Lamentations on Chemistry

One of the great websites out there is JibJab. Their animation is hysterical.  The have a video of Lewis Black from the 2006 show on Comedy Central recently.  This guy is great.

One of the really cool things about living near Boulder, Colorado, is all of the science that happens there.  Boulder is a COLLEGE TOWN.  I put this in capital letters because the effect of the campus on the area has been substantial; in fact it has in many ways defined the area. The campus and the “Boulder Lifestyle” along the Front Range has attracted many institutions and companies to the Boulder area. Boulder is sort of the Berkeley of Colorado.

Boulder was hit hard by the hippy movement in the 1960’s and has never fully recovered. Today you can still spot old hippies wearing tie-dye and grey pony tails, gimping out of their BMW’s and into their expensive condo’s.  I’ll never forget when the Danskin craze hit Boulder in the late 1970’s.  My god …. I was nearly blinded.

Boulder has a NIST (National Institue of Standards and Technology) facility, formerly the National Bureau of Standards, which broadcasts time signals from the atomic clock on radio station WWV.

Within spitting distance of NIST is NCAR- National Center for Atmospheric Research. A small bit of the Woody Allen movie “Sleeper” was filmed on the Mesa Laboratory site.  In addition to watching the earth’s atmosphere, they also monitor the sun.

NOAA also has a facility in Boulder.  I’m not sure exactly what the mission of NOAA is relative to NCAR, but I do know that they are concerned with the interaction of the oceans with the climate.

The University of Colorado at Boulder hosts JILA, the Joint Institute for Laboratory Astrophysics, as well as LASP, the Laboratory for Atmospheric and Space Physics.  The upshot is that a lot of folks go to CU Boulder to study space science. I went to a few colloquia where Carl Sagan gave talks about various space probes. It was sublime.

Well, I really didn’t mean to write a valentine to Boulder, but there is a lot of cool stuff happening there.  Anyway, I recall as a part time student at CU in the late 1970’s going into some departmental office in Duane Physics and plopping down at a table to look at print copies of the Palomar Sky Survey.

These prints were negative prints of the sky, where the stars and galaxies were black against a white background. And what an amazing thing they record!  My gawd.  Galaxies and clusters of galaxies of all descriptions. Spirals and barred spirals and irregulars. These weren’t just “things”, they were “places”!  When you take the time to examine a deep sky survey, the thing that hits you is the large number of galaxies that are out there.  In fact, it is mind boggling.

It is impossible to view these images and not give it some metaphysical processing.  The notion that this big universe was fabricated by some cranky, jealous diety to host a nudist garden of eden on planet earth so that a pair of hairless bipeds can spend their time heaping praise upon him is simply what it appears to be. It is just absurd.  

The biblical story of creation is what you might expect from a people whose known universe was geographically limited to a circle of a few hundred miles radius.  The human brain is well adapted to note contrasts and dichotomy.  Light and dark. Warm and cold. Pain and pleasure. Left and right. North and south. Up and down.  We are enchanted by extrema and boundary conditions.  It seems to me that the archetypes of good and evil are a default dichotomy that human consciousness (or neurology)  spontaneously organizes when looking at the external world. 

The conclusion that the world must have been “created” is the result of a self imposed limitation in scope. The notion of cosmic creation by an anthropomorphic diety as opposed to an evolutionary process of nature is what you might expect of a culture that does not embrace the process of rational analysis and falsifiable conclusions.  Religion relies on the sacred, which is to say claims that are transcendent and beyond worldly analysis.  Religion has already made it’s conclusions and religious scholarship seems to consist of justifications of the conclusions.

Science is built on clay feet. A new tide of data arrives and the foundations are washed away to allow for new structures of understanding. Part of the great intellectual adventure of life is to decide where you stand. On the ready-made pillar of religion or barefoot on the beach of science.

Note: This is a distillation of my thoughts on religious matters. I’m sure that not a single concept or even blank space between the words above is an original thought, given the long and tired history of the topic.

According to BASF Catalysts, Ruthenium closed the year at US$600 per troy oz. Corroborating this information is Johnson Matthey’s “Platinum Today“.  At the beginning of 2006, Ru was at ~$80 per troy oz. In March it jumped to ca $160 and stayed at or below $180 until the beginning of October, whereupon it launched into a hockey stick curve climbing steeply by the end of October until the present closing at $600. 

Nothing climbs indefinitely and certainly ruthenium won’t either. Whereas precious metals like Au, Ag, and Pt are subject to jewelry demand pressures in addition to industrial demand pressures, near as I can tell, Ru price pressures are limited to industial demand. That is, until De Beers decides to offer diamonds set in ruthenium pendants …

There is an interesting clue from the Lipmann Walton Ltd web site.  According to this site, a new generation of high power jet engines are being developed that have components that will incorporate 2-3 % Ru in some unspecified engine component alloy. These jet engines are for use in the new class of superjumbo meat wagons jets carrying 500 to 700 passengers.

Given that the world supply of Ru is only 13 to 15 metric tons according to Lipman Walton, and much of that is already influenced heavily by chloralkali electrode applications, there may be some enthusiastic speculation in anticipation of a big uptick in consumption. Hard to say- this is barely better than guesswork. Precious metal economics are deeply marbled with veins of intrigue and subterfuge.

When you squint into the jewel encrusted window of fabulous industry, you might naively conclude that the only truly powerful people in business are the show horses- the CEO’s, Presidents, and VP’s.  To be sure, these annointed ones do wield considerable power. They strut around like roosters, crowing the latest buzzwords with their Wharton MBA’s on their sleeves like the gold stripes on a Boeing 777 captain. They are, after all, ”upper management”.  

You see, power in industry is the ability to allocate resources, that is, throw money at projects run by your stable of lackeys and courtiers.  However, there is a class of functionaries that you might mistakenly dismiss as mere scribblers or spreadsheet monkeys.  They quietly control a force so unspeakably powerful that they can make or break businesses, careers, or at least cause an unsightly crease in your trousers.  These dark lords of business are the keepers of the mighty industrial purse. The cashiers dispensing the elusive coin.

No, I do not mean those bovines of the cube farm, the accountants. I refer to (with utmost respect since one may be watching) Purchasing Managers. Purchasing managers, or supply chain managers, are the kingpins that award business contracts to that unworthy class of rabble called the ”Vendor”. And what a loathsome bunch we are, always gnawing and clamoring nervously on our haunches across the moat for more scraps of fat. 

Just getting in to see a purchasing manager can be tricky. Forget about just popping in. Most businesses that buy specialty fine chemicals also have the réceptionniste sauvage who has -78 C acetone for blood.  Their role in life is to filter out the sales flotsam who may happen by.

You walk up to the reception desk in your dark suit with white shirt and blue and red tie and ask to see Mr. Smith.  In the world of sales men, fragrances are strictly for dandies from the European continent. Leave your airport duty-free store cologne in your suitcase where it belongs. 

The receptionist signs you in and phones the contact.  You stand there in waiting while Mr. Smith walks across the “campus” to meet you. He arrives and there is the exchange of pleasantries as security cards slap against sensors and you walk into a cubicle galleria. 

Mr. Smith leads you to a small sterile conference room with OfficeMax chairs where the clenched buttocks of countless other sales reps have plopped down before.  Bored looking people file in and business cards are exchanged with faint interest.  The door closes followed by what might be the faint slapping sound of sphincters slamming shut. The curtains open and you’re on center stage. It’s show time.

I recently picked up a book called “Excel for Chemists” by E. Joseph Billo.  The book is written for simpletons like myself who use MS Excel but, for one reason or another, haven’t invested the time to become “Power Users”. The book has a chapter on the deconvolution of data.  For those who may not know what this is, it is a technique of extracting individual signals from coincident signals that are overlapped and therefore summed in the detected signal. 

Thinking about this concept of apparent signals as actually consisting of summed components got me to consider how the concept shows up in nonscientific aspects of our lives as well.  In particular, the controversial matters of the evolution of life and the definition of marriage come to mind as separate examples of convoluted “signals”.

One of the more strident voices out there on the topic of marriage is Rep. (R-CO) Marilyn Musgrave.  Musgrave is doggedly pursuing a Marriage Amendment for the US Constitution.  She and her party are concerned that the granting of marriage rights to same sex partners somehow threatens the sanctity and stability of marriage. This issue of same sex marriage is a sure-fire initiator of moral outrage and blowtorch sermonizing by the evangelical Visigoths of the airwaves.

I have heard no public discourse taking into account the fact that in the US, marriage is typically sanctioned under two spheres of influence. Parenthetically, it is along the lines of what Stephen Jay Gould has called “non-overlapping magisteria“. 

(Note: try to ignore for a moment the fact that divorce is the biggest threat to marriage and instead focus on what marriage actually is so we can move forward with this argument.)

Here is the deconvolution part. There are really two domains of marriage- 1) Marriage under the state, and 2) Marriage under the church.  In domain 1) , the state has a compelling interest in regulating marriage in part because it will likely be called on to intervene in the dissolution of the marriage agreement.  The interest of the state is in the disposition of minor children, property, debt, and other aspects of settlement. It is called divorce. Marriage is a type of partnership that almost always entangles others in a community, so the state has imposed its presence in the matter.

In domain 2), the realm of the supernatural interface, women and men are married by exchanging vows in the presence of the community and in plain view of the diety. In the end, as the doctrine goes, persons are accountable only to their creator in regard to their marital conduct on earth. Rules of conduct have been rendered liturgical and passed down through this formalism we call religion.  The dominant religion in the US is obviously Christianity and it is widely interpreted that marriage specifies the union of a woman and a man to be united in a bonding under the all-seeing, unblinking eye of the creator. 

The taxonomy that has shaken out over the millenia is that the term “marriage” has been widely accepted to mean the union of male & female. It conveniently aligns with the biological imperative for reproduction.  Centuries of precedent have made a strong case for a fixed definition of “marriage”.

However, in modern times there is growing interest in sanctioned same-sex pairings. Proponents argue that same sex partners should be accorded the same rights that are taken for granted with partners in conventional marriage. The more politically astute have advanced the term”civil union” and have argued that the state should construct a statutory or constitutional safe harbor. 

In the domain of the state, marriage is a type of partnership not unlike business partnerships.  A civil union can be thought of as a type of partnership, but with spousal rights that might be a bit more far reaching than that found in business.

Use of the term “marriage” when applied to same sex pairing will drive some religious citizens barking mad. Conversely, use of the term “civil union” is cynically dismissed as a transparent ruse to demolish the meaning of marriage by application of a sly semantic subterfuge.

By deconvoluting the problem, we’re left with two domains that historically have input on the issue of same-sex marriage- The state and the church. The states authority is backed by the courts and the penal code for enforcement and punishment.  The church can offer excommunication or other forms of dis-affiliation as earthly punishment and threats of punishment by searing hellfire in the afterlife.  

Conclusion.  At the very best, this is an issue that affects only a small fraction of the population of citizens. I have seen nothing that serves as a tangible threat to married citizens.  While I think that reserving the term “marriage” for opposite sex parings is justified on the basis of precedent, I do think it is reasonable to codify similar rights and priviledges into an analogous partnership between same sex partners. It would be interesting to see if the Equal Protection clause applies. 

Note: This essay is a work in progress. Like a block of marble where the figure is inside waiting to be found by the artist, the rhetorical form of the point I’m trying to make is still partially buried in the marble. It takes me a while to get it out sometimes.  -Th’ Gaussling

For many of us, there have been a few characters in our past who have have made a deep and lasting impact. For me as a chemist, I have to report that one of those people was a physicist at a school I only went to part time.

Many years ago I was lucky to have taken a class at CU Boulder by Professor Albert A. Bartlett, or “A-squared” as he was affectionately known by a few. I recall that in true Boulder fashion, he was fond of wearing flannel shirts with a Bolo tie and heavy boots.  It was an elective class in the Physics & Society vein. Professor Bartlett was (and is) skilled in the art of back-of-the-envelope calculations to help people think about problems, even when you are lacking exact numbers- what science folk call “order of magnitude” estimates. He was good at looking at a problem, estimating key quantities, and sketching approximate trends and consequences.  This is a mark of a skilled scientist- peeling away the unnecessary details and deriving estimates from core phenomena or just F=ma.  

Professor Bartlett had written a paper called “The Forgotten Fundamentals of the Energy Crsis“.  Recently I happened to find it on the web while following another vein.  

Bartlett was fond of saying that one of our biggest downfalls as a society was the failure to appreciate the exponential function.  He reminded people that Malthus had already shown that the use of arithmetic was crucial to the understanding of population growth and by extension, the consumption of natural resources. 

To scientists, this is quite obvious.  But his audience was the general public. During his talks he would give the audience a small take-home gift. The ability to calculate doubling times by the “rule of 70″ as some call it. By simply dividing the number 70 (approximately 100 x ln2) by a constant growth rate, say 5 % population growth in a municipality, you would easily compute a doubling time of 70/5=14 years to double the population.

This handly little calculation helps one think critically about the consequences of growth when you hear a town council member state that some particular growth rate is desirable. In the above example, a 5 % annual growth rate will require the doubling of many city services in 14 years- a fact that often goes unnoticed by the council and public.

Professor Bartlett is a true crusader in the campaign against innumeracy.  His personal example of the use of basic math to reason his way through the consequences of unchecked consumption of natural resources and to make persuasive arguments to local government was an inspiration to many of us. 

I have been a devotee of calculator RPN notation since the mid 70’s. My first HP calculator was an HP 25C. For those who aren’t sure what it means, RPN stands for “Reverse Polish Notation”. For an eternity, in electronic industry years anyway, Hewlett Packard offered a variety of advanced calculators that used the RPN data entry format. Over the last 10 years or so, this blessed notation has been going the way of the Dodo.  Gradual extinction. 

As they explain it on the HP Museum of Calculators web site, RPN was named after a Polish mathematician named Jan Lukasiewicz who developed a logic in the 1920’s that allowed for the removal of parentheses in calculations.   Years later, computer scientists were able to apply the unique juxatposition of operators to the operands in first in last out (FILO) recursive stack manipulations. 

HP maintains that the term RPN is a type of homage to Lukasiewisz, and it may very well be. But, why isn’t it just “Polish Notation”? Here is my guess.  Up through the early 1970’s, the Archie Bunker years, Polish jokes were quite popular. In those days it wasn’t unusual for oddly configured devices to be referred to disparagingly with the adjective “Polish” and an especially strange contrivance might be further described as “reverse Polish”. My guess is that the word “Reverse” in RPN was from this vein of English usage.

I write to lament the decline of this intuitive and useful mode of computation. My guess is that onslaught of Japanese calculators (Sharp, etc) into the US market from the 1970’s onward with their algebraic entry format was an easier sell to the mathphobic masses.  Death by faint marketing.

College bookstores still offer a few versions of the RPN calculator and OfficeMax does offer the HP12 business calculators. But sadly, there does not appear to be any kind of revival anytime soon. There may be pockets of users out there, but we seem to be getting fewer in number.  It’s fun to watch people borrow your RPN calculator only to find that there is no “=” key. They quickly hand it back, grumbling as they look for another.

A few more blogs have been added to honored positions on the Illustrious Blogroll.  Check them out.  Lots of good bloggers (Bloggists?) with penetrating commentary on the current literature. 

Blogging is a bit harder for industrial folk. Or should I say riskier? One of the unfortunate realities of working in Fabulous Industry is the matter of secrecy.  You can’t discuss any of the fascinating stuff you work on with your buddies in academia. You know, chalk-talk stuff. The pay is good in industry (they fit you with golden handcuffs early) and the chemistry is fascinating, but the sad part is that it is nearly all confidential. When the conversation turns to sensitive material, people become noticeably uncomfortable. And they should.

Meetings with site visitors begin with the standard preamble- “You’ll recall that we are speaking under the conditions of our Non-Disclosure Agreement.  We at MegaLithium Company are in the XYZ business and have no need for any information from you beyond what is required to evaluate the project. We really don’t want to know your secrets.” Usually a well manicured and coiffed senior honcho says this. If the sleeves of his white shirt are not rolled up and his head shines with a high gloss, he is probably one serious SOB. This would be the alpha male and his underlings will studiously follow his lead. Often, there is a tour following the meeting.

As you take the tour you’ll find that the guides are not appreciative of breaching the decorum of secrecy, so blatantly nosey questions can cause them to throttle back the gee-whiz stuff. It’s always best just to nod appreciatively, pay attention, and be grateful for what you get to see.

I’ve been on both buy and sell sides of the secrecy matter.  I have hosted plant tours for visitors who were less than upfront with their intentions.  You see, in the custom chemical Business to Business (B2B) world when someone requests a price and availability, there is some chance that they have no intent on buying anything.  Their real intent may be to get scaled pricing and an estimate of the annual sales turnover for a product. It’s called competitive intelligence. And pricing intelligence is the most coveted of all.  Typically, this is only true for customers who may be competitiors. 

Here is some good advice.  If you’re about to sign a secrecy agreement, look for a clause providing for the reduction to writing for all Information to be considered Confidential.  These words are in bold because they are key words in a secrecy agreement. A good secrecy agreement will go to great pains to define what is meant by Information. If the other side is going to take you to task for a breach in confidentiality, then exact information that they consider sensitive had better be reduced to writing so you have a fair chance of avoiding a breach.

Many hearts have been broken in the attempt to get PLA on the market. In my case, I bailed from a tenure track asst prof slot to join a startup planning to scale up PLA production. It was quite exciting for a year and then it went belly up. These days, I’m a bit more cautious. I’m not bitter about it. It was a good introduction to polymer science and the marvels of chemical engineering.

In response to a question about PLA, I thought I’d elaborate on it a bit.

I’d be curious to find out more about the PLA experience, particularly the timing.  PLA is certainly a big hit right now.  Natureworks is sold out, and it has also found some niche applications - surgical staples for instance.   

The problem seems to be that if you develop the polymer first and the application second, then you will have a difficult sell.  If you go the other direction, it is an easy sell but you are left with lots of little applications.

Whereas we failed with PLA, Dow Cargill LLC has apparently turned it into an ongoing product called NatureWorks.

In case you haven’t heard, PLA is polylactic acid.  In its most common manifestation, it is the homopolymer of what is designated as the L enantiomer, which is produced from fermentation. Out of respect for my colleagues I won’t name the now defunct startup company.

Most everyone agrees that the marketing appeal of PLA is that it will biodegrade in the environment all the way to carbon dioxide and water, at least in principle. I qualify this assertion because it has been found that this biodegradation requires a fair amount of moisture to progress in a reasonable time. Landfills can be dry, fetid heaps that are not automatically conducive to rapid breakdown of organic materials. At least on the timescale of a few decades.  

In the microbial world, many microorganisms have the enzymatic machinery to biodegrade PLA to lactic acid (LA) and beyond.  LA is a natural compound that is judged to have a benign fate in the environment because it is such a common metabolite. In principle LA could be fully metabolized to CO2 and water once it is depolymerized from the PLA. So went the sales pitch.

In the 1990’s, people were concerned that landfills were rapidly filling to the brim with smelly disposable diapers and plastic junk.  There seems to be less public debate on this today, but I assume that the landfill issue remains largely unresolved.

PLA is made by an esterification reaction called ROP- ring opening polymerization. PLA is not made directly from LA. It is made from the ring opening polymerization of lactide, the cyclodimer of LA. This way there is no evolved water to add reversability to the polymerization.  And lactide is quite reactive.  Initiation of this highly strained monomer can be started with an initiator like an alcohol or an HO-terminated polyether in the presence of a Lewis acid catalyst (tin (II) octoate) in the lactide melt phase.

Lactide can be made by the direct cyclodimerization of lactic acid or by a back-biting reaction of oligomeric PLA made by heating LA.  I don’t know for sure, but I think that the back-biting reaction may be the major route to lactide today.

There is a lot of IP out there covering specialized applications of PLA. Medical and dental implants, sutures, timed released chemotherapy, etc.  PLA will slowly come apart in vivo over time, so it can serve as a kind of scaffold for bone or tissue regrowth or for metered drug release.  But this is a small and specialized market.

The big money is in packaging materials- blown films in particular. However, there are technical challenges here owing to a few of the properties of PLA homopolymer.  PLA has a relatively high Tg, so films will rattle and sharp package corners will crack.  PLA’s crystallinity can be good or bad depending on the application.  PLA also has a tendency to have an amber color and it’s films can block. 

Commodity polymer films have to be dirt cheap. The premium films  are colorless and low haze, have a high gloss, and have a low Tg.  There is a whole industry already producing such premium material from inexpensive feedstocks- the polyolefin industry. Sometimes people parse polystyrene and polyvinyl chloride as industries distinct from polyethylene and polypropylene. Polyethylene, polypropylene, polystyrene, and polyvinyl chloride are the predominant synthetic polymer feedstocks used by the packaging industry. They are well dug into the market with established feedstock supply lines and a global presence. 

Enter PLA.  PLA is ultimately a fermentation product. To get the right tacticity, you need enantiomerically pure LA. The best way to get it is to ferment sugars. LA must be fermented from a carbohydrate source, isolated from the broth (!!), converted to lactide, and polymerized.  Fermentation is a low space yield process. The microbes must be kept alive- excessive LA will kill them owing to low pH. You’ll need a cheap source of carbohydrates.

One of the best sources is corn starch, so a big corn wet mill will be required to produce it. The economics of PLA requires that a producer be vertically integrated from starch to fermentation to monomer production to polymerization. Energy and corn prices will have a large impact on your economics.

I’ll spare you the details going forward. Suffice it to say that PLA can’t compete with polyolefins on a price per pound basis at the present time.   PLA is boutique polymer at best for the forseeable future. My former company, the defunct PLA startup, felt that the best market segment for PLA was the market occupied by nylon films, due to the comparable cost and food contact and barrier properties. I have no idea what the economics look like now, 10 years later.

I wish all of the players well in the PLA business. It is a worthwhile endeavor and I wish that my experience had turned out differently. So it goes.

In the previous post I poured on the platitudes regarding working for a large company. Today I write about the other end of the spectrum- The startup company.

I encounter startup companies frequently in my work. Since I am not in the pharma business or fabulous biotech, my exposure to startups is limited to specialty and fine chemical feedstocks or reagents.

When you start a chemical company, it is assumed that you want to make lots of money. It turns out that you must have considerable cash flow just to pay the expenses of being in business, so you must be focused on cash flow. Chemical companies can have fairly high overhead costs, partly due to expensive staff (chemists and business managers) and partly due to the unique and expensive requirements of the physical plant.

Starting a chemical company is not a task for the timid.  You have lots of strikes against you from the very start. You see, a company is like a big angry animal. It has to be fed constantly with generous inputs of cash. Cash is King. Remember that. It’s all about the elusive spondulix. Investors can either give their money to Warren Buffett or to you.

I have seen many startups devolve into smoldering, groaning trainwrecks. Fortunes are lost, litigations burn like the fires of Mordor, and careers are lost or at least seriously stunted. Certainly no one starts a company with the intent of crashing it. So, how does it happen?

Usually, they run out of cash. There are many reasons that people use to justify the startup of a company. What they all have in common is the unwavering certainty that people will throw money at what they hope to offer. And if they have a patent- Lordy.  Nothing is meaner than an inventor in the thoes of patent sickness trying desperately to revive a dead one-act pony.

Many people start up a company with a one-act pony.  That is to say, a patented technology based on a highly specialized material or a process.  There are several ways to put a one-act pony or technology to work.  You can license out the technology. You can make certain compositions for sale. Or, you can make the pony do it’s one trick. 

If the pony’s one trick is good but not spectacular, selling licenses may be difficult. It is expensive and risky to upgrade technologies. There has to be a clear advantage and fairly rapid return on investment for the licensee.

If the materials made by the technology are “Me Too” products that are adequate but not exciting, you’re in for tough sledding. Especially if they’re commodities.  Companies in the polymer business know this. It is fantastically hard to get a new polymer to catch on in the market. Even giant companies have a hard go of it with exceptional products. The polymers market isn’t expanding very fast, so if you want market share, you have to take it based on price. Then it is a race to the bottom of the lake.

I was once roadkill along the trail of tears called PLA- Polylactic Acid.  It’s a great polymer for numerous applications. But low MW and the tendency to turn amber were problems that eventally caused us to flame out like a North Korean missile.

I’ve seen a lot of one-act pony startups fail because the pony died.  A startup may fail because show stoppers appeared that couldn’t be fixed, or the demand didn’t pan out. 

If you’re going to start a company, it is desirable to get cash flow going as soon as possible.  Use a plow horse to get some cash flow while you’re training the new pony.  Let existing products pay for the development of new technologies.  Learn how to make or formulate niche products that no one else is interested in. Plow the money back into product development and get into advanced technologies that way. Minimally, you’ll get to retain more of the ownership.

Another reason to build a business this way is to try to stay away from venture capitalists. But that is for another day.