reunion so the age of image, the clothing and other fashion items are not what's strange. Nor is the lack of PPE, giving the time the original photo was taken. The biggest question to me is why is the instructor holding a condenser(?) with the tip just few inches away from the throat of the student? It's looks like the poor lad is being force to read a signed confession or otherwise threatened. The round-bottom flask in apparent isolation is also odd.

The writing on the chalkboard is equally strange. Not the the left side, where you have the conversion between Fahrenheit and Celsius - that's fine. Rather it's the (repeated) equation in the middle that is the head scratcher. It's a formula for cutting speed and it's used with machining equipment.

Two worlds colliding - machinists and chemists. I strongly suspect that at the very least, the instructor had no chemistry experience. The same would be true of the photographer. And certainly no one thought that the photo would be preserved for 50 years. I haven't been able to find any further details; it's just an old photo kicking around that was made into a poster. Keep that in mind next time you take a photo. It may end up being a poster somewhere where you least expect it and no backstory to explain it. Rather frightening, huh?

Catching up with the Activist Investors at Dow and Dupont

2017-06-13T07:12:00.003-05:00

It's been quite a while since I wrote about the activist investors at Dow and Dupont, Daniel Loeb and Nelson Peltz, respectively. I figured the merger of the two companies would be the end of it, particularly since the merger would be immediately followed by splitting the company into three parts in order to satisfy regulatory bodies. And that splitting was what both activists desired when they initially took up their positions (that plus a seat on the company's respective boards). But as the merger has dragged on (it was first proposed in December of 2015(!) and still isn't done), it's time to update what Loeb and Peltz are up to.

Peltz first. His position is easy to describe. He's sold off most of it so that he can be now bug Proctor & Gamble, GE, Sysco and Mondelez. That's truly shocking. As one writer stated,

"[c]orporate executives might want to think twice before relying on hedge fund matchmakers. It appears they are not even patient enough to stick around for the wedding."

Loeb on the other hand, seems to be getting rather impatient and the longer he waits, the bigger of a slice of wedding cake he expects. He is asking why cut the cake into 3 slices when you can cut it into 6 slices, and we all know 6 is bigger than 3, right? (Just like an amp that goes to 11 is better than one that goes to just 10.) And in making the additional slices, everyone gets an extra $20 billion dollars.

If that math doesn't make sense to you, well, I've noted in the past that Loeb has the math skills of a high school student (1 and 2), and a lousy student at that. Having lots of money and wealthy friends doesn't make you intelligent, but it will get you access to a microphone, strangely. If Loeb really believes that the combined value of the new company cut 3 ways is worth an extra $20 billion, then the market will quickly realize its mistake and value the companies appropriately with a larger stock price. And if that still isn't fast enough, then I suggest that Loeb get some of his rich friends together to buy the undervalued companies and split them yourselves. It's an old idea, but I believe it's called "putting your money where your mouth is".

Plastic Bottles and Terror Attacks

2017-06-12T11:57:00.002-05:00

The Metropolitan Police released photos yesterday of some of additional "tools" used in the recent terror attacks on London Bridge. Surprisingly, they included plastic water bottles.

The bottles had been covered with duct tape to create an element of mystery or the unknown and were attached to a belt worn by the attackers. They weren't filled with anything, but I have to admit if I saw a group of knife-yielding attackers wearing such equipment (assuming I could completely overlook the knives), they would look real enough for me.

I'm assuming the bottles looked in better shape prior to the attack, and upon closer examination in an environment in which no one's safety is a concern, the lack of visible wires makes the devices look suspiciously fake. Even after the attackers were "neutralized", the bottles would still need to be considered a serious bomb threat until decided otherwise which leads to more concerns for authorities even after an event looks to be over. I don't know if this is the first time "duct-taped-water-bottles-as-real-looking explosive devices has been used, but I would expect to see more of them in future attacks around the world (a statement that saddens me to write).

All of this really emphasizes that "the belts made the bravery of those who took on the attackers even more remarkable".

Big Bread Clip

2017-06-08T09:37:00.000-05:00

I've never given much thought to bread clips, those small plastic devices used to seal bread bags. I admit that I've never been overly impressed with them, preferring to twist the end of the bag tightly and then tuck it under the loaf. But I was somewhat surprised that there is a bread clip monopoly. Yep, Big Bread Clip exists and it affects us all. Its existence is not because of a strong patent position (the original patent having expired decades ago), but instead because the company making them, Kwik-Lok, is able to sell them at a price high enough to be nicely, but not excessively profitable. If Kwik-Lok were to suddenly try and gouge the customers, competition would soon follow.

Polystyrene (PS) appears to be the resin of choice, and that seems to be reasonable given the brittleness of them. Cheaper raw materials exist (any of the olefins for instance), but the cycle time for molding with PS makes it a winner. PS becomes almost watery when heated, so you can pump it into the molds very quickly and with little pressure, and when you have a bazillion clips to make every year, speed is essential.

Kwik-Lok is headquartered in the small town of Yakima, Washington. If you had nefarious intent and wanted to cause worldwide panic amongst consumers fearing that they could be facing a long-term future of stale bread, take out Yakima, Washington. And there's one man that is up to the task:

Let's hope that the government has recognized the strategic importance of this area and is taking appropriate measures to protect it.

A Bag Ban gets Banned

2017-06-07T08:38:00.000-05:00

The City of Minneapolis passed a plastic bag ban last year that was supposed to kick in on June 1, but that never happened. The Minnesota legislature got involved and passed a state-wide ban on bag bans. This article has over 230 comments as of this morning, most of which are the predictable back-and-forth that we expect from the grand-and-glorious internet, but I'm going to comment on them rather than rehashing the pros and cons of a bag ban (and bag-ban bans!).

Consider this from marpie:

"It appears a lot of people making comments don't care about the incredible amount of time it takes for plastic to break down in our landfills. I didn't realize that we will never run out of space for our garbage.

While this may be true in a general sense, it is not true here. In Minneapolis, the garbage from the city (and greater Hennepin County) is taken to the incinerator downtown and burned (the thermal output being used to generate electricity). This incinerator is common knowledge (backing up against Target Field), widely discussed and was even mentioned in the article. For marpie and others to make comments about the horrors of landfilling plastic bags shows a profound ignorance about the local environment. And it's not just Minneapolis. The trash generated in St. Paul and its surrounding suburbs is also incinerated at a similar facility outside of St. Paul.

But just as importantly is what is not discussed in the comments: having the city accept plastic bags as part of their recycling collections. It's done in Washington County where I live. You take all the plastic bags and dry-cleaning films and such, put them into another plastic bag, tie it up and drop it into the (unsorted) recycling bin with the cans, bottles, paper and plastic containers. Creating the "bag-of-bags" makes it easy to separate it from the rest of the recyclables. Loose plastics bags would be a nightmare on general recycling equipment. Their high molecular weight makes them plenty strong (try stretching one with your bare hands) and the large surface area practically ensures that they will wrap themselves around moving mechanical parts, bringing the machinary to a halt. But that same high molecular weight makes them plenty appealing as a feedstock, so having a easy way to separate out bags and films is a real benefit and something that Minneapolis, St. Paul and other cities need to adopt.

But it is kinda amazing how us suburbanite eco-terrorists are able to take the lead on this issue, huh?

Will the Patient Survive?

2017-06-05T14:05:00.001-05:00

NURSE: Doctor! The blog! It's been in a coma for nearly 9 months, but it's starting to come to. What should we do?
DOCTOR: Nurse, give it 50 cc's of Ringer's lactate. STAT!
NURSE (looking incredulously): Uhhhh....why? The blog's electrolyte's are just fine.
DOCTOR (irate): Because that's what they always did on "Emergency". Besides, it's just a crummy little polymer blog with no health insurance filled with alternative facts. Nobody will miss it except his mom. (Hi Mrs. Spevacek!) It's not an important one like Derek Lowe's or Chemjobber's. Let it go. If it pulls through, fine, but I'm not spending anymore time on it.
NURSE: You never did in the first place. But I'll show you. I'll care for it and give it love and be the second person reading it on a regular basis besides his mom (Hello again, Mrs. Spevacek). And then someday when it is big and famous, I hope it denies you the plastic for the plastic surgery that you so desperately need for that big ugly nose of yours - the one that you can never find because it is always lodged up the Chief of Medicine's ...{/censored}...

Curses! Environmental Stress Cracking

2016-09-06T08:10:00.001-05:00

We've had a lot of aphids attacking plants in our garden this year. My usual approach is to use an insecticidal soap that I make by diluting down from a concentrate. "Normal" soap is the sodium salt of a fatty acid, while an insecticidal soap is just the potassium salt, which means the soap is relatively safe. It also works pretty well against the critters, and clean-up is easy. But they have gotten so out of hand that instead of making it up as needed, I made up a larger amount in a spray bottle and kept it in a cabinet.

Over the weekend, I knocked the bottle to the garage floor. No biggie; I picked it up and put it back in its place. But yesterday, I noticed that the soap had leaked out of the container. I picked up the bottle and saw this:

What an idiot I was. It was a polyethylene bottle with dilute soap in it and it had been stressed by the fall to the cement - a situation just begging for environmental stress cracking and that was what I got.

Environmental stress cracking (ESC) is where polyethylene and other plastics, when exposed to non-solvents and stress, break down unexpectedly. Soap and polyethylene. How can there by any interactions, especially at room temperature, especially when PE can withstand strong acids and bases, concentrated soaps and surfactants, bleach, hydrogen peroxide and more? And if you think you have an idea, then be prepared to explain why polypropylene doesn't experience ESC.

As you can imagine, I'll be on the lookout for a PP-based spray bottle for next year.

Previous Years

September 6, 2013 - A response to the ChemBark post (partially) about me

September 6, 2012 - Somewhere in a movie balcony...

September 6, 2011 - Polymorph Determination through Nanoindentation

September 6, 2007 - A resurgence of French?

A cool new fabric

2016-09-02T11:21:00.000-05:00

The tale of The Emperor's New Clothes is as much about marketing hype as it is about keeping up pretenses in a social setting. The hype over "smart clothing" is just that, but a new report (open access!) from Stanford researchers about a radiative-transparent fabric appears to offer some real potential in comfortable clothing.

As humans, we feel either warm, cold or just-right depending on the heat balance that our bodies keep with the environment. Conduction, convection and radiation all play a part, with radiation dominating at over 50% according to the researchers [*]. The radiation is in the mid-IR with a peak at 9.5 μm. Unfortunately, most of the fabrics that we wear absorb rather strongly in that region, preventing that heat loss. As a result, we feel hot and need to kick down the A/C a few degrees to compensate. Polyethylene (PE) does not absorb in that region however, and so the researchers used it as the basis for a fabric that is transparent in the mid-IR.

The researchers found that a nano-porous polyethylene (normally used in the construction of lithium ion batteries) was opaque in the visible range due to the pores scattering visible light, but still transparent in the mid-IR. The PE fabric by itself was rather weak, so they ended up creating a laminate with a coarse cotton mesh to provide a stronger fabric. Tensile testing showed the laminate to be rather brittle (only about 15% elongation before break, vs. 70% for cotton), but that can be easily addressed in the future with other constructions.

Two comments: First, the use of polyethylene as an IR-transparent clothing choice is not a new idea. It was proposed (and modeled as effective) over a year ago (and earlier research may well exist too). Second, the biggest challenge I foresee is coloring the fabric. Pigments are an option for monotonic colors (no, black is not an option since it will absorb the mid-IR), but for people that want flashy prints, it could be a real challenge.

Nonetheless, it will be interesting to see what happens to this concept. PE is plenty cheap, and so a fabric based on this could be quite affordable and all that much more valuable to people in hot areas where cooling cost can be budget busters. And the use of it in athletic wear, especially for endurance events, could prove significant as well.

[*] The researchers cite articles from 1937 and 1939 (!) for this datum. (References 18 and 19). Maybe someone should look into updating it, as I wonder how valid it truly is.

Previous Years

September 2, 2010 - How To Have A Brainstorming Session

You can't get there from here

2016-09-01T11:06:00.001-05:00

Being on a new campus this fall means getting lost. Finding the right building is the easy part. Finding a staircase in the building is also fairly simple. But the real challenge is deciding if it is the correct staircase.

The building that I my office is in and that I teach in is over 100 years old and was concocted in bits and pieces over time. And the result that the floor plans are pretty complicated. There are floors between floors. There are floors made of unconnected sections where you need to go to a different floor to get to the other section. Worse yet, not all staircases access all floors. It's so bad they long ago gave up on numbering the floors and named them by colors instead. And of course, the colors are NOT arranged according to the rainbow. (I think the order from bottom to top is green, yellow, black, silver, blue, red, yellow and brown, but I may be mistaken.)

But all that pales compared to this:

Two sets of stairs in a double helix arrangement! We're probably all use to that with escalators, but stairs? Worse, the two sets of stairs don't stop at all the floors, so you will often see students hop the handrails when they realize that the stairs they are in won't got to the floor they want, but that the other one will.

As for me, I know how to get from my office to my classrooms and back. I'll explore more in the future when I have a lunch packed, a huge bag of bread crumbs and plenty of energy.

Previous Years

September 1, 2011 - My Version of the Triple Witching Hour

September 1, 2010 - A New Basis for Measuring the Significance of Research

Slide Rule Giggles

2016-08-30T08:02:00.000-05:00

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.

Previous Years

August 30, 2013 - The Week that Snowballed Away from Me

August 30, 2012 - Viscoelasticity: It's Not Just for Polymers Anymore

Theology, Rheology and some freaky strange search results

2016-08-24T11:21:00.002-05:00

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.

Previous Years

August 24, 2011 - Review: "Social Marketing to the Business Customer"

August 24, 2010 - The Deborah and Weissenberg Numbers

August 24, 2009 - BASF as a hostile takeover target?

Polyiodide

2016-08-23T09:06:00.001-05:00

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 I_n^-.

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.

Previous Years

August 23, 2013 - Analysis of Silly Putty Swallowing a Magnet

August 23, 2011 - Plastics are Forever Jewelry

August 23, 2011 - How the Indian Supreme Court Indirectly Impacted PET Film Makers

The plastics revolution: we already had it

2016-08-19T08:19:00.000-05:00

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.

Previous Years

August 19, 2014 - The Death Ray returns to my backyard

August 19, 2013 - Defects in Crystalline Polymers - Part 1

August 19, 2010 - Updating Your Resume

August 19, 2009 - What I did for my summer vacation

Trash Talking Translational Research

2016-08-18T09:14:00.002-05:00

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.

Previous Years

August 18, 2014 - 9 Activities that BOTH Academic Researchers and Industrial Researchers Perform

August 18, 2011 - Names for Biobased Polymers

August 18, 2010

August 18, 2010 - The Wall Street Journal and "Glass Transition"

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

2016-08-16T10:25:00.001-05:00

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.

Previous Years

August 18, 2013 - If the Ocean Could Hire an Ad Agency...

August 18, 2012 - The Omics of Polymers

August 18, 2011 - The Ultimate Time Drain

August 18, 2010 - On the Loss of the Usenet

August 18, 2010 - Just Wondering

Behold the lowly syllabus...

2016-08-15T09:41:00.000-05:00

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.

Previous Years

August 15, 2013 - Another Monomer I Won't Work With

August 15, 2012 - Helmet Gels to Reduce Head Injuries in Sports

August 15, 2011 - An Issue on Nomenclature

How to NOT Write a Patent Claim for Plastic Films

2016-08-12T09:20:00.001-05:00

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.

Previous Years

August 12, 2013 - Combating Molecular Weight Reduction from Shear Forces

August 12, 2011 - Swirling Wine Clockwise and Counterclockwise

August 12, 2011 - Polymer Drone

August 12, 2010 - Pity the Resin Purchasing Manger

August 12, 2010 - Quick Thoughts

The Fettuccine Approach to Vinyl Siding

2016-08-08T08:49:00.000-05:00

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).

Previous Years

August 8, 2013 - Oh, We Tried That and It Didn't Work

August 8, 2012 - Swimming and Viscosity

August 8, 2011 - What's in a Name? What's in a Number?

August 8, 2008 - Accelerated Aging - Getting Bad Data Even Faster - 2nd in a Series

An Unexpectedly Quick Ending to my Summer

2016-08-05T09:52:00.003-05:00

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.

Previous Years

August 5, 2013 - Another Week, Another Attack on BPA

When Packaging Peanuts are Outlawed, only Outlaws will have Packaging Peanuts

2016-07-05T10:30:00.000-05:00

There a plethora of stories over the long weekend around a common theme of ocean plastic, so I'll just offer a few quick comments on them.

Oahu, Hawaii banned plastics bags a year ago, but surprisingly (?) the ban isn't working. The ban apparently covered thin plastic bags, and according to one advocate, "There's thick plastic bags because the stores replaced the thinner plastic with thicker ones. So we are seeing those on the ground. There are all of the food bags because those were never banned so there's really little to no change..." The ban specifically calls bags thicker than 2.25 mils (1 mil = 1/1000 of an inch = 25.4 μ) as reusable, so that appears to be the route that retailers are taking. With resin prices being so low, this option looks a lot more affordable than it did a few years ago.
California passed a referendum a last year to charge 10-cents for plastic bags, but that referendum will be revoted on this fall, kinda like a Brexit revote, I guess. But unlike a Brexit revote, there will also be a second related question: what is to be done with the 10-cent fee. Currently the retailers get to keep it (seriously?), but a group led by bag manufacturers wants the dime to support various environmental groups. I'm not sure how the exact question is worded, but I suspect that it might be done in such a manner as to confuse the issue.
San Francisco is stepping up their efforts to ban more styrofoam, only they don't include Styrofoam. That's probably a little confusing, but the confusion is from the fact that Styrofoam is a trademark owned by Dow for their brand of expanded polystyrene that is used to make rigid insulating foam - and only rigid insulating foam. (That's right, there is no such thing as a styrofoam coffee cup, or styrofoam food packaging or styrofoam egg containers or anything else.) Since Styrofoam is considered a durable object so everyone seems fine with it. However, the expanded ban does include peanuts, coolers, beach toys and more (see page 11+). I think the wording of the ban however, is going to be problematic. Look at Section 1605(c):
"No person may sell, offer for sale, or otherwise Distribute within the City any Packing Materials made, in whole or in part, from Polystyrene Foam, as prohibited in subsection (a)..."emphasis added
So does that mean that a shipping goods company that sells packing peanuts will now have to block access to their website to people from San Francisco? Will people be arrested for viewing such items? I think the definition of criminal solicitation just got a whole lot broader.
Lastly, greenwashing efforts to take advantage of ocean plastic are ongoing, with Adidas being the latest proponent. Using Parley Ocean Plastic (you know, the kind easily recovered from beaches rather than the much bigger and more challenging plastic thousands of miles offshore) and deep-sea gill nets, they have made 50 pairs of shoes, not as a kickoff effort, but as the entire product run. 50! Wow, that really reduces the amount of plastic in the ocean, and look at how much free publicity they get for it! Greenwashing, greenwashing, greenwashing.

Previous Years

July 5, 2011 - How to Torture a Chemist

July 5, 2011 - Bicycle Racing is a Team Sport...

A Plastic Object without any Temporal or Geographic Information

2016-06-29T10:37:00.002-05:00

If you are not already familiar with the writings of Ethan Zuckerman, let me introduce you. He is a director in MIT's Media Lab and has a wonderful blog, My Heart's in Accra. He doesn't write often, but when he does, it can introduce quite an expansion into your thinking. My favorite post of his, Desperately Seeking Serendipity was how I was first introduced to his work.

I wish I had found his blog earlier since just a month before that post, he had written about white Monobloc chairs. And as expected, he had an unusual take on them:

"Fifteen years ago, one of my jobs at Tripod was managing our abuse and legal teams. With several million webpages hosted on our service, some of them violated our terms of service and hosted pornography. That wasn’t a bit problem – we deleted pages that violated our TOS. But when we encountered pages that might be hosting child pornography, we had a more complicated procedure. We copied files to floppy disk (remember, it was 1996!) and mailed them to our regional FBI office, along with information on the IP address the user in question had signed up from.

One of the best guys on my team went to Boston for a week to train to become a “confidential informant”, so he could testify if we’d found evidence in a child pornography case that went to court. Curious guy that he was, he asked whether the information we were providing – the IP address signed up from – was helpful in building cases. Sure, he was told, but not as useful as the information in the photos. Almost every detail in a photo held information about the time and location the photo was taken. The shape of electrical outlets, labels on any consumer products, fabrics, clothing all were clues as to whether a photo was taken in the 1970s or last week, in Sweden or Schenectady.

Virtually every object suggests a time and place. The Monobloc is one of the few objects I can think of that is free of any specific context. Seeing a white plastic chair in a photograph offers you no clues about where or when you are. I have a hard time thinking of other objects that are equally independent of context. Asking friends to propose a similar object, most people suggest a Coke can… but I can tell you that Coke is presented very differently in different countries, in glass bottles as well as cans, with labels in local languages. The Monobloc offers no linguistic cues, no obvious signs that it’s been localized. Wherever you are, it’s at home."

An object so common that its presence tells you nothing.

If another such object exists, it would have to have the following characteristics:

A simple, fundamental design
Easy and cheap to make
Sold and used around the world
Made by multiple companies

To the average person (including me), an AK-47 would be potentially such an object. It meets the first 3 requirements above, but it is only produced (so far as I know) by one company. That means that there likely have been small design changes over the years that can provide some clues to time. So I've struck out. Anyone else want to suggest something?

Previous Years

June 29, 2016 - Resonance in Plastics and Metals

June 29, 2011 - BPA Followup (2/2)

June 29, 2010 - Tapes in Space

June 29, 2010 - Pretzel Logic from the Supreme Court

The mechanical properties of polymers arise from more than just entanglements

2016-06-28T10:05:00.001-05:00

I ran across a PR blurb from Stanford yesterday entitled How do you design a better polymer?" and am not sure whether to laugh or cry. Start with this highlight:

"The polymer research process has always followed a similar pattern. Researchers would synthesize a new polymer in the lab and send it off for testing to determine its physical properties – melt temperature, elasticity, tensile strength and so forth. Only then would its creators look for suitable commercial applications."

Sorry, but most polymers are designed with specific applications already in mind. What the researchers envision here occurs very infrequently.

But it get's worse:

" 'All polymers get their mechanical properties not from chemistry, but from the way that the individual molecules are entangled together,' says [Jian] Qin..."

Wow that is riddled with errors, and being a direct quote, we know that it wasn't some PR hack that is just trying to meet a deadline - it's from a professor that should know better.

"All polymers..."? How about just glassy ones, or maybe better yet, non-crystalline ones. Crystalline polymers derive much of their strength from being crystalline, which is why the Nobel Prizing winning research of Ziegler and Natta for polymer catalysis was so important. Prior to that, making crystalline polypropylene was extremely difficult. Amorphous polypropylene is a very weak, slightly tacky material. Crystalline polypropylene is a good strong plastic. The difference is from the crystallinity, not "...from the way that the individual molecules are entangled together..."
"...not from chemistry..." You can't just throw out inter- and intra-molecular interactions just because polymers get entangled. If that were true, we would be able to blend any polymer with any other polymer. But we can't. Compatible polymer blends are the exception and not the rule. Why? Because of chemistry. If the right van der Waals interactions, hydrogen bonds and other intermolecular forces aren't there, you don't get a blend, exactly the same as with non-polymeric materials. All of this then means that mechanical properties can and do arise from chemistry.

To be clear, entanglements are an important contributor to the mechanical properties of a polymer. But are the only contributor? Not by a long shot.

One more quote before I stop torturing you:

"The sort of knowledge that Qin is imparting to the field is also profoundly important to the multibillion-dollar plastics industry, among others. The manufacture of many well-known products that make up our lives, like a polyethylene water bottle, for instance, requires a complex balance of interrelated molecular stresses and fluid dynamics. This is no easy feat. The maker must create a precise blend of molecules to ensure a uniform and properly formed finished product."

Polyethylene is largely bought and sold on the basis of the melt flow, a single value that kinda resembles a viscosity measurement, but not really. The test is only performed at a single condition. Polymers are non-Newtonian and have viscosities that change in a non-linearly as the test conditions change, so for any melt flow value, there are dozens of different "blends" of molecules that can have the same melt flow index. "Precise blends"? Hahahahahaha.

The point of the blurb is to highlight the new professor's research in computer modeling of polymers.

May I kindly suggest getting some practical, hands-on experience first?