JPS59500331A - Method and device for measuring hydrogen flow - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method and device for measuring hydrogen flow The present invention relates to a method and apparatus for measuring hydrogen flow through a metal membrane.

Technical background In some chemical process industries, hydrogen-induced cracking or blistering Corrosion of the steel components will occur under these conditions. typical and technically An important example is a condensed liquid phase containing water and hydrogen oxide (along with other substances). Corrosion of natural gas vibrators and pressure vessels. This condensate is slightly acidic Yes, and the generation of hydrogen will corrode virtue. The presence of hydrogen sulfide is the molecule This inhibits the formation of hydrogen, and a significant portion of the hydrogen permeates into the steel, where it forms cracks. or cause damage in the form of blisters.

In some methods, hydrogen sulfide removal is achieved, for example by preventing condensation. or in some ways, e.g. by neutralization of the liquid phase or the formation of a protective film. By adding an inhibitor that enhances the hydrogen content, it is possible to reduce the amount of waste caused by hydrogen. Wear.

exposure of the steel constituents in question to enable monitoring of the effectiveness of such precautionary measures. It is necessary to measure the hydrogen absorption or hydrogen absorption rate of the region. This (1 some publicly known This is done based on the 11 constant principle of Hydrogen permeating into the exposed inlet 11111 of the steel wall diffuses through the steel wall and enters. It is based on the fact that it is liberated in gaseous (molecular) form on the side of the steel wall opposite to the mouth side. Ru. The rate of hydrogen evolution on the reaction side of the steel wall can be determined by known techniques, e.g. By measuring the rise in pressure during closing of the chamber or by measuring the rise in pressure during closing of the chamber, It may be measured by measuring the displacement of a droplet in a gas tube. The amount of hydrogen is also It can also be analyzed in various ways, for example by gas phase chromatography. Probably.

In order to measure the hydrogen evolution rate according to the physical measurement principle described above, several hydrogen measurements were carried out. A constant liver detector has been proposed. However, these hydrogen measuring devices are different. It has the following disadvantages. Some of these are rather primitive and have low sensitivity, while , and others (requiring constant management and for automatic data recording). It's not appropriate. Others are more sensitive and accurate, but expensive. And difficult to handle.

Electricity based on electrochemical oxidation of hydrogen permeating to the side opposite to the inlet of the steel wall Chemical measurement principles are also known. This technique was first developed by N.A.V. Devanathan (De vanathan) and 2-Stachorski therefore The constructed hydrogen detector or hydrogen cell is known as a hydrogen cell.

In this cell, the steel/metal constitutes the wall or membrane between the two compartments. first The compartment constitutes an experimental compartment in which the iron or steel material of the walls has a corrosive force, or V: or is exposed to other experimental influences that produce hydrogen in steel materials. The second compartment is deaerated containing an alkaline solution such as 1M potassium hydroxide. facing the second compartment The surface of iron or steel walls is permeable to hydrogen and stable in alkaline solutions. It is coated with a thin film of electrodeposited radium.・Zo radium counter electrode The poles are placed facing the iron or steel wall, and the reference electrode is also placed in the second compartment. and its tip is placed very close to the radium coating film. There is. To maintain a constant potential of palladium-coated iron or steel walls in alkaline solutions For this purpose, a potentiostat is used.

Generally, a potential of “H=+100 mV is used. At this potential, the wall Palladium coatings and iron or steel materials are passive. Therefore, no The dynamic current density is very small, typically ido, 01-0.1 μA/cm2. Ru.

Any hydrogen that diffuses through the iron or steel wall and its palladium coating will On the radium-coated side opposite to the inlet side, it is oxidized according to the following equation:

IH+ OH--+ H2O+ e- Therefore, the anodic current intensifier that exceeds the stationary background current is hydrogen passing through the wall. Corresponds to flow. The potential on the opposite side, i.e. on the radium coated inside of the wall. Assuming that the hydrogen activity can be maintained at approximately O, an iron or steel wall of a given thickness The hydrogen flow through a unit area of is determined by the activity of hydrogen outside the wall and the diffusion admittance of the wall. It is the product of Once the diffusion admittance is known, it can be based on the anode current of the cell. The activity of hydrogen in the first compartment can be calculated using The diffusion admittance is , by having a controlled electrochemical environment in the first compartment, or by having a controlled electrochemical environment in the first compartment; is measured by introducing a hydrogen atmosphere of known pressure into the compartment. iron or steel wall If the outside is covered with some radium, the cell becomes more sensitive to molecular hydrogen. It becomes.

Another laboratory measurement device based on the Devanathan measurement principle is described in reference 2. ing. In this measuring device, a steel plate houses an electrolyte, a reference electrode, and a counter electrode. It forms part of the wall of the cell containing the cell. In addition, potentioses are required to operate the device. Tutt discloses the necessary electrochemical cell, which It is based on the principles of ``Davanathan'' 11 fixed techniques. This cell consists of an electrolyte container, a working electrode forming a wall portion of the container and adapted to be exposed to the liquid during the test; A wire having an area corresponding to the working electrode and arranged close to and parallel to the working electrode. Comprising a radium/radium oxide reference electrode. Takumi explains one specific example of a cell. means for maintaining the working electrode at a constant potential with respect to the reference electrode; and means are provided for measuring the current flowing through the working electrode. child An example of this is used in conjunction with electronic means to maintain the working electrode at a constant potential. Must. In other embodiments of the measuring cell, the electronic means, the counter electrode , and the current Ji1 constant means are omitted. Instead, a working electrode and a reference electrode is connected to potential measuring means. In accordance with the disclosure of British Patent No. 1,385,070 For example, the potential difference between the electrodes is related to the hydrogen concentration at the working electrode. however, This specification explains that stable measurements can only be obtained at low hydrogen activities. ing.

From British Patent No. 1,524,017 another hydrogen measuring cell based on the same measuring principle known. The cell [so-called ", p, chi cell (Patch　Ce1l　)] is It is applied to ensure a liquid tight seal with the external surface of the steel or iron wall, and the inside of the wall is free from corrosion. exposed to eclipse. The cell quantifies all hydrogen emanating from the external surface of the steel or iron wall. 6 The amount of hydrogen produced on the internal surface of the steel or iron wall is then measured.

In the paper by Mansfeld et al. (Reference 5), the above-mentioned A measurement device based on the Devanathan measurement principle is disclosed. This device is suitable for metal samples. Cells fixed in a cylindrical magnet that serves to fixate when brought into contact with the body It has a measuring cell consisting of a body. The cavity of the cell body has Ni-NiO facing The electrodes contain additional Ni to check the potential of the counter electrode and the presence of a sufficient amount of electrolyte. -It is arranged together with the NiO electrode. An electrolyte is also placed in the cavity and its It is then absorbed into a cellulose sponge placed in the cavity of the cell body.

The cellulose sponge constitutes a carrier for the electrolyte, which on the one hand is Ni-Ni O in direct contact with the counter electrode, and on the other hand when the cell is in contact with the metal specimen body directly contact the metal sample body. In this measurement cell, the above-mentioned Devana Sun sensor The reference electrode, potentiostat and counter electrode of the module are a single Ni-NiO counter electrode. built into it. The measuring device further includes a current follower 2 instrument panel and 4 tabs. It has electronic measurement and timing circuitry including a timer. The entire device has an operating capacity of 5 hours. It operates on a storage battery with a certain amount of energy. This measuring device is based on electrochemical infiltration technique. Measurement of hydrogen concentration in steel 7 1 Information 59-500331 (4) It is intended for use in in the measuring cell, as described in the paper. The current generated during the stabilization process (passivat) immediately after one cell is assembled ion process). transient contribution originating from the source (transient c including contributions). The transmission current itself is a function of t2, but this These transient contributions decay with t-1. The sensitivity of the cell is approximately 1 μA/cm”. Ru. The first and second timers of the electronic measurement and timing circuit provide transient stabilization as described above. The third and fourth timers function for the removal of the contribution, and the third and fourth timers supplied from the measuring cell within a predetermined time determined by the timer. Controls a digital integrator that performs digital integration of current. It's stated in the paper In other words, the total current supplied from the measuring cell within a predetermined time Used to measure the original concentration of hydrogen in a sample body. As understood from the above, This device is used solely for making single measurements of the original hydrogen concentration in a metal sample. and is not used for long-term coupled monitoring of actual measurement sites.

Additionally, this device must be assembled before use and is therefore permanently sealed. It is not a ready-to-use device. This equipment also performs highly sophisticated electronic measurements and It depends on the timing circuit.

Brief description of the invention The method and apparatus of this invention are low cost to manufacture, require no maintenance, and are simple. Allows for stable and accurate measurement of hydrogen flow using a simple and accurate external measuring device make it possible.

The present invention includes a metal membrane in electrical communication with a side of the membrane opposite to the hydrogen inlet side. an electrolyte, a metal/metal oxide cathode in electrical communication with the electrolyte, and an external It comprises a lead wire for electrically connecting to a current measuring device, and the cathode converts hydrogen into water. The metal film can be oxidized to elemental ions, and the cathode and electrolyte can be oxidized to the device is housed in a constituting enclosure) and the device is If connected to a current measuring device with low internal impedance, it will cause a short circuit. Hydrogen can be selectively permeated from the hydrogen inlet side, and the hydrogen can be selectively permeated from the hydrogen entrance side. The present invention provides an apparatus for measuring hydrogen flow through a closed metal membrane.

That is, the measuring device of the invention only involves the use of two electrodes, one of which The membrane is made up of multiple components, making it a compact, simple and accurate measuring unit. It becomes possible to make a cut. The only external device required to make measurements is an ammeter. be. In order for the device of this invention to function properly, even when the device is in use ( (Short circuit through current meter) Even when not in use (Short circuit through direct connection between lead wires) It is very important that the short circuit is maintained.

A particular aspect of the invention provides a metal membrane, a side of the membrane opposite to the hydrogen inlet side and an electrically connected an electrolyte in communication with the electrolyte, and a metal/metal oxide in electrical communication with the electrolyte comprising a cathode, the cathode being capable of oxidizing hydrogen to hydrogen ions, and The electrolyte and cathode are contained in a permanently closed enclosure of which the membrane constitutes a wall. selectively allows hydrogen to permeate from the hydrogen inlet side. This is an inexpensive and simple device for measuring hydrogen flow through metal membranes.

The invention also provides an enclosure, in which hydrogen is oxidized to hydrogen ions. Place one pole in electrical communication with the electrolyte, and the electrolyte in the surrounding area. Inside the wall part, place a metal pattern so as to cover it, and connect it to the hydrogen inlet side of the metal film. The other side is in contact with the electrolyte, the metal membrane is sealed in the enclosure, and the metal membrane is placed in the metal/metal Current generated as a result of oxidation of hydrogen that ignites with the oxide cathode and passes through the membrane A metal that selectively allows hydrogen to permeate from the hydrogen inlet side. The present invention relates to a method for tracing hydrogen flow through a membrane.

Another aspect of the invention is to provide an enclosure in which hydrogen is oxidized to hydrogen ions. can and electric 410 A cathode is placed in electrical communication with the liquid, and at least a portion of the metal membrane is located on the wall of the enclosure. Place the enclosure in contact with the metal membrane so as to form a section opposite to the hydrogen inlet side of the metal membrane. side of the metal membrane is in contact with the electrolyte, said part of the metal membrane is sealed with respect to the container, and the metal membrane is and the metal/metal oxide cathode, and the metal film and the metal/metal oxide single electrode are short-circuited. Hydrogen input, characterized by continuous measurement of the current generated as a result of a short circuit. A method of measuring hydrogen flow through a metal membrane that selectively allows hydrogen to pass from the mouth side. Regarding.

When carrying out the method of this invention, the aforementioned apparatus of this invention can be used to achieve high reproducibility. It is preferable to obtain accurate measurement results.

Detailed description of the invention The metal membrane used in this invention must be selectively permeable to hydrogen. There is a point. In practice, metals useful for this purpose are steel/iron and moradium.

For many purposes, the metal membrane is coated with palladium on one side or both sides. made from a sheet of hardened steel/iron. The thickness of the membrane determines the measurement response time of the device.

・The thickness of the radium film or coating is usually 0.05 to 10 μm, preferably 01 to 0.5 μm. m, and one steel membrane is quite thick, typically about 20 μm to about 1 μm.

The metal/metal oxide cathode used in this invention is capable of oxidizing hydrogen to hydrogen ions. but also those that do not undergo undesirable oxidation reactions with other components present. should be. Therefore, the preferred cathode of this invention is Oxidation potential 200 to 1200 mV higher than the equilibrium potential of the hydrogen electrode, especially the pH of the electrolyte The equilibrium potential of the hydrogen electrode at 96 (jO ~ 1200 mV with a higher oxidation potential Ru. In the presently preferred embodiment, the equilibrium potential of the hydrogen electrode at the pH of the electrolyte is The voltage is approximately 900mV higher than that of the previous model.

For this reason, the metal oxide of the cathode is, for example, silver oxide.

It can be selected from mercury oxide and manganese dioxide. Metal/metal oxide shade Although the metal of the pole functions solely as an electrical conductor, the association with the metal oxide and the electrolyte The seed metal should be chemically virtually inert. For this reason, metals , kel, 2, kel-copper, '-i, and precious metals such as gold, palladium, and white. It is appropriate to choose from the genus.

Metal/Metal Oxide - The potential of the material is also in the range required for anodic oxidation of hydrogen on the metal film. It can also be expressed in terms of VEH, and a range of -100 to +300 mVEH is preferred.

The cathode has a sufficient amount of hydrogen to oxidize all the hydrogen that passes through the membrane under normal conditions of use. current can be supplied to the metal film while still maintaining the allowable potential range. should be designed accordingly.

Furthermore, it is desirable that the total capacity of the cathode exceed the normal service life of the metal membrane.

The electrolyte used in the invention and connecting the metal membrane and the metal oxide of the cathode is this The electrolyte must be appropriately applied to the type of metal oxide. Example of electrolyte As an alkaline aqueous solution with a concentration range of 01 to 14N, for example, sodium hydroxide or an aqueous solution of potassium hydroxide. For some uses, e.g. If measurements are carried out at high temperatures, acidic electrolysis in combination with suitable metal oxides is recommended. Preference is given to using a liquid such as sulfuric acid in combination with lead oxide.

In one embodiment of the device of the invention, the metal membrane is supported on a plastic foil. It will be done. In this embodiment, the metal membrane has a palladium coating on one or both sides. @/It may be an iron film, or it may be a radium film on a df plastic foil. It may be configured as follows. In this specific example, plastic, foil, and metal membranes are machined. preferably arranged so as to constitute the external surface of the device supporting the Drill holes in the plastic foil to allow the element to approach the metal film, or If the foil is provided with a hydrogen permeable plastic material, it will be affected by the actual corrosive forces. Not made of any plastic material, e.g. Mylar(TM) foil can be used. Instead of this, use hydrogen permeable plastic or foil as an example. For example, it can be made from polytetrafluoroethane (Teflon) (surface image).

In this embodiment of the device of the invention, the metal/metal oxide cathode is also located on the wall of the container. supported on a plastic foil, preferably a hydrogen permeable plastic foil. be able to. The plastic foil supporting the metal/metal oxide cathode is a strong, non-stretchable material. Preferably, it is made from a compressible, flexible plastic material, such as Mylar. stomach. Metal membrane and metal/metal oxide cathode supported on respective plastic foils When using They can be interleaved and sealed along the edges. In this specific example The so-called Gucci cell (Patch Ce1l-) is used, and this one is applied to be placed on the external surface of the steel or iron wall whose corrosion effects are to be measured. . In this so-called Gucci cell, the electrolyte is on the hydrogen inlet side of the metal membrane. The electrolyte ribbon layer is placed on the opposite side, thus supporting the metal membrane and the metal/gold layer. oxide cathode support foil. One is stuck in space.

In another embodiment of the invention, the device includes a device portion of Ml and a second device portion. Both are top 14 in which the first device part constitutes the active sensing element; , and a second device part sealed to exclude hydrogen constitutes the comparison element. . In this embodiment, the second device part is exposed to corrosive forces or induced by the first device part. It is applied in response to all environmental impacts other than those to be measured. vinegar That is, the second device part can constitute a temperature-responsive detector. appropriate measurements determined by the measurement results provided by the first device part. measurement results in which environmental effects other than corrosive effects are caused by the second device part; will be erased by Environmental influences other than corrosive influences include, for example, changes in temperature. be.

In an important embodiment of the method of the invention, the hydrogen stream is directed to the inlet surface of the membrane and to the inlet surface of the membrane. with an external fluid medium, such as a liquid or gas, with which the surface reacts chemically or electrochemically. occurs as a result of a chemical or electrochemical reaction. For this reason, they are made of the same material. 9 and as a model for any object subjected to a chemical or electrochemical reaction. by selecting membrane materials such that the hydrogen flow measured by the method of the invention is in the environment of interest. Representative of the hydrogen flow to which an object made of the same material would be exposed if exposed You can do it like this.

That is, in one embodiment, the inlet side of the membrane is exposed to fluids that corrode the surface of the membrane. In this important example, the membrane sample prepared by pickling, phosphating, stripping or in a water bath or in other electrogalvanic processes. Hydrogen corrosion is determined when exposed to chemical or electrochemical treatment. . The membrane can also be used in chemical lubricant or power plant process streams, or in natural gas 9 operations on steels exposed to corrosion when measuring or processing oil or geothermal power steam. You can also

The membrane may also be provided with an external protective coating or layer, which prevents it from being exposed to corrosive or other influences. The protective effect of the coating or debris is tested when Instead of this, the metal film test the corrosive effect of this coating or layer on the metal film. can do.

Furthermore, the method of the invention can be applied to construction materials such as concrete, insulation materials, wood, etc. ranging from atmospheric exposure to natural water and soil exposure, including exposure to or in Can be used to measure hydrogen absorption in steels exposed to corrosion in natural environments Wear.

According to the invention, the metal film can be exposed to the environment or material described above, and When applying solid materials to the membrane, and the equipment, the effects of hydrogen on steel This includes cases in which it is provided in or on the material to be measured.

A surface coating can be provided on the membrane depending on the desired simulation. chemically corrosive layers, paints, metal coatings, anti-corrosive layers, including wave coatings, etc. was carried out and its effect on hydrogen absorption or hydrogen absorption of metal membranes was tested or be monitored.

The size and shape of the exposed membrane is suitable for the purpose, e.g. to simulate the function of an engineering component. can be selected to start.

The membrane also has additional electrochemical controls that allow the study of cathodic protection effects, electrolysis. control or control, or any other means of control. .

Furthermore, the method of the present invention provides a test solution for conducting stress corrosion tests or hydrogen embrittlement tests. It can also be used to control (test or standardize) liquids.

A very important example of the measurement of hydrogen absorption in steel or iron exposed to corrosion in a natural environment It is a measurement of hydrogen absorption in the steel or iron walls of a container. In this case, gold the metal membrane is placed adjacent to the exterior surface of the steel or steel wall, and Measure the flow of hydrogen liberated from the

Brief description of the drawing The invention will be further described in conjunction with the drawings. That is, FIG. 1 is a vertical sectional view of a first specific example of the hydrogen detector or hydrogen monitoring cell of the present invention. and FIG. 2 is an example of a possible application of the hydrogen monitoring cell shown in FIG. FIG. 3 is a vertical cross-sectional view of a prototype measuring cell constructed according to the principles of the invention. the law of nature, Figure 4 is a diagram showing the current versus time in the test application of the prototype shown in Figure 3; can be, FIG. 5 shows a partial cross-section of a second specific example of the hydrogen detector or hydrogen monitoring cell of the present invention. FIG. 6 shows a portion of a third specific example of the hydrogen detector or hydrogen monitoring cell of the present invention. FIG. 7 is a cross-sectional view showing that the hydrogen detector structure of the present invention is a fourth component of the hydrogen monitoring cell. This is a partial cross-sectional view of an example, ``・R7 CH CELL (PATCHCELL) J. the law of nature· FIG. 8 is an exploded view of the specific example shown in FIG. do FIG. 9 is a partial sectional view of a fifth specific example of the hydrogen detector or hydrogen monitoring cell of the present invention. It is.

Detailed explanation of dense surfaces FIG. 1 shows a first embodiment of the hydrogen monitoring cell of the present invention, the main body of which is shown as 10. be. Cell 1o is a clock, pocket converter, hearing aid or similar device. It is constructed like a button-type power battery (mercury battery) of the type commonly used in Ru. Cell 1o is shown as two main elements, namely 11 and 12 respectively. It consists of a bottom part and a top part. The top part 12 constitutes the membrane wall of the measuring cell and is made of pure iron. steel sort, or the type commonly used in the secondary processing of tin plate in the Kan industry Made from steel plate. The inner surface of the top part 12, i.e. the surface facing away from the measuring cell. The surface is coated with radium. The bottom part 11 has a metal oxide filling 14 Together with gold, 'Ej constitutes the metal oxide cathode of the hydrogen monitoring cell. Metal/metal oxidation Material cathodes can be constructed in several ways using several combinations of metals and oxides. All that can be known from the structure of alkaline batteries. The bottom part 11 is a cathode metals that are not oxidized or only oxidized very slowly in solution at a potential of For example, nickel or nickel, Kel-coated steel, stainless steel, or silver, gold or... precious metals such as radium, or the above precious metals on steel or other suitable carriers. made by coating it with Metal oxides include manganese dioxide, silver oxide, mercury and other oxides, used alone or in combination with metal powders, Mercury or other additives provide conductivity, increase effective area, or improve cathode performance These are known separately from the cathode composition of alkaline power batteries. Ru.

The metal oxide filling 14 is placed at the bottom to obtain good contact between the metal and metal oxide. Press fit into part 11.

The two elements, bottom 11 and top 12, are sealed together and a seal 15 is attached to the top. Placed between 12 inwardly bent edges. The thickness of the top portion 12 is primarily determined by the Determined by the ability of the metal to form on the raised edges. However, the thickness of the metal It also determines the useful life of the constant cell and the response time of the measuring cell.

As expected, heavier metal sheets have a longer useful life, but Decreases the response time of the monitoring cell. Thickness 0 commonly used in can industry ．． A sheet of 25 m++ gives satisfactory results with respect to these above factors.

The thickness of the radium coating on the inner surface of the top part is preferably 0.05 to 10 μm, preferably is in the range of 01 to 05 μm.

In the hydrogen monitoring cell 10, the radium coating 13 and the metal oxide filling 14 are An electrolytic solution 16 and a separator 17 are provided in the space defined between the upper surfaces.

The electrolyte 16 is an alkali hydroxide, preferably with a concentration of 01 to 14 M1, preferably IM. Alternatively, a pure solution of sodium hydroxide or potassium hydroxide may be used. Separator 17 functions to prevent metal oxide particles from coming into contact with the radium coating, and polymeric fibers, such as those commonly used as separators in alkaline batteries. Made from propylene fiber.

In FIG. 2, a first embodiment of a hydrogen detector or hydrogen monitoring cell is shown at the end of tube 18. It is shown arranged and electrically connected thereto. The tube 18 is made of steel or iron. and has an internal flange portion 19.

The bottom 11 of the measuring cell 10 is located between the inner surface of the tube 18 and the outer surface of the bottom 11. It is insulated from the tube 18 by an insulating annular sealing member 20 disposed in the space.

In the insulating sealing material 23 in the central hole 21 of the flange portion 19, a cross-shaped contact 22 is inserted. is located. (For Ii soldering, the contact 22 is connected to the hair edge line 25 through the connection part 24. This completes the Ha to the external current measuring device, and furthermore, this A device is read into tube 18 (not shown). bent around the tube 18 An erodible tube 26 with a flange 27 is arranged. The pipe 26 has a flange 2 7 and the upper surface of the membrane 12 of the constant cell. It is isolated from the measuring cell 10 by 28. In addition, to keep the relationship broken It can be provided in the space between the tubes 18 and 22 for this purpose. Thus, the end of tube 18 The measuring cell mounted on the It is introduced into or withdrawn from the measurement environment by known methods.

In FIG. 3, a prototype according to the principles of the invention is shown. This original form is the book The body is shown as 30 and consists of a bottom part 31 and an enclosure. The top part 32 is made of resin. The two parts 31 and 32 are screw connectors. 33 and 34 and fixing the membrane 35 in the space between the two parts. . The membrane 35 has a thickness of 0.25 mm and is located on one side of the bottom part 31 facing ``1''. A non-tin plated plate coated with radium on the surface or a well polished plate. Made from burnt tin plate. The palladium coating was deposited from the following solution -) Ru.

Benzoic acid 3.5.9 Adjust the pH to 11 with ammonia.

Operating conditions: Temperature: 60-70℃ Current density 2 mA/cm2 Time: 2 to 4 minutes・ A radium coating with a thickness of approximately 0.1 to 0.2 μm is thus obtained. Copper film The uncoated sides of the pair provide an exposed area of 7α2 in the central annulus of the top part 32. Ru. The membrane 35 is arranged in an annular recess 38 provided in the upper surface of the bottom part 31 δ An annular seal 37 is secured and sealed with respect to the interior of the bottom 31. . Inside the bottom part 31 two coaxially arranged cavities or chambers 39 and 40 are provided. I'm being kicked.

The chamber 40 is connected to a metal wire connected to an insulated lead wire through a central hole 43 in the bottom 31. /metal oxide electrode 41. The metal/metal oxide electrode 41 is a ring It is secured in chamber 40 by a sealing material 44 which seals chamber 39 against the border. Seal The stoppers 37 and 44 are made of alkali-resistant rubber. Metal/metal oxide electrodes , by a nickel-coated shell filled with a mixture of equal weights of mercury oxide and metallic silver powder. configured.

The powder is compacted into a shell. The wire 42 is attached to the outer surface or bottom of the nickel-coated steel shell. No-nda is attached. High-purity IN hydroxide) IJ um electrolyte is sealed in chamber 39. entered.

When assembling cell 30, the cell is flushed with pure nitrogen and then degassed. Add the electrolyte solution.

Applying a vacuum while the cell is immersed in the electrolyte - This will prevent the cell from being sealed before sealing. Helps remove gases.

Five cells of the type shown in FIG. 3 were made according to the above principles. short-circuit these It was stored for 24 hours.

After 24 hours of storage, the cell has a current in the range of 01 to 5μA, typically 02μA. occurred. Since the internal area of the membrane is 16 cm2, the resulting current is Equivalent to a current density of approximately 0.01-0.03 μVcm2.

Figure 4 shows a diagram of the current generated in a prototype cell of the type shown in Figure 3 over time. It is shown as 70 mouths and 1. Zero current of the cell (shown in Figure 4) ) is 0.2 μA when measured as described above. At time 0 , immerse the cell in 0.2M H2SO4 solution. Within about 7 minutes (and The current rises to about 50% (125 μA) of the maximum current (250 μA). best electric After stabilizing in the flow, remove the cell from the solution at the point indicated by the arrow in Figure 4. . Current decreases very quickly. However, reducing (or increasing) the film thickness The transient response of the measuring cell will thereby increase (and decrease by 1d). In Figure 4 The same response as shown was obtained in three consecutive measurements. In other words, the cell Does not show steresis.

In FIG. 5, a second specific example of a hydrogen detector or a hydrogen detection cell is shown. The main body is shown as 50.

The hydrogen measurement detector 50 is made of steel or iron with a thin wall closed at one end 51a. The length of the tube 51 made by the manufacturer has a short sensing element, ie, a membrane. tube 51 Although not essential to the inherent functionality of the detector, the internal surfaces of the do. The detector further comprises a metal/metal oxide mixture 52 consisting of a bar of metal/metal oxide mixture 52. a compound electrode, said mixture being of the type described with respect to FIG. is compressed around a metal conductor 53, for example of nickel. Metal/gold oxide electrode 5 ．． A separator 54 is provided around 2.53. The separator is, for example, propylene fiber. made by. Assembly of metal/'metal oxide electrodes 52, 53 and separators 54 The tube is fixed to a plastic stopper 55, which has a third After filling the tube 51 with a degassed electrolyte 56 of the type described above with respect to the figures, the tube 51 is fixed by pushing it into the open end of the A metal conductor 53 projects through the plug 55 and It is connected to an insulated wire 57. Tube 54 is also connected to insulated wire 58. line 57 and 58 are connected to an external current measuring device, such as a commonly used sensitive ammeter.

A plastic jacket 59 is provided around the open end of the cheep 51 and around the lines 57 and 58. heat-shrinked into the surrounding area.

FIG. 6 shows a third specific example of the invention. shown in FIG. 6, and An embodiment of the invention, the body of which is designated as 60, is shown in FIG. It differs only slightly from the concrete example. Therefore, the same parts in the two embodiments have the same reference number. has been done.

Unlike the detector 50, the detector 60 is made of a metal impermeable to hydrogen, such as nickel. , Iron/2, Kel alloy or stainless steel Q-Pro 1. tube 61 The inside may be coated with alkali-resistant enamel. Plasti, plug 55 The end of the cheese 61 opposite the more fixed end is welded to the tube 61. A hardened steel or iron disc is provided. The disk 62 is based on the principle of this invention. Construct the metal membrane of the hydrogen measurement detector according to the following. This emission shown in Figures 5 and 6 A specific example of this is when measuring in situ, i.e. when the metal is subjected to an electrochemical process. intended for use in or applied to.

That is, the tube of the hydrogen detector, that is, the tube of the specific example shown in FIG. 51 and Q-Pro 1 of the specific example shown in FIG. processes normally carried out in the bath (e.g. washing, acid Washed and phosphated.

immersed in an electrochemical solution to simulate (exfoliation, electrolysis, electrodeposition, etc.) It will be done.

The long, narrow shape of the hydrogen detector 60 shown in FIG. 6 has additional useful properties. That is, this form of hydrogen detector allows the detector to be It can be easily applied to “access fitting”. materials with low thermal conductivity, such as stainless steel or iron/nickel alloy materials. When combined with a chip with a metal disc 62, for the length of the hydrogen detector. While holding the end of the tube in an electrochemical bath at a significantly higher temperature, It becomes possible to provide cooling at an appropriate angle to the end of the tube having the lock stopper 55. thus , the temperature dependence of the constant is reduced. Hydrogen impermeable Q-Pro 1 and hydrogen permeable De The combination of disks 62 allows for a particular, possibly user-supplied iron or It becomes possible to perform measurements on steel materials.

FIGS. 7 and 8 show a fourth embodiment of the hydrogen measuring device or the so-called "patch sensor". ' is shown.

The "patch cell" shown in Figures 7 and 8 is shown as 70, and placed on the exterior surface of steel or iron walls exposed to corrosion. In other words, "... "C-Cell" transmits through a steel wall within the measuring area defined by the physical dimensions of the measuring device. and to detect and measure hydrogen liberated from the external surface of iron or steel walls. Applicable. FIG. 7 shows the measuring device 70 assembled and ready for use. 8 is a vertical cross-sectional view, and FIG. 8 is an exploded view thereof. Therefore, Figures 7 and 8 Identical parts of are given the same reference numbers. The measuring device 70 is flexible and strong. External protection of a suitable non-stretchable plastic or plastic material, such as Mylar(TM). It has a protective foil 71.

A thin metal layer 72 is fixedly bonded to the plastic foil 71 and is attached to the gold plate of the measuring device. metal/metal oxide constitutes the metal part of the electrode. Metal layer 72 may be any suitable material, e.g. For example, it can be made of nickel or silver. Apart from supporting the metal layer 72 , Plasti.

The foil 71 provides environmental protection and insulation for the metal layer. The metal layer is a thin metal coating. A film can be deposited on plastic foil 71. metal/metal oxide The oxide portion of the electrode is designated by reference number 73. Metal oxides are metal acids The mixture of compound powder and metal powder is mixed in an intimate mixture, optionally further containing a binder. It can be made by compressing it into a compound. Metal oxide component is metal/metal acid applied to the metal component of the compound electrode, i.e. the metal layer 72, e.g. by thin film techniques. .

Similar to the previous embodiments of the invention, the measuring device 70 is made of a metal permeable to hydrogen. , for example made of palladium or an iron foil 77 coated with palladium on both sides. It has a metal film. Similar to the combination of plastic foil 71 and metal layer 72, gold A metal foil or membrane 77 is fixedly bonded to a supporting plastic foil 78. however , the plastic foil 78 has several holes 79 to bring the membrane 77 into contact with the outside. do.

Alternatively, the plastic foil can be replaced with a membrane permeable to hydrogen, e.g. It can also be made from fluoroethylene (Teflon).

The contact between the metal oxide 73 of the metal/metal oxide electrode and the metal film 78 is maintained by the separator 74. The separator 74 is made of alkali-resistant material made of polyzolopyrene fiber, for example. It can be made from sheets of grade F paper.

The edges of the separator 74 have layers 75 and 76 of plastic material on both sides, which The tick passes through the P material, and the measuring device acts as a glue or sealant when assembled. The thickness of layers 75 and 76 is 2 must fulfill two functions. In other words, first, the material passes through the pores of the separator. ' and must be satisfied; secondly, the material is the metal layer 72 and the metal film 79; must have adhesive properties to fix them together and seal the measuring device. stomach. As expected, plasti.

Ri foil 71. Metal layer 72 and metal oxide component 73 are made as one single unit. and another unit comprising a metal film 77 and a plastic foil 78, and a separator 7. 4 are connected and sealed by adhesive edge materials 75 and 76. Assemble the measuring device Before standing, an electrolyte is placed between the metal/metal oxide electrode and the metal membrane 77. electrolytic The liquid is preferably made into yeast using techniques known from battery manufacturing. It is a lukewarm electrolyte. The metal oxide portion 73 and the separator sheet 74 are immersed in the electrolyte. A further layer of electrolyte is applied onto the metal film 77. When assembling cells, Air (oxygen) must be excluded from the space between the metal/metal oxide electrode and the metal membrane. No. Additionally, the electrolyte must be prevented from coming into contact with adhesives 75 and 76. Must be. The cells are in contact with plastic foils 71 and 78 and are pressed together It is assembled using a suitably heated tool consisting of two parts.

Plasti, Rihaku71. Metal drop 72. The metal foil 77 and the plastic foil 78 are Each flap 71a.

72a, 77a and 78a. As shown in FIG. 7, the metal flap 7 2a is intended to be folded around the metal wire 82 and is The strip 77a is bent around the metal wire 83. Then, the plastic flap The plastic flap 71a and the plastic flap 78a insulate the metal flaps from each other and and insulate it from the environment. Metal wires 82 and 83 are used when the measuring device is stored. is intended to be short-circuited to the It is intended to be connected to a current measuring device.

Finally, to protect the exposed surface of the metal film 79 when the measuring device is not used, , foam wrappers or foam plastics with self-adhesive surfaces The compressible, flexible material 80 allows the outer surface of the plastic foil 78 to be coated with paper or Apply a cardboard cover. The adhesive surface of material 80 facing cover 81 is also It is also useful for applying the fixed device to measurement sites on steel or iron walls.

FIG. 9 shows a fifth specific example of the hydrogen measuring device of the present invention, the main body of which is 90 mm. is displayed as. The embodiment of the invention shown in FIG. It differs from the above specific example in that it consists of the same part or half. The first part is active configuring an active sensing element, and the second portion is neutralized or inert, or the second portion is the comparison element. applied in such a way that it is neutralized or inactivated to constitute. measurement Unlike the first part of the device, the second part or comparison element has a corrosive force or It is not intended to be exposed to other influences. Rather, the comparison element is It only responds to temperature changes. When connected vertically to a properly compensated difference measuring instrument, the The first part provides a measurement of the current, and the second part or comparison element provides a measurement of the current to the measuring instrument. functions to compensate for temperature when supplied with

The measuring device 90 has a metal sheet 91, for example a metal sheet, a metal sheet or a silver sheet. Money A generic sheet 91 is common to both said parts of the measuring device and supports them. It also adds physical strength to the measuring device as a whole. The active sensing part of the measuring device is on top. a first side of the metal sheet configured to closely contact the metal sheet 91; A metal oxide portion 92 is then applied.

The metal sheet 91 and the metal oxide portion 92 together form the active part of the measuring device. 1 metal/metal oxide electrode. A separator 93 is placed on the metal oxide portion 92. Placed. A metal film 94 is placed on the separator 93 . In addition, the measuring device Part 1 is an electrolyte sealed in the space between the metal/metal oxide electrode and the metal film 94. It has liquid. Basically, the parts of the measuring equipment described above (as shown in Figures 7 and 8) This is the same as the corresponding part of the embodiment of the present invention. And water that works for protection Transparent plastic or foil can be placed over the metal film 94.

The second part of the measuring device consists of the part described above, namely the metal oxide part 957 separator. c! 6. Metal film 97. and sealed in the space between the metal/metal oxide electrode and the metal film 97. It has basically the same parts as the electrolyte solution.

Additionally, the second portion of the measuring device 90 may completely enclose the second portion of the measuring device. and a corrosion-resistant foil 98 that protects the metal membrane 97 when the measuring device is exposed to corrosive forces. do. The foil 98 may be constructed as an integral part of the measuring device or may be configured as appropriate by the user. Metal sheet 91. Metal film 94. and metal film 98 U,,',, '.

Separate lines 99, 1.00, respectively. and 1-01, the above specific example is It is understood to be merely illustrative of the application of the principles of the invention. The nature and scope of this invention I hope it will be improved.

1 disadvantage 1, M, A, V, Devanathan and Z.

Stachurski (5tachurski): Proceedings - Oz The Row Yaruso Sayati (Procgeding of the Royal 5oc) iety z 1962.1A270 volume, 90 pages.

2, M, Maron, etc., metal groggy 3 Metal Progress, July 1981, p. 52.

3. British Patent Application No. 1,585,070.

4 British Patent Application No. 1,524,017.

5, G, -7 Mansfeld, S, Jane Jacquet ( Jeanjaquet') and ni, Roe, materialus no' ? -Homans (Materials Performance), 198 February 2nd year.

Submission of translation of written amendment C% Permission Act Article 184-7, Paragraph 1) October 9, 1981 Mr. Kazuo Wakasugi, Commissioner of the Patent Office 1 Display of patent application PCT/DK83100022 2 Name of the invention Method and device for measuring hydrogen flow 3% Applicant Address: 2860 Nohoruku, Tenmar-ku-DK.

Telephone bay 6 Name Hellescens Acty Cell Scab 4 Agent Address: 5, Shizuko Toranomon Hill, 8-10 Toranomon-chome, Minato-ku, Tokyo Year of submission of amendment time August 1, 1983 (reception date) 6 List of attached documents t+’+ 1 translation of the written amendment Scope of request for amendment 1. Metal film, electrically connected to the side opposite to the hydrogen inlet side of the metal film an electrolyte, a metal/metal oxide cathode in electrical communication with the electrolyte, and an external electrical The cathode contains a lead wire electrically connected to the current measuring device, and the cathode The electrolyte and the cathode can be oxidized into ions, and the metal film constitutes a wall portion. The device is housed in an enclosure consisting of a Virtually short-circuited by connecting to a current measuring device with low internal impedance Hydrogen is selectively permeated from the hydrogen inlet side. A device that measures the flow of hydrogen through a metal membrane.

2. A metal film, an electrolyte electrically connected to the opposite side of the metal film to the hydrogen inlet side. a metal/metal oxide cathode in electrical communication with the electrolyte; A cathode is capable of oxidizing hydrogen to hydrogen ions, and the electrolyte and cathode are connected to the membrane. is contained in an enclosure forming the wall portion, and the enclosure is permanently sealed. A metal membrane that selectively allows hydrogen to permeate from the hydrogen inlet side, which is characterized by A device that measures the hydrogen flow passing through it.

3. The device according to claim 1 or 2, wherein the membrane is a radium membrane.

2 4 The membrane has a thickness of 01 to 10 μm on one or both sides, preferably in the range of 01 to 5 μm. Claims 1 or 2 made of iron or steel with a palladium coating on the inside. equipment.

5 The cathode is 200 to 1200' below the equilibrium potential of the hydrogen electrode at the pH of the electrolyte. Any of claims 1 to 4 which has a high oxidation potential of mV. Place.

6 The oxidation potential of the cathode is less than the equilibrium potential of the hydrogen electrode at the pH of the electrolyte solution. 1200 mV high device according to claim 5.

7 The oxidation potential of the cathode is approximately 900% higher than the equilibrium potential of the hydrogen electrode at the pH of the electrolyte. The device according to claim 5, which has a high mV.

8. The metal oxide of the cathode is selected from silver oxide, mercury oxide, and manganese dioxide; The cathode metals are nickel, nickel-coated steel, silver, as well as gold, palladium, and Any one of claims 1 to 7 selected from precious metals such as platinum. The device described.

9 Sodium hydroxide or potassium hydroxide whose electrolyte has a concentration of 01 to IOM 9. The apparatus of claim 8, wherein the degassed alkaline solution is a degassed alkaline solution such as.

10. Any of the preceding claims in which the metal film is supported on a plastic foil. The device described in.

11. A plastic foil constitutes the external surface of the device, and hydrogen approaches the metal membrane. 11. The device of claim 10, wherein the device is perforated to provide access to the device.

12 Plastic, plastic foil constitutes the external surface of the device, and hydrogen permeable plastic 11. The device of claim 10, wherein the device is made of a solid material.

13 The metal/metal oxide is a hydrogen-permeable plastic that forms the wall of the enclosure. A device according to any of the preceding claims supported on foil.

14 The foil supporting the metal membrane and the foil supporting the metal/metal oxide cathode are attached to the separator. held in a more spatially separated relationship, and along the outer edges The device according to claims 1o to 12 and 13, which is hermetically sealed.

15 The electrolyte is placed in the electrolytic purchasing station located on the side opposite to the hydrogen inlet side of the metal membrane. 15. The device according to claim 14, wherein the layer is a layer.

16. Both the first device part and the second device part have all of the above characteristics. , the first device part constitutes the active sensing element and is sealed to exclude hydrogen. The second device part described in any of the preceding claims constitutes a comparative element. equipment.

17 Provide an enclosure in which hydrogen can be oxidized to hydrogen ions and A metal film is placed so as to form a wall portion that is electrically connected to the electrolyte, and the metal film is The side opposite to the hydrogen inlet side is brought into contact with the electrolyte, the metal membrane is sealed in the enclosure, and the metal membrane and the metal/metal oxide cathode, resulting in the oxidation of hydrogen passing through the metal membrane. selectively remove hydrogen from the hydrogen inlet side, consisting of measuring the current generated as A method of measuring the flow of hydrogen through a metal membrane that allows it to pass through.

18 Provide an enclosure, and add hydrogen in the enclosure so that hydrogen ions form the walls of the enclosure. Place the enclosure around the sea urchin, bring the side of the metal membrane opposite to the hydrogen inlet side into contact with the electrolyte, and The said part of the membrane is sealed with respect to the enclosure and the metal membrane and the metal/metal oxide cathode are short-circuited. and connect the current resulting from the short circuit between the metal film and the metal/metal oxide cathode. Gold that selectively permeates hydrogen from the hydrogen inlet, which consists of continuous measurement. A method for measuring hydrogen flow through a catalytic membrane.

19 Liquid or jd with which the inlet surface of the membrane and the surface of the membrane react chemically or electrochemically. Hydrogen as a result of a chemical or electrochemical reaction with an external fluid medium such as a gas 19. A method according to claim 17 or 18, wherein a flow is generated.

208 The inlet side of the membrane corrodes the surface metal of the membrane with the generation of hydrogen flow into the membrane. 20. The method of claim 19, wherein the method is exposed to a fluid.

21 If the membrane is washed, pickled, phosphated, stripped or exposed in a plating bath or in a battery cell. Hydrogen corrosion is determined when exposed to chemical or electrochemical treatments during decomposition processes. 21. A method as claimed in claim 19 or claim 20, wherein the method is made from a specimen of the steel type.

22. Membranes are used in chemical or power plant process streams or in natural gas exposed to corrosion when measuring or processing gas, oil, or geothermal steam. 21. A method according to claim 19 or 20, wherein the method is made of steel.

23. The metal film is provided with an external protective coating or layer and is not exposed to the influence of counterfeiting or other influences. Any of the claims 19 and 22 whose protective effect is tested when Method described in Crab.

24 An external coating or layer of material is applied to the metal film and its corrosive effect on the metal film is 23. A method according to any of claims 19 to 22, wherein the acoustics are tested.

25. The hydrogen flow released from the steel or iron walls of the gas or vessel is measured, and or claim 17, wherein a metal membrane is disposed adjacent the external surface of the steel or iron wall. The method according to paragraph 18.

international search report

Claims (1)

[Claims] J, a metal film, an electric current in electrical communication with the side opposite to the hydrogen inlet side of the metal film; an electrolyte, a metal/metal oxide cathode in electrical communication with the electrolyte, and an external C. The cathode is capable of oxidizing hydrogen into hydrogen ions, and the electrolyte and the cathode are capable of oxidizing hydrogen into hydrogen ions. , the metal membrane is housed in an enclosure constituting a wall portion, and the device is placed between the lead wires. or to a current measuring device with low internal impedance. from the hydrogen inlet side, characterized in that it remains substantially short-circuited, A device that measures the flow of hydrogen through a metal membrane that selectively allows hydrogen to permeate. 2 Metal film, hydrogen population of the metal film [Itll is electrically connected to the opposite side] a metal/metal oxide cathode in electrical communication with the electrolyte; C. The cathode is capable of oxidizing hydrogen into hydrogen ions, and the electrolyte and the cathode are capable of oxidizing hydrogen into hydrogen ions. , the membrane is housed in an enclosure forming a wall portion, and the enclosure is permanently integrated. It is characterized by being sealed, allowing hydrogen to selectively permeate from the hydrogen inlet side. A device that measures the flow of hydrogen through a metal membrane. 3 The membrane has a thickness in the range of 01 to 10 μm, preferably 0.1 to 5 μm on one or both sides. Claim 1 or 2 consisting of iron or steel with a taladium coating within the enclosure. The device described. 4 The cathode is 200 to 1200 m above the equilibrium potential of the hydrogen electrode at the pH of the electrolyte. The device according to any one of claims 1 to 3, which has a high oxidation potential. . 5 The oxidation potential of the cathode is 600% higher than the equilibrium potential of the hydrogen electrode at the pH of the electrolyte. 5. The device according to claim 4, which is ˜1200 mV higher. 6 The oxidation potential of the cathode is approximately 900% higher than the equilibrium potential of the hydrogen electrode at the pH of the electrolyte. The device according to claim 4, which has a high mV. 7. The anionic metal oxide is selected from silver oxide, mercury oxide, and manganese dioxide, The metal of the cathode is nickel, nickel-coated steel, silver, gold, palladium, and Any one of claims 1 to 6 selected from precious metals such as platinum and platinum. The device described. 8 Thorium hydroxide or potassium hydroxide whose electrolyte has a degree of 01 to IOM 9. The device according to claim 7, which is a degassed alkaline solution such as according to any of the preceding claims, wherein the metal membrane is supported on a silastic foil. Device. 10 A plastic foil constitutes the external surface of the device and hydrogen approaches the metal membrane. ) A hole is drilled on the ζ 36 10. The apparatus according to claim 9. 11, a plastic foil constitutes the external surface of the device, and a hydrogen permeable Norasti; 10. The device of claim 9, wherein the device is made of a material made of plastic. 12. Hydrogen-permeable plastic foil in which the metal/metal oxide constitutes the wall part of the enclosure Apparatus according to any of the preceding claims supported above. 13. The foil supporting the metal membrane and the foil supporting the metal/metal oxide cathode are placed in the separator. They are held in a more spatially separated relationship, and closer together along the outer edges. Apparatus according to closed claims 9-11 and 12. 14. The electrolyte is placed on the side of the metal membrane opposite to the hydrogen inlet side of the electrolyte paste. 14. The device of claim 13, wherein the device is a layer. 15. Both the first device part and the second device part have all of the above characteristics. , the first device part constitutes the active sensing element and is sealed to exclude hydrogen. as claimed in any of the preceding claims, in which the second device part represented by Load amount. 16 Provide an enclosure, in which hydrogen ions form the wall portion of the enclosure. Arrange the metal film, metal 37 Mochimote Showa 59-! '1UU331 (2) Membrane hydrogen inlet The opposite side is in contact with an electrolyte, the metal membrane is sealed in an enclosure, and the metal membrane and metal/ 1, as a result of the oxidation of hydrogen passing through the metal oxide cathode and passing through the metal membrane. selectively permeate hydrogen from the hydrogen inlet side by measuring the current generated by the hydrogen inlet. A method of measuring hydrogen flow through a permeable metal membrane. 17 Provide an enclosure, in which hydrogen is placed on the side opposite to the hydrogen inlet side of the hydrogen ion membrane. is brought into contact with the electrolyte, said portion of the metal membrane is sealed with respect to the enclosure, and the metal membrane and the gold metal/metal, oxide cathode, and short between metal film and metal/metal oxide cathode. from the hydrogen inlet, consisting of continuously measuring the current resulting from the circuit. A method of measuring hydrogen flow through a metal membrane that selectively allows hydrogen to permeate. 18. A liquid or gas that reacts chemically or electrochemically with the inlet surface of the membrane. Hydrogen flow as a result of a chemical or electrochemical reaction with an external fluid medium such as the body 18. The method according to claim 16 or 17, wherein: 19 The inlet side of the membrane generates a hydrogen flow to the membrane, causing a flow that corrodes the surface metal of the membrane. Scope of accountability exposed to the body 8 The method according to paragraph 18. 20 If the membrane is washed, pickled, phosphated, stripped or exposed in a plating bath or otherwise electrolytically Hydrogen corrosion is determined when exposed to chemical or electrochemical treatments during decomposition processes. 20. A method according to claim 18 or claim 19, wherein the method is made from a specimen of the steel type. 2.1. Membranes may be used in chemical or power plant process streams or in natural exposed to corrosion when measuring or processing gas, oil, or geothermal steam. 20. A method according to claim 18 or 19, wherein the method is made of steel. 22. The metal membrane is provided with an external protective coating or layer and is exposed to corrosive or other influences. Any of claims 18 to 21 whose protective effect is tested when The method described in. 23 An external coating or layer of material is applied to the metal film and its corrosive effect on the metal film is 22. A method according to any of claims 18 to 21, wherein the acoustics are tested. 24. The hydrogen flow released from the steel or iron walls of the guibe or container is measured, and Claim 16 or 10, wherein a metal membrane is disposed adjacent to the external surface of the steel or iron wall. The method according to paragraph 17.