Research Squatters. When Universities and Corporate Behemoths Collaborate.

13 Replies

Recently I had the good fortune to get to meet for a consultation with a young and talented chemistry professor (Prof X) from a state university elsewhere in the US. Prof X has an outstanding pedigree and reached tenure rather rapidly at a young age. This young prof has won a very large number of awards already and I think could well rise to the level of a Trost or a Bergman in time.

Not long ago this prof was approached by one of the top chemical companies in the world to collaborate on some applied research. What is interesting about this is that the company has begun to explore outsourcing basic research in the labs of promising academic researchers. I am not aware that this company has done this to such an extent previously.  They do have an impressive corporate research center of their own and the gigabucks to set up shop wherever they want. Why would they want to collaborate like this?

R&D has a component of risk to it. Goals may not be met or may be much more expensive that anticipated.  Over the long term there may be a tangible payoff, but over the short term, it is just overhead.

The boards and officers of public corporations have a fiduciary obligation to maximize the return on investment of their shareholders. They are not chartered to spread their wealth to public institutions. They have a responsibility to minimize their tax liability while maximizing their profitability. Maximizing profit means increasing volume and margins. Increasing margins means getting the best prices at the lowest operating expense possible.

Corporate research is a form of overhead expense. Yes, you can look at it as an investment of resources for the production of profitable goods and services of the future. This is what organic growth is about. But that is not the only way to plan for future growth. Very often it is faster and easier to buy patent portfolios or whole corporations in order to achieve a more prompt growth and increase in market share.

The thing to realize is that this is not a pollenization exercise. The company is not looking to just fertilize research here and there and hope for advances in the field. They are a sort of research squatter that is setting up camp in existing national R&D infrastructure in order to produce return on investment. Academic faculty, students, post-docs, and university infractructure become contract workers who perform R&D for hire.

In this scheme, research groups become isolated in the intellectual environment of the university by the demands of secrecy agreements. Even within groups, there is a silo effect in that a student working on a commercial product or process must be isolated from the group to contain IP from inadvertant disclosure. The matter of inventorship is a serious matter that can get very sticky in a group situation. Confidential notebooks, reports, and theses will be required.  Surrender of IP ownership, long term silence on ones thesis work, and probably secret defense of their thesis will have to occur as well.

While a big cash infusion to Prof X may seem to be a good thing for the professor’s group, let’s consider other practical problems that will develop. The professor will have to allocate labor and time to the needs of the benefactor. The professor will not be able to publish the results of this work, nor will the university website be a place to display such research. In academia, ones progress is measured by the volume and quality of publications. In a real sense, the collaboration will result in work that will be invisible on the professors vitae.

Then there is the matter of IP contamination. If Prof X inadvertantly uses proprietary chemistry for the professor’s own publishable scholarly work, the professor may be subject to civil liability. Indeed, the prof may have to avoid a large swath of chemistry that was previously their own area.

This privatization of the academic research environment is a model contrary to what has been a very successful national R&D complex for generations. Just have a look in Chemical Abstracts. It is full of patent information, to be sure, but it is full of technology and knowledge that is in the public domain. Chemical Abstracts is a catalog and bibliography that organizes our national treasure. Our existing government-university R&D complex has been a very productive system overall and every one of us benefits from it in ways most do not perceive. We should be careful with it.

ReactIR. Infrared spectroscopy revives in the age of NMR.

5 Replies

We have a brand new Mettler-Toledo ReactIR 15 sitting in my lab. It is rather simple to use- just dip the probe in your reaction mixture. It needs a little LN2 to chill the detector. The software is reasonable, bearing some resemblance to iControl of the RC1 sitting a few meters away.

The instrument is used to follow the progress of a reaction by monitoring the growth or extinction of IR absorptions. What is interesting for the user is that it is not necessary to identify any of the peaks in the course of an experiment. The software can integrate absorptions and plot their change over time. The fingerprint region of the IR spectrum is put to good use in that it is a fruitful region for numerous absorptions to appear.

The thing is still new to us, so we’re early in the learning curve. The probe in use has a wave number range from 2500 to  about 650 reciprocal centimeters. It is possible to detect up to 3000 wave numbers with a different probe. The probe is connected to the interferometer by a fibre optic cable comprised of a silver bromide optical pathway.

The thing is the size of a coffee maker and costs as much as a used helicopter. The ATR probe tip is small enough to be immersed in experiments at the scale of a scintillation vial or a 5 liter flask.

What it brings to the table is the ability to follow the progress of reactions in real time for process optimization. Pulling samples and trudging over to the NMR for in-process checks is tiresome and time consuming.

One limitation is the electrical classification. As with other electrical devices you have pay attention to the NFPA classification of the space it sits in. The ReactIR 15 is class 1, but not division 1. If the instrument must be used in this space, there are ways to fashion an enclosure to get around this, according to Mettler. Have a look at your computer as well. If your computer throws sparks and coal cinders, you may want to keep it away from that pool of pet ether on the floor.

Wireless Wierdness

5 Replies

I just can’t get over the absolute wierdness of being in a crowd, say at the airport, where a large fraction of people are jabbering into a phone plastered to their ear or they are standing, walking, sitting, or pacing with heads bowed down, pecking and stroking their mobile communication device. It is a kind of enchantment. A portal to other coordinates in the continuum. It allows us to receive or deliver stress all the damned time. Nobody is safe from the possibility of belligerent assholes reaching out for you while waiting at a stoplight or well-meaning associates braindumping all over your eardrum as you search aisle 5 at the supermarket for a can of chickpeas.

Driving yesterday, I took defensive measures as a dipshit in a red Ford Expedition overshot a turn while closing in on me. The distracted driver chose to complete a task on the handheld device before putting the oversized killing machine back between her yellow and white lines. I know this because the driver plastered the phone to her ear as she looked up when I passed by.

It has been 2 months now since I powered down my Facebook account. Facebook is a colossal time suck. It is a kind of gravitational well that can pull wandering bodies into orbit and lock them into some perverse synchrony for purposes unknown. Facebook is a kind of electronic teat that nurses us and keeps us from having to face our dark thoughts in quiet moments.  It is also a perfect venue for those who just have to broadcast their thoughts in every waking moment.

As a Facebooker, I was pretty boring. I don’t have photos of grandchildren or garden flowers to post. I’m a serial science nerd and nobody wants to hear about that. Okay, that’s fine. I soon realized that Facebook was only providing delayed and fragmented social awkwardness that I could be having face to face in real time and without having to pay for electricity. So I pulled the plug.

Tempest in a Teapot. Philosophy-v-Physics.

1 Reply

A minor snit has broken out between outspoken physicist Lawrence Krauss of Arizona State University and, well, the philosophers of the world. Krauss has become a darling of the cable TV world of NatGeo and the Science Channel. It seems that you can’t swing a dead cat without knocking over the same dozen television astronomer/cosmologists and quantum physicists. This rotating crew of scientists are filmed on various locations straining to explain the universe in terms of string theory, dark matter, and quantum wierdness using language with a Fog Index of 8 or less.

I’m not slighting these folks in the least. Using the English language to convey the essence of these concepts is difficult, as is preventing the reflexive use of the remote control by viewers with the attention span of a house cat.

Anyway, Krauss has managed to inflame those philosophers who pay attention to popular science.  His latest book, A Universe from Nothing: Why there is Something Rather than Nothing, has precipitated this argument. I don’t care about the merits of his argument here. The reader is invited to dive in.

What I am writing about is the social and intellectual mistake Krauss made. Like all physical scientists, he is a reductionist. The drive for a ToE, Theory of Everything, is the ultimate act of reductionism. His assertion that philosophy is obsolete in the face of discoveries in physics and the emergence of big subassemblies of a ToE has been received with dismay by philosophers.  A large fraction of people (adults, anyway) are hardwired to be receptive to mysticism and no amount of handwaving, no matter how logical and crisp, is going to cause the bell curve to skew substantially away from cherished mystical beliefs.

Krauss has fallen into the same trap as those in the 19th century who may have declared that physics was pretty much complete with Newtonian mechanics. While quantum mechanics provides a template for the description of how particles behave constrained to a region of space, it fails as a replacement for philosophy. That is, quantum mechanics and cosmology do not provide any concise analysis on how people should treat each other, how to conduct a worthwhile life, or how to interpret what the meaning of quantum mechanics is in your life.

This is the realm of philosophy and religion and these kinds of questions must be freshly examined by each generation born into this strange universe. The meaning of existence is not yet settled science.

Blogopithocene Man Smelts Tin. Meh.

3 Replies

The problem of the origin of Cu:Sn bronze has intrigued historians for many years. Bronze artifacts have been dated to 5000 BCE on the Iranian Plateau.  It is thought that the earliest bronzes were arsenical in nature. The presence of arsenic in copper metal or copper ore is not uncommon.

Copper can be found as the native metal but the smelting of copper ore appears to date back to ca 5000 BCE in southeastern Europe in what is now Serbia.

Most commonly today, the word bronze refers to a range of copper alloys comprising various proportions of copper (major, e.g., 88 %) and tin (minor, e.g., 12 %).  As the tin content increases, the resulting alloy changes properties and may have a unique purpose and name. For instance, a ratio of ca 2:1 :: Cu:Sn is called speculum and was prized for it’s ability to take a high polish for mirror applications.

Further down the composition range are varieties of pewter which are alloys comprised substantially of tin and a few percent of copper and antimony for hardening.  Many specalized compositions of pewter have been developed. Britanium or Britannia metal is an alloy comprised of 93 %Sn, 5 % Sb, and 2 % Cu. This alloy serves as the base metal Oscar Award Statue upon which gold is plated.  Pewters composed of Sn:Pb were commonly used as well.

Tin is not found in the metallic state in nature. It is oxophilic and occurs primarily as the tin (IV) oxide mineral, cassiterite. Tin ore was mined in Cornwall, England, for instance, for many centuries before recorded history.  Today, most of the worlds tin comes from Asia, South America, and Australia.

The jump to “engineered” bronze was a step change that involved the reduction of a tin mineral either in situ with copper or in isolation to produce discrete tin. It is thought that polymetallic copper ores were smelted, producing Cu:Sn bronze directly. Eventually, tin ore was identified as a source of smeltable metallic tin.  Why anyone would think to apply reduction conditions to a mineral as seemingly featureless and uninteresting as cassiterite is an intriguing question.

Below is a photo of the result of my first attempt at smelting a cassiterite simulant (SnO2, Aldrich). The SnO2 was treated with carbon black at 900 C for 4 hours in a covered porcelain crucible in a muffle furnace.  After a  failed attempt with a large excess of carbon, the ratio was reversed and heated for a longer period.  For the illustrated sample, the mass ratio of SnO2 to carbon black was ~2:1. All of the carbon black was consumed, leaving a white mass of needles on the granular solids.  Using a USB microscope I searched for evidence of reduction to the metallic state and found numerous examples of sub-millimeter sized pieces of metal.  The yield of metallic tin is estimated at < 1 %.

The purpose of this exercise (for me) is to try gain a better sense of what problems people might have faced smelting tin in antiquity.  Using basic principles, I strongly heated the SnO2 under reducing conditions until the carbon was consumed.  What I did not expect was the large amount of white crystalline material produced. It’s composition is as yet unknown to me.

Next I will make some charcoal or even wood shavings as a reductant for authenticity sake. Who knows, maybe some carbon monoxide generation might be helpful. The muffle furnace does not simulate a reverberatory furnace very well. It could be that gases from a reducing flame are important.

Smelting of Cassiterite Simulant

Mining Asteroids

6 Replies

The founders of the Silicon Valley startup, Planetary Resources, have announced plans for mining asteroids for valuable metals. Peter Diamandis, Eric Anderson and investors including director James Cameron and Google CEO Larry Page are behind this venture.

I’m trying to be positive here. Perhaps these fellows should visit some earthly mines and see what it takes to break actual rock and extract the value from it.

Earth bound ore bodies near the surface are commonly the result of concentration by hydrothermal flows. In the absence of water-based geothermal concentration processes, or recrystallization of PGM’s in magma chambers, the reality of economically viable ore bodies in asteroids is an open question. A lot of survey work needs to be done to answer this question.

Oh, and one more thing. When you blast rock on a largish planet like earth, the fragments fall back to the ground. This won’t happen on an itty bitty asteroid.

The talk about recovering water from asteroids to subsequently crack and make propellant is a large challenge all by itself.

I predict that civilization will slump back to a 19th century Dickensian-style world of robber barons and sharecroppers before any hardware gets to an asteroid.  Children will ask “Momma, what’s an iPad?” as they walk from their rundown subdivision to a quonset where they strip insulation from wire for copper to barter for food. It’s all so clear now …

Time to Leave Afghanistan

4 Replies

It is time to withdraw our soldiers from Afghanistan. The latest example of moral depravity exhibited by members of our armed forces shows the effects of prolonged war on our citizens. The US is at war with not so much an insurgency as an idea. An idea is not a form of concentrated power. It is a form of distributed power. You can’t take out a popular idea with a bomb or a 50 cal round.  We are occupying a “country” which exists by default as a void between other countries. Afghanistan is a collection of districts occupied by a weak confederation of tribes who adhere to seventh century cosmology and religion.  A coalition of like minded religious zealots are in the process of retaking the political void which is only weakly occupied by a corrupt, reluctant and treacherous Afghan government.

These latest instances of outrageous and indefensible behavior with Afghan corpses by US forces completely negates whatever moral high ground we once occupied. We have put our troops in a place and circumstance which is unwinnable. We have exposed good men and women to unspeakable horrors and memories.  There are too many public dots to connect now that outline our own corruption in the execution of foreign policy in Afghanistan.

War inevitably corrupts its participants. Our own enthusiasm for war reflects poorly upon us and we must get a grip on this.

Early Adventures with Nitrates and Tartaric Acid

2 Replies

It is a misconception that renaissance alchemists were only concerned with the philosophers stone. Hermetic alchemy was an overlap of alchemical practice within a mystical or spiritual framework. This branch of alchemy and its practitioners are perhaps better known in the popular literature than the alchemists who might be regarded as more pragmatic experimentalists.

Many alchemists over history were very practical and quite occupied with their trade in medicaments, tinctures, distillates, and elixirs or with metallurgical and compounding endeavors.  Paracelsus is regarded as an early practitioner of iatrochemical work, but within a hermetical framework.  Agricola and Biringuccio were 16th century chroniclers of metallurgy that had a basis in earlier alchemical progress.

Consider an entry from a translation of The Laboratory, or School of Arts; in which are faithfully exhibited and fully explain’d, I. A variety of curious and valuable experiments in refining … VI. A dissertation on the nature and growth of saltpeter; … Translated from the German, by Godfrey Smith, published 1738.  In this volume, available from ECCO, Eighteenth Century Collections Online, contains a passage under the heading of “To prepare Aurum Fulmina__s” (two letters obscured). I have retained the archaic character “f” in place of “s” for the reader to enjoy.

To prepare Aurum Fulmina__s

Take Gold that is refin’d with Antimony, beat it to thin Plates, put it into a Phial or Matrafs, pour Aqua Regis upon it, then fet the Phial or Mastrafs upon warm sand, till the Aqua regis is diffolv’d as much of the gold as it is able to contain, which you will knw when you fee the Ebullitions ceafe, pour your Solution by Inclination into another Glafs, and if you fee there remains any Gold in the Matrafs, dissolve it as before with a little frefh Aqua regis, mix your Diffolution, and pour to it five times as much common Water, afterwards drop into this Mixture, by Degrees, the Volatile Spirit of Sal Ammoniac, or Oil of Tartar, and you will see the Gold precipitate to the Bottom of the Glafs, let it reft a good while for the Gold to settle, then pour off the Water by Inclination, wafh your powder with warm Water, till grows infipid, dry it to the Substance of a Pafte, then form it in little round Corns, the Bignefs of a Hempfeed, dry them by the Sun, if you put one of them into a Fire, it will fly and difperfe with a terrible Noife, and beat about with great Violence. [Emphasis mine]

It seems likely that the worker is trying to refine the gold by dissolution of the Sb/Au blend by complete dissolution in aqua regia, followed by what we would now regard as a reduction of the gold solution. Quenching the aqua regia would be expected to cause the gold to reduce and fall out as the native metal. But gold chemistry is not what is interesting in this account.

The Spirit of Sal Ammoniac, meaning either ammonia itself or ammonium chloride, would do as follows: the ammonium would ion pair with nitrate and, upon drying, leave a residue of ammonium nitrate, which is an explosive. Simple open burning of  small kernels material enriched in ammonium nitrate might be expected to deflagrate or pop, as indicated in the end of the description.

The Oil of Tartar, however, might have an altogether different fate when dissolved in aqua regia. Oil of Tartar is a concentrated aqueous solution of potassium (or Na) tartrate.  In solution with aqua regia, one would reasonably expect the two hydroxy groups of tartaric acid to form the dinitro ester if appropriate nitrating species are present. A nitrate ester group is a common explosophore and consists of O2N-O-C comprising an oxygen linkage between NO2 and carbon. This linkage is sensitive to low levels of stimulus, making compounds with such linkages susceptible to rapid or explosive decomposition. The nitrite ester is listed as an explosophore as well.

The nitration of tartaric acid is described in US patent 1,506,728. This patent teaches the use of the standard H2SO4 catalyzed HNO3 nitration of the tartaric acid diol functionality to form a dinitro ester via the standard nitronium ion formation. In the case of aqua regia, the presence of NO2(+) is questionable. Aqua regia is known to produce nitrosyl chloride, ClNO which dissociates to Cl2 and NO.  Literature on the nitration of alcohols to nitro esters in aqua regia is non-existant in Chemical Abstracts. There are a few citations describing aromatic nitration by aqua regia, but no clear description of nitro ester formation.  Indeed, there are many descriptions of direct extraction of gold from aqua regia using isoamyl alcohol with no warnings of explosive or nitro formation.

There are, however, reports of the use of ClNO to produce organonitrites when reacted with a monohydroxy alcohol (Journal of the American Pharmaceutical Association (1912-1977) (1932), 21, 125-8). It is possible that a tartaric nitrite was formed which may be energetic to some extent.

But perhaps the application of Occams Razor is needed. Potassium or sodium tartrate would be mildly basic and upon addition to a mineral acid solution, it would neutralize the acid in sufficient quantities, affording potassium or sodium nitrate (saltpeter). On evaporation of water, the saltpeter residues would be comingled with tartaric acid, comprising a fuel/oxidizer mixture.

Small quantities of crude nitrate esters, nitrite esters, or nitrate salts could have been present in the dried paste, giving the pyrotechnic effect described. The formation of energetic materials was not the primary purpose of the procedure, although the observed behavior of the residues was apparently compelling enough to document.

Waterboarding in the Spanish Inquisition

3 Replies

The Spanish Inquisition lasted from 1478 to 1834 and was started by the monarchs Ferdinand II and Isabella.  The marriage of Ferdinand II of Aragon to Isabella of Castile united two kingdoms on the Iberian pennisula.  The Spanish Inquisition was set apart from the long running and contemporary papal inquisitions through a special papal bull issued from Pope Sixtus IV to the Spanish monarchy. The crown was able to gain political control over the appointment of inquisitors in Castile which, until then, had managed to avoid the implementation of inquisitions by the church.

The priviledged commission granted to the Spanish Inquisition afforded considerable magisterial control to the Spanish Monarchy and allowed it to focus on the eradication of Jewish and Muslim influence in Spain. Prior to the issuance of the bull, the church had a focus on the reconciliation of heretics back to the church.  Under the Spanish Crown, however, judiazing heretics were the subject of particularly enthusiastic prosecution. Under the guise of spiritual mandate, Jews were compelled to leave behind their wealth and exit Spain or convert to Christianity. But all would not bode well for the conversos.

Over time, the conversos and their decendants would be suspected of secret Judiazing and the practice of Mosaic law.  A kind of circuit court of inquisitors was instituted early in the Inquisition whereupon a select Grand Inquisitor would oversee the conduct of Inquisitions throughout the realm on behalf of the Crown.

A codified system of procedures and functionaries was put in place for the conduct of inquisitions.  Suspected heretics were always presumed guilty until they could prove their innocence.  An inquisition was conducted in a way so as to elicit a confession since this was regarded as the best form of evidence of guilt. Torture was instituted and performed when stubborn heretics failed to confess to the satisfaction of the inquisitors.

The variety of torture techniques included hanging the defendant by his wrists which were tied behind his back (the garrucha); stretching the defendant on the rack (the potro); or pouring water down the nose and throat of the defendant to simulate drowning (the toca).  These techniques were conducted in order to produce a satisfactory confession.

At the conclusion of the inquisition, the guilty defendant was “relaxed” to the constable for punishment or execution. In this system, there was no external authority such as the pope to contradict the will of the Crown in the roundup and prosecution of suspected heretics.

Of special interest is the toca. This seems to be a form of what we now call “waterboarding”.  It is generally agreed that when the Inquisitors performed it, it was regarded as a form of torture. The contemporary practice is defined as “enhanced interrogation”.

It was the Spain of this Inquisition period that set sail for the Americas in search of wealth and for natives to convert to Christianity. Unfortunately for the native people of the Americas, these visitors had a frothy zeal for heavy metals and Christ.

Reference:  Lu Ann Homza, The Spanish Inquisition, 1474-1614, 2006, Hackett Publishing Company, ISBN 0-87220-794-3.