Category Archives: CounterCurrent

Vannoccio Biringuccio. Sixteenth Century Chronicler of Metallurgy.

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By the early 16th century in Europe, metallurgy had become an established cottage industry in numerous locales. Artisans were sourcing copper, tin, zinc, antimony and iron ores for reduction, refinement and alloy production for cannon and bells among other products.  While there was no systematic science of chemistry in a form recognizable today, the necessity of constant proportions was understood and exploited to maximize the efficient use of scarce materials. Metallurgists of the 16th century would no doubt share the enthusiasm of developing technology with the same fervor as the technologists of today. 

Unfortunately for these 16th century technologists, the contribution of centuries of alchemy produced a confusing array of occult-based practices. These alchemical practices were based on Aristotelian notions of material “qualities” rather than a system of quantitative relationships of and between substances. It is thought that alchemy began with Grecian metalworker’s practical knowledge of metal preparation. Inevitably, this practical art was overprinted with a thick layer of theological mysticsm by the end of the first millenium. By the end of the alchemical age, any systematic theories of matter were blended into a Mulligan stew of early Roman Catholic mysticism,  incomprehensible nomenclature, and the false choices set forth by Aristotle in his theory of matter.

Fortunately for 16th century practitioners of the metallurgical arts, several encyclopedic works were published detailing the practical art of smelting and casting of metals and what we now know to be alloys.  A prominent early work published in 1540 was the Pirotechnia by Vannoccio Biringuccio (1480-1539). Born in Siena, Italy, over the course of his life Biringuccio traveled extensvely throughout Italy and Germany. His Pirotechnia is a series of books and chapters detailing foundry techniques that he witnessed first hand throughout his travels. He made every attempt to describe methods and techniques in enough detail to accurately capture the technique in question. Above all, he completely drops all the alchemical mysticism and bases his comments on process oriented details such as measured proportions and processing conditions.

Up to this point, what was missing from this very early form of chemistry was a systematic collection of facts and measurements and an accurate chemical model in which to give the facts meaning and predictive value.  Biringuccio, and later Agricola, would begin the disengagement of alchemical mysticism and provide a basis of metallurgical technology upon what might be called science. In a real sense, this helps to set into motion the western industrial revolution. Metallic goods would be produced by very pragmatic artisans who would continue to improve their art through the application of rudimentary measurement.  While it would be four centuries before atomic theory would be developed to make sense of the manner in which definite proportions operated, systematic methods of assay would begin to appear well before atomic theory. The ability to identify value in ores and quantitate it allowed the mass industrialzation of metals.

Devon Energy Sells Stakes to SINOPEC in Shale Gas Plays

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Devon Energy has raised $900 million in cash from Sinopec Group for a stake in Devon shale gas plays. These gas projects include the Utica, Niobrara, and Tuscaloosa formations. 

What is interesting is not so much that China has bought its way into the extraction of a resource that the USA has in some abundance. What is more troubling is that China has bought its way up the learning curve in horizontal drilling and fracturing. 

According to the article in Bloomburg Businessweek-

China National Petroleum Corp., Sinopec Group and Cnooc Ltd. are seeking to gain technology through partnerships in order to develop China’s shale reserves, estimated to be larger than those in the U.S.

“In these joint ventures, the partner does typically get some education on drilling,” Scott Hanold, a Minneapolis-based analyst for RBC Capital Markets, said today in an interview.

So, the business wizards at Devon in OKC have arranged to sell their drilling magic to the Sinopec for a short term gain on drilling activity. Way to go folks. Gas in the ground is money in the bank. These geniuses have arranged to suck non-renewable energy out of the ground as fast as possible.  Once again US technology (IP, which is national treasure) is piped across the Pacific to people who will eventually use it to beat us in the market.  Score another triumph for our business leaders!!

The market is like a stomach. It has no brain. It only knows that it wants MORE.    Th’ Gaussling.

 It’s a banner day for American Business.

Locust Capitalism- The Frass Machine.

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Here is a great catch phrase- Locust Capitalism. The article by David Waldman, describing the past business practices of one of our corporate persons, Bain Capital, uses this catchy phrase to characterize said corporate person. Of course, the irony of it all is plastered on the face of biological person Willard “Mitt” Romney who makes a show of being a job creator.

There is something that locusts do create- it is called frass.

I do not doubt Romney’s sincerity when he speaks. Like other candidates, he seems to live in the “eternal now” much like a dog. He wags his tail at the public hoping to curry favor for the treat of being president. If wagging his tail doesn’t work, he rolls over and puts up a paw hoping to win over the public. It is in the nature of these creatures to do this and while we cannot hold them blameless for their transgressions, we can at least understand them.

People who are able to think about business in an abstract way, that is, unencumbered by sloppy sentimentality for the fate of individuals, are well suited to become the captains and oligarchs of business. Romney seems to have been a captain. If the practices described by Waldman did in fact happen, then the locust analogy is very suitable and it says a lot about the character of the persons involved.

Waldman writes that Romney and cohorts bought companies holding ample commercial credit, charged them substantial management fees, and tapped out the credit lines while pocketing operating cash, driving the company into bankruptcy. They walk away from the remaining husk of what was a functioning organization with their neatly stacked pile of lucre.

If a real person did this, he/she might be described as a kind of sociopath. But somehow in the context of business there is no descriptor for such antisocial behavior.

Since we are now in the habit of referring to corporate personhood, perhaps we need to be a bit more analytical about it and characterize pathological behavior such as this.

Thorium and Rare Earths. A Possible Market Synergy.

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If one studies the economic geology of Rare Earth Elements (REE), it becomes clear that REE’s are frequently (usually?) found in deposits rich in other elements.  Deposits of zirconium, tantalum and niobium, for instance, are frequently co-located with REE’s.

The REE’s are found in ore bodies that are naturally enriched in either heavies (yttric or HREE’s) or lights, (ceric or LREE’s). The LREE’s seem to be the most common spread of the REE’s.  Molycorp’s Mountain Pass bastnasite deposit is a good example of this.

What is not so widely known is that thorium and/or uranium are nearly always found in these deposits.  This might be regarded as a good thing except that companies in the REE business seem to be less interested in actinides than lanthanides. The actinide business is fraught with complications related to the natural radioactivity of Th and U. If one is interested in rare metal production, the matter of radioactivity is unwelcome.

However, there is opportunity here if certain institutional thinking is allowed to expand. I refer to the global preference for uranium and plutonium in the nuclear fuel cycle. Nearly the entire world’s nuclear materials infrastructure was directed to the production of yellowcake and separation of U235 from U238 post WWII. While there has been some experimentation with thorium 232 in the US, and there are some limited initiatives in motion, it has been largely neglected in reactor design and the fuel cycle in favor of uranium and plutonium.

Rare earth element mining and processing naturally produces thorium and uranium. At present, those practicing REE extractive metallurgy have every incentive to avoid concentrating the actinide components owing to the radioactivity. However, if there were a coherent program for the development of an efficient thorium fuel program, this natural resource could be efficiently taken from the REE product streams now or in the future.

Our reliance on energy will trend substantially towards electricity. The greater absolute abundance of Th over U, as well as the ability to use 100 % of the predominant isotope makes thorium a good candidate for energy exploitation. The recent boom in REE exploration has uncovered new sources of thorium. The nuclear genie was let out of the bottle nearly 70 years ago. By now we should be a little smarter about how we use it.

After the Blockade

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So here is a short timeline of events that will unfold after the Iranians block the Strait of Hormuz. Beginning 48 hours after the blockade starts, at around 3:00 AM, RF jamming will begin and a US Navy man-of-war somewhere over the horizon will launch a barrage of cruise missiles at Iranian surface ships in the Straits. From an undisclosed location, a US nuclear submarine will launch more cruise missiles and a hunter-killer sub will close in on any Iranian subs that may be in the vicinity.

USAF strike force assets will be overhead and will provide electronic counter-measures, signal intelligence, and aerial reconn.

Thirty seconds before the cruise missiles arrive at their targets, the muffled slapping sound of 2000 sphincters slamming shut will be heard as Iranian seamen realize what is about to happen when the angry, armor piercing, high explosive warheads arrive. The reality of a torrent of supersonic incandescent pressurized gas, slurried with molten metal, penetrating the hull into inhabited space is too awful to contemplate.

The president will be given the choice of bombarding Iranian naval bases, but he will wisely decline.

By 9 AM, the remaining Iranian naval combatant will be disabled and listing.  Many men are in the oily water, more than a few of them corpses floating in the flooded interior spaces of their sunken vessels.

Anderson Cooper’s plane is wheels-up by noon Iran time, but the thing is over. US men-of-war steam toward the kill zone looking for survivors. The descendents of Xerxes and Rumi have been in the streets of Tehran since 7 am slapping their foreheads and shaking their fists. But who are they really mad at? The US or their government?

In reality, I don’t think this scenario will unfold. The US will gather a show of force and intimidate the Iranians to stand down. Individual Iranian ships making aggressive moves will be delt with swiftly, though.

Euphemisms and similes to avoid in 2012

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I propose a 20 year ban on the following overused and often mangled euphemisms and similes-

Rocket scientist–  “it doesn’t take rocket scientist to …”.  This one is really tiresome. I propose that it be banned indefinitely and that repeat offenders be tatooed with some humiliating symbol on their noses.

Holy Grail–  “… It’s like the Holy Grail of …”.  This was overused centuries ago and abusers should be called down on the carpet forcefully and publically. A good swatting with a rolled newspaper may be called for.

American taxpayers–  “… The American taxpayers are tired of …”.  You mean, American citizens. To play to the taxpayer’s emotional conflicts over taxes is a ham fisted rhetorical manipulation that bypasses the greater good of citizenship and responsible stewardship over our civilization. I am a citizen who pays taxes and I insist on being addressed as a citizen.

Perhaps the dear readers have even better examples of rhetorical ditties that should be retired.

 

Process development with calorimetry

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I’ve turned my attention to reaction calorimetry recently. A reaction calorimeter (i.e.,  Mettler-Toledo RC1) is an apparatus so constructed as to allow the reaction of chemical substances with the benefit of measuring the heat flux evolved. Reaction masses may absorb heat energy from the surroundings (endothermic) or may evolve heat energy into the surroundings (exothermic).

Calorimetry has been around for a very long time. What is relatively recent is the development of instrumentation, sensor, and automation packages that are sufficiently user friendly that RC can be plausibly used by people like me: chemists who are assigned to implement a technique new to the organization.  What I mean by “user friendly” is not this: an instrument that requires the full time attention of a specialist to operate and maintain it.

A user friendly instrument is one engineered and automated to the extent that as many adjustments as possible are performed by the automation and that the resulting sysem is robust enough that operational errors and conflicting settings are flagged prior to commencing a run.  A dandy graphic user interface is nice too. Click and drag has become a normal expectation of users.

An instrument that can be operated on demand by existing staff is an instrument that nullifies the need for specialists. Not good for the employment of chemists, but normal in the eternal march of progress. My impression is that RC is largely performed by dedicated staff in safety departments. What the MT RC1 facilitates is the possibility for R&D groups to absorb this function and bring the chemists closer to the thermal reality of their processes. Administratively, it might make more sense for an outside group to do focus on process safety, however.

In industrial chemical manufacture the imperative is the same as for other capitalistic ventures- manufacture the goods with minimal cost inputs to provide acceptable quality. Reactions that are highly exothermic or are prone to initiation difficulties are reactions that may pose operational hazards stemming from the release of hazardous energy.  A highly exothermic reaction that initiates with difficulty- or at temperatures that shrink the margin of safe control- is a reaction that should be closely studied by RC, ARC, and DSC.

It is generally desirable for a reaction to initiate and propagate under positive administrative and engineeering controls. Obviously, it is desirable for a reaction to be halted by the application of such controls. Halting or slowing a reaction by adjustment of feed rate or temperature is a common approach.  For second order reactions, the careful metering of one reactant to the other (semi-batch) is the most common approach to control of heat evolution.

For first order reactions, control of heat evolution is had by control of the concentration of unreacted compound or by brute force management of heating and cooling.

Safe operation of chemical processing is about controlling the accumulated energy in the reactor. The accumulated energy is the result of accumulated unreacted compounds. Some reactions can be safely conducted in batch form, meaning that all of the reactants are charged to the reactor at once. At t=0, the accumulation of energy is 100 %. A reliable and properly designed heat exchange system is required for safe operation (see CSB report on T2). In light of T2, a backup cooling system or properly designed venting is advised.

The issue I take with the designers of the process performed at T2 is this: They chose to concentrate the accumulated energy by running the reaction as a batch process. This is a philosphical choice. The reaction could have been run as a semibatch process by feeding the MeCp to the Na with a condenser on the vessel. Control of the exotherm could have been had by control of the feed rate and clever use of the evaporative endotherm. A properly sized vent with rupture disc should always be used. These are three layers of protection. 

Instead, they chose on a batchwise process relying on a now obviously inadequate pressure relief system, and the proper functioning of water to the jacket.

No doubt the operators of the facility were under price and schedule pressure. The MeCp manganese carbonyl compound they were making is an anti-knock additive for automotive fuels and therefore a commodity product. I have no doubt at all that their margins may have been thin and that resources may not have been there to properly engineer the process. This process has “expedient” written all over it in my view.

Reactions that have a latent period prior to noticeable reaction are especially tricky. Often such reactions can be rendered more reliable by operation at higher temperatures. Running exothermic reactions at elevated temperatures is somewhat counter-intuitive, but the issue of accumulation may be solved.  

Disclaimer: The opinions expressed by Th’ Gaussling are his own and do not necessarily represent those of employers past or present (or future).

Power Generation with Mercury Turbine

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The South Meadow generating station was operated by the Hartford Electric Company in Hartford, CT. The unit described in the 1931 Pop Sci article used 90 tons of mercury in the boiler. The article states that the South Meadow generator produced as much as 143 kWh from 100 lbs of coal, as opposed to an average of 59 kWh from conventional coal fired plants and 112 kWh from exceptionally efficient coal fired plants. The article describes an incident at the plant where a breech of containment from an explosion in the mercury vapor system occurred, releasing mercury and exposing workers to mercury vapor.

The Schiller Mercury Power Station in Portsmouth, NH, is described in this link.

The Chinese dig in.

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Here is a choice tidbit from the Washington Post. The Chinese, it seems, have been constructing a tunnels which some believe are meant to contain (possibly) strategic nuclear weapons and large numbers of people.

What China is actually up to and what it means for the control of nuclear proliferation is unclear. Generally, when a country builds fortifications like this alleged underground capacity, it is for a reason. They wish to be perceived as an irresistable force or an immovable object.

It is also worth considering that a massive, opaque, underground fortification with ICBM capacity is a step change away from the 20th century-style logic of Mutual Assured Destruction. MAD, as it was called, relied on opponents coming to the conclusion that there would be no winners in a nuclear exchange. If this structure is a fact, then it could mean that China means to survive nuclear war. The logic of MAD was based on holding the respective civilian populations hostage.  As crazy as that sounds, it worked.

One of the criticisms of Reagan’s Strategic Defense Initiative (SDI or Star Wars) of the 1980’s was that it undercut the balance imposed by MAD. In the end, the USSR collapsed at a time and circumstance that not even the CIA was able to forecast. The biggest threat that SDI posed to the Soviets was the inevitability of yet another crippling arms buildup.

A hardened and opaque Chinese missile capability will not go unnoticed by hawks in western governments. This development, real or not, may kick the mania for weaponization of space up a notch or two and tip the guns-or-butter equilibrium even further from butter.

To we Americans, like others throughout history, the impulse to devise new weapons is irresistable. We’ll throw hundreds of billions of dollars of national treasure at the arms and aerospace complex to come up with zesty new engines of war and call it just.  Yet we are unable to justify upgrading infrastructure or a plan to sustain an egalitarian society.

What the US needs to do at this point is to begin intense high level talks with the Chinese to bring strategic armament issues onto the table, if they have not already begun to do so.  China has built a friendly and industrious looking store front. But inside is a tightly wound and ambitious party-controlled military apparatus that is anxious to test its mettle against the US.

If Americans continue to parade around spouting this directionless free market blather instead of devising a more coherent national plan for thriving in the century of China, we will become the next fallen empire. Privatization is decentralization. Even businesses know that market share is not gained by fragmenting command and control. If the Chinese whip us, it will be for this reason.

Rare Earth Boom

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There is a rare earth exploration boom in progress at the present time. This boom is in response to the policy shift of the Chinese government toward greatly reduced export of crude rare earth feedstocks. This political phenomenon is the result of the grand geological lottery that has deposited mineral wealth around the world.

Billions of years ago the geological processes in play were causing the partitioning of the elements into minerals that afforded local concentrations of groups of elements. Over geological time magma rose and cooled, sequentially crystallizing out minerals that by virtue of the principles of chemistry, laid down zones of enrichment. Recrystallization, extraction, ion metathesis, hydrolysis, melting point depression, attrition, processing of melts, degassing- all processes recognizable to the chemist. These processes are responsible for the formation of mineral species as well as their transport and alteration.

But the earth is never finished processing its mineral horde. Land masses are subject to upheaval and erosion, geochemical synthesis and decomposition.  Any given formation at any given time is an overprinting of frozen events separated in time.

Large zones of continent may be subject to forces that cause it to break in networks of fractures. The forces may be in the nature of shear where fracture faces slide past one another. Other forces may lead to an upthrust of rock on the continental scale leading to mountain building.  The shear and bending applies forces that exceed the tensile strength of the rock, leading to fracturing. Over time these fractures may serve as channels for hydrothermal flows.

Hot, pressurized water over long periods will dissolve susceptible minerals in the rock faces and transport solutes and suspended solids throughout the fracture network. Established mineral species yield to the solvent effects of water and slough off part or all of their constituents. In doing so, the minerals are taken apart into anions and cations that will eventually reassemble elsewhere into different mineral species. Over time these fracture networks will fill with solids and self-seal. They are called veins.

Water is not innocent in its behavior. Water’s ever eager oxygen atom binds to oxophilic metals and metalloids, taking them down to the energy bargain basement of oxide or oxyanion formation.  Water with dissolved acids can digest whole formations leading to cavernous voids in susceptible rock.

Over time, geological processes have left formations of elements in bodies of economically viable concentrations called ore bodies.  In the case of rare earth ore bodies, these elements are found concentrated in veins and breccias, pegmatites, or dispersed at more dilute levels in many other kinds of minerals.  It is a truism that the lanthanide set of the rare earths are all commonly found in the same formation, but emphasizing the lights (LREE) or heavies (HREE).  Scandium and yttrium are the Group III elements grouped with the 15 lanthanides to form the rare earths. While yttrium is often found with the lanthanides, scandium is often scarce in deposits otherwise rich in the other rare earths (REE’s). It is not uncommon for REE deposits to contain significant levels of zirconium, hafnium, tantalum, niobium, thorium, and uranium.

China does not seek to deprive the world of products using REE’s. It has taken the position that the REE exports will be in the form of finished consumer products. The policy of China is that it will manage the output of rare earth-based products in a highly value added good as a means to extract the most value from it.  China’s market has a central nervous system that has devised manufacturing policy. It is much like an octopus. In the US, the prevailing wisdom is that the market should seek it’s own equilibrium without government interference. Our system is a distributed in the manner of a coral reef.

Today, mining exploration firms principally from Canada, Australia, and South Africa are exploring Africa, Australia, and the Americas for deposits of REE’s- and finding them.  In my survey of the field, it would seem that the US is poorly represented in the roster of rare earth exploration firms.