JPH0260584B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a deur bottle for liquefied gas and a method for manufacturing the same, and more particularly relates to a chemical treatment using corrosive agents of nitric acid and hydrofluoric acid. The result is a liquid-containing dual bottle with a low emissivity surface that is clean, smooth, matte, stain-free, and has an etched appearance that is free of discoloration and stains.

[Background of the invention]

Containers or bottles for keeping nitrogen or helium in a liquid cryogenic state are usually formed as metal cans into which the cryogenic liquid is charged. The can is usually surrounded by a shell. The space between the can and the shell is evacuated to reduce heat transfer from the outside of the shell to the inside of the can. In addition, it is usually desirable to minimize the transfer of radiant energy from the outside of the shell to the inside surface of the can.

In the prior art, a relatively small amount of radiation is transmitted between the shell and the outside of the can by forming both the can and the shell from high-purity (e.g., 99%) aluminum alloy. Ta. The inside of the shell and the outside of the can were usually machine polished to a high gloss polish, a process that substantially removed tool marks inflicted during machining of these parts. After the cans and shells are mechanically polished, they are steam degreased to remove filings, dust, and other foreign matter from the surfaces of the cans and shells, so that the surfaces are heated at liquid nitrogen temperatures (77°). about
It had a relatively low radiant energy emissivity of 0.024. Radiant Energy Emissivity can be defined in the usual way, ie as the ratio of the radiation emitted by a surface to the radiation emitted by a perfect black body at the same temperature.

While prior art techniques for reducing shell and can emissivity have been satisfactory for some purposes, emissivity has not been sufficiently reduced for other purposes. In particular, use nitrogen for long periods of time (e.g.
The emissivity of prior art cans and shells was too high for just polished aluminum when trying to maintain a liquid state (for several months).

[Summary of the invention]

According to the present invention, the emissivity of spun cans and shells made of aluminum alloy sheet utilized in deur bottles for liquid nitrogen is substantially reduced. This reduction in emissivity is due to the fact that the inner shell surface and the outer surface of the can are polished and then chemically treated with nitric acid and hydrofluoric acid, resulting in a clean, smooth, satin finish. (matte)
It has an etched appearance that is smooth, smut-free, and free of dicoloration and stains. Here, "clean" refers to the absence of dirt, deposits, or impurities on the aluminum surface.
"Smooth" refers to the aluminum surface being free of irregularities, roughness, and protrusions (metallic finish). "Nashiji"
(matte) refers to a smooth surface that reflects light but has a dull luster and is not mirror-like enough to form an image, with a uniformly white or grayish white finish.
"Smut free" refers to the absence of reaction products remaining on the aluminum surface after pickling, ie, the surface is not gray or black. "Discoloration" refers to the general loss of the normal color of the aluminum surface, and "stain" refers to the local change in color of the aluminum surface.
"Etched appearance" refers to the appearance of corroded aluminum surfaces. These surfaces are chemically treated with an caustic agent for 15 to 45 seconds (typically occurs when etching 0.0254 mm) until the desired appearance is achieved. If a surface is treated for less than a reasonable amount of time, it will not be fully cleaned, satined, or soiled and may become discolored or stained. If the surface is treated for too long, it will develop macroscopic depressions and will no longer be smooth. In either case, the emissivity of the surface increases relative to the emissivity for a suitable treatment time. Tests conducted on deur bottles having surfaces made in accordance with the present invention have shown that the emissivity is approximately 35% compared to the prior art.
% decrease.

Aluminum sheets can be polished either mechanically, electrochemically or chemically. When using mechanical means, the procedure is the same as in the prior art. Electrochemical, i.e., electropolishing in a 29.4 °C bath of fluoroboric acid (2.5% by weight), 0.011–0.22
Current density in amps/sq ft and 15 to 30
It is carried out for 5-10 minutes at a voltage of volts (US Pat. No. 2,108,603). When chemical polishing is used, it is polished with an aqueous bath of phosphoric and nitric acid as described in U.S. Pat. No. 2,729,551 or with a bath of phosphoric, acetic and nitric acids as described in U.S. Pat. .

While it is recognized that aluminum surfaces have traditionally been treated with nitric and hydrofluoric acid caustics after mechanical polishing, prior art techniques generally relate to the manufacture of vacuum equipment, where emissivity was not a problem. The present invention seeks to utilize prior art techniques to achieve the unexpected result of reduced radiant energy emissivity to assist in maintaining cryogenic dua bottles at liquid nitrogen temperatures.

According to another aspect of the invention, the vacuum space between the can for liquid nitrogen and the outer shell of the duer bottle has two surfaces with the same low emissivity properties as the inner surface of the shell and the outer surface of the can. A second shell made of a spatula-drawn aluminum alloy is included. The outer surface of the second shell thus absorbs a small proportion of the radiation emanating from the inner surface of the first shell, and the inner surface of the second shell emits a small proportion of radiant energy in the direction of the can.

[Purpose of the invention]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a new and improved dual-use bottle for containing liquids and a method of manufacturing the same.

Another object of the present invention is to provide a dual-use bottle for containing liquids with reduced radiant energy emissivity and a method for manufacturing the same.

Another object of the invention is to provide a new and improved deur bottle for containing liquids, which is capable of storing, for example, liquid nitrogen for a very long period of time, for example 90 days, and a method for manufacturing such a deur bottle.

The above objects and other objects, features, and advantages will become apparent from the following description of preferred embodiments of the present invention with reference to the drawings.

[Explanation of Examples]

Referring to the drawings, a dual bottle 10 is illustrated as being utilized in a nuclear magnetic resonance (NMR) spectrometer. The spectrometer includes a superconducting solenoid coil 11. This coil 11 provides a relatively high strength magnetic field H ₀ through the sample 12 located within the vial 13 in the direction of the longitudinal axis of the coil. Sample 12 is excited into a nuclear magnetic resonance state by rf energy applied to coil 14 by rf pulse source 15 . The coil 14 is wound so that its axis is perpendicular to the magnetic field H ₀ . A pickup coil 16 located close to the sample 12 is responsive to the energy radiated from the sample 12 and provides an appropriate signal to an RF receiver 17. The coil 16 is arranged such that its axis is perpendicular to both the axis of the coil 14 and to the direction of the magnetic field H ₀ . Receiver 17 may include a suitable Fourier analyzer to direct the output to an X-Y recorder 18, which records the spectral response of sample 13 to different frequencies of transmitter (pulse source) 15. Diagram. Power is initially supplied to coil 1 by DC power supply 19.
1 and the power is disconnected from the coil when the coil begins to operate in a sustained superconducting mode.

The coil 11 is placed in a cylinder 21 surrounded by a liquid helium reservoir 23 contained within a can 24, so that it is maintained in a superconducting state at the temperature of liquid helium (4.2〓). Can 24 is below the liquid nitrogen reservoir formed by can 25. Cans 24 and 25 are inside a shell 26 that forms the outside of the deur bottle. There is a vacuum between the outer surface of the can 24 and the inner surface of the shell 26, except where the can 25 is located. There are heat shields 27, 28, 2 in the vacuum section.
There are 9. The shield 27 is located between the outer surface of the can 24 and the inner surface of the shield 28 as well as the floor 3 of the can 25.
1 and the outer surface of the can 24. The shield 29 is located between the outer wall of the shield 28 and the inner wall of the shell 26, as well as the side wall 32 of the can 25 and the roof 3.
3 and the inner wall of the shell 26.

Cans 24 and 25, as well as shell 26 and shields 27, 28, 29, each have a substantially isothermal surface formed by spinning from a sheet of aluminum alloy with a very high percentage of aluminum. be. Preferably, the aluminum alloy is AAnumber (Aluminum
Association number) 1100-0 (it is also expressed and specified as the JIS alloy number, hereinafter referred to as high-purity aluminum alloy), and is manufactured by many manufacturers such as Reynolds and Alcoa. It is an easily available alloy. The aluminum content of this alloy is at least 99%,
Iron and silicon have a maximum of 1%, copper a maximum of 0.2%, manganese a maximum of 0.05%, and zinc a maximum of 0.1% or less.

To minimize the transfer of radiant energy between the interior surface of the shell 26 and the exterior surface of the can 25, the interior surface of the shell, the exterior surface of the can, and both surfaces of the shield 29 are clean and pitted. It has a low thermal emissivity because it is smooth, matte, smut-free, and specially treated to have an etched appearance with no discoloration or stains. here,
"Nashiji" means a smooth surface with a uniform white or gray-white finish that reflects light but is not mirror-like enough to form an image. All of these surfaces are treated in the same way to achieve the desired results.

After the can 25, shell 26 and shield 29 are drawn, they are either mechanically, electrolytically or chemically polished. Mechanical polishing is the same as in the prior art, in which a normal buffing operation is carried out so that the surface has a high gloss luster;
As a result, all tool flaws due to the spatula drawing process are virtually eliminated. For electrolytic polishing, 29.4
in a bath of fluoroboric acid (2.5% by weight) at °C.
Current density from 0.011 to 0.022 ampere/ ^cm2 and from 15 to
Polishing is done by soaking for 5-10 minutes at a voltage of 30 volts. In the case of chemical polishing, polishing is performed by immersion in an aqueous bath of phosphoric acid and nitric acid, or a bath of phosphoric acid, acetic acid, and nitric acid. Electropolishing or chemical polishing is much cheaper and therefore more desirable than mechanical polishing, and may be performed as described above. After the surface has been polished, the parts are vapor degreased in a steaming liquid trichlorethylene bath to remove dust, shavings, and other foreign matter. Next, the parts are Oakite (trademark), which is manufactured by Oakite Products, Inc.
Available from New York, NY. ) 27 or the like, which is removed from the parts by hot water rinsing.

The surface is then coated with nitric acid of approximately 20% (by volume), hydrofluoric acid of 4% (by volume), and the remainder of The etching solution consists of deionized water at room temperature. Corrosives are 15-45
erodes the surface for seconds, resulting in removal of approximately 0.0254mm, so any phosphates or chromates that may have adhered to the surface during chemical polishing are removed and the surface is as smooth and matte as desired. No dirt,
It has an etched appearance with no discoloration or staining. Initially, the etching bath has the above proportions. After using it for a while, the ratio will change somewhat. Acid content is adjusted according to periodic tests of specific gravity and chemical analysis. If the test shows a significant change in the acid percentage, such as a decrease in percentage by a factor of about 4, add additional amounts of acid or clean the tank containing the bath and use a new mixture.

The parts are then rinsed under cold running water and then rinsed twice with deionized water. Following a second deionized water rinse, the parts are dried in a suitable tunnel, cooled, and then placed in a polyethylene bag for protection.

The duer bottle is assembled by suitably joining the various parts together as shown. Then, the duer bottle 10 is inserted through the hole 35 of the shell 26.
Vacuuming the entire area evacuates all areas between the various cans and shields to approximately 10 ^-5 Torr. The can 25 is then filled with liquid nitrogen through the hole 36, and the can 23 is finally lowered to the temperature of liquid nitrogen. The can 23 is then filled with liquid helium through a hole (not shown) to lower the temperature of the superconducting solenoid 11 to the temperature of the liquid helium, 4.2㎓.

It has been found that the surfaces of shell 26, can 25 and shield 29 prepared in accordance with the present invention provide a significantly lower radiant energy emissivity than those of the prior art. Prior art spatula-drawn aluminum surfaces made from the same alloys used to fabricate can 25, shell 26 and shield 29 have been mechanically, electrochemically or chemically polished, but with nitric acid and If not etched with a hydrofluoric acid mixture, it generally has a radiant energy emissivity of about 0.024 at 77〓. In contrast, the surfaces of the present invention chemically treated with nitric acid and hydrofluoric acid etchants have a radiant energy emissivity of about 0.016 at 77〓. The radiant energy emissivity was measured as follows. A standard duer bottle and a duer bottle made of a new material to be monitored in the same shape as the standard duer bottle are prepared, refrigerant is supplied to them, and the evaporation rate of the refrigerant per unit time is monitored. I compared them. From the above, the emissivity characteristics of the extremely pure 1100~0 Hera drawn sheet aluminum alloy parts treated with the nitric acid and hydrofluoric acid baths of the present invention are approximately
It was found that the improvement was 35%.

Therefore, the duer bottle according to the present invention has a low emissivity and low heat transfer, so it retains a low temperature well. Therefore, the evaporation of liquid nitrogen can be slowed down, and liquid nitrogen can be stored for a long period of time, that is, 90 days, making it a great contribution to low-temperature technology.

[Brief explanation of drawings]

The figure is a cross-sectional view of a durable bottle made in accordance with the present invention. 10... Duur bottle, 23... Liquid helium storage tank, 24... Spatula-drawn can, 25... Can (liquid nitrogen storage tank), 26... Shell body, 27, 28, 2
9...Heat shield.

Claims (1)

[Scope of Claims] 1. Consists of a spatula-drawn can made of a high-purity aluminum alloy for containing liquid, and a spatula-drawn shell made of a high-purity aluminum alloy surrounding this can, and this shell body is attached to the outer surface of the can. having an inner surface facing;
A vacuum is maintained between these surfaces, and all of the surfaces are polished and then treated with liquid etchants of nitric and hydrofluoric acids to ensure that these surfaces are clean, smooth, matte, and free from dirt. and has an etched appearance free from discoloration and blotches, and has a radiant energy emissivity of not more than 0.016 at 77〓, so that the energy radiated from the inner surface toward the outer surface is substantially reduced, and CLAIMS 1. A detour bottle for maintaining a liquid at a low temperature, characterized in that the heat absorbed by the outer surface is reduced and the heat conducted through the can to the liquid is reduced. 2. A dua bottle according to claim 1, wherein the high purity aluminum alloy is machine polished to a high gloss luster to remove substantially all tool marks. Dua bottle. 3. A duer bottle as claimed in claim 1, wherein the high-purity, spatula-drawn aluminum is chemically polished to a high gloss polish to remove substantially all tool marks, and the corrosive agent is chemically polished to remove substantially all tool marks. The deur bottle removes all chemical agents that have adhered to the surface. 4. A method for producing a low-temperature liquid dua bottle from a can made of a high-purity aluminum alloy sheet and a shell made of a high-purity aluminum alloy sheet, which eliminates substantially all tool flaws. polishing the outer surface of the can to a high gloss polish to remove any tool marks; and polishing the inner surface of the shell to a high gloss polish to remove substantially all tooling scratches. Process and fluoride with nitric acid until the outer surface of the can is smooth, matte, free from dirt, has an etched appearance free from discoloration and staining, and has a radiant energy emissivity not exceeding 0.016 at 77㎓. A process of chemical treatment with a liquid caustic agent of hydrogen acid and a radiation radiation not exceeding 0.016 at 77〓, giving the inner surface of the shell a smooth, matte, stain-free, etched appearance without discoloration or staining. chemically treating with a liquid caustic agent of nitric acid and hydrofluoric acid until it has an energy emissivity; stopping the chemical treatment; assembling a de-ure bottle so that the shell surrounds the can; and the step of evacuating the space between the can and the can. 5. The method according to claim 4, comprising:
A method in which the surface is mechanically polished. 6. The method according to claim 4, wherein the surface is chemically polished and a corrosive agent is used to remove the chemical agent attached to the surface by chemical polishing. 7. The method according to claim 4, wherein the surface is electrochemically polished. 8. The method according to claim 4, wherein the caustic agent is about 4% (by volume) of hydrofluoric acid and 20% (by volume) of hydrofluoric acid.
(volume) of nitric acid. 9. The method of claim 4, wherein the surface is treated with a corrosive agent for 15 to 45 seconds.