A catalyst walks into a bar. The bartender says, “We can’t serve you.”
The catalyst asks, “Why not?”
The bartender says, “The last time you were here, you started something.”
Robert Buxbaum, July 14, 2023 (Bastille day). If you like this, maybe you’d like another, chemistry joke or this physics joke.
As mentioned in a previous post, wood is more among the strongest materials per unit weight, making it ideal for table tops and telephone polls. On a per pound basis, most species of wood are more than twice as strong as aluminum or mild steel. Wood’s structure is is the reason; it’s a natural composite of air-filled, aligned tubes of crystalline cellulose, held together by natural glue, lignin.
In terms of raw strength though, pounds/in2, wood is not particularly strong, only about 7000 psi (45MPa) both in tension and compression, about half the strength of aluminum. It is thus not well suited to supporting heavy structures, like skyscrapers. (I calculate the maximum height of a skyscraper here), but wood can be modified to make it stronger by removing most of the air, and replacing it with plastic. The result is a stronger, denser, flexible composite, that is typically transparent. The flower below is seen behind a sheet of transparent wood.
To make a fairly strong, transparent wood, you take ordinary low-density wood (beech or balsa are good) and soak it in alkali (NaOH). This bleaches the wood, softens the cellulose, and dissolves most of the lignin. You next wash off the alkali and soak the wood in a low viscosity epoxy or acrylic. Now, put it in a vacuum chamber to remove the air — you’ll need a brick to hold the wood down in the liquid. You’ll see bubbles in the epoxy as the air leaves. Then, when the vacuum is released, the wood soaks up the epoxy or acrylic. On curing, you get a composite strong and transparent, but not super strong.
To make the wood really strong, super-strong, you need to compress the uncured, epoxy soaked wood. One method is to put it in a vice. This drives off more of the air and further aligns the cellulose fibers. You now cure it as before (you need a really slow cure epoxy or a UV-cure polymer). The resultant product have been found to have tensile strengths as high as 270 MPa in the direction of alignment, over 40,000 psi. This is three times stronger than regular aluminum, 90 MPa, (13,500 psi). It’s about the strength of the strongest normal aluminum alloy, 6061. It’s sort of expensive to make, but it’s flexible and transparent, making it suitable for space windows and solar cells. It’s the lightest flexible transparent material known. It’s biodegradable, and that’s very cool, IMHO. See here for a comparison with other, high strength, transparent composites.
Robert Buxbaum, November 10, 2022. I think further developments along this line would make an excellent high school science fair project, college thesis, or PhD research project. Compare different woods, or epoxies, different alkalis, and temperatures, or other processing ideas. How strong and transparent can you make this material, or look at other uses. Can you use it for roof solar cells, like Musk’s but lighter, or mold it for auto panels, it’s already lighter and stronger, or use it as bullet-proof glass or airplane windows.
A hydrogen molecule consists of two protons held together by a covalent bond. One way to think of such bonds is to imagine that there is only one electron is directly involved as shown below. The bonding electron only spends 1/7 of its time between the protons, making the bond, the other 6/7 of the time the electron shields the two protons by 3/7 e– each, reducing the effective charge of each proton to 4/7e+.
We see that the two shielded protons will repel each other with the force of FR = Ke (16/49 e2 /r2) where e is the charge of an electron or proton, r is the distance between the protons (r = 0.74Å = 0.74×10-10m), and Ke is Coulomb’s electrical constant, Ke ≈ 8.988×109 N⋅m2⋅C−2. The attractive force is calculated similarly, as each proton attracts the central electron by FA = – Ke (4/49) e2/ (r/2)2. The forces are seen to be in balance, the net force is zero.
It is because of quantum mechanics, that the bond is the length that it is. If the atoms were to move closer than r = 0.74Å, the central electron would be confined to less space and would get more energy, causing it to spend less time between the two protons. With less of an electron between them, FR would be greater than FA and the protons would repel. If the atoms moved further apart than 0.74Å, a greater fraction of the electron would move to the center, FA would increase, and the atoms would attract. This is a fairly pleasant way to understand why the hydrogen side of all hydrogen covalent bonds are the same length. It’s also a nice introduction to muon-catalyzed cold fusion.
Most fusion takes place only at high temperatures, at 100 million °C in a TOKAMAK Fusion reactor, or at about 15 million °C in the high pressure interior of the sun. Muon catalyzed fusion creates the equivalent of a much higher pressure, so that fusion occurs at room temperature. The trick to muon catalyzed fusion is to replace one of the electrons with a muon, an unstable, heavy electron particle discovered in 1936. The muon, designated µ-, behaves just like an electron but it has about 207 times the mass. As a result when it replaces an electron in hydrogen, it forms form a covalent bond that is about 1/207th the length of a normal bond. This is the equivalent of extreme pressure. At this closer distance, hydrogen nuclei fuse even at room temperature.
In normal hydrogen, the nuclei are just protons. When they fuse, one of them becomes a neutron. You get a deuteron (a proton-neutron pair), plus an anti electron and 1.44 MeV of energy after the anti-electron has annihilated (for more on antimatter see here). The muon is released most of the time, and can catalyze many more fusion reactions. See figure at right.
While 1.44MeV per reaction is a lot by ordinary standards — roughly one million times more energy than is released per atom when hydrogen is burnt — it’s very little compared to the energy it takes to make a muon. Making a muon takes a minimum of 1000 MeV, and more typically 4000 MeV using current technology. You need to get a lot more energy per muon if this process is to be useful.
You get quite a lot more energy when a muon catalyzes deuterium fusion or deuterium- fusion. With these reactions, you get 3.3 to 4 MeV worth of energy per fusion, and the muon will be ejected with enough force to support about eight D-D fusions before it decays or sticks to a helium atom. That’s better than before, but still not enough to justify the cost of making the muon.
The next reactions to consider are D-T fusion and Li-D fusion. Tritium is an even heavier isotope of hydrogen. It undergoes muon catalyzed fusion with deuterium via the reaction, D+T –> 4He +n +17.6 MeV. Because of the higher energy of the reaction, the muons are even less likely to stick to a helium atom, and you get about 100 fusions per muon. 100 x 17.6 MeV = 1.76 GeV, barely break-even for the high energy cost to make the muon, but there is no reason to stop there. You can use the high energy fusion neutrons to catalyze LiD fusion. For example, 2LiD +n –> 34He + T + D +n producing 19.9 MeV and a tritium atom.
With this additional 19.9 MeV per DT fusion, the system can start to produce usable energy for sale. It is also important that tritium is made in the process. You need tritium for the fusion reactions, and there are not many other supplies. The spare neutron is interesting too. It can be used to make additional tritium or for other purposes. It’s a direction I’d like to explore further. I worked on making tritium for my PhD, and in my opinion, this sort of hybrid operation is the most attractive route to clean nuclear fusion power.
Robert Buxbaum, September 8, 2022. For my appraisal of hot fusion, see here.
Platinum catalysts can be very effective at removing hydrogen from air. Platinum promotes the irreversible reaction of hydrogen with oxygen to make water: H2 + 1/2 O2 –> H2O, a reaction that can take off, at great rates, even at temperatures well below freezing. In the 1800s, when platinum was cheap, platinum powder was used to light town-gas, gas street lamps. In those days, street lamps were not fueled by methane, ‘natural gas’, but by ‘town gas’, a mix of hydrogen and carbon monoxide and many impurities like H2S. It was made by reacting coal and steam in a gas plant, and it is a testament to the catalytic power of Pt that it could light this town gas. These impurities are catalytic poisons. When exposed to any catalyst, including platinum, the catalyst looses it’s power to. This is especially true at low temperatures where product water condenses, and this too poisons the catalytic surface.
Nowadays, platinum is expensive and platinum catalysts are no longer made of Pt powder, but rather by coating a thin layer of Pt metal on a high surface area substrate like alumina, ceria, or activated carbon. At higher temperatures, this distribution of Pt improves the reaction rate per gram Pt. Unfortunately, at low temperatures, the substrate seems to be part of the poisoning problem. I think I’ve found a partial way around it though.
My company, REB Research, sells Pt catalysts for hydrogen removal use down to about 0°C, 32°F. For those needing lower temperature hydrogen removal, we offer a palladium-hydrocarbon getter that continues to work down to -30°C and works both in air and in the absence of air. It’s pretty good, but poisons more readily than Pt does when exposed to H2S. For years, I had wanted to develop a version of the platinum catalyst that works well down to -30°C or so, and ideally that worked both in air and without air. I got to do some of this development work during the COVID downtime year.
My current approach is to add a small amount of teflon and other hydrophobic materials. My theory is that normal Pt catalysts form water so readily that the water coats the catalytic surface and substrate pores, choking the catalyst from contact with oxygen or hydrogen. My thought of why our Pd-organic works better than Pt is that it’s part because Pd is a slower water former, and in part because the organic compounds prevent water condensation. If so, teflon + Pt should be more active than uncoated Pt catalyst. And it is so.
Think of this in terms of the Van der Waals equation of state:
where 
Now, I’m going to assume that the effect of a hydrophobic surface near the Pt is to reduce the effective value of a. This is to say that water molecules still attract as before, but there are fewer water molecules around. I’ll assume that b remains the same. Thus the ratio of Tc and Pc remains the same but the values drop by a factor of related to the decrease in water density. If we imagine the use of enough teflon to decrease he number of water molecules by 60%, that would be enough to reduce the critical temperature by 60%. That is, from 647 K (374 °C) to 359 K, or -14°C. This might be enough to allow Pt catalysts to be used for H2 removal from the gas within a nuclear wast casket. I’m into nuclear, both because of its clean power density and its space density. As for nuclear waste, you need these caskets.
I’ve begun to test of my theory by making hydrogen removal catalyst that use both platinum and palladium along with unsaturated hydrocarbons. I find it works far better than the palladium-hydrocarbon getter, at least at room temperature. I find it works well even when the catalyst is completely soaked in water, but the real experiments are yet to come — how does this work in the cold. Originally I planned to use a freezer for these tests, but I now have a better method: wait for winter and use God’s giant freezer.
Robert E. Buxbaum October 20, 2021. I did a fuller treatment of the thermo above, a few weeks back.
Some years ago I wrote a largely negative review of Brown’s gas, but the COVID crisis in India makes me want to reconsider. Browns gas can provide a simple source of oxygen for those who are in need. First, an explanation, Browns gas is a two-to-one mix of hydrogen and oxygen; it’s what you get when you do electrolysis of water without any internal separator. Any source of DC electricity will do, e.g. the alternator of a car or a trickle charger of the sort folks buy for their car batteries, and almost any electrode will do too (I’d suggest stainless steel). You can generate pressure just by restricting flow from the electrolysis vessel, and it can be a reasonable source of small-scale oxygen or hydrogen. The reaction is:
H2O –> H2 + 1/2 O2.
The problem with Brown’s gas is that it is explosive, more explosive than hydrogen itself, so you have to handle it with care; avoid sparks until you separate the H2 from the O2. Even the unseparated mix has found some uses, e.g. as a welding gas, or for putting in cars to avoid misfires, increase milage, and decrease pollution. I think that methanol reforming is a better source of automotive hydrogen: hydrogen is a lot safer than this hydrogen-oxygen mix.
The mix is a lot less dangerous if you separate the oxygen from the hydrogen with a membrane, as I show in the figure. at right. If you do this it’s a reasonable wy to make oxygen for patients who need oxygen. The electrolysis cell can be a sealed bottle with water and the electrodes; add a flow restriction as shown to create the hydrogen pressure that drives the separation. The power can be an automotive trickle charger. You can get this sort of membranes from REB Research, here and many other suppliers. REB provide consulting services if you like.
In a pinch, you don’t even need the membrane, by the way. You can rely on your lungs to make the separation. A warning, though, the mix is dangerous. Avoid all sparks. Also, don’t put salt into the water. You can can put in some baking soda or lye to speed the electrolysis, but If you put salt in, you’ll find you don’t make oxygen, but will instead make chlorine. And chlorine is deadly. If you’re not sure, smell the gas. If it smells acrid, don’t use it. This is the chlorine-forming reaction.
2NaCl + 2 H2O –> H2 + Cl2 + 2NaOH
Ideally you should vent the hydrogen stream out the window, but for short term, emergency use, the hydrogen can be vented into your home. Don’t do this if anyone smokes (not that anyone should smoke about someone on oxygen). This is a semi-patentable design, but I’m giving it away; not everything that can be patented should be.
Robert Buxbaum, May 13, 2021.
When I was eight or nine year old, I went to the 1963-64 World’s Fair in New York. Among the attractions, in “the kitchen of the future”, I saw the first version of an amazing fry-pan that was coated with plastic. You could cook an egg on that plastic without any oil, and the egg didn’t stick. The plastic was called teflon, a DuPont innovation, whose molecule is shown below.
Years later, I came to understand that Teflon’s high-temperature stability and non-stick properties derive from the carbon-fluorine bonds. These bonds are much stronger than the carbon-hydrogen bonds found in food, and most solid, organic things. Because of the strength of the carbon-fluorine bond, Teflon is resistant to oxidation, and to chemical interaction with other molecules, e.g. in food. It does not even interact with water, making it hydrophobic and non-wetting on metals. The carbon-carbon bonds in the middle remained high temperature stable, in part because they were completely shielded by the fluorine atoms.
But as remarkable as teflon’s non-stick properties are, perhaps the most amazing thing was that it somehow sticks to the pan. For the first generation pans I saw, it didn’t stick very well. Still, the DuPont engineers had found a way to stick non-stick Teflon to a metal for long enough to cook many meals. If they had not found this trick, teflon would not have the majority of its value, but how did they do it? It turns out they used a thin coating of a di-functional compound called PFAS, a a polyfluoro sulphonyl (or polyfluoroalkyl) substance. The molecular structure of a common PFAS, is shown above.
Each molecule of PFAS has one end that’s teflon-like and another end that’s different. The non-Teflon end, in this case a sulfonyl group, is chosen to be both high temperature stable and sticky to metal oxides. The sulphonyl group above is highly polar, and acidic. Acidic will bind to bases, like metal oxides. The surface of the metal pan is prepared by applying a thin layer of oxide or amidine, making it a polar base. The PFAS is then applied, then Teflon. The Teflon-end of the PFAS is bound to teflon by the hydrophobicity of everything else rejecting it.
There are many other uses for PFAS. For example, PFAS is applied to clothing to make it wrinkle free and stain resistant. It can also be used as a super soap, making uncommonly stable foams and bubbles. It is also used in fire-fighting and plane de-icing. Finally, PFAS is the main component of Nafion, the most common membrane for PEM fuel cells. (I can think of yet other applications..) There is just one small problem with PFAS, though. Like teflon, this molecule is uncommonly stable. It doesn’t readily decompose in nature. That would be a small problem if we were sure that PFAS was safe. As it happens it seems safe, but we’re not totally sure.
The safety of PFAS was studied extensively before PFAS-teflon pans was put on the market, but the methodology has been questioned. Large doses of PFAS were fed to test animals, and their health observed. Since the test animals showed no real signs of ill-health though some showed a slight liver enlargement, PFAS was accepted as safe for humans at a lower exposure dose. PFAS was approved for use on pans and allowed to be dumped under conditions where humans would be exposed to 1/1000 of that used on the animals. The assumption was that there would be little or no health hazard at these low exposure levels.
But low risk is not no risk, and today one can sue for even the hint of an effect though use of a class action suit. That is, lawyers sue on behalf of all the people who might have been damaged. My city was sued successfully this way for complicity in sewage over-flows. Of course, since the citizens being paid by the suit are the same ones who have to pay for the damage, only the lawyers benefit. Still, the law is the law, and at least for some judges, putting anyone at risk is enough evidence of willful disregard to hand down a stinging judgement against the evil doer. Judges have begun awarding large claims for PFAS too. While no individual can get the claim more than a tiny amount of money, the lawyers can do very well.
There is no new evidence that PFAS is dangerous, but none is needed if you can get yourself the right judge. In this regard, an industry of judicial tourism has sprung up, where class-action lawyers travel to districts where the judges are favorable. For Teflon suits, the bust hunting grounds are in New York, New Hampshire, and California, and the worst are blood-red states like Wyoming and Utah. Just as different judges promote different precedents, different states allow vastly different PFAS concentrations in the water. A common standard, one used by Michigan, is 70 ppt, 1 billion times stricter than the amounts tested on animals. This is roughly 500 times stricter than the acceptable concentratios for lead, a known poison. The standard in New York is 7 times stricter than Michigan, 10 ppt. The standard in North Carolina is 140,000 ppt, in in several states there is no legal limit to PFAS dumping. There is no scientific logic to all of this, and skeptical view is that the states that rule more strictly for PFAS than lead do so make money for lawyers. Lead is everyone in the natural environment, so you can’t sue as easily for lead. PFAS is a man-made intruder, though, and a strict standard helps lawyers sue. You can find a summary of state by state regulations here.
Any guideline stricter than about 1000 ppt, presents a challenge to the water commissioner who must measure it and enforce the law. There are tricks, though. You can use the surfactant quality of PFAS to concentrate it by a factor of 100 or more. To do this, you take a sample of river water and create bubbles. Any bubbles that form will be highly concentrated in PFAS. Once PFAS can be identified this way, and the concentrators estimated, the polluters can be held liable. Whether we benefit from the strict rulings is another story. If I were making the law for Michigan, I’d probably choose a limit about 1 ppb, but I’m not making the law. The law, as written, may be an idiot, as Bumble said, but the Law is the Law.
In terms of Michigan fishing, while some rivers have PFAS concentrators above the MI-legal limit, they are generally not far over the line. I would trust the fish in the Huron River, even west of Wixom road but I’d suggest you avoid any foam you find floating there. The PFAS content of foam will be much higher than that of the water in general.
Robert E. Buxbaum, June 30, 2020, edited July 8, 2020. There are seven compounds known as PFAS’s: perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorobutanesulfonic acid (PFBS).
Our county, like many in the US and Canada, is served by thousands of miles of lead pipes. Some of these are the property of the government, others sit beneath our homes and are the property of the home-owner. These pipes are usually safe, but sometimes poison us. There is also problem of lead-tin solder. It was used universally to connect iron and copper pipes until it was outlawed in 1986. After years of sitting quietly, this lead caused a poisoning crisis in DC in 2004, and in Flint in 2015-16. Last month my town, Oak Park, registered dangerous lead levels in the drinking water. In an attempt to help, please find the following summary of the relevant lead chemistry. Maybe people in my town, or in other towns, will find some clue here to what’s going on, and what they can do to fix it.
Left to itself, lead and solder pipe could be safe; lead is not soluble in clean water. But, if the water becomes corrosive, as happens every now and again, the lead becomes oxidized to one of several compounds that are soluble. These oxides are the main route of poisoning; they can present serious health issues including slow development, joint and muscle pain, memory issues, vomiting, and death. The legal limit for lead content in US drinking water is 15 ppb, a level that is far below that associated with any of the above. The solubility of PbO, lead II oxide, is more than 1000 times this limit 0.017 g/L, or 17,000 ppb. At this concentration serious health issues will show up.
PbO is the yellow lead oxide shown in the center of the figure above, right; the other pipes show other oxides, that are less-soluble, and thus less dangerous. Yellow lead oxide and red lead oxides on the right were used as paint colors until well into the 20th century. Red lead oxide is fairly neutral, but yellow PbO is a base; its solubility is strongly dependent on the PH of the water. In neutral water, its solution can be described by the following reaction.
PbO + H2O(l) –> Pb2+(aq) + 2 OH–(aq).
In high pH water (basic water), there are many OH–(aq) ions, and the solubility is lower. In low pH, acidic water the solubility is even higher. For every 1 point of lower pH the lowubility increases by a factor of 10, for every 1 point of higher pH, it decreases by a factor of ten. In most of our county, the water is slightly basic, about pH 8. It also helps that our water contains carbonate. Yellow lead forms basic lead carbonate, 2PbCO3·Pb(OH)2, the white lead that was used in paint and cosmetics. Its solubliity is lower than that of PbO, 110 ppb, in pure water, or within legal limit in water of pH 8. If you eat white lead, though, it reacts with stomach acid, pH 2, and becomes quite soluble and deadly. Remember, each number here is a factor of ten.
A main reason lead levels a very low today are essentially zero, even in homes with lead solder or pipe, involves involves the interaction with hypochlorite. Most water systems add hypochlorite to kill bacteria (germs) in the water. A side benefit is significant removal of lead ion, Pb2+(aq).
Pb2+(aq) + 2 ClO–(aq) –> Pb(ClO)2(s).
Any dissolved lead reacts with some hypochlorite ion reacts to form insoluble lead hypochlorite. Lead hypochlorite can slowly convert to Lead IV oxide — the brown pyrophilic form of lead shown on the left pipe in the figure above. This oxide is insoluble. Alkaline waters favor this reaction, decreasing solubility, but unlike with PbO, highly alkaline waters provide no significant advantage.
PbClO+(aq) + H2O(l) –> PbO2(s) + 2 H+(aq) + Cl–(aq)
Lead IV oxide, PbO2 was used in old-fashioned matches; it reacts violently with phosphorus or sulfur. People were sometimes poisoned by sucking on these matches. In the stomach, or the presence of acidic drinking water, PbO2 is decomposed forming soluble PbO:
PbO2(s) +2 H+(aq) + 2 e– –> PbO(s) + H2O(l).
You may wonder at the presence of the two electrons in the reaction above. A common source in water systems is the oxidation of sulphite:
SO3-2(aq)–> SO4-2(aq) + 2 e–.
The presence of sulphite in the water means that hypochlorite is removed.
ClO–(aq) + 2 H+(aq) + 2 e– —> Cl–(aq) + H2O(l).
Removal of hypochlorite can present a serious danger, in part because the PbO2(s) slowly reverts to PbO and becomes soluble, but mostly because bacteria start multiplying. In the Flint crisis of 2016, and in a previous crisis in Washington DC, the main problem, in my opinion was a lack of hypochlorite addition. The lead crisis was preceded by an uptick in legionnaires disease; It killed 12 people in Flint in 2014 and 2015, and 87 were sickened, all before the lead crisis. Eventually, it was the rise of legionaries disease that alerted water officials in Virginia that there was something seriously wrong in Flint. Most folks were unaware because Flint water inspectors seem to have been fudging the lead numbers to make things look better.
Most US systems add phosphate to remove lead from the water. Flint water folks could have stopped the lead crisis, but not the legionnaires, by adding more phosphate. Lead phosphate solubility is 14 ppb at 20°C, and my suspicion is that this is the reason that the legal limit in the US is 15 ppb. Regulators chose 15 ppb, I suspect, not for health reasons, but because the target could be met easily through the addition of phosphate. Some water systems in the US and Canada disinfect with chloramine, not hypochlorite, and these systems rely entirely on phosphate to keep lead levels down. Excess phosphate is used in Canada to lower lead levels below 10 ppb. It works better on systems with hypochlorite.
Chloramine is formed by reacting hypochlorite with ammonia. It may be safer than hypochlorite in terms of chlorite reaction products, a real problem when the water source is polluted. But chloramine is not safe. It sickened 72 soldiers, 36 male and 36 female in 1998. They’d used ammonia and bleach for a “cleaning party” on successive days. Here’s a report and first aid instructions for the poisoning. That switching to chloramine can expose people to lead is called “the chloramine catch”.
Unlike PbO, PbO2 is a weak acid. PbO2 and PbO can react to form red lead, PbO•PbO2(s), the red stuff on the pipe at right in the picture above. Red lead can react with rust to form iron plumbable, an insoluble corrosion resister. A simple version is:
PbO•PbO2(s) + Fe2O3(s) —> 2FePbO3(s).
This reaction is the basis of red-lead, anti-rust compounds. Iron plumbable is considered to be completely insoluble in water, but like PbO it is soluble in acid. Bottom line, slightly basic water is good, as are hypochlorite in moderation, and phosphate.
Robert Buxbaum, November 18, 2019. I ran for water commissioner, and might run again. Even without being water commissioner, I’ll be happy to lend my expertise, for free, to any Michigan town or county that is not too far from my home.
The oil tanker Palo Alto is one of several major ships made with concrete hulls.
Modern concrete is a wonderful construction material. Major buildings are constructed of it, and major dams, and even some ships. But under the wrong circumstances, concrete has a surprising tendency to crack and fail. I thought I’d explain why that happens and what you can do about it. Concrete does not have to crack easily; ancient concrete didn’t and military or ship concrete doesn’t today. A lot of the fault lies in the use of cheap concrete — concrete with lots of filler — and with the cheap way that concrete is laid. First off, the major components of modern concrete are pretty uniform: sand and rock, Portland cement powder (made from cooked limestone, mostly), water, air, and sometimes ash. The cement component is what holds it all together — cements it together as it were — but it is not the majority of even the strongest concretes. The formula of cement has changed too, but the cement is not generally the problem. It doesn’t necessarily stick well to the rock or sand component of concrete (It sticks far better to itself) but it sticks well enough that spoliation, isn’t usually a problem by itself.
What causes problem is that the strength of concrete is strongly affected (decreased) by having lots of sand, aggregate and water. The concrete used in sidewalks is as cheap as possible, with lots of sand and aggregate. Highway and wall concrete has less sand and aggregate, and is stronger. Military and ship concrete has little sand, and is quite a lot stronger. The lowest grade, used in sidewalks, is M5, a term that refers to its compressive strength: 5 Mega Pascals. Pascals are European (Standard International) units of pressure and of strength. One Pascal is one Newton per square meter (Here’ a joke about Pascal units). In US (English) units, 5 MPa is 50 atm or 750 psi.
Ratios for concrete mixes of different strength; the numbers I use are double these because these numbers don’t include water; that’s my “1”.
The ratio of dry ingredients in various concretes is shown at right. For M5, and including water, the ratio is 1 2 10 20. That is to say there is one part water, two parts cement, 10 parts sand, and 20 parts stone-aggregate (all these by weight). Added to this is 2-3% air, by volume, or nearly as much air as water. At least these are the target ratios; it sometimes happens that extra air and water are added to a concrete mix by greedy or rushed contractors. It’s sometimes done to save money, but more often because the job ran late. The more the mixer turns the more air gets added. If it turns too long there is extra air. It the job runs late, workers will have to add extra water too because the concrete starts hardening. I you see workers hosing down wet concrete as it comes from the truck, this is why. As you might expect, extra air and water decrease the strength of the product. M-10 and M-20 concrete have less sand, stone, and water as a proportion to cement. The result is 10 MPa or 20 MPa strength respectively.
A good on-site inspector is needed to keep the crew from adding too much water. Some water is needed for the polymerization (setting) of the concrete. The rest is excess, and when it evaporates, it leaves voids that are similar to the voids created by having air mix in. It is not uncommon to find 6% voids, in commercial concrete. This is to say that, after the water evaporates, the concrete contains about as much void as cement by volume. To get a sense of how much void space is in the normal concrete outside your house, go outside to a piece of old concrete (10 years old at least) on a hot, dry day, and pour out a cup of water. You will hear a hiss as the water absorbs, and you will see bubbles come out as the water goes in. It used to be common for cities to send inspectors to measuring the void content of the wet (and dry) concrete by a technique called “pycnometry” (that’s Greek for density measurement). I’ve not seen a local city do this in years, but don’t know why. An industrial pycnometer is shown below.
Pycnometer used for concrete. I don’t see these in use much any more.
One of the main reason that concrete fails has to do with differential expansion, thermal stress, a concept I dealt with some years ago when figuring out how cold it had to be to freeze the balls off of a brass monkey. As an example of the temperature change to destroy M5, consider that the thermal expansion of cement is roughly 1 x 10-5/ °F or 1.8 x10-5/°C. This is to say that a 1 meter slab of cement that is heated or cooled by 100°F will expand or shrink by 10-3 m respectively; 100 x 1×10-5 = 10-3. This is a fairly large thermal expansion coefficient, as these things go. It would not cause stress-failure except that sand and rock have a smaller thermal expansion coefficients, about 0.6×10-5 — barely more than half the value for cement. Consider now what happens to concrete that s poured in the summer when it is 80°F out, and where the concrete heats up 100°F on setting (cement setting releases heat). Now lets come back in winter when it’s 0°F. This is a total of 100°F of temperature change. The differential expansion is 0.4 x 10-5/°F x 100°F = 4 x10-4 meter/meter = 4 x10-4 inch/inch.
The force created by this differential expansion is the elastic modulus of the cement times the relative change in expansion. The elastic modulus for typical cement is 20 GPa or, in English units, 3 million psi. This is to say that, if you had a column of cement (not concrete), one psi of force would compress it by 1/3,000,000. The differential expansion we calculated, cement vs sand and stone is 4×10-4 ; this much expansion times the elastic modulus, 3,000,000 = 1200 psi. Now look at the strength of the M-5 cement; it’s only 750 psi. When M-5 concrete is exposed to these conditions it will not survive. M-10 will fail on its own, from the temperature change, without any help needed from heavy traffic. You’d really like to see cities check the concrete, but I’ve seen little evidence that they do.
Water makes things worse, and not only because it creates voids when it evaporates. Water also messes up the polymerization reaction of the cement. Basic, fast setting cement is mostly Ca3SiO5
2Ca3SiO5 + 6 H2O –> 3Ca0SiO2•H2O +3Ca(OH)2•H2O.
The former of these, 3Ca0SiO2•H2O, forms something of a polymer. Monomer units of SiO4 are linked directly or by partially hydrated CaO linkages. Add too much water and the polymeric linkages are weakened or do not form at all. Over time the Ca(OH)2 can drain away or react with CO2 in the air to form chalk.
Portland limestone cement strength versus curing time. Slow curing and damp helps; fast dry hurts. Carbonate formation adds little or no strength. Jehan Elsamni 2011.
Sorry to say, the chalk adds little or no strength, as the graph at right shows. Concrete made with too much water isn’t very strong at all, and it gets no stronger when dried in air. Hardening goes on for some weeks after pouring, and this is the reason you don’t drive on 1 too 2 day old concrete. Driving on weak concrete can cause cracks that would not form if you waited.
You might think to make better concrete by pouring concrete in the cold, but pouring in the cold makes things worse. Cold poured cement will expand the summer and the cement will detach from the sand and stone. Ideally, pouring should be in spring or fall, when the temperature is moderate, 40-60°F. Any crack that develops grows by a mechanism called Rayleigh crack growth, described here. Basically, once a crack starts, it concentrates the fracture forces, and any wiggling of the concrete makes the crack grow faster.
Based on the above, I’ve come to suspect that putting on a surface coat can (could) help strengthen old concrete, even long after it’s hardened. Mostly this would happen by filling in voids and cracks, but also by extending the polymer chains. I imagine it would be especially helpful to apply the surface coat somewhat watery on a dry day in the summer. In that case, I imagine that Ca3SiO5 and Ca(OH)2 from the surface coat will penetrate and fill the pores of the concrete below — the sales pores that hiss when you pour water on them. I imagine this would fill cracks and voids, and extend existing CaOSiO2•H2O chains. The coat should add strength, and should be attractive as well. At least that was my thought.
I should note that, while Portland cement is mostly Ca3SiO5, there is also a fair amount (25%) of Ca2SiO4. This component reacts with water to form the same calcium-silicate polymer as above, but does so at a slower rate using less water per gram. My hope was that this component would be the main one to diffuse into deep pores of the concrete, reacting there to strengthen the concrete long after surface drying had occurred.
Trump tower: 664′, concrete and glass. What grade of concrete would you use?
As it happened, I had a chance to test my ideas this summer and also about 3 years ago. The city inspector came by to say the concrete flags outside my house were rough, and thus needed replacing, and that I was to pay or do it myself. Not that I understand the need for smooth concrete, quite, but that’s our fair city. I applied for a building permit to apply a surface coat, and applied it watery. I used “Quickrete” brand concrete patch, and so far it’s sticking OK. Pock-holes in the old concrete have been filled in, and so far surface is smooth. We’ll have to see if my patch lasts 10-20 years like fresh cement. Otherwise, no matter how strong the concrete becomes underneath, the city will be upset, and I’ll have to fix it. I’ve noticed that there is already some crumbling at the sides of flags, something I attribute to the extra water. It’s not a problem yet, but hope this is not the beginning of something worse. If I’m wrong here, and the whole seal-coat flakes off, I’ll be stuck replacing the flags, or continuing to re-coat just to preserve my reputation. But that’s the cost of experimentation. I tried something new, and am blogging about it in the hope that you and I benefit. “Education is what you get when you don’t get what you want.” (It’s one of my wise sayings). At the worst, I’ll have spent 90 lb of patching cement to get an education. And, I’m happy to say that some of the relatively new concrete flags that the city put in are already cracked. I attribute this to: too much sand, air, water or air (they don’t look like they have much rock): Poor oversight.
Dr. Robert E. Buxbaum. March 5, 2019. As an aside, the 664 foot Trump Tower, NY is virtually the only skyscraper in the city to be built of concrete and glass. The others are mostly steel and glass. Concrete and glass is supposed to be stiffer and quieter. The engineer overseeing the project was Barbara Res, the first woman to oversee a major, NY building project. Thought question: if you built the Trump Tower, which quality of concrete would you use, and why.
Most people assume that alkaline batteries are one-time only, throwaway items. Some have used rechargeable cells, but these are Ni-metal hydride, or Ni-Cads, expensive variants that have lower power densities than normal alkaline batteries, and almost impossible to find in stores. It would be nice to be able to recharge ordinary alkaline batteries, e.g. when a smoke alarm goes off in the middle of the night and you find you’re out, but people assume this is impossible. People assume incorrectly.
Modern alkaline batteries are highly efficient: more efficient than even a few years ago, and that always suggests reversibility. Unlike the acid batteries you learned about in highschool chemistry class (basic chemistry due to Volta) the chemistry of modern alkaline batteries is based on Edison’s alkaline car batteries. They have been tweaked to an extent that even the non-rechargeable versions can be recharged. I’ve found I can reliably recharge an ordinary alkaline cell, 9V, at least once using the crude means of a standard 12 V car battery charger by watching the amperage closely. It only took 10 minutes. I suspect I can get nine lives out of these batteries, but have not tried.
To do this experiment, I took a 9 V alkaline that had recently died, and finding I had no replacement, I attached it to a 6 Amp, 12 V, car battery charger that I had on hand. I would have preferred to use a 2 A charger and ideally a charger designed to output 9-10 V, but a 12 V charger is what I had available, and it worked. I only let it charge for 10 minutes because, at that amperage, I calculated that I’d recharged to the full 1 Amp-hr capacity. Since the new alkaline batteries only claimed 1 amp hr, I figured that more charge would likely do bad things, even perhaps cause the thing to blow up. After 5 minutes, I found that the voltage had returned to normal and the battery worked fine with no bad effects, but went for the full 10 minutes. Perhaps stopping at 5 would have been safer.
I changed for 10 minutes (1/6 hour) because the battery claimed a capacity of 1 Amp-hour when new. My thought was 1 amp-hour = 1 Amp for 1 hour, = 6 Amps for 1/6 hour = ten minutes. That’s engineering math for you, the reason engineers earn so much. I figured that watching the recharge for ten minutes was less work and quicker than running to the store (20 minutes). I used this battery in my firm alarm, and have tested it twice since then to see that it works. After a few days in my fire alarm, I took it out and checked that the voltage was still 9 V, just like when the battery was new. Confirming experiments like this are a good idea. Another confirmation occurred when I overcooked some eggs and the alarm went off from the smoke.
If you want to experiment, you can try a 9V as I did, or try putting a 1.5 volt AA or AAA battery in a charger designed for rechargeables. Another thought is to see what happens when you overcharge. Keep safe: do this in a wood box outside at a distance, but I’d like to know how close I got to having an exploding energizer. Also, it would be worthwhile to try several charge/ discharge cycles to see how the energy content degrades. I expect you can get ~9 recharges with a “non-rechargeable” alkaline battery because the label says: “9 lives,” but even getting a second life from each battery is a significant savings. Try using a charger that’s made for rechargeables. One last experiment: If you’ve got a cell phone charger that works on a car battery, and you get the polarity right, you’ll find you can use a 9V alkaline to recharge your iPhone or Android. How do I know? I judged a science fair not long ago, and a 4th grader did this for her science fair project.
Robert Buxbaum, April 19, 2018. For more, semi-dangerous electrochemistry and biology experiments.
I’m a chemical engineer running for Oakland county water resources commissioner, and as the main job of the office is sewage, and as I’ve already written on the chemistry, I thought I might write about an aspect of the engineering. Specifically about toilet paper. Toilet paper is a remarkable product: it’s paper, compact and low in cost; strong enough to clean you, smooth on your bum, and beyond that, it will disintegrate in turbulent water so it doesn’t clog pipes. The trick to TP’s dry strength and wet-weakness, is that the paper pulp, wood cellulose, is pounded very thin, yet cast fluffy. For extra softness, the paper is typically coated with aloe or similar. Sorry to say, the same recipe does not work for wet-wipes, paper towels or kleenex (facial tissues); all of these products must have wet-strength, and this can cause problems with sewer clogs.
Patent 117,355 for perforated toilet paper on a roll. It’s claimed as an improved wrapping paper.
Before there was toilet paper, the world was a much sadder, and smellier place. Much of the world used sticks, stones, leaves, or corn cobs, and none of these did a particularly thorough job. Besides, none of these is particularly smooth, or particularly disposable, nor did it fall apart — not that most folks had indoor plumbing. Some rich Romans had plumbing, and these cleaned themselves with a small sponge on the end of a stick. They dipped the sponge end in water for each use. It was disgusting, but didn’t clog the pipes. I’ve seen this in use on a trip to Turkey 25 years ago — not in actual use, but the stick and sponge was there in a smelly bucket next to the hole in the ground that served as the commode.
The first reasonably modern toilet was invented in 1775 by Alexander Cummings, and by 1852 the first public flush toilets were available. The design looked pretty much like it looks today and the cost was 1¢. You got a towel and a shoe-shine too for that penny, but there was no toilet paper as such. Presumably one used a Roman sponge or some ordinary, standard paper. A popular wipe, back in the day was the Sears-Roebuck catalog. It came free to most homes and included a convenient hole in the corner allowing one to hang it in and outhouse or near the commode. It was rough on the bum, and didn’t fall apart. My guess is that it clogged the pipes too, for those who used it with flush toilets. The first toilet-specific paper wasn’t invented till 1859. Joseph Gayetty, an American, patented a product from pulverized hemp, a relatively soft fiber, softened further with aloe. This paper was softer than standard, and had less tendency to clog pipes.
Toilet paper is either touted to be soft or strong; Modern Charmin touts wet strength, while Cottonelle touts completeness of wipe: ‘go commando.”
The next great innovation was to make toilet paper as a perforated product on a roll. These novelties appear as US Patent #117,355 awarded to Seth Wheeler of Albany, NY 25 July 1871 (Wheeler also invented the classic roll toilet paper dispenser). Much of the sales pitch was that a cleaner bum would prevent the spread of cholera, typhoid, and other plagues and that is a legitimate claim. As the market expanded, advertising followed. Some early brands touted their softness, others their strength. Facial tissues, e.g. Kleenex, were sold specifically as a soft TP-like product that does not fall apart when wet. Sorry to say, this tends to go along with clogged toilets; do not flush more than one kleenex down at a flush. Kleenex is made with the same short fibers and aloe as toilet paper, but it contains binders (glue) to give it wet-strength. My guess is that Charmin is made the same way and that it isn’t great on your plumbing.
Paper towels and most baby wipes are worse to flush than Kleenex. They are made with lots of binder and they really don’t fall apart in water. Paper towels should never be flushed, and neither should most baby wipes, even brands that claim to be ‘flushable.” When flushed, these items tend to soak up fat and become fat bergs – the bane of sewer workers everywhere. There is a class action law suit against flushable wipe companies, and New York City is pursuing legislation to prevent them from claiming to be flushable. Still, as with everything, there are better and worse moist-wipe options. “Cottonelle” brand by Kleenex, and Scott flushable wipes are the best currently. In a day or less they will dissolve in water. These products are made with binders like kleenex, but the binder glue is a type that dissolves in any significant amount of water. As a result, these brands fall apart eventually. For now, these are the only flushable brands I’d recommend flushing, and even then I suggest you only flush one at a time. In tests by Consumer Reports, other brands, e.g. Charmin and Equate flushable wipes do not dissolve. These manufacturers either have not quite figured out how to make dissolvable binders, or they can’t get around Kleenex’s patents.
Robert Buxbaum. October 10, 2016. If you live in Oakland County, MI, vote for me for water commissioner. Here’s my web-site with other useful essays. I should mention Thomas Crapper, too. He invented the push-button flush and made some innovations in the water cistern, and he manufactured high-end commodes for Parliament and the royal family, but he’s irrelevant to the story here.
