Roman Concrete

I hope all of you had a Merry Christmas and a Happy New Year, and 2023 is shaping up well for you. They say the end of the year is a time to look back, so why not look really back? Quite some time ago, I visited Rome, and I have always been fascinated by the Roman civilization, so why not start this year by looking that far back?

Perhaps one of the more rather remarkable buildings is the Pantheon, which has the world’s largest unreinforced concrete dome. That was built under the direction of Marcus Vipsanius Agrippa, the “get-things-done” man for Augustus. No reinforcement, and it lasted that long. Take a look at modern concrete and as often as not you will find it cracks and breaks up. Concrete is a mix of aggregate (stones and sand) that provides the bulk, and a cement that binds the aggregate together. We use Portland cement, which is made by heating limestone and clay (usually with some other material but the other material is not important) in a kiln up to about 1450 degrees Centigrade. The product actually depends to some extent on what the clay is, but the main products are bellite (Ca2SiO4) and alite (Ca3SiO5). If the clays contain aluminium, which most clays do, various calcium aluminosilicates are formed. Most standard cement is mainly calcium silicate to which a little gypsum is added at the end, which makes the end surface smoother.

Exactly what happens during setting is unknown. The first thing to note is that stone does not have a smooth surface at close to the molecular level, and further, stones are silicates, in which the polymer structure is perforce terminated at the surface. That would mean there are incomplete bonds. An element like carbon would fix this problem by forming double bonds but silicon cannot do that so these “awkward” surface molecules react with water to form hydroxides. What I think happens is the water in the mix hydrolyses the calcium silicate and forms silica with surface hydroxyls, and these eliminate with hydroxyls on the stone, with the calcium hydroxide also taking part, in effect forming microscopic junctions between it and stone. All of this is slow, particularly when polymeric solids cannot move easily. So to make a good concrete, besides getting the correct mix you have to let it cure for quite some time before it is at its best.

So what did the Romans do? They could not make cement by heating clay and lime up to that temperature easily, but there were sources where it was done for them: the silicate around volcanoes like Vesuvius. The Roman architect and engineer Vitruvius used a hot mix of quicklime (calcium oxide) that was hydrated and mixed with volcanic tephra. Interestingly, this will also introduce some magnesiosilicates, which are themselves cements, but magnesium may fit better than calcium onto basaltic material. For aggregate Vitruvius used fist-sized pieces of rock, including “squared red stone or brick or lava laid down in courses”. In short, Vitruvius was selecting aggregate that was much better than ordinary stone in the sense of having surface hydroxyl groups to react. That Roman concrete lasted so long may in part be due to a better choice of aggregate.

A second point was the use of hot mixing. One possibility is they used a mix of freshly slaked lime and quicklime and by freshly slaking the mix became very hot. This speeds up chemical reactions, and also allows compound formation that is not possible at low temperatures. By reacting so hot it reduced setting times. But even more interestingly, it appears to allow self-healing. If cracks begin to form, they are more likely to form around lime clasts, which can then react with water to make a calcium-rich solution, which can react with pozzolanic components to strengthen the composite material. To support this, Admir Masic, who had been studying Roman cement, made concretes using the Roman recipe and a modern method. He then deliberately cracked the samples and ran water through them. The Roman cement self-healed completely within two weeks, while the cracks in the modern cement never healed.

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Rocky Planets and their Atmospheres

The previous post outlined how I consider the rocky planets formed. The most important point was that Earth formed a little inside the zone where calcium aluminosilicates could melt and phase separate while the star was accreting, as when the disk cooled down this would create a dust that, when reacted with the water vapour in the disk, would act as a cement. The concept is that this would bind basaltic rocks together, especially if the dust was formed in the collision between the rocks. The collisions were, by and large, gentle at first, driven by the gas sweeping smaller material closer to bigger material. Within this proposed mechanism, because the planet grows by collisions with objects at low relative velocities, the planet starts with a rather porous structure. It gradually heats up due to gravitational potential energy being converted to heat as more material lands, and eventually, if it gets to 1550 degrees, iron melts and runs down the pores towards the centre, while aluminosilicates, with densities about 0.4 – 1.2 g/cm³less than basalt, move upwards. The water is driven from the cements and also rises through the porous rock to eventually form the sea. The aluminosilicates form the granitic/felsic continents upon which we live.

Earth had the best setting of aluminosilicates because after the accretion disk cooled, it was at a temperature where these absorbed water best. Venus is smaller because it was harder to get started, as the cement was sufficiently warm that water had trouble reacting, but once it got going the density of basaltic and iron-bearing rocks was greater. This predicts Venus will have small granitic/felsic cratons on its surface; we have yet to find them. Mercury probably formed simply by accreting silicates and iron during the stellar accretion stage. Mars did not have a good supply of separated aluminium oxides, so it is very short of granite/felsic rock, although the surface of Syrtis Major appears to have a thin sheet of plagioclase. Because the iron did not melt at Mars, its outer rock would have contained a lot of iron dust or iron oxide. Reaction with water would have oxidised it subsequently. Most Martian rocks have roughly the same levels of calcium as Earth, about half the aluminium content, and about half as much again of iron oxide, which as an aside, may be why Mars does not have plate tectonics: because of the iron levels it cannot make eclogite which is necessary for pull subduction.

However, there is also a lot of chemistry going on in the stage 1 accretion disk in addition to what I have used to make the planets. In the vapour phase, carbon is mainly in the form of carbon monoxide in the rocky planet zone, but this can react catalytically with hydrogen to make methanol and hydrocarbons. These will have a very short lifetime and would be what chemists call reactive intermediates, but they would condense on silicates to make carbonaceous material, and they will react with oxides and metal vapour to make carbides. At the temperatures of at least the inner rocky planet zone, nitrogen reacts with oxides to make nitrides, and with carbides to make cyanamides, and some other materials.

Returning to the planet while it is heating up, the water coming off the cement should be quite reactive. If it meets iron dust it will oxidise it. If it meets a carbide there will be options, although the metal will invariably become an oxide. If the carbide was of the structure of calcium carbide it will make acetylene. If it oxidises anything, it will make hydrogen and the oxide. For many carbides it may make methane and metal oxide, or carbon monoxide, and invariably some hydrogen. Carbon monoxide can be oxidised by water to carbon dioxide, making more hydrogen, but carbon monoxide and hydrogen make synthesis gas, and a considerable variety of chemicals can be made, most of which are obvious contenders to help make life. Nitrides react with water largely to make ammonia, but ammonia is also reactive, and hydrogen cyanide and cyanoacetylene should be made. In the very early stages of biogenesis, hydrogen cyanide is an essential material, even though now it is poisonous.

This explains a little more of what we see in terms of the per centage composition. Mars, as noted above, has extremely little felsic/granitic material, and has a much higher proportion of iron oxide. It has less carbon dioxide than expected, even after allowing for some having escaped to space, and that is because since Mars was cooler, the high temperature carbide formation was slower. It has less water because the calcium silicates absorb less, although there is an issue here of how much is buried under the surface. The nitrogen is a puzzle. Mars has extremely little nitrogen, and the question is, why not. One possibility is that the temperatures were too low for significant nitride production. The other possibility, which I proposed in my novel Red Gold, is that at least some nitrogen was there and was emitted as ammonia. If so, it solves another puzzle: Mars has clear signs of ancient river flows, but all evidence is it was too cold for ice to melt. However, ammonia dissolves in ice and melts it down to minus eighty degrees Centigrade. So, in my opinion, the river flows were ammonia/water solutions. The carbon would have been emitted as methane, but that oxidises to carbon dioxide in the presence of water vapour and UV light.  Ammonia reacts with carbon dioxide first to form ammonium carbonate (which will also lower the melting point of ice) then urea. If I am right, there will be buried deposits of urea, or whatever it converts to after billions of years, in selected places on Mars.

The experts argue that methane and ammonia would only survive for a few years due to the UV radiation. However, smog would tend to protect them, and Titan still has methane. Liquid water also tends to protect ammonia. There are two samples from early Earth. One is of the atmosphere encased in rock at Isua, Greenland. It contains methane (as well as some hydrogen). The other is from Barberton (South Africa) which contains samples of seawater trapped in rock. The concentration of ammonia in seawater at 3.2 Gy BP was such that about 10% of the planet’s nitrogen currently in the atmosphere was in the sea in the form of ammonia.

We finally get to the initial question: why is Venus so different? The answer is simple. It will have had a lower per centage of cement and a high per centage of basalt simply because it formed at a hotter place. Accordingly, it would have much less water than Earth. However, it would have had more carbides and nitrides, and that valuable water got used up making the atmosphere, and in oxidising sulphur to sulphates. Accordingly, I expect Venus to have relatively small deposits of granite on the surface.

There is also the question of the deuterium to hydrogen ratio, which is at least a hundred times higher than solar. If the above mechanism is right, all the oxygen in the oxides, and all the nitrogen in the atmosphere, came from water reacting. My answer is that just about all the water was used up making the atmosphere, sulphates, and whatever. The initial reaction is of the sort:

R – X  + H2O  ->  R –OH + H – X

In this, one hydrogen atom has to transfer from the water to the X (where it will later be dislodged and lost to space). If there is a choice, the atom that is most weakly bonded will move, and deuterium is bonded quite more strongly than hydrogen. The electronic binding is the same, but there are zero point vibrations, and hydrogen, being lighter uses more of this as vibrational energy. In general chemistry, the chemical isotope effect, as it is called, can make the hydrogen between four and twenty-five times more likely to move, depending on the activation energy. Venus did not need to lose the supply of water equivalent to Earth’s oceans to get its high deuterium content; the chemical isotope effect is far more effective.

Further details can be found in my ebook “Planetary Formation and Biogenesis”http://www.amazon.com/dp/B007T0QE6I.

How do Rocky Planets Form?

A question in my last post raised the question of how do rocky planets form, and why is Venus so different from Earth? This will take two posts; the first covers how the planets form and why, and the second how they evolve immediately after formation and get their atmospheres.

First, a quick picture of accretion. At first, the gas cloud collapses and falls into the star, and in this stage the star the size of the sun accretes something like 2.5 x 10^20 kg per second. Call that stage 1. When the star has gobbled up most of the material, such accretion slows down, and in what I shall call stage 2 it accretes gas at least four orders of magnitude slower. The gas heats due to loss of potential energy as it falls into the star, although it also radiates heat from the dust that gets hot. (Hydrogen and helium do not radiate in the infrared easily.) In stage 1, the gas reached something like 1600 degrees C at 1 A.U. (the distance from Earth to the sun). In stage 2, because far less gas was falling in, the disk had temperatures roughly what bodies have now. Even in stage 2, standard theory has it that boulder-sized objects will fall into the star within about a hundred years due to friction with the gas.

So how did planets form? The standard explanation is that after the star had finished accreting, the dust very rapidly accreted to planetesimals (bodies about 500 km across) and these collided to form oligarchs, and in turn these collided to form planets. I have many objections to this. The reasons include the fact there is no mechanism to form the planetesimals that we assume to begin with. The calculations originally required one hundred million years (100 My) to form Earth, but we know that it had to be essentially formed well before that because the collision that formed the Moon occurred at about 50 My after formation started. Calculations solved the Moon-forming problem by saying it only took 30 My, but without clues why this time changed. Worse, there are reasons to believe Earth had to form within about 1 My of stage 2 because it has xenon and krypton that had to come from the accretion disk. Finally, in the asteroid belt there is evidence of some previous collisions between asteroids. What happens is they make families of much smaller objects. In short, the asteroids shatter into many pieces upon such collisions. There is no reason to believe that similar collisions much earlier would be any different.

The oldest objects in the solar system are either calcium aluminium inclusions or iron meteorites. Their ages can be determined by various isotope decays and both had to be formed in very hot regions. The CAIs are found in chondrites originating from the asteroid belt, but they needed much greater heat to form than was there in stage 2. Similarly, iron meteorites had to form at a temperature sufficient to melt iron. So, how did they get that hot and not fall into the sun? The only time the accretion disk got sufficiently hot at a reasonable distance from the sun was when the star was accreting in stage 1. In my opinion, this shows the calculations were wrong, presumably because they missed something. Worse, to have enough material to make the giants, about a third of the stellar mass has to be in the disk, but observation of other disks in stage 2 shows there is simply not enough mass to make the giants.

The basic argument I make is that whatever was formed in the late stages of stellar accretion stayed more or less where it was. One of the puzzles of the solar system is that most of the mass is in the star, but most of the angular momentum resides in the planets, and since angular momentum has to be conserved and since most of that was with the gas initially, my argument is any growing solids took angular momentum from the gas, which sends then mass further from the star, and it had to be taken before the star stopped accreting. (I suggest a mechanism in my ebook.)

Now to how the rocky planets formed. During primary stellar accretion, temperatures reached about 1300 degrees C where Mars would form and 1550 degrees C a little beyond where Earth would grow. This gives a possible mechanism for accretion of dust. At about 800 degrees C silicates start to get sticky, so dust can accrete into small stones there, and larger ones closer to the star. There are a number of different silicates, all of which have long polymers, but some, especially aluminosilicates are a little more mobile than others. At about 1300 degrees C, calcium silicate starts to phase separate out, and about 1500 degrees C various aluminosilicates phase separate. This happens because the longer the polymer, the more immiscible it is in another polymer melt (a consequence of the first two laws of thermodynamics, and which makes plastics recycling so difficult.) If this were the only mechanism for forming rocky planets, the size of the finished planet would diminish significantly with distance from the star. Earth, Venus and Mercury are in the wrong order. Mercury may have accreted this way, but further out, stones or boulders would be the biggest objects.

Once primary stellar accretion ends, temperatures were similar to what they are now. Stones collide, but with temperatures like now, they initially only make dust. There is no means of binding silicates through heat. However, if stones can come together, dust can fill the spaces. The key to rocky planet formation is that calcium silicate and calcium aluminosilicates could absorb water vapour from the disk gases, and when they do that, they act as cements that bind the stones together to form a concrete. The zone where the aluminosilicates start to get formed is particularly promising for absorbing water and setting cement, and because iron starts to form bodies here, lumps of iron are also accreted. This is why Earth has an iron core and plenty of water. Mars has less water because calcium silicate absorbs much less water, and its iron is mainly accreted as fine dust.

Finally, Mars is smaller because the solids density is less, and the disk is cleared before it has time to fully grow. The evidence for the short-lived disk is from the relatively small size of Jupiter compared with corresponding planets around similar sized stars that our sun cleared out the accretion disk sooner than most. This is why we have rocky planets, and not planets like the Neptune-sized planets in the so-called habitable zone around a number of stars. Venus is smaller than Earth because it was harder to get going, through the difficulty of water setting the cement, which is partly why it has very little water on its surface. However, once started it grows faster since the density of basaltic rocks is greater. Mercury is probably smaller still because it formed a slightly different way, through excessively mobile silicates in the first stage of the accretion disk, and by later being bombed by very large rocky bodies that were more likely to erode it. That is somewhat similar to the standard explanation of why Mercury is small but has a large iron core. The planets grow very quickly, and soon gravity binds all dust and small stones, then as it grows, gravity attracts objects that have grown further away, which perforce are large, but still significantly smaller than the main body in the zone.

Next post: how these rocky planets started to evolve to where they are now.

Rocky Planet Formation

In the previous posts I have argued that the evidence strongly supports the concept that the sun eliminated its accretion disk within about 1 My after the star formed. During this 1 My, the disk would be very much cooler than while the sun was accreting, and the temperatures were probably not much different from those now at any given distance from the star in the rocky planet zone. Gas was still falling into the star, but at least ten thousand times slower. We also know (see previous posts) that small solid objects such as CAIs and iron bearing meteorites are much older than the planets and asteroids. If the heavier isotope distributions of xenon and krypton are caused by the hydrodynamic loss to space, which is the most obvious reason, then Earth had to have formed before the disk cleanout, which means Earth was more or less formed within about 1 My after the formation of the sun.

The basic problem for forming rocky planets is how does the rocky material stick together? If you are on the beach, you may note that sand does not turn into a solid mass. A further problem is the collisions of large objects involve huge energies. Glancing collisions lead to significant erosion of both objects, and even direct hits lead to local pulverization and intense heat, together with a shock wave going through the bodies. When the shock wave returns, the pulverized material is sent into space. Basically craters are formed, and a crater is a hole. Adding holes does not build up mass. Finally, if the two are large enough and about equal sized, they each tend to shatter as a consequence of the shock waves. This is why I believe the Monarchic growth makes more sense, where what collides with the major body is much smaller. Once the forming object is big enough, it accretes all small objects it collides with, due to gravity, but the problem is, how do small bodies stick together?

The mechanism I developed goes like this. While the star is accreting, we get very high temperatures and anything over 1000 degrees will lead to silicates softening and becoming sticky. This generates pebbles, stones and boulders that get increasingly big as we get closer to the star, because more of the silicates get more like liquids. At 1550 degrees C, iron melts, and the iron liquids coalesce. That is where the iron meteorites come from. By about 1750 – 1800 degrees silicates get quite soft, and it may be that Mercury formed by a whole lot of “liquids” forming a sticky mass. Behind that would be a distribution of ever decreasingly sized silicate masses, with iron cores where temperatures got over 1550. This would be the origin of the cores for Earth, Venus and Mercury. Mars has no significant iron core because the iron there was still in the very small particulate size.

The standard theory says the cores separated out with heavier liquids sinking, but what most people do not realize is that the core of the Earth does not comprise liquid silicates, at least not the mobile sort. You have no doubt heard that heat rises by convection at hot spots, but it is not a sort of kettle down there. The rate of movement has been estimated at 1 mm per year, which would mean the silicates would rise 1000 km every billion years. We are still well short of one complete turnover. Further an experiment where two different silicates were heated to 2000 degrees C under pressure of 26 Gpa showed that the silicates would only diffuse contents a few meters over the life of the Earth. They may be “liquid” but the perovskite silicates are so viscous nothing moves far in them. So how did the core form so quickly? In my opinion, the reason is the iron has already separated from the silicates, and the collision of a whole lot of small spherical objects do not pack well; there will be channels, and molten iron that already exists in larger masses will flow down them. Less-viscous aluminosilicates will flow up and form the continents.

The next part unfortunately involves some physical chemistry, and there is no way around it. I am going to argue that the silicates that formed the boulders separated into phases. An example is oil and water. Molecules tend to have an energy of association, that is all the water molecules have an energy that tends to hold them all together as a liquid as opposed to a gas, and that tends to keep phases separate because one such energy between like molecules is invariably stronger than the energy between different ones. There is also something called entropy, which favours things being mixed. Now the heat of association of polymers is proportional to the number of mers, while the entropy is (to a first approximation) proportional to the number of molecules. Accordingly, the longer the polymers, the less likely they are to blend, and the more likely to phase separate. That is one of the reasons that recycling plastics is such a problem: you cannot blend them because if the polymers are long, they tend to separate in processing, and your objects have “faults” running through them.

The reason this is important, from my point of view, is that at about 1300 degrees C, calcium silicate tends to phase separate from the rest, and about 1500 degrees C, a number of calcium aluminosilicates start to phase separate. These are good hydraulic cements, and my argument is that after cool down, collisions between boulders makes dust, and the cements are particularly brittle. Then if significant boulders come together gently, e.g. as in the postulated “rubble piles”, the cement dust works it way through them, and water vapour from the disk will set the cement. This works up to about 500 degrees C, but there are catches. Once it gets significantly over 300 degrees C, less water is absorbed, and the harder it is to set it. Calcium silicate only absorbs one molecule of water, but some aluminosilicates can absorb up to twenty molecules per mer. This lets us see why the rocky planets look like they do. Mars is smaller because only the calcium silicate cement can form at that distance, and because iron never melted it does not have an iron core. It has less water because calcium silicate can only set one molecule of water per cement molecule, and it does not have easily separable aluminosilicates so it has very little felsic material. Earth is near the optimum position. It is where the iron core material starts, and because it is further from the sun than the inner planets, there is more iron to sweep up. The separated aluminosilicates rise to the surface and form the felsic continents we walk on, and provided more water when setting the cement. Venus formed where it was a little hot, so it was a slow starter, but once going, it will have had bigger boulders to grow with. It has plenty of iron core, but less felsic material, and it started with less water than Earth. This is conditional on the Earth largely forming before the disk gases were ejected. If we accept that, we have a platform for why Earth has life, but of course that is for later.