JP5923072B2 - Determination method for chemical ammunition - Google Patents

Description

  The present invention relates to a method for determining a filling such as a chemical bullet.

  As a configuration of military ammunition (cannonball, bomb, landmine, mine, etc.), a structure in which a glaze or chemical agent is provided inside a steel shell is known.

  In Okinawa Prefecture, where the battlefield of World War II was created, suspicious materials that cannot be excluded from the possibility of chemical bombs made in the United States may still be found. It is important to determine whether it is an agent.

Examples of fillers such as chemical bombs (synonymous with fillers such as chemical bombs) include those disclosed in Non-Patent Document 1, such as bromoacetone, bromobenzyl cyanide, phosgene, chloroacetophenone and chloropicrin. A mixture of chloroform, titanium tetrachloride, a mixture of sulfuric acid trioxide and chlorosulfonic acid, mustard (without heel), mustard (with heel), mixture of chloropicrin and tin chloride, chloropicrin, yellow phosphorus, etc.) ing.

  As a method for appraising such a chemical bullet or the like, a method using a non-destructive inspection device called a neutron appraiser owned by the US military is known.

Potential Military Chemical Biological Agents and Compounds (Army Filed Manual No. 3-9, Navy Publication No. P-467, Air Force Manual No. 355-7, December 1990).

  However, there are no companies or institutions in Japan that have a practical neutron detector. In addition, such a neutron detector is very expensive, and the Japanese have not used it in Japan for the purpose of identifying fillers such as chemical bombs so far. Legal approval is required for use in Japan.

  The present invention has been made in view of the above points, and an object of the present invention is to provide a method capable of determining a packing material such as a chemical bullet safely and at low cost without using a neutron identification device.

  In order to solve the above-mentioned problems, the present inventor has intensively studied and found that the above problems can be solved by a method having the following configuration.

  In other words, the method for determining a chemical bullet or the like according to one aspect of the present invention is based on whether the chemical bullet or the like is liquid or solid at a predetermined temperature using X-rays. And the step of determining the packing based on the melting point, wherein the temperature is adjusted by bathing or cooling the chemical bullet or the like.

  With such a configuration, it is possible to determine a filling such as a chemical bullet in a simple, safe and low cost manner.

  The determination method further includes adjusting the temperature stepwise as necessary, and repeating a hot bath or cooling of the chemical ammunition or the like and an X-ray inspection. Thereby, it is considered that the packing can be determined more safely by adjusting the temperature in stages. Further, if the temperature is adjusted stepwise by repeating the warm bath or cooling, the possibility that various types of fillers can be specified increases.

  Further, in the determination method, at room temperature, the packing such as the chemical bomb is inspected using X-rays to determine whether the packing is liquid or solid. If the packing is liquid, the packing is bromoacetone, bromobenzyl cyanide, Determined to be phosgene, a mixture of chloroacetophenone and chloropicrin and chloroform, titanium tetrachloride, a mixture of sulfuric acid trioxide and chlorosulfonic acid, mustard (no heel), a mixture of chloropicrin and tin chloride or chloropicrin, If it is a solid, warm the chemical bomb etc. at 45-60 ° C., and then use X-rays to check whether the chemical bomb is filled in liquid or solid. When the object is yellow phosphorus or solid, the filler may be determined to be mustard (with heel).

  By such a method, when the filler is yellow phosphorus or mustard (with heel), the filler can be more reliably determined.

  Furthermore, if the chemical bullets are chemical bullets manufactured during the Second World War, it is considered that the determination method of the present invention can determine the packing more reliably.

  In the determination method, it is preferable to pack the chemical bullets or the like in an aluminum laminate bag when warming up. As a result, the hot water used for the hot bath does not come into direct contact with chemical bullets, etc., and even if chemical agent leaks out of the bullet, it does not leak out of the aluminum laminate bag, thus reducing the risk of filler leakage. Can do.

  In the determination method, it is preferable that X-ray imaging is performed with chemical bombs or the like fixed obliquely in an examination using X-rays after a warm bath or cooling. Thereby, it is considered that it is easier to determine whether the filling is liquid or solid.

  As described above, according to the present invention, it is possible to determine a filling such as a chemical bullet with simple, safe and low cost.

It is a cross-sectional schematic diagram which shows one embodiment of the warm bath process in the determination method which concerns on this invention. It is a cross-sectional schematic diagram which shows one embodiment of the X-ray inspection in the determination method based on this invention. It is a flowchart which shows one embodiment of the determination method of this invention.

  Hereinafter, although the embodiment of the method of determining the packing material such as a chemical bullet according to the present invention will be specifically described, the present invention is not limited to these.

  The method for determining a chemical bullet or the like according to the present embodiment includes a step of inspecting whether a chemical bullet or the like is liquid or solid at a predetermined temperature using X-rays, and the filler based on the melting point. And adjusting the temperature by performing a warm bath or cooling the chemical bullet or the like.

  The chemical bomb or the like, which is the subject of the present embodiment, usually has a shape extending in the axial direction, and a steel shell (outer shell) and a packing (a harmful substance) contained in the shell. A certain chemical agent).

  In the present embodiment, X-ray imaging is performed on a chemical bomb or the like as a subject in, for example, a horizontal state, an obliquely fixed state, or an upright state. There is no particular limitation on the X-ray imaging apparatus that can be used, and an X-ray source that is usually used for film imaging at any inspection site can be used. It is preferable that the first X-ray imaging first performed for determining a chemical bullet or the like is performed in all of a horizontal state, an obliquely fixed state, and an upright state.

  The basic principle of the determination method of the present embodiment is to check whether the packing such as chemical bullets is liquid or fixed by the X-ray imaging, and what is the packing based on the melting point of the substance. It is to determine whether.

  Since the melting point varies depending on the substance, if it cannot be determined by a single inspection, place chemical bombs at various temperatures and repeat the inspection with X-rays as necessary. Identify the filling.

  As the means for adjusting the temperature, for example, as shown in FIG. 1, there is a method of immersing a chemical bullet 1 or the like in a hot tub 3 adjusted to a predetermined temperature by adding hot water 4. At this time, from the viewpoint of safety, it is preferable that the temperature of the hot water is gradually increased from room temperature (about 25 to 35 ° C.). When warming chemical bullets etc., pack the chemical bullets etc. in aluminum laminate bags so that the hot water used for the warm bath does not come into direct contact with chemical bullets and reduce the risk of filling leakage. It is preferable to take a warm bath. There is no particular limitation on the aluminum laminated bag to be used, and those normally used for food packaging, retort packaging, seasoning packaging and the like can be appropriately used.

  On the other hand, if it is already found to be liquid at room temperature, the chemical bomb etc. is cooled to a predetermined temperature by, for example, immersing it in a water tank containing ice water, and the temperature at the time of becoming a solid is measured with X-rays. By using and confirming, it is considered that the filler can be specified. When cooling, it is preferable to lower the temperature stepwise, and when immersed in ice water, it is preferable to pack chemical bullets or the like in the aluminum laminate bag as described above.

  The X-ray imaging after the warm bath or cooling as described above is preferably performed in an obliquely fixed state as shown in FIG. For example, when the filling 2 of the chemical bullet 1 or the like becomes liquid by performing a warm bath at a predetermined temperature, the liquid level of the filling 2 is confirmed by X-ray imaging, so an inspection using X-rays By this, it becomes possible to specify the filler 2.

  Various substances are known as harmful substances (chemical agents) as packing materials such as chemical bullets. Currently, chemical bullets, etc. that can be found in Japan, What needs to be determined is mainly chemical bombs that may have been brought to Japan during the Second World War. That is, there is a need for a determination method that uses chemical bombs manufactured mainly in the United States in the 1930s and 1940s as subjects.

  As packing materials such as chemical bombs manufactured in the United States in such an era, substances such as those disclosed in Non-Patent Document 1 (bromoacetone, bromobenzyl cyanide, phosgene, chloroacetophenone, chloropicrin, and chloroform are used. Mixtures, titanium tetrachloride, mixtures of sulfuric acid trioxide and chlorosulfonic acid, mustard (without heel), mustard (with heel), mixture of chloropicrin and tin chloride, chloropicrin, yellow phosphorus, etc.) have been reported .

  These compounds are known compounds, but chemical bombs such as those mentioned above have been in production for over 60 years since they were produced during World War II, and the packing changes due to aging, The melting point is considered to have changed.

  On the other hand, in general, the melting point of the chemical substance that can be known in literature is a melting point in a state immediately after production. Therefore, it is not possible to search in the publicly available literature etc. how the melting point of the aging packing changes as a result of the change of the packing due to aging and the melting point of the packing.

  The present inventors have knowledge about fillers that have deteriorated due to secular changes by engaging in research and business for detoxifying various domestic and foreign chemical weapons that have been manufactured for over 60 years.

  According to the findings, Table 1 shows melting points of substances that may be packing materials such as chemical bullets that have passed 60 years or more after manufacture.

  For example, mustard (HD), which is one of the packings that may be contained in chemical bombs, is a liquid immediately after production, and its melting point is 14 ° C. according to literature. Yes. However, from the above findings, it is assumed that the mustard may be in a liquid state or polymerized (Heel) and transformed into a solid due to aging. When mustard is polymerized and becomes a solid, the melting point is assumed to rise from a melting point (14 ° C.) shortly after production to 76 ° C. or higher.

  Literature (TOXICOLOGICAL PROFILER FOR SULFURE MUSTARD, US Department Of Health And Human Service (9 May 2003); Parameter for the Evaluation of the Fate, Transport, and Environmental Impacts of Chemical Agents in Marine Environments, noblis issue (July 2007) ) And the like, the mustard (HD) may contain a residue called a heel (eg, a gel-like substance that does not flow), and its composition is 14 to 53% mustard, 42-86% cyclic sulfur ions (S- (2-chloro Chill) -1,4 Jichianiumu chloride) and is believed to be a metal such as iron sulfide. With respect to this composition, the melting point of the mustard (with heel) can be assumed to be about 76 ° C. by estimating the melting point according to the atomic group contribution formula by Joback.

On the other hand, if the mustard is left liquid, its melting point, melting point after manufacture shortly state (14 ° C.), it is assumed to fall to 1 4 ° C. or less.

Furthermore, the melting point of yellow phosphorus (WP) is usually 44 ° C. However, chemical products containing chemical agents tend to decrease in melting point due to contamination by impurities during production at the manufacturing plant. It is thought that there is. For example, according to the literature (Potential Military Chemical Biological Agents and Compounds (Army Filed Manual No. 3-9, Navy Publication No. P-467, Air Force Manual No. bromo-7, 1955-12). In the case of cyanide (C A ), the product produced in the manufacturing plant has a melting point drop of 7 ° C. compared to the pure product, and in the case of mustard, compared to Levinstein mustard (H) containing about 30% sulfur impurities. As a result, the melting point rises by 2 to 5 ° C.

  Based on the above, it is assumed that yellow phosphorus (WP) filled in chemical bullets etc. also has a melting point falling to about 40 ° C. according to the above tendency, and other packings except HD (Heel) and H (Heel) Even when filled, it is assumed that its melting point has dropped.

  Based on the melting point values in Table 1 obtained from such knowledge, the determination method of the present embodiment can be used to determine the filling of chemical ammunition safely and simply without using an expensive device. Will be possible.

  The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to these examples.

  For unidentified shells discovered in Okinawa Prefecture, the packing was determined. A flowchart showing the procedure of the determination method is shown in FIG. X-ray imaging of the shell was performed using a “portable X-ray inspection apparatus (type: 300 HP)” manufactured by Exlon International.

  Hereinafter, an example in which the method for determining a shell filling according to the present embodiment will be described with reference to FIG.

  As shown in FIG. 3, in the start stage, as a candidate for a filling material as a specimen, bromoacetone, bromobenzyl cyanide, phosgene, a mixture of chloroacetophenone, chloropicrin, and chloroform, titanium tetrachloride, sulfuric acid trioxide, and chloro Eleven candidate compounds such as a mixture with sulfonic acid, mustard (without heel), mustard (with heel), a mixture of chloropicrin and tin chloride, chloropicrin, and yellow phosphorus are listed (Category 0).

  First, prior to X-ray imaging, the shell to be determined was subjected to appearance inspection, dimension measurement, liquid sound confirmation, and shell surface temperature measurement at room temperature (about 30 ° C.).

  Next, X-ray imaging was performed in a horizontal state, a diagonally fixed state, and an upright state. As a result, since the liquid level of the filling could not be confirmed, it was determined that the shell filling was solid at room temperature (about 30 ° C.).

  Based on the above results, a candidate compound group (Category 1) having a melting point of normal temperature (about 30 ° C.) or higher, ie, mustard (with heel) and yellow phosphorus, and a candidate compound group having a melting point of normal temperature (25 to 35 ° C.) or lower. (Category 2), ie, bromoacetone, bromobenzylcyanide, phosgene, a mixture of chloroacetophenone, chloropicrin and chloroform, titanium tetrachloride, a mixture of sulfuric acid trioxide and chlorosulfonic acid, mustard (no heel), chloropicrin Candidate compounds could be divided into two groups: a mixture of tin and tin chloride, and chloropicrin.

  Since the cannonball filling was solid at room temperature, as a next step, the cannonball for which the filling was determined to be category 1 was subjected to a warm bath (35 ° C. × 30 minutes). During the warm bath, the shell was packed with an aluminum laminate bag (manufactured by Wintex Co., Ltd.) so as to cover the entire surface, and then immersed in warm water.

  Then, when X-ray imaging was performed again in a state where it was fixed obliquely, the liquid level of the filling material could not be confirmed yet (Category 1-1). That is, it has been found that the shell filling is still solid.

  Therefore, the temperature of the hot water was raised, the shell was subjected to a second warm bath (55 ° C. × 60 minutes), and X-ray photography was again performed in an obliquely fixed state.

  As a result, since the liquid level of the filling was confirmed, it was found that the melting point of the filling was 55 ° C. or lower. The melting point of the compound belonging to Category 1 is about 76 ° C. for mustard (with heel) and about 40 ° C. for yellow phosphorus, so it is determined that the shell filling is yellow phosphorus (Category 1-1-1). I was able to.

  If it is confirmed that the shell is solid, it is estimated that the cannonball filling can be determined to be mustard (with heel) (section 1-1-2).

  As described above, according to the determination method of the present invention, it was possible to safely and easily determine what the shell filled with without using an expensive device.

1 Chemical ammunition 2 Packing material (subject)
3 Hot Tub 4 Hot Water 5 Aluminum Laminated Bag

Claims (6)

A method for determining a chemical bullet or the like,
Using X-rays to inspect whether a chemical bomb or other filler is liquid or solid at a predetermined temperature; and
Determining the packing based on the melting point,
The adjustment of the temperature is performed by warming or cooling the chemical bullet etc.
Judgment method for chemical bullets and other packing materials.   The determination method according to claim 1, further comprising adjusting the temperature step by step as necessary, and repeating a hot bath or cooling of the chemical bullet or the like and an X-ray inspection. At room temperature, X-rays are used to check whether the chemical bombs are liquid or solid. If they are liquids, the packings are bromoacetone, bromobenzyl cyanide, phosgene, chloroacetophenone, chloropicrin and chloroform. , A mixture of titanium tetrachloride, a mixture of sulfuric acid trioxide and chlorosulfonic acid, mustard (without heel), a mixture of chloropicrin and tin chloride or chloropicrin,
If it is a solid, warm the chemical bomb etc. at 45-60 ° C., and then use X-rays to check whether the chemical bomb is filled in liquid or solid. When the object is yellow phosphorus or solid, it is determined that the filler is mustard (with heel).
The determination method according to claim 1.   The determination method according to any one of claims 1 to 3, wherein the chemical bullet or the like is a chemical bullet or the like manufactured during World War II.   The determination method according to any one of claims 1 to 4, wherein the chemical bullet or the like is packed in an aluminum laminate bag when warm bathing. The determination method according to any one of claims 1 to 5, wherein X-ray imaging is performed while fixing a chemical bullet or the like obliquely in an inspection by X-ray after warm bath or cooling.

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