Tag Archives: vacuum

A hydrogen permeation tester

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Over the years I’ve done a fair amount of research on hydrogen permeation in metals — this is the process of the gas dissolving in the metal and diffusing to the other side. I’ve described some of that, but never the devices that measure the permeation rate. Besides, my company, REB Research, sells permeation testing devices, though they are not listed on our site. We recently shipped one designed to test hydrogen permeation through plastics for use in light weight hydrogen tanks, for operation at temperatures from -40°C to 85°C. Shortly thereafter we got another order for a permeation tester. With all the orders, I thought I’d describe the device a bit — this is the device for low permeation materials. We have a similar, but less complex design for high permeation rate material.

Shown below is the central part of the device. It is a small volume that can be connected to a high vacuum, or disconnected by a valve. There is an accurate pressure sensor, accurate to 0.01 Torr, and so configured that you do not get H2 + O2 reactions (something that would severely throw off results). There is also a chamber for holding a membrane so one side is help in vacuum, in connection to the gauge, and the other is exposed to hydrogen, or other gas at pressures up to 100 psig (∆P =115 psia). I’d tested to 200 psig, but currently feel like sticking to 100 psig or less. This device gives amazingly fast readings for plastics with permeabilities as low as 0.01 Barrer.

REB Research hydrogen permeation tester cell with valve and pressure sensor.

REB Research hydrogen permeation tester cell with valve and pressure sensor.

To control the temperature in this range of interest, the core device shown in the picture is put inside an environmental chamber, set up as shown below, with he control box outside the chamber. I include a nitrogen flush device as a safety measure so that any hydrogen that leaks from the high pressure chamber will not build up to reach explosive limits within the environmental chamber. If this device is used to measure permeation of a non-flammable gas, you won’t need to flush the environmental chamber.

I suggest one set up the vacuum pump right next to the entrance of the chamber; in the case of the chamber provided, that’s on the left as shown with the hydrogen tank and a nitrogen tank to the left of the pump. I’ve decided to provide a pressure sensor for the N2 (nitrogen) and a solenoidal shutoff valve for the H2 (hydrogen) line. These work together as a safety feature for long experiments. Their purpose is to automatically turn off the hydrogen if the nitrogen runs out. The nitrogen flush part of this process is a small gauge copper line that goes from the sensor into the environmental chamber with a small, N2 flow bleed valve at the end. I suggest setting the N2 pressure to 25-35 psig. This should give a good inert flow into the environmental chamber. You’ll want a nitrogen flush, even for short experiments, and most experiments will be short. You may not need an automatic N2 sensor, but you’ll be able to do this visually.

Basic setup for REB permeation tester and environmental chamber

Basic setup for REB permeation tester and environmental chamber

I shipped the permeation cell comes with some test, rubbery plastic. I’d recommend the customer leave it in for now, so he/she can use it for some basic testing. For actual experiments, you replace mutest plastic with the sample you want to check. Connect the permeation cell as shown above, using VCR gaskets (included), and connect the far end to the multi-temperature vacuum hose, provided. Do this outside of the chamber first, as a preliminary test to see if everything is working.

For a first test live the connections to the high pressure top section unconnected. The pressure then will be 1 atm, and the chamber will be full of air. eave the top, Connect the power to the vacuum pressure gauge reader and connect the gauge reader to the gauge head. Open the valve and turn on the pump. If there are no leaks the pressure should fall precipitously, and you should see little to no vapor coming out the out port on the vacuum pump. If there is vapor, you’ve got a leak, and you should find it; perhaps you didn’t tighten a VCR connection, or you didn’t do a good job with the vacuum hose. When things are going well, you should see the pressure drop to the single-digit, milliTorr range. If you close the valve, you’ll see the pressure rise in the gauge. This is mostly water and air degassing from the plastic sample. After 30 minutes, the rate of degassing should slow and you should be able to measure the rate of gas permeation in the polymer. With my test plastic, it took a minute or so for the pressure to rise by 10 milliTorr after I closed the valve.

If you like, you can now repeat this preliminary experiment with hydrogen connect the hydrogen line to one of the two ports on the top of the permeation cell and connect the other port to the rest of the copper tubing. Attach the H2 bleed restrictor (provided) at the end of this tubing. Now turn on the H2 pressure to some reasonable value — 45 psig, say. With 45 psi (3 barg upstream) you will have a ∆P of 60 psia or 4 atm across the membrane; vacuum equals -15 psig. Repeat the experiment above; pump everything down, close the valve and note that the pressure rises faster. The restrictor allows you to maintain a H2 pressure with a small, cleansing flow of gas through the cell.

If you like to do these experiments with a computer record, this might be a good time to connect your computer to the vacuum reader/ controller, and to the thermocouple, and to the N2 pressure sensor. 

Here’s how I calculate the permeability of the test polymer from the time it takes for a pressure rise assuming air as the permeating gas. The volume of the vacuumed out area after the valve is 32 cc; there is an open area in the cell of 13.0 cm2 and, as it happens, the  thickness of the test plastic is 2 mm. To calculate the permeation rate, measure the time to rise 10 millitorr. Next calculate the millitorr per hour: that’s 360 divided by the time to rise ten milliTorr. To calculate ncc/day, multiply the millitorr/hour by 24 and by the volume of the chamber, 32 cc, and divide by 760,000, the number of milliTorr in an atmosphere. I found that, for air permeation at ∆P = one atm, I was getting 1 minute per milliTorr, which translates to about 0.5 ncc/day of permeation through my test polymer sheet. To find the specific permeability in cc.mm/m2.day.atm, I multiply this last number by the thickness of the plastic (2 mm in this case), divide by the area, 0.0013 m2, and divide by ∆P, 1 atm, for this first test. Calculated this way, I got an air permeance of 771 cc.mm/m2.day.atm.

The complete setup for permeation testing.

The complete setup for permeation testing.

Now repeat the experiment with hydrogen and your own plastic. Disconnect the cell from both the vacuum line and from the hydrogen in line. Open the cell; take out my test plastic and replace it with your own sample, 1.87” diameter, or so. Replace the gasket, or reuse it. Center the top on the bottom and retighten the bolts. I used 25 Nt-m of torque, but part of that was using a very soft rubbery plastic. You might want to use a little more — perhaps 40-50 Nt-m. Seal everything up. Check that it is leak tight, and you are good to go.

The experimental method is the same as before and the only signficant change when working with hydrogen, besides the need for a nitrogen flush, is that you should multiply the time to reach 10 milliTorr by the square-root of seven, 2.646. Alternatively, you can multiply the calculated permeability by 0.378. The pressure sensor provided measures heat transfer and hydrogen is a better heat transfer material than nitrogen by a factor of √7. The vacuum gauge is thus more sensitive to H2 than to N2. When the gauge says that a pressure change of 10 milliTorr has occurred, in actuality, it’s only 3.78 milliTorr.  The pressure gauge reads 3.78 milliTorr oh hydrogen as 10 milliTorr.

You can speed experiments by a factor of ten, by testing the time to rise 1 millitorr instead of ten. At these low pressures, the gauge I provided reads in hundredths of a milliTorr. Alternately, for higher permeation plastics (or metals) you want to test the time to rise 100 milliTorr or more, otherwise the experiment is over too fast. Even at a ten millTorr change, this device gives good accuracy in under 1 hour with even the most permeation-resistant polymers.

Dr. Robert E. Buxbaum, March 27, 2019; If you’d like one of these, just ask. Here’s a link to our web site, REB Research,

Of God and gauge blocks

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Most scientists are religious on some level. There’s clear evidence for a big bang, and thus for a God-of-Creation. But the creation event is so distant and huge that no personal God is implied. I’d like to suggest that the God of creation is close by and as a beginning to this, I’d like to discus Johansson gauge blocks, the standard tool used to measure machine parts accurately.

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A pair of Johansson blocks supporting 100 kg in a 1917 demonstration. This is 33 times atmospheric pressure, about 470 psi.

Lets say you’re making a complicated piece of commercial machinery, a car engine for example. Generally you’ll need to make many parts in several different shops using several different machines. If you want to be sure the parts will fit together, a representative number of each part must be checked for dimensional accuracy in several places. An accuracy requirement of 0.01 mm is not uncommon. How would you do this? The way it’s been done, at least since the days of Henry Ford, is to mount the parts to a flat surface and use a feeler gauge to compare the heights of the parts to the height of stacks of precisely manufactured gauge blocks. Called Johansson gauge blocks after the inventor and original manufacturer, Henrik Johansson, the blocks are typically made of steel, 1.35″ wide by .35″ thick (0.47 in2 surface), and of various heights. Different height blocks can be stacked to produce any desired height in multiples of 0.01 mm. To give accuracy to the measurements, the blocks must be manufactured flat to within 1/10000 of a millimeter. This is 0.1µ, or about 1/5 the wavelength of visible light. At this degree of flatness an amazing thing is seen to happen: Jo blocks stick together when stacked with a force of 100 kg (220 pounds) or more, an effect called, “wringing.” See picture at right from a 1917 advertising demonstration.

This 220 lbs of force measured in the picture suggests an invisible pressure of 470 psi at least that holds the blocks together (220 lbs/0.47 in2 = 470 psi). This is 32 times the pressure of the atmosphere. It is independent of air, or temperature, or the metal used to make the blocks. Since pressure times volume equals energy, and this pressure can be thought of as a vacuum energy density arising “out of the nothingness.” We find that each cubic foot of space between the blocks contains, 470 foot-lbs of energy. This is the equivalent of 0.9 kWh per cubic meter, energy you can not see, but you can feel. That is a lot of energy in the nothingness, but the energy (and the pressure) get larger the flatter you make the surfaces, or the closer together you bring them together. This is an odd observation since, generally get more dense the smaller you divide them. Clean metal surfaces that are flat enough will weld together without the need for heat, a trick we have used in the manufacture of purifiers.

A standard way to think of quantum scattering is that the particle is scattered by invisible bits of light (virtual photons), the wavy lines. In this view, the force that pushes two flat surfaces together is from a slight deficiency in the amount of invisible light in the small space between them.

A standard way to think of quantum scattering of an atom (solid line) is that it is scattered by invisible bits of light, virtual photons (the wavy lines). In this view, the force that pushes two blocks together comes from a slight deficiency in the number of virtual photons in the small space between the blocks.

The empty space between two flat surfaces also has the power to scatter light or atoms that pass between them. This scattering is seen even in vacuum at zero degrees Kelvin, absolute zero. Somehow the light or atoms picks up energy, “out of the nothingness,” and shoots up or down. It’s a “quantum effect,” and after a while physics students forget how odd it is for energy to come out of nothing. Not only do students stop wondering about where the energy comes from, they stop wondering why it is that the scattering energy gets bigger the closer you bring the surfaces. With Johansson block sticking and with quantum scattering, the energy density gets higher the closer the surface, and this is accepted as normal, just Heisenberg’s uncertainly in two contexts. You can calculate the force from the zero-point energy of vacuum, but you must add a relativistic wrinkle: the distance between two surfaces shrinks the faster you move according to relativity, but measurable force should not. A calculation of the force that includes both quantum mechanics and relativity was derived by Hendrik Casimir:

Energy per volume = P = F/A = πhc/ 480 L4,

where P is pressure, F is force, A is area, h is plank’s quantum constant, 6.63×10−34 Js, c is the speed of light, 3×108 m/s, and L is the distance between the plates, m. Experiments have been found to match the above prediction to within 2%, experimental error, but the energy density this implies is huge, especially when L is small, the equation must apply down to plank lengths, 1.6×10-35 m. Even at the size of an atom, 1×10-10m, the amount of the energy you can see is 3.6 GWhr/m3, 3.6 Giga Watts. 3.6 GigaWatt hrs is one hour’s energy output of three to four large nuclear plants. We see only a tiny portion of the Plank-length vacuum energy when we stick Johansson gauge blocks together, but the rest is there, near invisible, in every bit of empty space. The implication of this enormous energy remains baffling in any analysis. I see it as an indication that God is everywhere, exceedingly powerful, filling the universe, and holding everything together. Take a look, and come to your own conclusions.

As a homiletic, it seems to me that God likes friendship, but does not desire shaman, folks to stand between man and Him. Why do I say that? The huge force-energy between plates brings them together, but scatters anything that goes between. And now you know something about nothing.

Robert Buxbaum, November 7, 2018. Physics references: H. B. G. Casimir and D. Polder. The Influence of Retardation on the London-van der Waals Forces. Phys. Rev. 73, 360 (1948).
S. Lamoreaux, Phys. Rev. Lett. 78, 5 (1996).

Camless valves and the Fiat-500

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One of my favorite automobile engine ideas is the use of camless, electronic valves. It’s an idea whose advantages have been known for 100 years or more, and it’s finally going to be used on a mainstream, commercial car — on this year’s Fiat 500s. Fiat is not going entirely camless, but the plan is to replace the cams on the air intake valves with solenoids. A normal car engine uses cams and lifters to operate the poppet valves used to control the air intake and exhaust. Replacing these cams and lifters saves some weight, and allows the Fiat-500 to operate more efficiently at low power by allowing the engine to use less combustion energy to suck vacuum. The Fiat 500 semi-camless technology is called Multiair: it’s licensed from Valeo (France), and appeared as an option on the 2010 Alfa Romeo.

How this saves mpg is as follows: at low power (idling etc.), the air intake of a normal car engine is restricted creating a fairly high vacuum. The vacuum restriction requires energy to draw and reduces the efficiency of the engine by decreasing the effective compression ratio. It’s needed to insure that the car does not produce too much NOx when idling. In a previous post, I showed that the rate of energy wasted by drawing this vacuum was the vacuum pressure times the engine volume and the rpm rate; I also mentioned some classic ways to reduce this loss (exhaust recycle and adding water).

Valeo’s/Fiat’s semi-camless design does nothing to increase the effective compression ratio at low power, but it reduces the amount of power lost to vacuum by allowing the intake air pressure to be higher, even at low power demand. A computer reduces the amount of air entering the engine by reducing the amount of time that the intake valve is open. The higher air pressure means there is less vacuum penalty, both when the valve is open even when the valve is closed. On the Alfa Romeo, the 1.4 liter Multiair engine option got 8% better gas mileage (39 mpg vs 36 mpg) and 10% more power (168 hp vs 153 hp) than the 1.4 liter cam-driven engine.

David Bowes shows off his latest camless engines at NAMES, April 2013.

David Bowes shows off his latest camless engines at NAMES, April 2013.

Fiat used a similar technology in the 1970s with variable valve timing (VVT), but that involved heavy cams and levers, and proved to be unreliable. In the US, some fine engineers had been working on solenoids, e.g. David Bowes, pictured above with one of his solenoidal engines (he’s a sometime manufacturer for REB Research). Dave has built engines with many cycles that would be impractical without solenoids, and has done particularly nice work reducing the electric use of the solenoid.

Durability may be a problem here too, as there is no other obvious reason that Fiat has not gone completely camless, and has not put a solenoid-controlled valve on the exhaust too. One likely reason Fiat didn’t do this is that solenoidal valves tend to be unreliable at the higher temperatures found in exhaust. If so, perhaps they are unreliable on the intake too. A car operated at 1000-4000 rpm will see on the order of 100,000,000 cycles in 25,000 miles. No solenoid we’ve used has lasted that many cycles, even at low temperatures, but most customers expect their cars to go more than 25,000 miles without needing major engine service.

We use solenoidal pumps in our hydrogen generators too, but increase the operating live by operating the solenoid at only 50 cycles/minute — maximum, rather than 1000- 4000. This should allow our products to work for 10 years at least without needing major service. Performance car customers may be willing to stand for more-frequent service, but the company can’t expect ordinary customers to go back to the days where Fiat stood for “Fix It Again Tony.”

How hydrogen and/or water can improve automobile mileage (mpg)

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In case you’ve ever wondered why it was that performance cars got such poor milage, or why you got such bad milage in the city, the biggest single problem has to do with the vacuum drawn by the engine, some of the problem has to do with the speed of combustion, some has to do with rolling friction, and some with start/stop loss too. Only a very small fraction of the energy is lost on air friction until you reach highway speeds.

Lets consider vacuum loss first as it is likely the worst offender. A typical US car, e.g. a Chevy Malibu, has a 3.5 liter engine (a performance car has an engine that’s much larger). As you toodle down a street at 35 mph, your engine is going at about 2000 rpm, or 33 rps. Since the power required to move the car is far less than the 200 hp that the car could deliver, the air intake is throttled so that the engine is sucking a vacuum of about 75 kpa (10 psi for those using English units). To calculate the power loss this entails, multiply 33*3.5*80; this is about 8662 Watts, or 12 hp. To find the energy use per mile, divide by your average speed, 25 mph (it would be 35 mph, but you sometimes stop for lights). 8 kW/25 mph = .21 kW-hr/mile. One finds, as I’ll show that the car expends more energy sucking this vacuum than pushing the car itself. This is where the majority of the city mpg goes in a normal car, but it’s worse in a high performance car is worse since the engine is bigger. In city driving, the performance mpg will be lower than for a Malibu even if the performance car is lighter, if it has better aerodynamics (it does), and if you never stop at lights.

The two other big places were city mileage goes is overcoming rolling friction and the need to stop and go at lights, stop signs, etc. The energy used for rolling friction is the force it would take to push your car on level ground when in neutral times the distance. For a typical car, the push force is about 70 lbs or 32 kgs or 315 Nt; it’s roughly proportional to the car’s weight. At 35 mph, or 15.5 m/s, the amount of power this absorbs is calculated as the product of force and speed: 15.5*315 = 4882 W, or about 6.5 hp. The energy use is 4.9 kW/35 mph =.14 kWhr/mile. The energy loss from stop lights is similar to this, about .16 kWhr/mile, something you can tell by getting the car up to speed and seeing how far it goes before it stops. It’ll go about 2-3 blocks, a little less distance than you are likely to go without having to stop. Air resistance adds a very small amount at these speeds, about 2000 W, 2.7 hp, or .05 kWhr/mile; it’s far more relevant at 65 mph, but still isn’t that large.

If you add all this together, you find the average car uses about .56 kWhr/mile. For an average density gasoline of 5.6 lb/gal, and average energy-dense gasoline, 18,000 BTU/lb, and an average car engine efficiency of 11000 BTU/kWhr, you can now predict an average city gas mileage of 16.9 mpg, about what you find experimentally. Applying the same methods to highway traffic at 65 mph, you predict .38 kWhr/mile, or 25 mpg. Your rpms are the same on the highway as in the city, but the throttle is open so you get more power and loose less to vacuum.

Now, how do you increase a car’s mpg. If you’re a Detroit automaker you could reduce the weight of the car, or you the customer can clean the junk out of your trunk. Every 35 lbs or so increases the rolling friction by about 1%. These is another way to reduce rolling friction and that’s to get low resistance tires, or keep the tires you’ve got full of air. Still, what you’d really like to do is reduce the loss to vacuum energy, since vacuum loss is a bigger drain on mpg.

The first, simple way to reduce vacuum energy loss is to run lean: that is, to add more air than necessary for combustion. Sorry to say, that’s illegal now, but in the olden days before pollution control you could boost your mpg by adjusting your carburator to add about 10% excess of air. This reduced your passing power and the air pollution folks made it illegal (and difficult) after they noticed that it excess air increased NOx emissions. The oxygen sensor on most cars keeps you from playing with the carburator these days.

Another approach is to use a much smaller engine. The Japanese and Koreans used to do this, and they got good milage as a result. The problem here is that you now had to have a very light car or you’d get very low power and low acceleration — and no American likes that. A recent approach to make up for some of the loss of acceleration is by adding a battery and an electric motor; you’re now making a hybrid car. But the batteries add significant cost, weight and complexity to these cars, and not everyone feels this is worth it. So now on to my main topic: adding steam or hydrogen.

There is plenty of excess heat on the car manifold. A simile use of this heat is to warm some water to the point where the vapor pressure is, for example, 50 kPa. The pressure from this water adds to the power of your engine by allowing a reduction in the vacuum to 50 kPa or less. This cuts the vacuum loss at low speeds. At high speed and power the car automatically increases the air pressure and the water stops evaporating, so there is no loss of power. I’m currently testing this modification on my own automobile partly for the fun of it, and partly as a preface to my next step: using the car engine heat to run the reaction CH3OH + H2O –> CO2 + H2. I’ll talk more about our efforts adding hydrogen elsewhere, but thought you might be interested in these fundamentals.

http://www.rebresearch.com