Category Archives: Chemistry

Beryllium Mining

The aerial view above shows the location of the Brush Wellman beryllium mine near Spor Mountain, Utah. It is reportedly the only major beryllium mining operation in the USA and one of the very few economic beryllium ore locations in the world. The host materal is called “tuff”- a compacted and cemented volcanic ash composition. Coincident with this Be deposit is low grade uranium and fluorspar. Occurances of Cu, Au, and other base metals can be found in the area.

The concentration of Be in the ore body is thought to be due to the mineralization action of meteoric and hydrothermal fluids. The region is marked by the presence of 3 Oligocene-era calderas, with the Spor mountain Be mineralization found along the ring structure of the Thomas caldera.

The action of hot, saturated aqueous flows transporting solublized components from distant host bodies is one of the chief mechanisms for the appearance of “ore bodies” near the surface of the earth. Very often, such deposits are found in regions of faults and fractures of various kinds of rock formations. Mineral laden water follows the fracture system and, as it moves toward the surface, begins to cool and deposits the burden of now insoluble compounds. Deposition can occur due to simple solubility properties, redox from exposure to atmospheric oxygen, or via ion exchange with available chemical species to form high Ksp compositions.

This is nothing new to geologists who have been aware of these mechanisms for generations. But for a non-geochemical chemist like myself, the matter of how elements like beryllium come to be concentrated is less than familiar. Indeed, the question of how any element comes to be concentrated in rock formations is a question of increasing interest to Th’ Gaussling. I hope to spend a lot of time in the future exploring this matter.

Liptonian Symbolism

Never one to allow reason to interfere with sentimentality, my blackened heart is softened somewhat by the recent shipment of Lipton Tea bags delivered to Th’ Gaussling from an online admirer via the US Postal Service. 

The tea in this gift shall be symbolically applied to the local waterway, but not before being used to formulate some refreshing iced beverage via aqueous extraction.  A vessel filled with aqueous goodness (OPE-Our Pure Essence) will be charged with the anthocyanin and alkaloid laden forest litter for extended exposure to solar radiation. Brownian motion will be relied upon to disperse the colloidal value away from the biomass.

Once so processed, the fortifying beverage will be passed through a pair of kidneys as a symbol of my dark contempt for the IRS. This nephro-raffinate will be discharged into the municipal fluid collection system for a kind of Nicene rectification that will provide further philosophical processing of the symbolic gesture. Finally, after the Liptonian fluids have been subjected to Libertarian aeration and Calvinist filtration, the clarified symbol will be discharged into the river for its turbulent hero’s journey to the drinking water inlets of New Orleans and beyond.

The Cresson Vug

The history of the Territory and State of Colorado is inextricably tied to base metals and precious metals. Gold and silver strikes were a big draw for the migration of population to Colorado from the 1859 Pikes Peak Gold Rush onward.  A map of the ore geology of Colorado reveals a few key districts or zones of enhanced mineral abundance. The Colorado Mineral Belt (CMB) is a band of ore deposits that are positioned diagonally across the middle of the mountainous part of the state, SW to NE, roughly from Durango to Boulder.

Other districts containing economically viable ore bodies exist outside of the CMB, notably the Thirtynine Mile Volcanic Field west of Colorado Springs. While rich deposits of gold were found near Central City and many other locations in the CMB, the relatively rare  gold/tellurium ore found near Cripple Creek and Victor on the periphery of the Thirtynine Mile Volcanic Field have provided approximately half of all the gold mined in Colorado. Gold has an affinity for tellurium and may be found combined with it in the form of the mineral calaverite.

In particular, the Cresson mine near Cripple Creek has been an especially rich producer of gold. In November of 1914, a 4 m x 8 m x 13 m cavity or “vug” at the 1200 ‘ level was found to be lined with gold telluride and other minerals.  Depending on which source you believe, it is reported that from 20,000 to 60,000 ounces of gold were removed from this small space.

The Cripple Creek volcanic complex is a highly altered, highly brecciated formation that has been described in detail elsewhere. The link provides a more detailed description and a bibliography.

Links updated 7/2/19.

Energetic Materials Manufacture

Everyday in factories around the world, people manufacture energetic materials at the commercial scale. Yet we do not witness a continuous stream of reports describing industrial tragedies at these facilities. Plants for the manufacture of energetic compositions are often purpose built with many layers of protection (LOP) built-in. Such facilities may be constructed in remote locations and with assets separated by large distances.

What is telling about explosive chemical manufacturing is the extent to which the operators possess a deep level of knowledge of their materials and processes. The explosives industry has at its fingertips a wide variety of tests that assay certain manifestations of sensitivity.  There are many tests that assay for friction sensitivity and for shock sensitivity. Impact and electrostatic stimuli are also important dimensions not only for manufacture, but for use in the field.

For instance, a material with a high detonation velocity may have a large critical diameter, meaning that the packing density and bulk geometry must be sufficiently large for it to propagate a shock. Knowledge of impact sensitivity, shock sensitivity, or detonation velocity alone does not tell the whole story of the explosive.

There are several causes for this depth of knowledge. Easiest to see is the history of US explosives manufacture.  There have been many spectacular industrial accidents going as far back as the revolutionary war. Much has been learned about manufacture and handling at a very high cost to lives and property. The explosives industry has had to learn to develop safe manufacturing practices to prevent the loss of life and business interruption.

Another motivating influence for explosives safety is perhaps less than obvious to outside observers. Over time, the US military has been revising and modifying its munitions designs and specifications.  It is highly desirable that explosives and propellants provide maximum energy density for performance requirements, but at the same time be sufficiently insensitive to inadvertant stimulus so as to provide maximum safety for those handling the munitions.

The properties of military explosives- a major market driver- are highly specified by military procurement. The current library of explosive compositions have been highly refined through many years of evaluation and field testing. The effect has been that the compositions presently in the field are quite well understood in terms of their operational boundaries.

In addition to being driven by material specifications, manufacturing facilities and quality control systems are also driven by a selection process that is quite stringent.  We see fewer explosive plant disasters today not only because the explosives are safer, but also because plants are managed better.

The lesson in this for fine chemical operators is that depth of knowledge of materials and reaction mixtures can be highly desirable and potentially very useful. In particular, an intimate understanding of the behavior and sensitivity of materials under process conditions as well as off-normal conditions can lead to safer plant operations.

Seems like a “No-Brainer”. But the fact is that the activity leading to such knowledge can be difficult, time consuming, and expensive to obtain. The push to get product out the door can be irresistable and the urge to cut corners can happen quietly and without fanfare. It is very easy for institutional knowledge to be lost in the struggle to maintain output and profitability.

Fine chemical manufacturers can be hobbled in their understanding in other ways. On the producers side or on the users side of fine chemicals, it is not unusual for chemists to specify methods of analysis that are familiar to them. NMR or GCMS or a variety of wet chemical methods set up on the benchtop are commonly used to set specifications and to validate certificates of analysis. 

However, familiar methods of analysis tend to give profiles of familiar properties. Unfamiliar properties or contaminants may be invisible to any given method of analysis. A compound with a low threshold to decomposition or one that will exotherm vigorously and shed mass aggressively may reveal this attribute only through happenstance to an alert chemist.

What is especially interesting about explosives testing is the extent to which compositions are subjected to challenge tests. Rather than looking for a spectral signature, materials are subjected to a variety of stimuli in a manner that provides an unambiguous outcome. The card gap test for instance looks at the sensitivity of a composition to a standard stimulus that has been attenuated through a variable gap (set of spacers) of polymethylmethacrylate or air. Does it produce a hole in the witness plate or not?

There are people who go to work in nitroglycerin factories everyday knowing that they are working with a shock sensitive high explosive. Others may work in a lead styphnate factory filling primer cartridges by hand.

There are also people who go to work everyday in plants that have banned the use of diethyl ether or require peer review of even the simplest reaction they run in their fume hoods. The range of what is considered acceptable risk varies greatly.

Today, there is a mandate for IM- Insensitive Munitions. Here is the scenario- a TNT filled projectile is impacted by a large caliber projectile or shrapnel. There is a good chance the stimulus provided by the impacting body will initiate the TNT and cause the charge to explode, causing death or harm to those in the area.  It is desirable to have high explosives that detonate or deflagrate only when properly initiated.

A major push is being made at government and industrial labs to produce explosive compositions that are insensitive to inadvertant stimulus, yet energetic enough to perform the task.  One desired end of this activity is to phase out TNT in military explosives. The lack of US manufacturers of TNT is nearly as important a motivating factor as the sensitivity issues are. From the industrial hygiene side, some workers reportedly become sensitized to TNT, so the elimination of this toxicological dimension is desirable as well.

Green munitions are also part of a phase change in the munitions field. At first blush it seems silly to make explosive devices more environmentally friendly. However, explosive chemicals and their decomposition products can be widely dispersed in the environment as the result of warfare and training. The reduction of toxic residues can be considered a reduction in collateral damage.

Green Propellants

Notes from the Field-

There appears to be a movement in the gun and rocket propellant field away from perchlorates.  Propellants that are comprised of substances that pose minimal potential for the dispersal of adverse and environmentally persistant substances are referred to as “green propellants”.  Substances that qualify as adverse include arylamines, perchlorates, and certain rheology modifiers. Substances that are thought to be endocrine disrupters have been specially targeted for replacement.

While it may seem absurd to attempt to produce a weapon system having a reduced toxic signature, the  fact is that between practice projectiles and warshots, a good deal of hazardous residues are released in the use of these devices. Reducing the chemical environmental insult is a step in the direction of reduced collateral damage.

One expert in the area of perchlorates said that people with adequate iodine intake shouldn’t worry about perchlorate contamination of water. Hmmm. While that may be true, it sounds like a poor basis for policy.

Mea Culpa

Today I found myself attending a talk on mortar propellants. It was delivered by a shy young woman who looked to be no older than a high school senior- she looked like a babysitter you’d hire to stay at home with the kid while you treated the wife unit to a night out on the town. Yet she was an expert in mortar shell propellants.

Next, I attended a talk on flare compositions delivered by a tiny woman who could barely see above the podium.

I rounded the day off by attending a talk by a woman who presented her results on igniter design and in developing a new explosive propellant manufacturing process. During the Q&A, my questions on ignition mechanisms were answered by yet another woman who was exceedingly knowlegeable in this field.

What I have noticed is that the gun and rocket propellant R&D field is populated with women to a much greater degree than the industrial organic or organometallic chemistry waters in which I normally swim.

Before you fire a rude comment alleging some sexist malfeasance, please understand that I was raised by a single mother as the eldest of 5 kids. That, and having witnessed the birth of my child, I have no doubt whatsoever about the robustness and Ability of women.

That women do this isn’t news. What is noteworthy is the extent to which my ignorance remains so great at age 51. My caveman misconception was that explosives chemistry would not appeal to women. I had mistakenly and foolishly assumed that a career with explosives was largely a male domain and driven by male fascination with power. Holy cats. I was quite mistaken.

I seem to be wrong about  a lot of things these days.

Research and Playfulness

As a kid I noticed that many cats seemed to lose their playfulness as they matured. What were once playful kittens would mature into rather less playful adult animals with irritability issues. Many humans I know seem to have “matured” away from a general disposition to playfulness in a similar way. It is a shame. Playfulness is an important expression of brain vitality.

Play can be manifested in many ways. One form is where one teases out a response from a stimulus. It can be done for simple joy, as in the case of teasing your sister. Or it can be directed to somewhat more useful and enduring outcomes as in the case of research.

As I look back on my meager list of useful developments in the laboratory, I can see that most were the result of play. I was just curious as to a particular outcome. If I had simply paid more attention to my boss and focused on getting expected results (a production activity), it is unlikely that I would have fallen into some interesting and useful insights. No doubt almost every scientist can make the same claim.

On the other hand, if I had paid more attention to my boss, perhaps I’d be  a tenured prof at a decent university or a mid-career manager at Pfizer. Hmmm.

What happens to many people when they age is the same thing that happens to cats. They settle into comfortable patterns and try to exclude surprises from their lives. Just like it takes discipline to get regular exercise, it also takes some discipline to keep imagination and playfulness a central part of your consciousness.  Go out there and try something that has been on your mind all these many months! See if it works.

Safety Communication by Walking Around

For people who are working in the chemical process business, there is always the question of adequate information for the safe conduct of a process. How does one fold new process safety details into an organizational structure so as to gain the greatest benefit?

One method is to simply issue memos and rely on management SOP’s for enforcement.  This kind of passive distribution of information must compete with all the other channels of information flowing into the brains of coworkers. Memos that are badly written or bursting with details are sure to be poorly absorbed. Eventually, people cannot reliably digest additional information on top of an already complex task.

The word that always comes up is “communication”. True enough, but too often communication comes in the form of training which consists of a PowerPoint recitation to a passive audience. This is not training- it is a briefing.

Communication often manifests as a memo or as a new folder on some disk drive. Again, this is a passive form of communication that does not necessarily engage the recipient.

I think that effective safety communication requires “management by walking around”. If safety information arises that is critical, then what better way than to walk around and collect disciples of safety? Mobility and strength of personality can be far more effective than even the best memo, SOP, or policy. 

Much of specialized expertise resolves to a finite number of rules and specialized awareness on top of a foundation of more generic knowledge.  Specialized expertise may be difficult to acquire, but in practice it is of finite scope. An engaging and ebullient manager can help people absorb complex information by breaking it down into a hierarchy of pieces and rules. The practice of filing information into a folder and relying on people to go out and look for it is a poor substitute for active engagement.

Software from Symyx

I was interested to learn that Symyx offers a chemical structure drawing package called Symyx Draw 3.1. Naturally, a company as deep into cheminformatics as Symyx is has much to offer in regard to data management. The company offers a large variety of software packages. Unfortunately, I was unable to get any pricing information straight off the web. They require that you contact them for a quotation. Having been in sales, I understand the reasons for this, but it is still less than convenient.

It would be interesting to hear from readers who have used Symyx Draw do a compare and contrast with ChemDraw.

The lab as a shop

Just sent multiple kgs of a rare earth reagent out the door. It may have been one of the larger scaleups of this stuff. I hope it does the job for the customer. Meeting certain specs turned out to be more difficult and time consuming that I had anticipated. But getting it certed and shipped is quite satisfying.

Lots of new projects in the shop for examination and custom synthesis. Some process safety tests, some analytical development, and some synthesis. It’s a good mix and quite diverse in chemical elements.