The FFC -Cambridge (Metalysis) Metal . . . esp. Ti . . . reduction process

F/N: A key breakthrough, from the Adv Materials & Processes article:

https://www.asminternational.org/documents/10192/1884362/amp16202p051.pdf/c40e8850-2fc7-456b-a0ec-b4b6e650e9bd Working in the Materials department at Cam-bridge University in the early 1990’s, Derek Fray, Tom Farthing, and George Chen were investigating methods for eliminating the oxide film from the surface of titanium. The work yielded an unex-pected and very dramatic result: They found that if they applied an electric current, they could con-vert the titanium oxide directly to metal. Further work showed that molten-salt electrolysis could convert samples of titanium dioxide directly to ti-tanium metal (Fig. 1 [--> see OP]). The simplicity of the process surprised the team, who were amazed that the phenomenon had not already been discovered. In fact, the main reason for this was that they were using a titanium oxide cathode, an idea that had not been previously con-sidered because it is an electrical insulator. The rev-olutionary discovery became known as the FFC Cambridge Process, taking its name from the in-ventors and their university.

So, the key insight was to use an unexpected material in a familiar context, a molten salt electrolytic process; namely an insulator. Shades of TRIZ and of lateral thinking. Further to this, we are looking at something that is inherently highly modular at efficient scale: an electrolytic cell. That means, once low cost electricity is available, we can pick the cheaper of, build near a transportation nexus, build near the electrical source, build near an ore source; or in the ideal case, cluster all three. Where, of course, nowadays, fibre optic cable brings in industrial strength access to the infosphere. (For solar system colonisation, we can connect the system-wide network using inter-planetary microwave or possibly maser or laser relays.) As a comparison, the Ruhr industrial zone was strategic because it was on the Rhine and had coal. Iron ore could be brought in. Then, once the metals are won, it is convenient to add value by manufacturing products nearby, using the industrial metals and alloys. This then opens up the circle of economic growth and development, with the construction industry as a key catalytic step. Population and commerce will be attracted, thence services; climbing the Hayek value added triangle and creating the economic base for reasonable taxation to provide key services. Opening up a new industrial order, in short. Also, showing how lengthening the tail of the Hayek triangle into the productivity core of knowledge, innovation, strategic resources and networks, sci and tech with sound government can potentially trigger transformation. KFkairosfocus

December 14, 2019

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F/N: Now that I can see how to get acceptably formatted chem eqns, here is Wiki on the FFC process:

Process The process typically takes place between 900 and 1100 °C, with an anode (typically carbon) and a cathode (oxide being reduced) in a bath of molten CaCl2. Depending on the nature of the oxide it will exist at a particular potential relative to the anode, which is dependent on the quantity of CaO present in CaCl2. The cathode is then polarised to a more negative voltages versus the anode. This is simply achieved by imposing a voltage between the anode and cathode. When polarised to more negative voltages the oxide releases oxygen ions into the CaCl2 salt, which exists as CaO. To maintain charge neutrality, as oxygen ions are released from the cathode into the salt, so oxygen ions must be released from the salt to the anode. This is observed as CO or CO2 being evolved at the carbon anode. In theory an inert anode could be used to produce oxygen. When negative voltages are reached, it is possible that the cathode would begin to produce Ca (which is soluble in CaCl2). Ca is highly reductive and would further strip oxygen from the cathode, resulting in calciothermic reduction. However, Ca dissolved into CaCl2 results in a more conductive salt leading to reduced current efficiencies. Cathode reaction mechanism The electro-calciothermic reduction mechanism may be represented by the following sequence of reactions. (1) MOx+ x Ca --> M + x CaO When this reaction takes place on its own, it is referred to as the "calciothermic reduction" (or, more generally, an example of metallothermic reduction). For example, if the cathode was primarily made from TiO then calciothermic reduction would appear as: TiO + Ca --> Ti + CaO Whilst the cathode reaction can be written as above it is in fact a gradual removal of oxygen from the oxide. For example, it has been shown that TiO2 does not simply reduce to Ti. It, in fact, reduces through the lower oxides (Ti3O5, Ti2O3, TiO etc.) to Ti. The calcium oxide produced is then electrolyzed: (2a) x CaO --> x Ca2+ + x O2- (2b) x Ca2+ + 2x e- --> x Ca and (2c) x O2- --> x/2 O2 + 2x e- Reaction (2b) describes the production of Ca metal from Ca2+ ions within the salt, at the cathode. The Ca would then proceed to reduce the cathode. The net result of reactions (1) and (2) is simply the reduction of the oxide into metal plus oxygen: (3) MOx --> M + x/2 O2 Anode reaction mechanism The use of molten CaCl2 is important because this molten salt can dissolve and transport the O2? ions to the anode to be discharged. The anode reaction depends on the material of the anode. Depending on the system it is possible to produce either CO or CO2 or a mixture at the carbon anode: C + 2O2- --> CO2 +4 e- C + O2- --> CO + 2 e- However, if an inert anode is used, such as that of high density SnO2, the discharge of the O2? ions leads to the evolution of oxygen gas. However the use of an inert anode has disadvantages. Firstly, when the concentration of CaO is low, Cl2 evolution at the anode becomes more favourable. In addition, when compared to a carbon anode, more energy is required to achieve the same reduced phase at the cathode. Inert anodes suffer from stability issues. 2O2- --> O2 + 4 e-

KFkairosfocus

December 14, 2019

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F/N: Wiki summary of Kroll Ti reduction:

Prior to the Kroll process, titanium is separated from its ores by the chloride process. For this process, the feedstock consists of refined rutile or ilmenite. This mixture reduced with petroleum-derived coke in a fluidized bed reactor at 1000 °C. The resulting mixture is then treated with chlorine gas, affording TiCl4 and other volatile chlorides, which are subsequently separated by continuous fractional distillation:[2] FeTiO 3 + C --> Fe + TiO 2 + CO TiO 2 + 2 C + 2 Cl 2 --> TiCl 4 + 2 CO In the Kroll process, the TiCl4 is reduced by liquid magnesium at 800–850 °C in a stainless steel retort to ensure complete reduction:[3][4] TiCl 4 + 2 Mg --> Ti + 2 MgCl 2 Complications result from partial reduction of the TiCl4, giving to the lower chlorides TiCl2 and TiCl3. The MgCl2 can be further refined back to magnesium. The resulting porous metallic titanium sponge is purified by leaching or heated vacuum distillation. The sponge is jackhammered out, crushed, and pressed before it is melted in a consumable carbon electrode vacuum arc furnace. The melted ingot is allowed to solidify under vacuum. It is often remelted to remove inclusions and ensure uniformity. These melting steps add to the cost of the product. Titanium is about six times as expensive as stainless steel.

KFkairosfocus

December 14, 2019

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See the potential synergy between industrial advancement and dissemination for broad based development (breaking the poverty trap) and onward sol system colonisation?kairosfocus

December 14, 2019

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F/N: Refocussing the FFC process, let's see a few points. I have also added a couple of illustrations to the OP. First, on the process:

https://www.chemeurope.com/en/encyclopedia/FFC_Cambridge_process.html History and invention The method was invented by three scientists, George Z. Chen, Derek J. Fray and Tom W. Farthing, between 1996 and 1997 in the University of Cambridge, from the names of whom derive the three letters in the name of the process. Chen was the first to discover in late 1996 that oxide scales on titanium foils can be reduced to the metal by molten salt electrochemistry. After seeing the evidence with thick oxide scales, Fray suggested an experiment to reduce small pellets of titanium dioxide powder, which Chen carried out successfully between late 1996 and early 1997. Farthing, who first suggested to electrochemically remove oxygen from titanium metal, later commented on the discovery as "completely out of expectation". Chemistry of the process The basic underlying principle of the FFC Cambridge process is that metallic calcium - unlike sodium or magnesium - is quite soluble in its own molten chloride salt: molten calcium chloride dissolves up to a few mole percent calcium metal (3.9 mol% Ca at 900 °C). This molten salt dissolved, molten calcium metal is free to wander about in the melt, including diffusing into and reducing crystalline titanium and other metal oxides. The calcium mobility in the melt is both a blessing and a curse: it's a blessing for providing this calciothermic reduction of titanium dioxide, but a curse when it comes to current efficiency, because the cathode-reduced metallic calcium can also wander back to the anode, and get reoxidised with the evolved gases there. For this reason, the electrolytic production of pure calcium metal from its molten chloride involves an iron rod cathode that must be gradually raised, and a layer of calcium metal deposits as a continuation of the iron rod. Should the calcium rod be left to soak in the molten salt, it would simply wash away as it forms, and recycle to the anode. For this and other economic reasons, the commercial calcium metal production is done via the aluminothermic reduction/calcium vapor vacuum distillation route instead of an electrolytic one, similar to how magnesium is produced via the silicothermic Pidgeon process. Still, considering that the highly uneconomical batch-based Kroll process can take 2-5 days for a single batch to complete, the coulombic current efficiency losses in the FFC Cambridge process — due to ion recycling between cathode and anode, which can be helped by using suitable electrolyte separating diaphragms — might be quite tolerable. The new method is much simpler in operation and uses less energy than many current industrial technologies, such as the Kroll process, and promises a great potential for cheap production of useful reactive metals such as titanium, zirconium and tantalum. Its other advantage is to produce various metal alloys directly from mixed metal oxide powders, which will offer more saving in energy and operation cost. It is also scientifically interesting because the electrolysis can be carried out on an insulator oxide, such as zirconia and silica. Furthermore, the process can extract pure oxygen gas from oxide based minerals. This is useful, for example, for generating oxygen gas on the Moon from lunar rocks (ilmenite, FeTiO3) to support space travelling and even living by humans.

Observe also:

https://www.asminternational.org/documents/10192/1884362/amp16202p051.pdf/c40e8850-2fc7-456b-a0ec-b4b6e650e9bd The FFC Cambridge process, patented globally in 1998, is a novel electrolytic method for reducing metal oxide to metal in a molten salt. Although originally de-veloped for titanium, the process economics indi-cate that other metal powders, including chromium, tantalum, silicon, cobalt, molybdenum, vanadium, tungsten, and niobium, can be produced at a frac-tion of the current cost. In the 1950s, the Kroll process produced titanium commercially for the first time, and for the next 40 years millions of dollars were expended searching for a less expensive technology. Kroll had actually predicted that his process would be replaced by an electrolytic process, and finally, in the late 1990’s, the FFC Cambridge process was discovered in the Materials department at Cambridge University. A simple one-step electrochemical method that re-duces metal oxide to metal powder, it is currently being scaled up for the production of a wide range of metals beyond titanium, including tantalum and zirconium.

Si, of course, is the base for modern solid state electronics, as well as being a useful ingredient for steel alloys. Cr, V, Mo, Co and the like are key ingredients for stainless and other high performance steel alloys. Where, today, such alloys are increasingly produced by high pressure fusion of powders, including otherwise hard to combine components. Powder approaches also control size of carbide zones (and allow pervasive nitriding) controlling brittleness and other banes of the steel family of alloys. Notice, here, on universality . . . i.e. potentially a key technology for general production of metals and alloys, including as noted the revolutionary direct production of otherwise hard to manufacture super alloys based on pressure and melting of powdered combinations . . . note, that includes the wave of Nitrogen rich steel alloys with high performance:

https://www.scientific.net/KEM.436.13 The FFC-Cambridge process is a molten salt electrochemical deoxidation method that was invented at the Department of Materials Science and Metallurgy of the University of Cambridge one decade ago [the paper of which this is the abstract, is a decade old]. It is a generic technology that allows the direct conversion of metal oxides into the corresponding metals through cathodic polarisation of the oxide in a molten salt electrolyte based on calcium chloride. The process is rather universal in its applicability, and numerous studies on metals, semimetals, alloys and intermetallics have since been performed at the place of its invention and worldwide. The electro-winning of titanium metal is a particularly rewarding target because of the disadvantages of the existing extraction methods. This article summarises the research work performed on the FFC-Cambridge process at the University of Cambridge and its industrial partners with a focus on the electro-winning of titanium metal from titanium dioxide. Topics addressed encompass the invention of the process, early proof-of-concept work, the identification of the reaction pathway, and the investigation and optimisation of the key process parameters. Also discussed are aspects of technology transfer and some of the development work undertaken to date.

First Industrial plant announced, 2017 - 18:

https://www.materialstoday.com/metal-processing/news/metalysis-powers-up-first-industrial-scale-plant/ Metalysis, a UK powder production company, has opened its first commercial plant in Wath upon Dearne, South Yorkshire, U.K. The project was mechanically completed in Q4 2017 and has since undergone hot commissioning, trial runs, optimisation and handover to operations. The handover shows Metalysis’ transition into commercial production following more than a decade of phased technology development. Metalysis uses a solid-state, modular, electrochemical process to produce metal alloy powder. On an industrial scale, the process could produce tens-to-hundreds of tonnes per annum of niche and master alloys, the company said. The alloys are suitable for industries such as aerospace, automotive, batteries, light-weighting, magnets, mining and 3D printing consumables. The technology has a multi-metal capability which enables the company to produce alloy ‘recipes’ that comparable processing routes reportedly cannot. Currently it can commercially produce a product mix of titanium alloys, master alloys including scandium-aluminide, complex alloys including high entropy alloys, magnet materials, high temperature materials and platinum group metal alloys. ‘In powering up and operating our industrial plant, Metalysis is poised to achieve its target to generate significant profits from our new South Yorkshire production facility,’ said Dr Dion Vaughan, CEO.

That's already interesting. Now, here is the Lunarpedia view, where their primary point of concern is to manage Chlorine, the element they suggest as hard to get on the Moon:

https://lunarpedia.org/w/FFC_Cambridge_Process The FFC Cambridge Process reduces oxides to their metal components by electrolysis in a bath of molten calcium chloride. The process has potential to directly produce oxygen and metal from virtually any oxide. The process works by placing the oxide to be refined into a bath of molten calcium chloride and creating a voltage differential between the oxide component (which forms the cathode) and an anode which is also placed in the bath. Oxygen is stripped off the cathode, where it forms calcium oxide, which is soluble in the calcium chloride bath. This oxide is split at the anode, producing oxygen. The cathode meanwhile is gradually reduced to a porous metallic sponge. The process is currently being developed by Metalysis[1] for terrestrial metal production, specifically for the production of titanium; the developers hope it will eventually replace the Kroll Process. Application To Lunar Colonization In a lunar environment, this process could enable much simpler resource extraction. Experiments have already been done using pellets of sintered lunar regolith stimulant, as well as a non-consumable anode, producing metalized pellets and oxygen[2]. Aluminum/Silicon/Calcium Production from Anorthite Anorthite (CaAl2Si2O8), which makes up much of the Lunar Highlands, could be separated from the regolith by grinding, followed by electrostatic/magnetic beneficiation, and then pressed/sintered into an appropriate cathode. As the oxygen is stripped off, metallic aluminum, silicon, and calcium are produced. The calcium is soluble in the calcium chloride bath, and would need to be continuously distilled out to keep the calcium concentration from becoming too high (which can reduce current efficiencies). Since silicon is not very soluble in aluminum at bath temperatures (900-1100 C), the aluminum and silicon should separate, the silicon remaining solid, the aluminum melting. This molten aluminum is denser than calcium chloride, and should drip out and collect at the bottom, where it can be siphoned off. Once the anorthite cathode is completely reduced, a very porous sponge of silicon remains. For every metric ton of Anorthite processed in this manner, approximately 460 kg oxygen, 193 kg aluminum, 201 kg silicon, and 144 kg calcium would be obtained. Iron/Titanium Production from Ilmenite Ilmenite (FeTiO3), is found in abundance on the lunar Maria and is easily separated through magnetic means. This substance could be processed in the same fashion as Anorthite, resulting in a 54% Iron, 46% Titanium sponge. Separating this alloy into iron and titanium could be done by either distillation or carbonyl extraction. Another option is to first subject the Ilmenite to Hydrogen Reduction, producing Iron and titanium dioxide. The iron could then be separated by carbonyl extraction, distillation, grinding followed by use of a magnet, or by melting and then allowing the products to separate out. The remaining titanium dioxide could then be run through the FFC Cambridge process, producing a titanium sponge. The end result for each ton would be approximately 316 kg Oxygen, 316 kg Titanium, and 368 kg Iron. Other Products Lunar Chromite could also be reduced in the same fashion, producing Ferrochrome, which could be used to add Chromium content to Iron alloys. [--> stainless steels start at 13% Chromium content, useful esp for chemical processes and as a gateway to supersteel alloys useful where strength, toughness, edge holding and resistance to rust are important] Many of the above listed reductions would also contain amounts of Magnesium and Sodium (Lunar Ilmenite in particular is known to be highly enriched with Magnesium), which could be distilled out fairly easily due to their low boiling points.

In short, we see here what looks like a promising general reduction and alloying technology suitable for industrial transformation and for solar system colonisation. Where, the key is low cost electricity. Win, win, win. Now, ask yourself, why something like this -- great news for technological progress to the common benefit [just think, medical alloys and uses in engines and transportation systems] is not getting the splash headline, news channel chyron tickertape, talking head panel with remotes from the site 24/7 news and views cycle treatment. KFkairosfocus

December 14, 2019

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Doubter, in due course we will see just how much of a pipe dream long term -- I am thinking 100 - 200 years as opening phase -- sol system colonisation etc are. Recall, though, that targets 1, 2 and 3 are the Moon, Mars and the Asteroid belt, all of which are resource rich and none of which have hellish conditions. Onward, would be gas giant Moons. Where, the key point would be, resources not population centres in the first instance. Where, too, we should reflect on flight c. Dec 16, 1903 and how what we now routinely see all around must have then seemed an opium pipe dream; indeed, it took years for people to believe and take the Wrights seriously. Where also, a simple, readily accessible calculation will show that at 4 people per family, 7.5 billion people could occupy 1-acre plots in the land area of Australia; that sort of space per family can come pretty close to self-sufficiency, esp. for food and perhaps basic energy use. Though, I am more thinking of small, village like settlements capable of using an open source industrial civ. 2.0 base of technologies. (No, not Kibbutzes.) Our real challenge is not population (which is trending demographic collapse actually, currently) but energy and resources. That's part of why I have pointed to the FFC-Cambridge molten salt electro reduction process as precisely a key breakthrough for winning strategic metals for high tech development, starting with Titanium. Onward, I intend to point to an alternative industrial strategy that can open the way to transformation of our planet while opening up technologies and systems that would support solar system colonisation. And, part of why I am raising this is that it is beginning to seem evident that by needlessly or in part artificially cramping our horizons and promoting a sense of overcrowding and almost hopeless crisis, there has been a long term trend of indoctrination and softening up for subjugation under a de facto global superstate and under supportive power centres in the media, unis, thinktanks, foundations, world-level big boys clubs etc, ruled by unaccountable mandarins. We need to deliberately break out of the globalist elite-controlled business as usual agendas and seemingly ironclad but actually utterly fallacious and cramping frames of thought. KF PS: If you think such a view of the global elites is overly suspicious, I suggest that you have a look at the early wills of the notorious rapist of Africa and founder -- not coincidentally -- of the Rhodes Scholarships, Cecil B Rhodes.kairosfocus

December 12, 2019

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....but first let us ponder the idea of open source re-industrialisation as a kick-starter for development and tech base for solar system colonisation.

Solar system "colonization" is a pipe dream, mainly because none of the other Solar system planets (or any of the asteroidal bodies) are anything else than hellish wastelands to Earth life, especially humans. Extremely hostile environments, all of them, requiring a lot of very high technology mostly not yet developed, to protect fragile human bodies. Intolerable temperatures, pressures, poisonous atmospheric gases, the list goes on. Probably the worst is high radiation levels, requiring some kind of shield technology that is as of yet pure science fiction. Certainly the notion of self-sustaining colonies is pure science fantasy. I think there is no practical or feasible "plan B" involving human survival in outer space colonies - we are stuck with our very privileged Earth, which we are rapidly ruining.doubter

December 12, 2019

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Thinking about moving civilisation forward: The FFC -Cambridge (Metalysis) Metal . . . esp. Ti . . . reduction process . . .kairosfocus

December 12, 2019

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