JP3466269B2 - Metal processing method - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to an internal deposits tissue voids metal eluted is <br/> Ru technique related to how to clean the metal structure voids.

[0002]

2. Description of the Related Art Conventionally, methylene chloride has been used as a metal cleaning solution, and in the cleaning of semiconductors and metal products, the metal is directly immersed in the methylene chloride solution.

[0003]

The present invention does not directly immerse a metal in a solution of methylene chloride as in the above-mentioned prior art, but once vaporizes methylene chloride and water, and then the methylene chloride and water are evaporated. By applying steam to the metal, the surfactant vapor and the methylene chloride and water vapor are permeated into the metal tissue voids, and the deposits that have penetrated into the metal tissue voids and are adhering are washed out. It is a thing. Simultaneously with this cleaning action, weather resistant rust is secondarily generated on the metal, and this rust constitutes a passivation film that prevents the generation of further rust,
It also prevents metal corrosion.

[0004]

The problems to be solved by the present invention are as described above. Next, the means for solving the problems will be described. In claim 1, a methylene chloride solution and water are mixed and heated to generate methylene chloride vapor and steam, and the methylene chloride vapor and steam are filled in a treatment tank in which a metal is sealed to form a metal structure void. The metal treatment method is characterized in that the deposit is permeated and the deposits in the voids of the metal structure are eluted.

In the second aspect, a methylene chloride solution, water and a surfactant liquid are mixed to form a mixed liquid, and the mixed liquid is heated to generate methylene chloride vapor, water vapor and surfactant vapor, The metal treatment method is characterized in that vapor is filled in a treatment tank in which a metal is sealed so as to permeate the metal tissue voids, and deposits in the metal tissue voids are eluted.

[0006] In the third aspect, in the metal processing method according to claim 1 or 2, the processing tank and the negative pressure state, metal processing, which comprises treating the metal with deaerated state
It is a logical method .

According to a fourth aspect of the present invention, in the metal treatment method according to the second aspect, the weight ratio of the methylene chloride solution, water and the surfactant liquid is approximately 5.4.1, and the ratio of the surfactant liquid is 1 or less. And the heating temperature of the mixture is 80-
The metal treatment method is characterized in that the temperature is set to 100 ° C.

[0008]

[Operation] Next, the operation will be described. The methylene chloride vapor or the methylene chloride vapor, water vapor, and surfactant vapor of the present invention penetrates to the portion of the metallographic structure void of the metal W, elutes the deposits and residues in the metallographic structure void, and removes the metal or metal. The sex relics are washed.

[0009]

EXAMPLES Next, examples will be described. The chemical formula of methylene chloride is CH 2 Cl 2 and the molecular weight is 84.93.
Is the substance of. The chemical name is methylene chloride, and in addition to methylene chloride as a general name, dichloromethane,
It may be referred to as methylene dichloride. Boiling point is 40.
At 4 ° C, the melting point is -96.8 ° C. Further, the surfactant is classified into an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the anionic surfactant include sodium alkylsulfate, sodium amidosulfate, sodium secondary alkylsulfate, sodium alkylsulfonate, sodium amidosulfonate, sodium alkylallylsulfonate, sodium alkylnaphthalenesulfonate and the like.

Examples of the cationic surfactant include amine salt of acetic acid, alkyltrimethylammonium chloride, dialkylmethylammonium chloride, alkylpyridinium halide and alkyldimethylbenzylammonium chloride. As the amphoteric surfactant,
There are carboxylic acid type, sulfonic acid type, sulfuric acid ester type and the like.

Examples of the nonionic surfactants include polyoxyethylene alkylphenol, polyoxyethylene fatty alcohol, polyoxyethylene fatty acid, polyoxyethylene acid amide, polyoxyethylene fatty amine, and polypropylene glycol. Metal processing method of the present invention
In the method , if the alkalinity becomes strong, Cl2 is liable to be generated, so it is necessary to avoid this.
Polyoxyethylene alkylphenol and polyoxyethylene fatty alcohol, which are alcohol-based nonionic surfactants that are relatively stable to alkali, are effective in this respect. However, all the surfactants are effective for eluting the deposits in the metal structure voids.

In the metal treatment method of the present invention, methylene
The weight ratio of chloride solution, water, and surfactant solution should be approximately 5
・ 4 ・ 1, and the ratio of surfactant liquid is less than 1
Then, the heating temperature of the mixed solution is set in the range of 80 to 100 ° C.
ing. As in the present invention, when a mixed solution of methylene chloride solution, water and surfactant liquid is heated, in addition to methylene chloride vapor, water vapor and surfactant vapor, the following gases and compounds Is occurring. That is, HCHO, HF, HCl, HBr, NH3, Cl2
(Small), CH4, CO, CO2, organic acids, organic compounds. Examples of the organic acid include phosphoric acid, citric acid, pyruvic acid, malic acid, succinic acid, lactic acid, formic acid, acetic acid, levulinic acid, pyroglutamic acid, propionic acid, isobutyric acid and isovaleric acid. In addition, when the organic compound is subjected to mass spectrometry by gas chromatography, the organic compound derived from the essential oil contained in the chain saturated hydrocarbon and the metal deposit such as sesterpene and sesterpene alcohol is analyzed. In these, the deposits in the voids of the metal structure are eluted with methylene chloride and a surfactant.

FIG. 1 is a basic structural drawing of the metal processing method of the present invention, FIG. 2 is a drawing showing the process and procedure of the metal processing method by opening and closing a valve mechanism, and FIG. 3 is a processing tank T, a lid 22 and a metal mount. 4 is a side view of a portion of the table 26, FIG. 4 is a side view of the processing tank T with the lid 22 closed, FIG. 5 is a front view of the lid 22, FIG. 6 is a front sectional view of the processing tank T, and FIG. FIG. 8 is a front view of a state in which the metal W is placed on the metal placing table 26, and FIG. 8 is a sectional view of the inside of the processing tank T in the processing state.

In FIG. 3, FIG. 4, FIG. 5, FIG. 6 and FIG.
The configurations of the processing tank T, the lid 22, and the metal mounting table 26 will be described. That is, the processing tank T constitutes a pressure vessel,
In the metal treatment method of the present invention, 5
Since it becomes 0 Torr and 200 Torr at the time of vapor recovery of methylene chloride, the pressure vessel is configured to withstand this. A lid 22 is provided on the front surface, and the lid 22 is formed integrally with the metal mounting table 26. The metal mounting table 26 moves on a moving rail 25 provided inside the processing tank T, and also the lid 22.
Is a portion of the moving rail 24 below the lid supporting portion 23, and both can be integrally moved.

The metal W to be processed is placed on the metal placing table 26 which is integrally drawn out and inserted into the lid 22. With the portion of the metal mounting table 26 inserted in the processing tank T, the lid 22 and the processing tank T are hermetically fixed and pressure is applied. A heating / cooling pipe 20 is arranged at the inner bottom portion of the processing tank T, and in the case of heating, steam of several tens of degrees centigrade is supplied from the boiler B. In the case of cooling, the cooling water tank 18
Cooling water is supplied. The mixed solution of methylene chloride and water may be directly injected into the processing tank T, or may be supplied to the processing tank T in a mixed vapor state in the spare tank portion. In the embodiment shown in FIG. 1, the mixed liquid is supplied to the inside of the processing tank T.

Then, in the state of the mixed liquid, in the state of injecting the mixed liquid to the extent that the heating / cooling pipe 20 is immersed,
Water vapor of 100 to several tens of degrees Celsius is supplied from the boiler B to the heating / cooling pipe 20, and not only methylene chloride having a boiling point of 40 degrees but also water is vaporized. The steam and methylene chloride vapor are supplied at the same time by softening the outer peripheral structure of the metal W by the steam to promote the elution of the deposits in the metal tissue voids, and then the methylene chloride vapor causes the metal tissue voids to flow. It promotes its penetration into the interior of the. In the present invention, the mixed solution of methylene chloride, water, and the surfactant is formed only under the metal mounting table 26 even if the liquid level is maximum as shown in FIG. 6, and the metal is not immersed in the mixed solution. There is no. To the end, the vapor of the mixed liquid is absorbed by the metal for processing.

Next, referring to FIG. 1, the basic structure of the metal processing method of the present invention will be described. The equipment mainly comprises a processing tank T and a mixed liquid tank 14, and a mixed liquid in which methylene chloride, water and a surfactant are mixed is put into the mixed liquid tank 14. Further, the boiler B supplies steam into the pipe to vaporize the mixed liquid as described above, and the compressor C returns the mixed liquid inside the processing tank T to the mixed liquid tank 14 after the processing is completed. It applies pressure.

Further, the vacuum pump P is for sucking the methylene chloride vapor remaining inside the processing tank T and inside the metal structure void of the metal W after the mixed solution is pushed out. And the sucked methylene chloride vapor is
Since it cannot be discharged to the atmosphere, it is cooled and liquefied in the condenser 16 and returned to the mixed liquid tank 14 from the portion of the condenser pipe 21. The chiller 15 cools the cooling water inside the condenser 16.
Further, a filter 19 is provided to filter impurities such as dust in the mixed solution extruded from the processing tank T by the compressor C. The cooling water tank 17 is a pan for cooling water used for liquefying the mixed liquid vapor.

An electromagnetic valve is arranged in each part. The electromagnetic valve is configured to open and close at regular time intervals by an automatic control device, and the process steps are "metal degassing", "mixed liquid feeding", "metal cleaning", "mixed liquid cooling", "Mixed liquid tank return", "Mixed liquid vapor recovery",
As shown in FIG. 2, the opening / closing operation is automatically performed in the order of “collection of mixed liquid in condenser”. At the same time, compressor C
The boiler B, the vacuum pump P, and the chiller 15 are automatically stopped. One stroke of this process is configured to be completed in 24 hours.

Next, FIG. 2 shows the state of the electromagnetic valve in each step of the metal processing method . First, in the process of "metal degassing", the vacuum pump P is driven. Then, the electromagnetic valve 1 of the circuit that connects the vacuum pump P and the condenser 16 is opened, and the electromagnetic valve 3 that connects the condenser 16 and the processing tank T is also opened. All other solenoid valves are closed. As a result, the inside of the processing tank T is 50T
The vacuum becomes about orr, and the air in the metal structure void of the metal W is drawn out.

Next, in the "mixed liquid feeding" step, the electromagnetic valve 4 that connects the processing tank T and the mixed liquid tank 14 is opened, and the other electromagnetic valves are closed. As a result, the mixed solution tank 14 and the processing tank T are arranged at substantially the same level, so that the mixed solution is treated so that the mixed solution tank 14 and the processing tank T are at the same level.
Move in.

Next, in the process of "metal cleaning", the electromagnetic valve 7 between the boiler B and the processing tank T and the electromagnetic valve 9 which connects the drain from the processing tank T to each other are opened,
The other solenoid valve is closed. This allows the boiler B
High-temperature steam from the heating and cooling pipes 2 in the processing tank T
0, the mixed liquid in the processing tank T becomes methylene chloride vapor, water vapor, and surfactant vapor, and permeates into the metal structure void of the metal W. This "metal cleaning" step is performed for about 6 hours.

Next, the process of "mixed liquid cooling" will be described.
In this case, the electromagnetic valve 8 that connects the cooling water tank 18 and the processing tank T, the processing tank T, and the cooling water tank 1
The electromagnetic valve 10 communicating with 7 is opened. The other solenoid valve is closed. As a result, the cooling water passes through the inside of the heating / cooling pipe 20, and the inside of the processing tank T becomes 40 ° C. or lower, which is the boiling point of methylene chloride, so that both methylene chloride and steam return to the chemical liquid.

Next, the process of "returning the mixed liquid tank" will be described. In this case, the electromagnetic valve 2 is opened to release the air in the processing tank T, the electromagnetic valve 5 under the processing tank T and the electromagnetic valve 6 that connects the compressor C and the processing tank T are opened, and the compressor C is opened. Driven. Also,
Electromagnetic valve 1 between filter 19 and mixed solution tank 14
2 and the electromagnetic valve 1 that connects the mixed liquid tank 14 to the atmosphere
3 opens. As a result, a certain amount of pressure is applied to the processing tank T, so that the liquefied mixed liquid is pushed back into the mixed liquid tank 14.

Next, the process of "collection of vapor mixture in tank" will be described. In this case, the vacuum pump P is driven. Then, the electromagnetic valve 1 that connects the vacuum pump P and the capacitor 16 and the electromagnetic valve 3 that connects the capacitor 16 and the processing tank T are opened. The other solenoid valve is closed. In this state, the vacuum pump P collects the vapor of methylene chloride that has penetrated into the processing tank T and the metal structure voids of the metal W. The degree of vacuum at this time is 200 To
Lower to about rr. Next, in the process of “collecting the mixed liquid inside the condenser”, the electromagnetic valve 2 communicating with the atmosphere
Then, the electromagnetic valve 11 that connects the condenser pipe 21 and the mixed liquid tank 14 is opened. This allows the capacitor 1
The mixed liquid such as methylene chloride accumulated in the condenser pipe 21 of No. 6 can be collected in the mixed liquid tank 14. Each of these steps is completed in 24 hours.

Next, referring to FIG. 8, a sectional view of the inside of the processing tank T in the processing state will be described. A heating / cooling pipe 20 is arranged below the inside of the processing tank T, and a metal mounting table 26 is provided above the heating / cooling pipe 20.
Are movably arranged. The metal W is placed on the metal mounting table 26. The liquid mixture of water Wa, the surfactant liquid S, and the methylene chloride solution Me has a higher liquid level than the heating / cooling pipe 20, but does not immerse the metal W on the metal mounting table 26. It is injected so that it becomes the rank.

Since the specific gravity of the water Wa is 1.00 and the specific gravity of the surfactant liquid S is 1.04, the liquid levels are almost the same, and the surfactant liquid S dissolves in the water Wa and becomes integral. As shown in FIG. 8, a liquid layer of water Wa + surfactant liquid S is formed. On the other hand, a methylene chloride solution Me
Has a specific gravity of 1.33 and does not dissolve in water Wa,
A layer is formed under the layer of water Wa + surfactant liquid S. Then, when steam heated to 160 ° C. is supplied to the heating / cooling pipe 20 arranged in the layer of water Wa + surfactant liquid S, the temperature around the heating / cooling pipe 20 rises. The heating / cooling pipe 20 is made of water Wa + surfactant liquid S.
Are arranged in the layer of the above, and the temperature of the portion is raised first.

When the temperature of the heating / cooling pipe 20 gradually rises and reaches about 40 ° C., the methylene chloride solution M
e reaches the boiling point, changes to methylene chloride vapor and water W
a + the surface of the surfactant liquid S as bubbles to pass through the metal W
Then, the metal W penetrates into the metal structure voids. Metal W
In the case of 1, the heating is performed to about 80 ° C., and the methylene chloride vapor passes through the liquid of the water Wa and the surfactant liquid S and reaches the metal W, and the treatment is continued. Then, while the methylene chloride Me passes through the water Wa and the surfactant liquid S, Cl2 (chlorine gas) generated from methylene chloride is absorbed by the water Wa to suppress the generation of Cl2 which adversely affects the treatment. . In addition, the vapor of the methylene chloride, with the surfactant liquid S added thereto, penetrates into the metal structure void of the metal W. This makes it possible to improve the breakage of elution.

As described above, the water Wa, the surfactant solution S, and the methylene chloride solution Me are mixed as a mixed solution and heated by the heating / cooling pipe 20, whereby the vapor of the methylene chloride Me forms an interface with the water Wa. After passing through the activator liquid S, it is evaporated in the processing tank T, so that Cl2 is reduced. The methylene chloride vapor is a metal W
Penetrate into the perforations of. In addition, since the surfactant liquid S enters the perforation in a mixed state, it is easy to cut when depositing substances are eluted, and a large amount of methylene chloride vapor can be generated at a low temperature. There is no need to heat the inside to treat it.

In the present embodiment, the embodiment of treating metal has been described. However, the sword and metal relics which have been processed and produced for decades, hundreds, or thousands of years have been restored or restored. In, it is possible to use the metal treatment method of the present invention. That is, a metal relic that has been aged for many years is placed in the processing tank T, and a methylene chloride solution, water, and a surfactant solution are mixed, and steam of the mixed liquid is applied to the remnant to remove deposits remaining inside the metal relic. Can be eluted,
At the same time, all the dirt and soot on the surface can be drained. By this operation, the old metal relics can be cleaned from the inside. The washing operation also produces a bactericidal effect due to methylene chloride, and the surface is hardened after the adhered substances are eluted, so that the product can be displayed as it is on a constant temperature display device. This restoration / restoration can be performed on metals excavated during the survey of ruins and metal relics, regardless of metal relics. By the washing, it can be put into a state in which it can be stored for a long period of time.

[0031]

Since the present invention is constructed as described above, it has the following effects. That is, since it is configured as in claim 1, the methylene chloride vapor and the water vapor are
By penetrating into the inside of the metal, it is possible to easily elute the deposits in the voids of the metal structure.

According to the second aspect of the present invention, it is possible to elute the deposits in the voids of the metal structure by the methylene chloride, the surfactant and the water vapor. Particularly, by mixing the surfactants, the deposits can be dissolved. It is possible to improve separation and breakage from the metal structure voids after melting. Therefore, similarly, methylene chloride vapor and water vapor should be pressurized and absorbed, and the surfactant vapor should be absorbed by the metal mechanism, as compared with the case where the metal is immersed in a solution of methylene chloride. However, the elution effect of the deposits in the metal structure voids can be improved about three times. At the same time as this cleaning action, weather resistant rust is secondarily generated on the metal, and the rust also forms a passivation film that prevents the generation of further rust, thereby preventing metal corrosion. is there.

According to the third aspect of the invention, the metal W is degassed in the vacuum processing tank before the methylene chloride vapor, the water vapor and the surfactant vapor are permeated. Since the methylene chloride vapor can be permeated in the state where the air inside is removed, the permeation can be further permeated, and the deposits in the metal structure voids can be smoothly eluted.

According to the fourth aspect of the present invention, the vapor of methylene chloride Me is mixed with the layer of water Wa and the surface of the surfactant liquid S in the state of a mixture of water Wa, the surfactant liquid S and the methylene chloride solution Me. Since it is supplied to the metal W after passing through the layer of Cl.sub.2, Cl.sub.2 is absorbed by water as HCl, so that the generation rate thereof can be suppressed, the structure of the metal W is not destroyed, and after the treatment is completed. By making the pressure inside the processing tank T negative and making it vacuum, the vapor of methylene chloride can be easily sucked and recovered. Further, the tissue destruction of the metal W after recovery of this methylene chloride has not occurred. In addition, since the methylene chloride vapor is completely recovered immediately, it can be reused as it is cooled and liquefied. This allows
The amount of the methylene chloride solution Me used can be reduced and the cost required for the treatment can be reduced.

By mixing the surfactant, vaporization of methylene chloride or water can be promoted at a low temperature. Usually 100 water
Although it vaporizes at a temperature of ° C, it can be converted into water vapor at a low temperature by mixing a surfactant.
Since a sufficient pressure can be obtained within the range of 80 to 100 ° C without raising the temperature to 0 ° C or higher, 130 ° C.
There is no need to obtain high pressure by obtaining steam at a temperature higher than C.

[Brief description of drawings]

FIG. 1 is a basic configuration drawing of a metal processing method of the present invention.

FIG. 2 is a drawing showing a process and a procedure of a metal processing method by opening and closing a valve mechanism.

FIG. 3 is a side view of a processing tank T, a lid 22, and a metal mounting table 26.

FIG. 4 is a side view of the processing tank T with a lid 22 closed.

FIG. 5 is a front view of a lid body 22.

FIG. 6 is a front sectional view of a processing tank T.

FIG. 7 is a front view showing a state where a metal W is placed on the metal placing table 26.

FIG. 8 is a sectional view of the inside of the processing tank T in a processing state.

[Explanation of symbols]

Me methylene chloride solution C compressor B boiler T treatment tank P vacuum pump W metal Wa water S Surfactant liquid 14 Mixture tank 15 chillers 16 capacitors 18 Cooling water tank 21 condenser pipe

Claims (4)

(57) [Claims] 1. A methylene chloride solution and water are mixed and heated to generate methylene chloride vapor and water vapor,
The methylene chloride vapor and water vapor, is filled in the processing tank filled with metal to penetrate the metal structure voids, metal processing, characterized by eluting the deposits of the metal structure in the voids
Reasoning method . 2. A methylene chloride solution, water and a surfactant liquid are mixed to form a mixed liquid, and the mixed liquid is heated to generate methylene chloride vapor, steam and a surfactant vapor, and the mixed vapor is converted into a metal. The method for treating metal is characterized by filling a treatment tank in which the metal is filled and permeating into the metal tissue void to elute the deposit in the metal tissue void. Wherein <br/> the metal processing method according to claim 1 or 2 fraud and mitigating risk processing tank a negative pressure state, a metal treatment method, which comprises treating the metal with deaerated state. 4. The metal treatment method according to claim 2, wherein the weight ratio of the methylene chloride solution, water and the surfactant solution is
A metal treatment method , characterized in that the ratio of the surfactant liquid is approximately 5.4.1, the ratio of the surfactant liquid is 1 or less, and the heating temperature of the mixed liquid is in the range of 80 to 100 ° C.