Liquid Stone

It’s being called Geopolymer.

The claim is that it explains how the Egyptians made the pyramids. While I’m “not so sure” about that (it would take a closer look at the stones of the pyramids; plus we have this eye witness report from Solon that they were assembled using ‘machines’ of some sort, no mention of buckets of slop…) But in any case, we have that as the impetus, and someone then figured out an interesting new technology.

It is not just Portland Cement / concrete…

This has sent me off for a couple of weeks (at odd times of day) learning more about silicate chemistry. The basic effect looks to be that in strong alkali, the silicate monomer tends to become a silicate polymer and that SiO2 – SiO4 range ions come off of various minerals and react.

We typically make Portland Cement with one of these silicates and a particular alkali.
( Lime, Calcium Silicate)

From the wiki on Portland Cement:

Portland cement clinker is a hydraulic material which shall consist of at least two-thirds by mass of calcium silicates (3 CaO·SiO2 and 2 CaO·SiO2), the remainder consisting of aluminium- and iron-containing clinker phases and other compounds. The ratio of CaO to SiO2 shall not be less than 2.0. The magnesium oxide content (MgO) shall not exceed 5.0% by mass.

It goes on to describe some of the other standards (that one is the European) and some of the other formulas.

Portland cement clinker is made by heating, in a kiln, a homogeneous mixture of raw materials to a sintering temperature, which is about 1450 °C for modern cements. The aluminium oxide and iron oxide are present as a flux and contribute little to the strength. For special cements, such as Low Heat (LH) and Sulfate Resistant (SR) types, it is necessary to limit the amount of tricalcium aluminate (3 CaO·Al2O3) formed. The major raw material for the clinker-making is usually limestone (CaCO3) mixed with a second material containing clay as source of alumino-silicate. Normally, an impure limestone which contains clay or SiO2 is used. The CaCO3 content of these limestones can be as low as 80%. Second raw materials (materials in the rawmix other than limestone) depend on the purity of the limestone. Some of the second raw materials used are clay, shale, sand, iron ore, bauxite, fly ash and slag. When a cement kiln is fired by coal, the ash of the coal acts as a secondary raw material.

That last line about “acts as a secondary raw material” has a bit of hint in it. There are two common reactions in cement. One that makes the basic cement, the other that is a reaction with various kinds of embedded silicate materials. The Romans used a cement that was mostly based on this reaction and used volcanic ash for their silicate source. Who’s to say other similar paths are not available?

http://en.wikipedia.org/wiki/Pozzolanic_reaction

The Pozzolanic reaction is the chemical reaction that occurs in hydraulic cement, a mixture of slaked lime (calcium hydroxide) with amorphous siliceous materials (namely, pozzolan or pozzolana, a finely divided volcanic ash, rich in obsidian, a mineral glass commonly found in lava), forming non-water-soluble calcium silicate hydrates. It is the main reaction involved in the Roman concrete invented in Ancient Rome and used to build, for example, the Pantheon.

At the basis of the Pozzolanic reaction stands a simple acid-base reaction between calcium hydroxide, also known as Portlandite, or (Ca(OH)2), and silicic acid (H4SiO4, or Si(OH)4). Simply, this reaction can be schematically represented as follows:

Ca(OH)2 + H4SiO4 → Ca2+ + H2SiO42- + 2 H2O → CaH2SiO4 · 2 H2O

The “question” is this: Are there OTHER potential reactions that can also give us ‘liquid stone’? The answer looks to be ‘yes’…

First, some links to the Geopolymer site:

The general thesis is presented here, in brief:

http://www.geopolymer.org/archaeology/pyramids/artificial-pyramid-stone-new-analysis

The abstract reads: “A comparison was made of the solid-state 29Si, 27Al and 43Ca MAS NMR spectra of the outer casing stone from Snefru’s Bent Pyramid in Dahshour, Egypt, with two quarry limestones from the area. The NMR results suggest that the casing stones consist of limestone grains from the Tura quarry, cemented with an amorphous calcium-silicate gel formed by human intervention, by the addition of extra silica, possibly diatomaceous earth, from the Fayium area.”

That “amorphous calcium-silicate gel” is another way of saying ‘Portland cement’ of a very particular form.

The site also sells a book about it, with the first chapter available as a download pdf here:

http://www.geopolymer.org/fichiers_pdf/pyramid_chapt1.pdf

In it, just a little ways down, is a very striking photograph of several Egyptian style busts, all moulded out of different colors of ‘geopolymer’ or liquid stone.

kaolin, natron salt and chalk, could be poured out and compacted into moulds just as concrete is, directly on the site of the pyramids.

Natron is an alkaline sodium salt, rather than an alkaline calcium salt, but the effect ought to be the same. Silicate from the clay reacting with calcium from the chalk, forming a Calcium Silicate cement (either in a crystalline form or the amorphous form called a ‘gel’ – but it is still a hard stone…)

This causes me to wonder how many OTHER alkaline catalyzed or alkaline facilitated silicate forming chemistries might exist that we have not explored? Feldspars, for example, are a silicate (but containing other metal ions – Potassium, Sodium, Aluminum, etc). Might it be possible to make ‘liquid stone’ using feldspars? Diorite, for example, is very hard but still just another silicate. In Peru are giant stones with ‘interior carving’ made of diorite that folks frequently say “We don’t know how to carve these even today!” (usually followed by pronouncements about extraterrestrial visitation…) Yet the local legends talk about liquid stone and folks making the stone liquid. Rather than some alien rock softening ray gun, might it just be possible to make an alkali catalyzed feldspar that makes a ‘diorite like’ stone on hardening?

The stones do look like various shapes we see in cast concrete. We cast very large objects in concrete, too. Is it THAT far a leap to think we might not have found all ‘liquid stone’ methods? Have we even looked, once we found Portland Cement?

The wiki says some folks are looking:

Geopolymer binders and geopolymer cements are generally formed by reaction of an aluminosilicate powder with an alkaline silicate solution at roughly ambient conditions. Metakaolin is a commonly used starting material for laboratory synthesis of geopolymers, and is generated by thermal activation of kaolinite clay. Geopolymer cements can also be made from sources of pozzolanic materials, such as lava or fly ash from coal. Most studies on geopolymer cements have been carried out using natural or industrial waste sources of metakaolin and other aluminosilicates. Industrial and high-tech applications rely on more expensive and sophisticated siliceous raw materials.

Notice this reaction proceeds at ambient conditions. That “alkaline silicate” is a bit vague, but could be something as simple as water glass. Simple sodium silicate. I first ran into this stuff when my Dad needed to fix a cover over the floor furnace. It had a kind of ‘window’ about 2 inches in diameter that you would vaguely see flickers of fire through… nice to know when it was running. Pour some water glass on, heat, viola! Fresh “glass”…

So mix water glass with clay. Got it ;-)

How do you make it? Mix sodium carbonate with silicon dioxide and heat. That’s natron with quartz sand.

Kaolin is a clay mineral:

Kaolinite is a clay mineral, part of the group of industrial minerals, with the chemical composition Al2Si2O5(OH)4. It is a layered silicate mineral, with one tetrahedral sheet linked through oxygen atoms to one octahedral sheet of alumina octahedra. Rocks that are rich in kaolinite are known as kaolin or china clay.

The name is derived from Kao-ling (Chinese: 高岭/高嶺; pinyin: Gaoling), a village near Jingdezhen, Jiangxi province, China. The name entered English in 1727 from the French version of the word: “kaolin”, following Francois Xavier d’Entrecolles’s reports from Jingdezhen.

Kaolinite has a low shrink-swell capacity and a low cation exchange capacity (1-15 meq/100g). It is a soft, earthy, usually white mineral (dioctahedral phyllosilicate clay), produced by the chemical weathering of aluminium silicate minerals like feldspar. In many parts of the world, it is colored pink-orange-red by iron oxide, giving it a distinct rust hue. Lighter concentrations yield white, yellow or light orange colors. Alternating layers are sometimes found, as at Providence Canyon State Park in Georgia, USA.

So, aluminum silicate instead of calcium silicate. Made by weathering feldspar.

When mixed with natron, a sodium carbonate salt, might we not get some kind of mixed silicate ‘cement’ formed between grains of feldspar? Making something that looks enough like Diorite to be accepted as it?

In this link:

http://www.geopolymer.org/applications/geopolymer-cement

There is an interesting video about some of the chemistry involved, along with a discussion in print of a trademarked cement, named Pyrament, made using some of these geopolymer ideas.

In 1991, the world was impressed on how fast the US Air Force managed to build and equip temporary military airports in the wilderness of Saudi Arabia during the Gulf War. One of the reasons for this efficiency might result from the application by the US Air Force Engineering of a very new rapid high strength and high performance cement, the Pyrament®. Sources: US Air Force Command report and Pyrament brochure.

The American Cement Company, Lone Star Industries, introduced this exceptional cement in 1988. It was the result of an unique collaboration that started in 1983 between the Lone Star Industries Research Center in Houston, Texas, and the Geopolymer Institute. Geopolymer chemistry, in particular the Poly(sialate-siloxo) based system, improves the properties of Portland cement and regular concrete. In the recently updated book Geopolymer Chemistry & Applications several chapters are dedicated to geopolymer , metakaolin-based, rock-based and fly ash-based cements and concretes, see in Chapters 8, 9, 10, 11, 12, 24 and 25. You may also go to the Geopolymer Library and download several papers.

The Pyrament® blended-cement is the ideal material for repairing runways made of concrete, industrial pavements, and highway roads. In the case of a runway, a 4-6 hours hardening is enough to allow the landing of an Airbus or a Boeing. The geopolymeric cement reaches a compression strength of 20 Mpa after 4 hours, whereas plain concrete gets to this strength after several days.

Yeah, 4 to 6 hours to ‘hard as rock’…

There are other interesting products being made as well, though likely not at ‘ambient temperatures':

http://glasscellisofab.com/sheets/calcium/data_sheets/Quads%20&%20Blocks.pdf

Has Calcium Silicate (anhydrous) forms being used to replace asbestos in various heat demanding applications. They also sell an intriguing “silicate based glue” for installing it:

http://glasscellisofab.com/en/calcium.html

The Russians also made a cement similar to Pyrament, but have generally only sold finished product and not talked much about the formula, as near as I can tell, other than calling it ‘soil cement’.

So, about that ‘secondary reaction’ in cement. Is it the same thing or similar? Yup.

Back To Egypt

There is an interesting bit of testament to some kind of Egyptian “liquid stone”, plus a couple of other hints that they worked in this general area of chemical technology.

First we have a “stele” or stone marker enscrptions:

The “Irtysen Stele”:

http://www.relevant-television.com/arikat/proof_irtysen.htm

The Louvre gallery in Paris is where the Irtysen Stele is preserved. This ancient stone inscription does not go back quite as far as the era when the Great Pyramid was built. But it is very old. Some four thousand years old…

It is the autobiographical funerary stele of Irtysen a master craftsman of the priestly caste, who lived 2.000 years BC. In this text Irtysen says he possesses a “secret knowledge” to fabricate stone statues, not by carving them but by casting them in molds.

Irtysen affirms he used a material mixture that hardened when cast inside molds to reproduce any kind of object or figure – a material that fire could not consume, nor water dilute. This suggests that Irtysen worked with a chemically-produced binding matter that could be mixed with certain minerals and poured into a mold, to produce statues.

Sure sounds like ‘liquid stone’ to me. There are a variety of old Egyptian “stone” artifacts that would just be hell to carve, but straight forward to cast or mould. There are some stone dishes that look like fine china, with smooth nearly liquid folding to the ‘petals’.

Then we have two ‘chemically related’ materials. Faience and Egyptian Blue.

http://en.wikipedia.org/wiki/Egyptian_faience

Faience has been defined as the first high technology ceramic, to emphasize its status as an artificial medium, rendering it effectively a precious stone. Egyptian faience is a non-clay based ceramic composed of crushed quartz or sand, with small amounts of calcite lime and a mixture of alkalis, displaying surface vitrification due to the soda lime silica glaze often composed of copper pigments to create a bright blue-green luster. While in most instances domestic ores seem to have provided the bulk of the mineral pigments, evidence suggests that during periods of prosperity raw materials also available locally, such as lead and copper, were imported. Plant ash, from halophitic plants typical of dry and sea areas, was the major source of alkali until the Ptolemaic Period, when natron based alkalis almost completely replaced the previous source. Although the chemical composition of faience materials varies over time and according to the status of the workshop, also as a cause of change of accessibility of raw materials, the material constitution of the glaze is at all times consistent with the generally accepted version of faience glazing.

Do we REALLY know if Egyptian faience was fired, other than for glazing? It has about the right chemical composition for a geopolymer, and we have a stele telling us of the maker claiming to cast similar objects…

Egyptian Faience Statue

Egyptian Faience Statue

Original Image

Another iconic Egyptian technology was “Egyptian Blue”. Widely used, and traded, as a semi-precious material and used as a very blue permanent pigment (the Egyptians really liked blue!)

http://en.wikipedia.org/wiki/Egyptian_blue

What is the chemical formula for Egyptian Blue?

Egyptian blue is chemically known as calcium copper silicate (CaCuSi4O10 or CaO·CuO·4SiO2). It is a pigment used by Egyptians for thousands of years. It is considered to be the first synthetic pigment. The pigment was known to the Romans by the name caeruleum. Vitruvius describes in his work ‘”De architectura” how it was produced by grinding sand, copper and natron and heating the mixture, shaped into small balls, in a furnace. Lime is necessary for the production as well, but probably lime-rich sand was used. After the Roman era, Egyptian Blue fell from usage and the manner of its creation forgotten.

The ancient Egyptian word wedjet signifies blue, blue-green and green, and the same word is used for the human eye, and the protective Eye of Ra.

Couple of things here. Clearly they are working with silicates. They have furnace formed Egyptian Blue, and wet formed (then fired) faience that may or might not need firing. In the case of Egyptian Blue, the product is a Calcium Silicate (not hydrated) but with Copper substituted to some extent to give a nice color. These folks knew something about silicate chemistry…

What was “the mix”?

Silicate sand, copper, natron salt. Heated and formed. With a bit of lime.

Is there any reason to think that mixing lime with silicate could cause it to harden? To form ‘stone like’ materials? Perhaps even if NOT fired? Well, yes. Dumping lime on soft clay soils is a common technique in building and road building to stabilize and harden the soil…

Lime Stabilized Soils and Related

This is a fascinating old PDF about lime stabilized clay. I’ll leave the common construction uses for folks to key word search on their own.

http://www.clays.org/journal/archive/volume%2012/12-1-359.pdf

ABSTRACT
Calcium hydroxide was allowed to react with various clays, other silicates, and quartz at slightly elevated temperatures for several months. The reaction products were examined by X-ray diffraction, DTA, and electron microscopy, and were shown to be poorly crystallized calcium silicate hydrates of the tobermorite family, and calcium aluminate hydrates. Quaternary phases were not detected, but some isomorphous substitution probably occurred. The extent of reaction was shown to be such that under appropriate conditions almost all of the clay mineral was decomposed. Electron micrographs of the reacted materials indicated that attack occurred from the edges of the particles, and in general the remaining unattacked portion of the clay did not suffer appreciable loss of crystallinity. It was postulated that the reaction involved progressive dissolution of the mineral at the edges of the particles in the strongly basic environment maintained by calcium hydroxide solution, followed by separate precipation of the reaction products. In these experiments the calcium silicate hydrate generated by the reaction between lime and quartz was uniformly calcium silicate hydrate gel (CSH (gel)); reaction with kaolinite mid montmorillonite produced either CSH (gel) or calcium silicate hydrate (I) (CSH (I)) depending on the conditions of the reaction. At 60 degrees C the alumina-bearing phase was tricalcium aluminate hexahydrate; at lower temperature the phase produced was a hexagonal material closely resembling 4CaO.Al2O3.13H20 (C4AH13) but retaining a constant 7.6 Angstrom basal spacing regardless of its state of wetness or dryness. It was found that under appropriate conditions the formation of CSH(I) resulted in as effective a cementation as did the formation of CSH (gel).

Gee, mixing lime with silicate sand forms hard materials… Same thing with clay.

This other paper is mostly looking at using minerals to clean water. But it does talk a lot about silicate chemistry. Of particular importance is that it shows the degree of longer chains of silicate increases with more alkaline pH.

http://scholar.lib.vt.edu/theses/available/etd-07102000-22360009/unrestricted/davis-etd.pdf

It basically finds that many metal ions (in particular things like iron, aluminum, and arsenic) can be bound to silicate and that the tendency for this to happen increases at more alkaline pH. (Plus a whole lot more…)

So lets put some of this together…

In Conclusion

We have reasonably well demonstrated silicate chemistry involving many different metal ions, with or without water and / or heat, making a variety of stone like materials. We have the Egyptians making at least two demonstrable products using these materials. We have a demonstration that with increasing alkalinity the silicate polymer is longer and the reaction rates are faster (sometimes much faster). We have the Egyptians making various ‘burned alkali’ materials.

Is it really THAT far a leap to think that there might be a ‘liquid stone’ formula that used more potassium and ended up with a silicate that was a CaK (silicate) or feldspar like material? Perhaps even just by using potassium hydroxide (as used in soap making…) as the alkaline agent? Or perhaps that the Peruvians knew something of similar technologies?

My instinct tells me ‘this fits’. That this is just Yet Another Ancient Technology we are rediscovering. I doubt if much work has been done on mixes of natron, lime, lye (even potassium lye), quartz sand, clay, and feldspars. With just that list and an “in / out” you have 2^7 combinations to try (minus a couple of obvious non-starters like ‘only one, others out’) and if you add in various proportions and various treatments of heating, drying, wetting… Rather rapidly there is a huge area to search. (I would suggest starting with micro crystalline structure of the ‘rocks’ in Peru and Egypt and looking at what the ‘cementing part’ is, and how it relates to the ‘stone grain’ parts).

We know that K, potassium, participates in such reactions and makes kinds of stones. Are we, perhaps, “going there” and don’t even realize it?

http://www.tufchem.com/newsletterarticleshtml/TheAmazingAcidResistanceofPotassiumSilicateConcrete.html

MATERIALS OF CONSTRUCTION
The Amazing Acid Resistance of Potassium Silicate Concrete

You may not even notice potassium silicate concrete’s most amazing performance feat. Properly mixed and applied, you won’t notice any sign of weakening after it is exposed to some of the strongest acids for days, weeks, or months on end. Unlike Portland Cement based concrete, potassium silicate based polymer concrete is resistant to immersion in all concentrations of nitric, hydrochloric, phosphoric acids, and sulfuric acids, including oleum. And with compressive strengths hovering around 4,000 psi, with appropriate design, it can be used for structural applications such as footings and foundations in acid-contaminated “brownfield” sites.

What makes potassium silicate concrete resistant to acid? Let’s first examine why Portland Cement based concrete is not resistant to acid. Portland Cement, the binder that holds the aggregate in concrete together is an alkaline material that reacts with acid. This reaction between the Portland Cement and acid conveniently neutralizes the dangerous acid, but at a considerable expense to the concrete’s structural integrity. Once weakened, the products of this neutralization reaction are susceptible to erosion, often leaving only the larger aggregate behind, remnants of the mighty concrete that once was.

Potassium silicate concrete is a polymer concrete, meaning it contains no Portland Cement binder. It relies on inorganic potassium silicate binder technology. Once cured, potassium silicate polymer concrete does not react with acid in a way that leaves the material weaker. Under certain conditions, potassium silicate concrete gains strength in the presence of acid.

Gee… “potassium silicate binder”… that sounds familiar… Now if we just make it Potassium Calcium Silicate, that is different from feldspar how?

Ancient Egyptian Diorite Vase

Ancient Egyptian Diorite Vase

Original Image

One of the hardest stones around that, supposedly, needs diamond to cut it (though you can pound of bits) carved into a fine vase. Or, perhaps, cast? Might it even be possible that with alkali treatments the Egyptians made the surfaces of some stones softer and easier to carve, only hardening back to full strength after acid neutralizing?

Diorite has a lot of feldspar in it. What does that formula look like?
Well, there are several kinds:

“Feldspars (KAlSi3O8 – NaAlSi3O8 – CaAl2Si2O8) are a group of rock-forming tectosilicate minerals which make up as much as 60% of the Earth’s crust.”

The ‘key bits’ being soduium / potassium / or Calcium mixed with Aluminum in a silicate. So mix clay and quartz then add alkali? Just saying… if a thin layer of such a material were binding together larger bits of natural stone, would we even notice without microscopic examination?

No, I don’t know “the magic formula”. But it is pretty clear from all the kinds of ‘cements’ we are making today, that we are slowly expanding into the non-Portland Cement silicates. We’ve done this in just a few hundred years. The Egyptian Empires lasted 4,000+. I think they had time to work it out; and they were ‘working in that area’…

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About E.M.Smith

A technical managerial sort interested in things from Stonehenge to computer science. My present "hot buttons' are the mythology of Climate Change and ancient metrology; but things change...
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46 Responses to Liquid Stone

  1. Pingback: Liquid Stone | Cranky Old Crow

  2. Jason Calley says:

    @ E.M. Fascinating stuff! If you ever get a chance, read Professor Davidovits’s book “The Pyramids: An Enigma Solved”. I picked up a copy in a remainder bin some years back and bought it more as a joke than in earnest — you know, “Ha! The pyramids made from concrete?! This should be amusing!” The more I read, the less I laughed. Granted, it is a very odd idea at first, but he has some nice pictures of nummulitic limestone, both quarried and then pieces from the pyramid. The shells in the natural stone lie pretty much in strata as one would expect. The pyramid stone has the shells all tumbled together. Odd thing, that, enough to make you say, hmmmmm.

    If you decide to try some experiments, you might find water glass hard to find these days. Check your automotive store for radiator sealant. Some of those still have sodium silicate as their main ingredient.

  3. adolfogiurfa says:

    Current urban myths, and education too, make us believe in “solids”, “mass” and energy, as different things…and the “states of mater” and so on. Fortunately chemistry is closer to reality and perfectly describes “solid solutions” and common “hard” and “solid” objects, like glass being alkaline or acid, i.e. having a pH. Do you know what this means?, easy: CHARGE.
    There is no distinction whatsoever between energy and energy, ….except of course for the academia of sciences of Flintstone Town, presided by the famous Fred Flintstone, the one who calls himself astrophysicist, because he counts stones all over the sky.

  4. George says:

    It should be easy enough to tell if the pyramid stone was cast or cut by analysis of the stone, I would think.

    Are there any stratification of the stone from depositional irregularities during its formation?

  5. Serioso says:

    As an aside, the one factor that determines the viscosity of lava is the concentration of SiO2. When this is around 70% or more (felsic), the viscosity can be 10^10 greater than when the SiO2 concentration is under 50% (mafic). The reason is remarkably simple: SiO2 forms SiO4 tetrahedra which can share faces, edges or corners, and the interaction strength is greatest when the SiO2 concentration is high relative to other elements so that face-sharing is possible. Much the same trend is surely true in determining the relative strengths of cements of varying SiO2 concentration.

  6. E.M.Smith says:

    Well…. Adding potassium chloride to ordinary portland cement makes it stronger:

    http://www.isca.in/rjcs/Archives/vol1/I2/14.pdf

    if causes Mica to form in the cement…

    From 1918, a solution to the ‘potash shortage’… You know, the one the “Running OUT!!!” folks are sure is just around the corner? Seems that in the making of either cement or iron you can also get byproduct potash… Just dump in some slate or some feldspar….

    http://books.google.com/books?id=j-pIAAAAYAAJ&pg=RA2-PA68&lpg=RA2-PA68&dq=feldspar+cement&source=bl&ots=d7MNyKVSW9&sig=z9T1CIeQVBv8ta8gx4gYWMGsOGM&hl=en&sa=X&ei=2dnzTuf2D6WziQKBs-WQDQ&ved=0CEkQ6AEwBQ#v=onepage&q=feldspar%20cement&f=false

    As they note, there are ‘enormous’ quantities of slate laying around…

  7. E.M.Smith says:

    From:

    http://www.sciencedirect.com/science/article/pii/0008884677900461

    Abstract

    The reaction of calcium hydroxide with feldspars in aqueous suspensions at 39°C and also at room temperature gives tetracalcium aluminate hydrates, free alkalies, alkali silicates and hydrogarnets, depending on the type of feldspar. A theory related to cement-aggregate reactions is advanced.

    So we know that mixing lime with feldspar will react, will produce it’s own alkali silicates (along with hydro-garnets) and free alkali. When that neutralizes, wonder what you get?… Now if you have some clay in the mix, would the aluminum silicates react with the tetracalcium aluminate to make anything more interesting? Does the equilibrium return toward making feldspar again as the alkalinity drops? Gotta wonder…

    I could see a very interesting “possible” of a two phase mix. Feldspar and lime on one side, a more acidic mix with clay on the other. Kind of like a 2 part epoxy. Mix A with B, you have 10 minutes to pour… I’d guess about 6 months of lab time to find a mix with promise, then somewhere around a year to work out the bugs. Wonder if it’s already been done, or if there is a market for it…

    At this point we KNOW that silicates can become a wet phase, it is just down to finding the order of mix and exact reagents that cause a firm set and result in a product that looks like natural stone. Somehow I think that geopolymer guy has already done it…

  8. E.M.Smith says:

    @George:

    A search on something like “pyramid limestone strata” gave a link to a google book result that discussed strata in this context. Seems there are strata in the pyramid stones but they are ‘wavy’, which is held to be consistent with pour marks by the “pro” guys and held to be natural by the “anti” folks.

    I think you need to get into the weeds of where there are natural limestone beds nearby and what kind of strata they have…

    Did find another article that says someone else has partial support:

    http://www.nationmaster.com/encyclopedia/Egyptian-pyramid-construction-techniques

    Down under the limestone poured part…

  9. Jason Calley says:

    @ George “It should be easy enough to tell if the pyramid stone was cast or cut by analysis of the stone, I would think.”

    Well, that was pretty much what I thought at first too, but apparently it is not so simple. My understanding of it is that most natural agglomerated stones are held together by a matrix which is basically some variety of zeolite. The geopolymers are synthetic zeolites and most simple chemical analysis will not differentiate the natural from the synthetic. I suspect that a more rigorous analysis with something that checks crystalline structures would be needed to tell the difference. Also, it turns out that samples of pyramid stone are not easy to come by, and the Egyptian antiquities agencies do not consider the geopolymer idea to have enough merit to justify (in their eyes) handing over a sample for rigorous testing.

    By the way, in reference to some of the South American stone work, check this video at about 40 seconds in. It is certainly easier to imagine these stones having been cast rather than cut!

  10. The size and shapes of the stones in Peru and how tight the fits definitely seem to scream some type of casting or moulding process!!

    Here is a list of the 50 largest man made stones.

    http://www.ancient-wisdom.co.uk/top50stones.htm

    Wonder how many may have been cast in place instead of carved??

    Some more pics of for the post:

    http://members.tripod.com/~kon_artz/cultures/stonetec.htm

    http://www.theglobaleducationproject.org/egypt/articles/stonetech.php

  11. kuhnkat says:

    Dang, almost forgot. Did you do any thinking about how they would handle molds that large and moving tons of liquid?? Gotta have something resembling machines in there probably with hoses and pumps!!

    Here there is a picture of a couple of Egyptians using what is interpreted as electrical tubes. Maybe not electronic but a sprayer with a pump?

    http://nephiliman.com/ancient_technology_dendera_lamps.htm

    The monkey headed guy could actually be holding TROWELS!!

    Some solid engineering and more speculation!!

    http://sentinelkennels.com/Research_Article_V41.html

    definitely have a pump, but, what about the sound and possible piezo effects??

  12. kuhnkat says:

    Has a similarity to the pulse jets!! 8>)

  13. P.G. Sharrow says:

    The part about needing massive forms for “casting” these large blocks has never worked with these materials. Actually they “set up” rather slowly, Due to the clay content, you mix, let age, form in place like working stiff clay,add layer by layer scrapping and shaping as you go and keep damp. Turns to stone with age. About15 to 20% clay and sand like filler, addition of salts to change characteristics. The important thing is to “develop” the clay and get rid of the air. I have been making use of “soil cement”, actually subsurface clay and old volcanic ash in some of my projects. Very low tech, little in the way of forms, lots of work, some masonry lime. Rammed earth is a similar concept.
    Very interesting post and comments. KISS construction! pg

  14. bruce says:

    working stiff clay? I don’t think so, it works you.

  15. H.R. says:

    @kuhnkat (05:13:52)

    Not being funny here… maybe thieves stole the copper wires in ancient Egypt just like they do today. (Once or twice a year you hear about some geniuses getting fried while trying to steal copper from a substation.)

    The question comes to mind, though; King Tut’s tomb was one of the few undisturbed tombs found so where are the light bulbs and wires? Why didn’t they find a light switch on the left side just as you walk into the tomb?

    @George
    You made a good point a few weeks ago on another thread that we’re not finding evidence of early occupations because the seas have risen and covered the evidence. So maybe all the good evidence of widespread use of concrete is covered by the sea. Machu Pichu would survive being up high. Perhaps the pyramids were surrounded by water when they were built and the cement was floated on barges to be poured – no pumps needed.

  16. Tim Clark says:

    Well, one thing leads to another.

    Now your mission, if you decide to accept it, is to find every tablet with the A34 or A35 heiroglyph from Gardiner’s list and reinterpret the writings in the context one or the other represents cement.

    You can wait until after the holidays.

  17. Jason Calley says:

    My apologies for swerving a bit off topic, but while looking at videos of South American stonework, I ran across these nice pictures of a red haired elongated skull.

    I know that E.M. has speculated on the ancient paths of our red haired ancestors, and there have been reports that the ruling class during the Incan times (and I would guess before then, as well) were red heads. Same with the Easter Island rulers. Ever notice that top stone of red lava that sits on the statues?

    The gentleman who posted this video has a very interesting collection of You Tube videos which he has made in South America. Looking over them, I see very much conflicting evidence for and against the cast stone theory. Certainly, the complexity of some of the stones supports the cast theory. Also, casting solves the transport problem. (How do you transport a hundred ton stone? One basket of rubble at a time.) On the other hand, there are numerous sites where isolated stones, already cast, carved or shaped, have been apparently abandoned on hillsides far from the nearest structures. Certainly for the large stones, if they were cast, they would have been cast on site, not cast and then moved.

    If someone will buy me a ticket to Puma Punku I would measure very closely — with special attention to any anomalies — some of the identical looking stones. If they were cast one would expect to find some exact repetitions of shape and size, including errors or anomalies.

  18. adolfogiurfa says:

    @kuhnkat (05:13:52) :
    Very interesting that hydraulic ram pump, the same can be done with any “fluid”, be it water or light (an example of this last one is laser). They are resonant systems. …Sound, music; the octave also has two “check valves”, one between C/D (input), the second one between A/B (output).

  19. adolfogiurfa says:

    @Jason Calley: “Puma Punku” is in Tiahuanacu, high on the lake Titicaca plateau. When the cronicle writer of the spanish conquest, Garcilaso de La Vega, a man son of an spaniard and an inca woman of noble origin, asked his grandparents if those temples have been built by ancient Incas, they laughed at him saying that many generations before the Inca empire was founded, those buildings were already ruins from the distant past.(“Comentarios Reales de los Incas”-Royal commentaries of the Incas- )
    http://en.wikipedia.org/wiki/Garcilaso_de_la_Vega_(El_Inca) http://en.wikipedia.org/wiki/Pumapunku

  20. Jason Calley says:

    @ adolfogiurfa Thanks for the tip on De La Vega. I have read his “La Florida del Inca” which detailed his travels with De Soto, but did not know he had written the Commentarios. My wife has such books; I will see if she has a copy!

  21. E.M.Smith says:

    @Tim Clark:

    http://www.afrostyly.com/gardiner/list/a/

    A6 “purification” looks to me like someone under a lightbulb! Maybe a UV tanning booth? ;-)

    @Kuhnkat:

    That ‘pyramid as water pump’ is just spooky. I mean, what are the odds?…

    Maybe it was a giant lawn ornament, with water shooting from the ‘vent’ shafts out the sides, and moaning / vibrating a 440 Hz. ;-)

    @P.G.Sharrow:

    That ‘working without forms’ reminds me of the odd rounded edges of the stones in Peru at Machu Pichu. GIANT stones cut in interesting interlocking but sort of free form shapes, and at the joints they have an almost troweled rounded edge into the joint.

    @Bruce:

    Cement too ;-)

    @H.R.:

    Keep in mind that then copper would be worth even more than it is now. Used for bronze in weapons too. The statue at Rhodes was melted down for war materials in recorded history. (It had fallen and broken, but the broken bits had tons of bronze). Nobody would leave “unused” copper around.

    Heck, the old UK Penny was about the size of a silver dollar coin US and had significant value. Our penny today, if real copper, is about 2.4 cents value. It would literally be money laying around (medium of exchange AND store of value).

    I also think they didn’t see this as ‘for the common man'; it was a priests and magicians thing. So you get maybe a dozen lighting sets at any one time in existence.

    @Jason Calley:

    Has the fine hair texture too… (Redheads have more hairs / inch than others)

    There are historical records of a battle on, IIRC, Hawaii where the light skinned redheads were killed by the other tribes in a battle that drove them onto a peninsula. The fire trench used to hold of the attackers is still in evidence (vaguely). There are occasional redheads in the Polynesian population….

    Somewhere I saw on a link that someone claimed to have interpreted some inscriptions on some Pacific islands using an Afro-semitic language (IIRC using some kind of modification of Egytian) but I was looking for cement stuff at the time and let it go, so details are fuzzy and not link :-(

    I didn’t play it up, but notice :

    The ancient Egyptian word wedjet signifies blue, blue-green and green, and the same word is used for the human eye, and the protective Eye of Ra.

    That does not look like an accident to me. God has blue eyes…

    The word for “teacher” is a two glyph symbol. The two”

    Star, Gate.

    Queue spooky music…

    BTW, make that TWO tickets and toss in a return trip though the pyramid complex…

    @Adolfo:

    A “music pump”… oh, the visuals ;-)

  22. kuhnkat says:

    H.R.,

    not pushing the electricity direction although there have been acid cell batteries built into jugs or vases with little to show what they were used for!!

    http://www.ancientskyscraper.com/114601.html

    One hypothesis is that they were used for electroplating. Can’t imagine how they stumbled on that in so short of a time!! Must have been geniuses back then compared to now. of course, without so many things being taught to us that are WRONG we might do better ourselves.

  23. EM great summary. Was it my references to Imhotep, the stele in the Louvre and the Geopolymer Institute that got you thinking?
    I have a presentation on the history of construction materials which starts with lime and limestone, the use of lime in smelting, order of metal production (lead, silver, copper, tin, bronze, iron), the Egyptian geopolymer for the pyramids & statues, and finishing with Roman cement (which actually was first made in Greece- volcanic ash from Santorini is used today as a cement extender). Happy to email it to you.
    The cementafriend pseudonom is meant to be friendly -binding friendship but I do know a bit about cement.
    By the way lime(CaO) + natron (Na2CO3)+water > caustic soda(NaOH)+limestone(CaCO3). In wood ash there is K2CO3(potash) so mixing it with lime gives KOH which is a bit more reactive than NaOH.
    The other interesting thing that the Egyptians did was to cast columns from plaster which looked like Marble. Larfarge about 20yrs ago (re)found how this was done. There is lots of gypsum in Eygpt. Gypsum is CaSO4.2H2O. Plaster of Paris CaSO4.1/2H2O is made by heating to about 240C and grinding the material. By heating the gypsum to around 560C all the water is driven off but it is still active so it can revert to gypsum in time. Various coloring agents (eg copper sulphate) can be added while it is a thick paste to give a marble look. The Romans had plenty of marble and did not need to copy the technology.

  24. E.M.Smith says:

    @Kuhnkat:

    What a remarkable page!

    I’ve often pondered the lighthouse at Alexandria. It has ‘certain issues’ in the story that are very much loose ends. Like it had a fire, but not at the top. And it had a mirror at the top, with a bright light (well attested) but what could that mirror reflect at night?

    Never thought to connect a carbon arc lamp to a thermoelectric generator.

    It all “works”. Yes, there as a fire. Yes, it was in the bottom. Running a thermoelectric generator… that was more than enough to power a carbon arc, that really wants a mirror behind it.

    Damn…. All it takes is a fire, a stack of two different metals, some wire, a couple of chunks of carbon, and a mirror. Damn damn damn…
    I ought to have thought of that…

    Oh well, at least someone did…

    The Lalande cell is interesting. Wonder if one could make a ‘beer can battery’ using aluminum / air… and if you get more than the 5 cent deposit of electricity from it ;-)

    The Clamond thermoelectric generator cranking out 109 volts is a hoot too. In 1879 (!) 3 feet in diameter, 20 inches high, and coal powered. Now I’m going to have to think about the potential for Egyptian lighting to have been done with thermoelectrics… they had many different metals, knew chemistry reasonably well (just WHEN did we finally reinvent Egyptian Blue…) and could easily have made one of these. Just need to add a gas discharge and / or carbon arc. It would explain a lot, and the lack of artifacts would just be because folks constantly recycle metals.

    Stumbling on electroplating isn’t all that hard. Once you have a couple of metals in an electrolyte, stuff tends to plate out somewhere. I could easily see a connection of one battery to another of different chemistry and seeing the metal move ‘backwards’ into a plating. Iron and copper do it without electricity IIRC so it would be a small leap to zinc iron and then on to other metals.

  25. E.M.Smith says:

    @Cementafriend:

    It was that comment, though I lost track of where it was… so h/t to you!

    Yes, I’d like to read the write up…

  26. adolfogiurfa says:

    Men of antique, way back before “illuminati” and “illustration”, way back to your ancestors, the celts, the ligurian, the druids and druidesses (later burnt at the stake by the church) knew the fundamentals laws of nature, which are out there until now to be known by us….but this is continuously frustrated by consensus science, built on purpose to manage power and wealth.

  27. Thanks, EM have sent a email. I hope I have the correct address from “about”. Also the attachment is 10.1 MB as it is mainly pictures. Have a look at the stars on the roof on one of the pyramid passageways (slide 83). This has to have been wooden plank formwork (even shows the gap between the planks). Slide 80 is a picture of a mural from a tomb showing how they prepared the blocks.
    I sent it using a very slightly different email address (net instead of com) in case you reply. I have a filter which blocks some gmail and aol addresses due to spam. I also pay for a spam filter at the server. I used to get many emails from African, Russian and European sources offering rewards for money laundering. The highest was 20% of $US350M but no spam for the last two years so something is working.

    Merry Christmas and a properous healthy New Year to all

  28. pyromancer76 says:

    Great intelligence, imagination, and experience, including respect for “ancient” intelligence in all of chiefio.com. What better gift for the holiday season than this. I thank you, E.M., and all your productive followers. (I can mainly read and appreciate, much of which ability came from a father who could do and learn almost anything he set his mind to. In this sense my comment offers gratitude to fathers who are the main pursuers in these areas.) May good sense and respect for the scientific method return to us in 2012. Merry Christmas and a wonderful holiday season to all. Prosperity is a very good thing, too.

  29. E.M.Smith says:

    @Adolfo:

    You have got me wondering, given how The Church treated Galileo and how even Newton kept things hidden that would be a church issue, just how much folks have “done what the bosses wanted”. We now have a clear example of it in modern times via ClimateGate 1&2.

    @Cementafriend:

    Well, guess I’ll need to read my email now… it’s only been a couple of months ;-) I think AOL may choke on 10 MB, but that was a few years back so they may have changed that by now. We’ll see.

    @Pyromancer:

    I just recognize that the ancients were at least as smart as we are…

    BTW, it was my Mother who taught me the love of language… So don’t forget the value added by Moms world wide too ;-)

    Yes, wealth and prosperity are good. Panic and paranoia about living well are signs of encumbered thinking processes.

    I think you will like my Santa posting too ;-)

    Merry Christmas and best wishes to all.

  30. Jason Calley says:

    @ E.M. and the regular crew as well

    Thank you E.M. especially for hosting such a wonderful and diverse group of thinkers, scientists, engineers, poets and mystics! I am continually surprised by the wealth of insight and information which you all bring to the site. I am grateful.

    Merry Christmas to you all. :)

    Speaking of the Pharos and its mirror…some years back I had a friend recount to me part of an autobiography which I cannot track down right now. Some days my Google-fu is stronger than others. I will try though to get the facts right. A young German man was captured by the Turks during, IIRC, the 14th Century and placed into slavery. As a slave, the young man spent some time in Alexandria, and while there was told the story of how the Pharos was disabled and its mirror destroyed. It seems that the rulers of Alexandria used the mirror not only to project a beam at night, but during the daytime had a man stand in front of the mirror (at its prime focus) and scan the distant sea for enemy ships. In this way the city was warned of invaders a couple of days before their arrival. This technique had been used successfully several times to prevent invaders from Europe who wished to use Alexandria as a base to help solidify the various waves of the Crusades to recapture the Holy Land for the Church. Thus, the Pope gave special permission to one of his agents to pretend to be Muslim. This person defected to Alexandria and over a period of decades managed to work his way up in the Islamic ranks until he was the Imam of the mosque which occupied the base of the Pharos. One day, he locked all the access doors to the lighthouse, climbed to its peak and broke the mirror. I do not remember if the priest got away… On the other hand, the German did in fact eventually make it back to Germany and wrote his autobiography there. If anyone is interested, I will try to track down the name of the German who wrote the story. I find it interesting in that it is the only version I know that purports to tell what happened to the mirror.

    And on the subject of electroplating — yes, it certainly looks like some of the ancient Middle Eastern cultures knew how to electroplate. Oddly enough, there are some jewelry pieces from pre-Columbian South America which appear to be electroplated, but are not! Here is how the Amerindians did the same thing, but without electricity. They made an alloy of copper and gold, mostly copper, but maybe 10% or so of gold. Make some jewelry out of it, then soak the jewelry in acid. Even vinegar will do. The copper is dissolved away from the surface, leaving a thin layer of spongy gold. The gold is burnished to flatten and compact it, leaving an artifact that is nearly indistinguishable from electroplated gold.

    Pretty bright for people who did not have digital watches!

  31. Serioso says:

    @Jason Calley

    I’ll bet the gold-copper mix was more like 50% copper, i.e., 12-caret gold. Gold and copper both melt around 1050C (if memory serves), while the 50-50 mix melts 200C lower and is hence much easier to work (and is harder).

  32. Jason Calley says:

    @ Serioso Well, I just learned something, due to you!

    Looking around, I find that the alloy used — mainly copper and gold — was called “tumbaga.” Here is a quote from http://www.precolumbiangold.com/materials.htm
    “The proportion of gold to copper in artifacts varies wildly; items have been found with as much as 97% gold while others instead contain 97% copper. Some tumbaga has also been found to be comprised of metals besides gold and copper, up to 18% of the total mass of the tumbaga.”

    I found several references of the lower melting point you mentioned, though they did not give figures. If you are right about the 200 degree difference, then a 50/50 mix would be a really good choice. Remind me to hire you if I ever start business making jewellery. :)

  33. E.M.Smith says:

    @Jason Calley:

    Look at eutectic metal mixes. They are used for that property all over the place. From the ‘melt plugs’ in sprinklers to eutectic salts in passive solar home heat storage. Precise melt temperature too. (So the fire sprinklers only come on at a particular temperature and the house holds 72 F or whatever).

    Also used in solders for a single setting temperature to reduce ‘cold solder joints’

    http://en.wikipedia.org/wiki/Eutectic_system

    Also part of why bronze is so easy to work while copper is still a red hot solid…

  34. H.R. says:

    @kuhnkat (04:23:14) :

    Thanks! Fun and interesting link.

  35. Waterglass was still readily available and cheap around 20 years ago when I purchased 200 litres of Vitrosol N42 from ICI in Melbourne Vic. I use it for fungal disease control in my apples. 200 litres was the smallest volume they sold and more than a lifetime supply for me. It was very inexpensive compared to more modern fungal disease control materials. You might want to source it locally as it is much denser than water.

    A local orchardist here in the Huon told me that before the War, housewives made their own waterglass in the fireplace.

    Thanks for stimulating my brain cells as usual E.M.

  36. E.M.Smith says:

    @thepompousgit:

    Thanks for the pointers. I’ll likely just try a simple lye or cooked lime (quicklime) treatment of some sand and clay to see what happens… but it will likely be next spring when it’s warm before I go for it ;-)

    I’m also thinking it might be fun to make a potassium analog of waterglass, but that’s a ways off…

  37. Jason Calley says:

    Just remembered the German man who reported the destruction of the mirror at the Pharos!

    “The Bavarian Hans Schiltberger, whose odyssey as a captured crusader in Europe, Asia, and Africa lasted from 1396 to 1427, related that in a tower near the port of Alexandria “not long ago” there was mirror allowing one to see toward Cyprus “those who were on the sea; and whatever they were doing.” His story of the mirror’s eventual destruction reflects his position as onetime pris-
    oner of the infidels, and perhaps the sheer length of his captivity as well. As Schiltberger told it, a priest from Cyprus, after gaining permission from the pope to pretend to abjure, went to Alexandria, converted, “learnt their writing,” and became a trusted Islamic cleric. Eventually given a choice of any mosque in the city, he selected the one equipped with the mirror, and after nine years
    of pious fakery he summoned at last the warships of the king of Cyprus. As his allies were approaching, he struck the mirror three times, and though the object broke, the noise of his blows alarmed the citizens, and the trapped priest perished when he jumped from the tower into the sea. The king of Cyprus did, however, take the city, and with this allusion to Peter of Lusignan’s capture of Alexandria in October 1365, Schiltberger narrowed the gap between what he portrayed as a functioning and non-necromantic mirror—albeit one of questionable substance and design—and the moment of his visit to Alexandria to less than four decades.”
    http://www.aic.ac/en/books/no58works01hakluoft_bw.pdf

    See also Chapter 43 of http://www.scribd.com/doc/55475706/The-Bondage-and-Travels-of-Johann-Schiltberger

  38. Jason Calley says:

    @ E.M. “I’ll likely just try a simple lye or cooked lime (quicklime) treatment of some sand and clay to see what happens… but it will likely be next spring when it’s warm before I go for it ;-) ”

    Maybe you can make your own sodium silicate (water glass) with lye and glass (or sand).

  39. Caleb says:

    Thanks. Came here through a link you left at WUWT.

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  41. E.M.Smith says:

    @Caleb:

    You are most welcome!

    @Jason:

    Making waterglass isn’t all that hard but the typical way is to use molten 2NaCO2 and SiO2 (CO2 leaves). I suppose using lye instead would make it happen at lower temps… (part of why I was thinking of using it to make “liquid stone”. But see below. As lye is made from Lime, it looks to me like a step or two can be combined. Create the lye at the moment of consumption in making new stone. Ought to end up with a mix of CaC03 and mixed slicates as the cementing species. Using feldspars or some clays in with the mix might make feldspar itself in with the Ca species. If waterglass is made and used as a distinct agent, you ought to be able to make a silicate ‘cement’ that is the same as natural rock to all casual observations.

    Per the Mirror at Alexandria: IF the story is correct, it argues strongly for a glass mirror of some sort.

    Went to all my local hardware stores, including Lowes. No lye.

    Lowes DID have a “crystal drain cleaner” that listed NaOH on the ingredient list. Bought it.

    At home found that (at $4 / lb) I’d bought a blue died mix of two different little round prills with shreds of shiny aluminum in it. I’m sure there is Lye in there somewhere, but…

    They had a similar dry Drano product on the shelf next to it at about $10 / lb.

    So “still looking for lye”… but not very hard…

    Found how to make it. Not hard. Take Lime (not ‘slaked lime’ or ‘hydrated lime’ but CaOH) and add to 2NaCO3 – washing soda or Sodium Carbonate. CaCO3 precipitates. (calcium carbonate) leaving lye solution.

    Next trip to the hardware store I’ll see if “plain old lime” is available.

    If not, it adds one roasting step in a very high temp oven. (Charcoal, limestone, high temp tray).

    Don’t particularly want to “go there”, but the notion that making lye is hard is, well, silly.

    Roast limestone. Add to natron (sodium carbonte). Mix water. Remove solution and dry.

    I suspect that if you take the dry powder ( lime / natron mix) and add it to feldspar crumbles / old granite bits with a touch of clay and / or quartz sand you can make a synthetic stone ( as in Egyptian Liquid Stone). So I’d see a dry mix of lime / natron / feldspar (mica / clay / kaolin / rotted granite / crushed limestone) when made wet turning into “Liquid Stone” that would rapidly harden into a variety of different “rocks” depending on what was in the mix.

    (One of my reasons for wanting Lye was to try some “Liquid Stone” experiments. This actually gets me closer to what the Egyptians likely did…)

    So there you have it. I’m also going to duplicate this comment back on the Egyptian Liquid Stone posting where it will be more easily found in historical searches.

  42. Jason Calley says:

    Yes, lye is becoming very difficult to find locally. Why? Your tax dollars at work; lye is now considered to be a drug precursor (just like ephedrine, it can be used in the drug manufacture process) and while it is not exactly illegal to sell it at the grocery store, most businesses have dropped it just to be on the safe side. You can still buy it online: http://www.lehmans.com/store/Personal___Soaps_and_Soapmaking___Soapmaking___Sodium_Hydroxide_for_Soapmaking___36240240#36240240

    By the way, some brands of radiator sealant are almost 100% water glass, some have powdered metal added. Check a few brands at your local auto parts store.

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