JP5018847B2 - Surface treatment method and surface treatment apparatus for metal member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment method and a surface treatment device of a metal member where cleaning capacity to deposits on the surface of a metal is sufficiently high, even if the same is exhausted to the environment such as the air, the environment is not contaminated, and large-sized equipment is not required. <P>SOLUTION: Heated and pressurized water is jetted from a self-generation two fluids nozzle 101 to the surface of a metal strip 1a, and the heated and pressurized water is boiled under ordinary pressure so as to generate gas-liquid two fluids (self-generation two fluids), thus an oily substance on the surface of the metal strip 1a is removed. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a surface treatment method and a surface treatment apparatus for metal members such as copper, particularly metal members such as strips and wires.

  In the manufacturing method of a metal strip and a metal wire including a copper strip and a copper wire, after processing the raw material copper wire into a predetermined cross-sectional shape by cold rolling, the deposits on the surface are removed by a cleaning treatment. Examples of the deposit on the surface include lubricating oil used for rolling and metal powder (copper powder) generated during rolling.

  FIG. 13 shows a conventional metal member surface treatment apparatus, in which a metal strip 1a from a metal strip reel 1 before cleaning is sent out from an uncoiler 11 and the surface is cleaned through a surface treatment chamber 21 for cleaning. The deposits on the surface of the recoiler 12 are removed, dried in the drying chamber 22 and wound on the reel 2 of the recoiler 12.

  Conventionally, as a method for removing deposits in the surface treatment chamber 21, as disclosed in Non-Patent Document 1, for example, there is a technique (prior art 1) for dissolving and removing lubricating oil by immersing in an organic solvent. is there. Non-Patent Document 1 also discloses a technique (prior art 2) for removing fine particles by irradiating an object to be cleaned with ultrasonic waves in a liquid.

  Moreover, there exists a technique (prior art 3) which irradiates a two-fluid spray as described in Patent Documents 1 to 6. Further, there is a technique (conventional technique 4) using a two-fluid spray composed of water vapor and water as described in Patent Documents 7 to 9. Moreover, there exists a technique (prior art 5) which discharges water vapor | steam and spray water toward a process surface as described in patent document 10. FIG. Moreover, there exists a technique (prior art 6) using a high pressure jet as described in Patent Document 11. These are used in combination as necessary.

Japanese Patent No. 2995963 Japanese Patent No. 3498837 JP-A-10-156229 JP 2005-294819 A JP 2005-109112 A JP 2006-255603 A Japanese Patent No. 3860139 JP 2001-250773 A JP 2003-249474 A JP 2007-216158 A JP-A-10-92707 JP 2003-154205 A

Ready-to-use cleaning technology (Industry Research Committee, 2001), p. 262, p. 138

  The problem with Prior Art 1 is that it can cause pollution of the work environment and the atmosphere as the organic solvent volatilizes.

  According to the Air Pollution Control Law revised in 2005, it is required to reduce the generation amount of volatile organic compounds (hereinafter referred to as VOC) by 30% by 2010 compared to the fiscal 2000 level.

  Copper strips and copper wires have a long overall length, and even when wound on a reel or the like, the diameter and width of the reel are large, making it difficult to store the entire material in a sealed device.

  Therefore, in general, a copper strip or a reel of copper wire is installed in a delivery device installed outside the device, introduced into the device from the introduction port and processed, and then sent out from the discharge port to the outside of the device. It is wound on a new reel by an installed winding device or the like.

  That is, as described with reference to FIG. 13, the inside of the apparatus in the surface treatment chamber 21 communicates with the atmosphere outside the apparatus through at least two openings, that is, the introduction port and the discharge port, and cannot be sealed. Therefore, in order to recover the organic solvent, it is necessary to introduce a facility for sucking with a large air volume so that the organic solvent does not leak from the opening of the surface treatment chamber 21, and further, processing of the recovered organic solvent occurs. A new problem arises.

  As a countermeasure, when water is used without using an organic solvent, a new problem arises that the metal surface is oxidized. When the surface of a metal material such as copper is oxidized, the adhesion between the resin and the metal is lowered in the subsequent resin coating process, for example, or a hole called a pit is generated in the plating process. A problem occurs.

  The problem with prior art 2 is that the cleaning capability is not necessarily high enough. When the ultrasonic output is increased for the purpose of improving the cleaning ability, there is a high possibility that the ultrasonic transducer is damaged, and a new problem arises that the device management is costly.

  The problem with the prior art 3 is that the liquid evaporates as the gas and the liquid come into contact with each other, the latent heat of vaporization is lost, and the temperature decreases. In general, the higher the temperature, the lower the viscosity of the liquid, so that the diffusion of contaminants into the cleaning liquid is faster as the temperature is higher. Therefore, it is effective to increase the temperature of the cleaning liquid in order to increase the cleaning capability, but it is difficult to increase the temperature using the conventional technique 3. There is also a problem that the exhaust equipment must be enlarged in order to consume a large amount of gas.

  The problem with the prior arts 4 and 5 is that the cleaning ability is insufficient. None of Patent Documents 7 to 10 discloses the removal of oily liquids such as rolling process oil adhering to metal members. Patent Documents 8 and 9 disclose a method for removing a resist. Taking this as an example, the minimum time required for removal can be read as, for example, 30 seconds or more from FIG. 5 of Patent Document 9. However, metal strips including copper strips to be cleaned are generally cleaned while traveling at a speed exceeding 10 m / min even at low speeds and exceeding 100 m / min at high speeds. If a cleaning time of 30 seconds is required, the length of the cleaning zone is at least 5 m, which increases the size of the equipment and increases the investment.

  The problem with prior art 6 is that a large-scale device is required. Patent Document 11 discloses a method of discharging a cleaning liquid pressurized to 5 MPa or more toward a surface to be cleaned. However, a large-scale facility for pressurizing to this pressure is required, and capital investment increases.

  Therefore, in view of such problems, the object of the present invention is a metal member that has a sufficiently high cleaning ability for deposits on the metal surface, does not pollute the environment even when discharged to the atmosphere, and does not require a large facility. It is an object to provide a surface treatment method and a surface treatment apparatus.

In order to achieve the above object, the invention of claim 1 uses a gas-liquid two-fluid (self-generated two-fluid) obtained by boiling heated and pressurized electrolytic ionic water under normal pressure. An oily substance on a surface of a member is removed.

  The invention according to claim 2 is the metal member surface treatment method according to claim 1, wherein the pressure of the heated and pressurized water is 0.45 MPa or less.

  The invention according to claim 3 is the metal member surface treatment method according to claim 1, wherein the temperature of the gas-liquid 2 fluid is 40 ° C. or higher.

  Invention of Claim 4 is the surface treatment method of the metallic member in any one of Claims 1-3 in which the said gas-liquid 2 fluid consists of water vapor | steam and water, and the droplet diameter of water is 1 micrometer-100 micrometers. .

The invention of claim 5 is a metal member surface treatment apparatus for removing an oily substance on the surface of a metal member, wherein the heated and pressurized water is boiled under normal pressure to produce a gas-liquid two fluid (self-generated Self-generated two-fluid generating means for generating two fluids) and a surface treatment chamber for performing surface treatment by bringing the gas-liquid two-fluid (self-generated two-fluid) into contact with the metal member ,
The self-generated two-fluid generating means is connected to a water pressurizing and heating supply means for pressurizing and heating water, and a self-generated two fluid that is connected to the water pressurizing and heating supply means and generates gas-liquid two fluid (self-generated two fluid). Comprising an electrolytic cell that electrolyzes a liquid mainly composed of water, and selected one of electrolytic ionic water selected from the anode side or the cathode side generated by electrolysis in the electrolytic cell. A mixer that supplies the self-generated two-fluid nozzle and mixes and discharges the other electrolytic ionic water and the other electrolytic ionic water after contacting the metal member and performing the surface treatment. This is a surface treatment apparatus for a metal member.

According to a sixth aspect of the present invention, the self-generated two-fluid generating means is a heated and pressurized water jetted when the water heated and pressurized by the water pressurizing and heating supply means is jetted by the self-generated two-fluid nozzle. The metal member surface treatment apparatus according to claim 5, wherein the self-generated two fluids are generated by the steam generated by boiling due to the pressure drop and sprayed onto the surface of the metal member.

According to a seventh aspect of the present invention, the self-generated two-fluid nozzle has an injection unit that injects pressurized and heated water and a spray pattern of the gas-liquid two fluid (self-generated two-fluid) injected by the injection unit. It is a surface treatment apparatus of Claim 5 or 6 which consists of a rectifying wall nozzle which regulates.

The invention according to claim 8 is the surface treatment apparatus for a metal member according to any one of claims 5 to 7 , wherein the pressure of the water to be heated and pressurized is 0.45 MPa or less in the water pressurizing and heating supply means. is there.

The invention of claim 9, the surface treatment apparatus of the metal member according to any one of claims 5-8 in which the temperature of the gas-liquid two-fluid injected on the surface of the metal member is characterized in that at 40 ° C. or higher It is.

  According to the present invention, the self-generated two fluids can be heated to a temperature at which a necessary cleaning ability can be obtained, the cleaning process can be completed in a short time, and the occurrence of VOC can be suppressed. It exhibits an excellent effect that the influence on the working environment and air pollution can be further suppressed.

It is a figure which shows the surface treatment apparatus which enforces the surface treatment method of the copper strip by this invention. It is a figure which shows the effect of the copper strip washing | cleaning of Example 1 using the apparatus of FIG. It is a figure which shows the effect of the copper strip washing | cleaning of Example 2 using the apparatus of FIG. It is a figure which shows the temperature of 2 fluid with respect to the distance from the self-generated 2 fluid nozzle tip in Example 2 using the apparatus of FIG. It is a figure which shows other embodiment of the surface treatment apparatus which enforces the surface treatment method of the copper strip of this invention. In this invention, it is a figure which shows the effect which the pressure and temperature of self-generated 2 fluid exert on cleaning performance. It is a figure which shows typically the self-generated 2 fluid when a normal 1 fluid nozzle is used as a self-generated 2 fluid nozzle used for this invention. It is a figure which shows typically the self-generated 2 fluid using the self-generated 2 fluid nozzle which has a baffle wall nozzle part concerning Example 4 of this invention. It is a figure which shows other embodiment of the surface treatment apparatus which enforces the surface treatment method of the copper strip of this invention. It is a figure which shows the effect of the copper strip washing | cleaning concerning Example 5 using the apparatus of FIG. In this invention, it is a figure which shows typically the production | generation of 2 fluids using a general nozzle as a fluid self-generated 2 fluid nozzle. It is a figure which shows the washing | cleaning method of the copper strip by a prior art in detail. It is a figure which shows the washing | cleaning method of the copper strip by a prior art.

  A preferred embodiment of the present invention will be described below in detail with reference to the accompanying drawings.

  The present invention pressurizes a liquid containing water as a main component to a pressure (P0) that is equal to or higher than the pressure (P1) of the cleaning zone, and heats the liquid to a pressure not lower than the boiling point at pressure P1 and not higher than a boiling point at pressure P0. The liquid is discharged from the nozzle toward the surface of the metal member that is the object to be cleaned, and a mixture of droplets and water vapor is formed by boiling accompanying the pressure drop at that time, and the liquid is expanded by volume expansion during the boiling process. By accelerating and colliding the droplets toward the surface of the object to be cleaned, it is possible to remove oily liquid such as rolling process oil adhering to the surface of the metal member.

  First, a surface treatment apparatus for carrying out a method for cleaning a metal strip (copper strip) as a metal member according to the present invention will be described with reference to FIG.

  The metal strip 1 a wound around the reel 1 is sent out from the uncoiler 11, enters the surface treatment chamber 21 through the inlet 211 of the cleaning device, and goes out of the surface treatment chamber 21 through the carry-out port 212.

  The metal strip 1a inside the surface treatment chamber 21 includes a self-generated two-fluid nozzle 101 and water pressurizing and heating supply means 120 for supplying water by pressurizing and heating the self-generated two-fluid nozzle 101. Surface treatment is performed by the self-generated two-fluid generating means 100 to remove oily liquid such as rolling oil adhering to the surface.

  The self-generated two-fluid generating means 100 will be described.

  A self-generated two-fluid nozzle 101 is disposed in the surface treatment chamber 21. The water pressurization heating supply means 120 is configured by connecting a water tank 114 to a pipe 31 connected to a self-generated two-fluid nozzle 101 via a heater 115, a flow control valve 111, a flow meter 112, and a pump 113. The Here, by setting the pump 114 and the flow rate adjusting valve 111 to appropriate values, the water is pressurized to a pressure equal to or higher than the pressure (P1) in the cleaning zone and fed. The water pressure at this time is P0. Moreover, water is heated more than the boiling point in P1 by making the heater 115 function appropriately. The water thus heated and pressurized is discharged from the self-generated two-fluid nozzle 101 and boiled due to a pressure drop, and spontaneously generates a gas-liquid two fluid composed of water and water vapor. That is, the gas-liquid two fluid can be generated in a self-generated manner by appropriately setting the temperature and pressure without introducing a gas separately from the liquid as in the case of the normal two fluids.

  Hereinafter, the gas-liquid 2 fluid generated in this way is referred to as self-generated 2 fluid.

  The self-generated 2 fluid sprayed from the self-generated 2-fluid nozzle 101 is sprayed onto the metal strip 1 a, so that the deposits on the surface of the metal strip 1 a are removed and collected in the tray 220 below, and appropriately drained from the tray 220. Is done.

  Needless to say, the self-generated two fluids are almost composed of only water, so that even when discharged to the atmosphere, the load on the environment is small.

  Here, Patent Document 11 discloses a method using a cleaning liquid pressurized to 5 MPa or more. However, as a result of investigations by the inventors, when self-generated two fluids are used, the pressure is at most 0.45 MPa. Even if it exists, it became clear that the cleaning capability more than the capability currently disclosed by patent document 11 can be acquired.

  Since the self-generated two fluids are generated by utilizing the boiling of the liquid, the temperature immediately after the generation is equal to the boiling point. On the other hand, for example, even if liquid and gas near 100 ° C. are supplied to the two-fluid spray nozzle under atmospheric pressure to generate gas-liquid two fluid, the temperature of the generated two fluids decreases to about 70 ° C. For example, when steam and water at about 100 ° C. are supplied to a two-fluid spray nozzle to generate gas / liquid 2 fluid, gas / liquid 2 fluid at about 100 ° C. is generated. Another problem occurs.

  Patent Documents 7, 8, and 10 disclose cleaning techniques using water and water vapor, but all use water and water vapor introduced into the nozzle through separate pipes, and the respective temperatures, pressures, flow rates, etc. Must be controlled independently.

  In contrast, in the present invention, the self-generated two fluids can be used to reduce the parameters to be controlled. As a result, the apparatus cost can be reduced and the process management load can be reduced.

  Self-generated two fluids can also take advantage of the fact that the volume expands with boiling to accelerate the droplet velocity.

  For normal two fluids, for example, Patent Document 4 discloses a desirable gas flow rate of 10 to 100 L / min (norma1), and Patent Document 4 discloses that a desirable liquid flow rate is 100 to 200 mL / min. . If this gas is generated from water, it is 8.0 to 80 mL / min. Therefore, by heating and pressurizing 18 to 280 mL / min of water and discharging it from the nozzle, it is described in the same patent using a simpler facility consisting of one supply system without using the method of Patent Document 4. It is possible to produce a gas-liquid two fluid having a desired flow rate. By contacting the self-generated two fluids thus generated with the surface of the metal strip, the surface of the metal strip is cleaned.

  Patent Documents 1 to 4 disclose a method of generating two fluids using water and gas introduced into a nozzle through separate pipes, but the nozzle structure becomes complicated due to the introduction of two fluids, and Parameters such as temperature, pressure, and flow rate must be controlled independently. To generate a self-generated two-fluid, a simple one-fluid nozzle can be used.

  Here, the mechanism by which the contamination is removed is as follows as a result of examination by the inventors.

  In other words, the metal powder or processing lubricant oil that is a deposit receives kinetic energy from the colliding droplet, and desorbs from the metal surface when the magnitude is greater than the bond energy with the metal surface. In addition, when oil-based contamination that is insoluble in water, such as processing lubricating oil, is brought into contact with the gas-liquid 2 fluid mainly composed of water, the oil-based contamination cannot be dissolved in the droplets constituting the gas-liquid 2 fluid. Collects at the interface with the gas. However, since the metal surface is covered with a liquid film having a certain thickness, oily contamination that could not be collected at the interface with the gas of the droplets reattaches to the metal surface with a certain probability. Accordingly, the larger the area of the gas-liquid interface that the droplets constituting the gas-liquid 2 fluid have, the higher the cleaning capability. Therefore, if the amount of liquid forming the gas-liquid 2 fluid is the same, the smaller the droplet diameter, the higher the cleaning capability . According to the study by the inventors, an appropriate droplet diameter range is 1 μm or more and 100 μm or less.

  Furthermore, the higher the temperature, the lower the viscosity of the oily substance, and the smooth movement of the droplet from the metal surface to the gas-liquid interface. As a result of the study by the inventors, the efficiency of cleaning and removing with the gas-liquid 2 fluid is improved when the temperature of the gas-liquid 2 fluid is 40 ° C. or higher, further improved when the temperature is 65 ° C. or higher, and further improved when the temperature is 80 ° C. or higher. Confirmed to do. When the removal efficiency is improved, the removal process can be performed in a short time. As described above, since the metal strip and the metal wire are processed while running, if the processing time is short, the length of the processing zone can be shortened.

  Patent Document 5 discloses a method for cleaning a tape-like member that travels at a linear velocity of 3 m / min, but does not disclose that oily substances can be removed.

  Further, Patent Document 9 discloses that pressurized hot water is directly blown out, and a water vapor body and a water mist body are produced by boiling due to a pressure drop when the hot water is blown out. The effect is used for photolithography. It is only disclosed that the resist can be removed, and there is no disclosure that the oily substance can be removed. That is, the fact that the oily substance can be washed and removed using the self-generated two fluids has been revealed for the first time by the inventors' investigation.

  In order to generate the self-generated two fluids, a general nozzle that discharges one fluid (hereinafter referred to as one fluid nozzle) can be used. Will improve. That is, the spray discharged from one fluid nozzle diffuses at a certain angle. At this time, the temperature is lowered because heat is exchanged in contact with the surrounding atmosphere. In order to use a higher temperature spray, it is desirable to use a nozzle with a rectifying wall to block contact with the surrounding atmosphere. The rectifying wall may be an integral structure with the nozzle or may be a separated structure.

  For removal of oily contamination, a self-generated two-fluid generated by heating and pressurizing only water has a sufficient effect, but it is desirable to use electrolytic ionic water to further increase the removal rate. That is, electrolytic ionic water is generated in the vicinity of the anode and the cathode by electrolysis of water (hereinafter referred to as anode water and cathode water, respectively), and one of the anode water and the cathode water is heated and pressurized to generate two self-generated fluids. What is necessary is just to introduce | transduce into a nozzle, mix with the other, and discharge | emit after a washing process.

  Patent Document 6 discloses a method for removing fingerprints by gas-liquid two fluid using electrolytic ion water, but does not disclose any removal of oily substances such as lubricating oil adhering to metal material processing. . In general, fingerprints and lubricating oils have greatly different properties even if they are the same organic matter, and the amount of adhesion is greater in the lubricating oil after machining. The fact that the oily substance can be washed and removed by the self-generated two fluids using electrolytic ionic water has been revealed for the first time by the inventors' investigation.

  Next, another embodiment of the present invention will be described with reference to FIG.

  The surface treatment apparatus of FIG. 5 is basically the same as the surface treatment apparatus of FIG. 2, but as the water pressurization heating supply means 120, a liquid is pumped by gas pressurization without using a pump.

  First, a self-generated two-fluid nozzle 101 is disposed in the surface treatment chamber 21.

  The water pressure heating supply means 120 is connected to a water tank 114 via a heater 115, a flow rate adjustment valve 111, and a flow meter 112 to a pipe 31 connected to the self-generated two-fluid nozzle 101. 114 is connected to a gas cylinder 124 via a pipe 32, and a gas pressure regulator 123, a gas flow meter 122, and a gas flow rate adjustment valve 121 are connected to the pipe 32 from the gas cylinder 124 side to the water tank 114. .

  Moreover, the heater 115 is provided in both the middle of the piping 31 and the water tank 114.

  In the form of FIG. 5, the gas from the gas cylinder 124 is adjusted by the gas pressure regulator 123, the gas flow meter 122, and the gas flow rate adjustment valve 121, and is supplied to the water tank 114. Two self-generated fluids can be generated and sprayed onto the metal strip (copper strip) 1a.

  FIG. 9 shows still another embodiment of the present invention, in which electrolytic ionic water on the anode side or the cathode side is supplied from the water pressure heating supply means 120 connected to the self-generated two-fluid nozzle 101, and the electrolytic ionic water is supplied. The self-generated two fluids generated using the are ejected.

  In FIG. 9, the metal strip 1 a wound around the reel 1 is sent out from the uncoiler 11, enters the surface treatment chamber 21 through the inlet 211 of the surface treatment chamber 21, and enters the outside of the surface treatment chamber 21 through the carry-out port 212. Get out.

  A self-generated two-fluid nozzle 101 is disposed in the surface treatment chamber 21.

  The water pressurizing and heating means 120 is configured by connecting a water electrolysis tank 51 to a pipe 31 connected to a nozzle 101 via a flow rate adjusting valve 111, a flow meter 112 and a pump 113.

  The water electrolysis tank 51 is separated into two chambers, an A electrode chamber 52 in which an electrode A 521 is disposed, and a B electrode chamber 53 in which an electrode B 531 is disposed, by a partition wall 54 that does not hinder the movement of ions. A direct current power supply 55 is connected to the electrode A521 and the electrode B531, and electrolysis is performed by using one of the A-pole chamber 52 and the B-pole chamber 53 as an anode and the other as a cathode, so that electrolytic ionic water is supplied to the self-generated two-fluid nozzle 101. Can be supplied.

  Electrolytic ion water is supplied to the self-generated two-fluid nozzle 101 by setting the pump 113 and the flow control valve to appropriate values, and the self-generated two fluid discharged from the nozzle 101 is brought into contact with the surface of the metal strip 1a. Thus, the surface of the metal strip 1a is cleaned. The self-generated 2 fluid discharged to the surface of the metal strip 1a is discharged out of the surface treatment chamber from the tray 220 as cleaning waste liquid.

  The electrolytic ionic water generated in the B electrode chamber 53 of the water electrolysis tank 51 is transported by the pipe 33 via the pump 171, mixed with the cleaning waste liquid in the surface treatment chamber 21 by the mixer 71, and neutralized to obtain the final waste liquid. Discharged.

Example 1
In FIG. 1, the rolling lubrication oil on the surface of the copper strip was removed using a copper strip after completion of the rolling as the metal strip and a tank filled with pure water as the water tank.

  The copper strip sent out from the uncoiler 11 is introduced into the surface treatment chamber 21 through the introduction port 211, subjected to a cleaning process for a predetermined time, and then taken out from the carry-out port 212 to the outside of the surface treatment chamber. The water is pressurized and sent from the water tank 114 by the pump 113, and reaches the nozzle 101 via the flow meter 112 and the flow rate adjustment valve 111. Heated by a heater 115 provided in the middle of the pipe 31.

  A spray system HB-1 / 4-VV-SS-80-0050 nozzle was used as the self-generated two-fluid nozzle 101 that discharges the self-generated two fluid. The spray angle is about 80 ° and the orifice diameter is 50 μm.

  As a comparative example, a copper strip was immersed in each of an organic solvent, pure water, and microbubble water using the equipment shown in FIG. 12, and the removability of the rolling lubricant on the surface of the copper strip was evaluated. In addition, as the organic solvent listed in the comparative example, decane heated to 35 ° C. was used, and microbubble water generated by the method described in Patent Document 12 was used as the microbubble water.

  In Example 1 and the comparative example, the length of the cleaning zone was 2 m. In Example 1, the nozzles were arranged so that the spray was not interrupted over the entire cleaning zone, and in the comparative example, the length of the cleaning tank was the length of the cleaning zone. The cleaning time was adjusted by changing the linear velocity of the copper strip.

  The evaluation result of the residual oil concentration after washing is shown in FIG.

  It was confirmed that the amount of residual contamination could be reduced in a shorter time when self-generated two-fluid cleaning was used as compared with pure water immersion and microbubble water immersion.

(Example 2)
Cleaning was performed in a shorter time using the same spray nozzle as in Example 1. The spray pattern at a position 20 mm from the nozzle was a 10 × 30 mm rectangle, and the width direction of the copper strip was made to coincide with the long side of the spray pattern, and cleaning was performed. The linear velocity of the copper strip was 60 m / min. At this time, the time for passing under one spray is 0.01 seconds. A desired cleaning time was obtained by arranging 1 to 30 nozzles in the surface treatment chamber 21 and changing the number of nozzles with a constant linear velocity.

FIG. 3 shows the results of washing using a copper strip having an oil concentration of about 100 mg / m ² and measuring the residual oil concentration after washing. In Example 2, it was confirmed that the sample was cleaned even in a shorter time than Example 1 shown in FIG.

  Here, the temperature distribution from the nozzle tip is shown in FIG.

  As a comparative example, the result of a two-fluid spray generated by a two-fluid nozzle (B-1 / 4JBC-SS manufactured by Spraying Systems) using heated water (100 ° C.) and nitrogen gas is shown.

  From FIG. 4, the temperature of the self-generated 2 fluid was almost 100 ° C. just below the nozzle, and was 78 ° C. even 40 mm away from the nozzle. On the other hand, in the conventional two-fluid spray, it was 70 ° C. at a position 20 mm from the nozzle that actually performs cleaning. With self-generated two fluids, a temperature equal to or higher than that of the conventional two-fluid spray can be secured even 40 mm away from the nozzle. That is, the self-generated two fluid is an optimal method for generating two fluids of 80 ° C. or higher that could not be realized by the conventional two-fluid spray.

(Example 3)
Using the surface treatment apparatus described with reference to FIG. 5, self-generated two fluids were generated and washed.

  That is, the surface treatment apparatus of FIG. 5 is the same as the surface treatment apparatus of FIG. 1, but pumps liquid by gas pressurization without using a pump. In addition, heaters are provided both in the middle of the piping and in the tank.

  Here, two self-generated fluids were generated in two ways.

  In system A, the temperature was kept constant at 105 ° C., and the pressure was adjusted by the pressure of the gas used for pumping. Since the vapor pressure of water at this temperature is 0.15 MPa, when a pressure higher than this pressure is required, gas was introduced and pressurized.

  In the other method B, no gas was introduced, and heating was performed so that the vapor pressure of water became a predetermined pressure.

  The self-generated two fluids were generated using the pressurized heated water generated in this manner, and cleaning was performed. The analysis result of the residual oil concentration after washing is shown in FIG.

  In method A, the residual oil concentration does not change even when gas is introduced and the liquid feeding pressure is increased, whereas in method B, the residual oil concentration decreases with increasing pressure and temperature. That is, it was shown that the higher the temperature of the supplied water, the better.

  In the third embodiment, evaluation is performed using a spray nozzle different from the experiment shown in FIG. 3 of the second embodiment. Therefore, the results are different even when processing is performed at the same temperature and pressure. For example, the 0.01 second treatment in FIG. 3 and the 0.15 MPa treatment in FIG. 6 have the same temperature, pressure, and treatment time conditions, but different residual oil concentrations.

Example 4
Various nozzles were attached to the apparatus shown in FIG. 5, and the copper strip was washed in the same manner as in Example 3. The temperature was set to 145 ° C., and gas was fed from the outside using water vapor pressure without supplying gas.

  The self-generated two-fluid nozzle 101 used is shown in FIGS. 7, 8 (a), and 8 (b).

  For comparison, a conventional two-fluid nozzle 301 is shown in FIG.

  The self-generated two-fluid nozzle 101 of FIG. 7 shows a general one-fluid nozzle, and the nozzle body 102 has a nozzle hole 104 formed below the pressurized / heated water storage chamber 103, and the nozzle hole 104 is an orifice. The self-generated two-fluid nozzle used in the third embodiment (FIG. 7) is formed by forming a diameter-expanded portion 104b having a fan-shaped or conical spray pattern to widen the spray range from the portion 104a and the orifice portion 104a. The spray pattern of the enlarged diameter portion 104b is also a fan shape of about 80 °. For this reason, the irradiation area increases as the distance from the tip of the self-generated two-fluid nozzle 101 increases. Since the volume flow rate of the two fluids to be supplied is substantially constant, the linear velocity decreases as the distance from the tip of the self-generated two-fluid nozzle 101 increases. As a result, the two fluids exchange heat with the surrounding atmosphere, and the temperature decreases.

  On the other hand, a self-generated two-fluid nozzle 101 that is particularly suitable for the present invention includes a nozzle body 102 having a storage chamber 103 and a nozzle hole 104 as shown in FIGS. The rectifying wall nozzle unit 106 prevents the spray pattern of the two fluids ejected from the nozzle hole 104 of the spraying unit 105 from spreading. In FIG. In FIG. 8B, the self-generated two-fluid nozzle 101 is integrally formed, and the injection unit 105 and the rectifying wall nozzle unit 106 are separately formed. By providing a gap between the injection unit 105 and the rectifying wall nozzle unit 106 as in the self-generated two-fluid nozzle 101 of FIG. 8B, for example, the size of the injection pattern can be flexibly matched to the size of the workpiece. Can be changed.

  The self-generated two-fluid nozzle 101 shown in FIGS. 8A and 8B is provided with a rectifying wall nozzle portion 106 so as to prevent the injection area from increasing as the distance from the tip of the nozzle hole 104 of the injection portion 105 increases. Therefore, the effect of the rectifying wall is expected to prevent a decrease in linear velocity and a decrease in temperature.

  The results after washing are shown in Table 1.

  Compared with the case of using a general one-fluid nozzle, the residual oil concentration is lower when the one-fluid nozzle having the rectifying wall nozzle portion is used. That is, the effect of the rectifying wall nozzle portion was confirmed. In addition, although the shape of the rectifying wall nozzle portion is a cylindrical shape in FIG. 8A, it may be a substantially rectangular column shape.

  In addition, the number of self-generated two-fluid nozzles 101 used in this example is one, the length of the cleaning region in the copper strip traveling direction is 10 mm, and the copper strip traveling speed is 60 m / min. It is. Accordingly, the cleaning time is 0.01 seconds. Further, the self-generated two-fluid nozzle used in this example has the same ratio of the discharge flow rate to the supply pressure as the self-generated two-fluid nozzle used in Example 3.

(Example 5)
Using the apparatus shown in FIG. 9, anodic water and cathodic water are generated by water electrolysis, and a gas-liquid two fluid (self-generated two fluid) is generated using them, and the copper strip surface is cleaned in the same manner as in Example 1. Processed.

  In FIG. 9, the metal strip 1 a wound around the reel 1 is sent out from the uncoiler 11, enters the surface treatment chamber 21 through the inlet 211 of the cleaning device, and goes out of the surface treatment chamber 21 through the carry-out port 212. . A self-generated two-fluid nozzle 101 that generates a self-generated two-fluid is arranged in the surface treatment chamber 21, and a pipe 31 connected to the nozzle 101 is connected to the water electrolysis tank 51 via a flow meter 112 and a pump 113. It is connected. The water electrolysis tank 51 is separated into two chambers, an A electrode chamber 52 in which an electrode A 521 is disposed, and a B electrode chamber 53 in which an electrode B 531 is disposed, by a partition wall 54 that does not hinder the movement of ions. By performing electrolysis using one of the A-pole chamber 52 and the B-pole chamber 53 as an anode and the other as a cathode, self-generated two fluids can be supplied to the self-generated two-fluid nozzle 101.

  By setting the pump 113 and the flow rate adjustment valve 111 to appropriate values, electrolytic ion water is supplied to the self-generated two-fluid nozzle 101 for generating the gas-liquid two-fluid, and the gas-liquid mixed phase discharged from the self-generated two-fluid nozzle 101 is used. By bringing the fluid into contact with the surface of the metal strip 1a, the surface of the metal strip 1a is cleaned. The gas-liquid mixed phase fluid discharged to the surface of the metal strip 1a is discharged out of the surface treatment chamber as cleaning waste liquid.

  The electrolytic ion water generated in the B electrode chamber 53 of the water electrolysis tank 51 is transported by the pipe 33 via the pump 171 and mixed with the cleaning waste liquid in the mixer 71 inside or outside the surface treatment chamber 21 to obtain the final waste liquid. Discharged.

  Using the above equipment, the water electrolysis tank 51 was filled with a 0.1 mol / L potassium sulfate aqueous solution, electrolyzed with water using the electrode A521 as a cathode, and the copper strip surface was washed in the same manner as in Example 2. It was.

  For comparison, the copper strip surface was cleaned in the same manner as in Example 2 using pure water with the equipment shown in FIG.

  The results are shown in FIG. It is clear that the residual oil concentration decreases in a shorter time when electrolytic ionic water is used than when pure water is used.

  Moreover, the hydrogen ion index of the final waste liquid was 7.2, which was a level at which it could be discarded into sewage or discharged into the river after oil-water separation treatment.

  In this example, the water electrolysis tank was filled with a 0.1 mol / L potassium sulfate aqueous solution, but an aqueous solution of an appropriate concentration and electrolyte can be used without being limited thereto. In this embodiment, the electrode A is a cathode. However, the present invention is not limited to this, and the electrode A may be used as an anode depending on the type of contaminant to be removed by cleaning. For example, when the contamination to be removed is mainly composed of a rolling lubricating oil containing an ester, an alkaline aqueous solution generated in the A electrode chamber by using the electrode A as a cathode causes the ester to hydrolyze. It can be removed efficiently. At this time, an acidic solution is generated in the B pole chamber. Further, for example, when the contamination to be removed is mainly composed of a metal ion and a salt made of carboxylic acid called metal soap, an acidic aqueous solution generated in the A electrode chamber by using the electrode A as an anode, It can be efficiently removed by dissolving the soap. At this time, an alkaline aqueous solution is generated in the B pole chamber. In any case, the cleaning waste liquid is neutralized by mixing the electrolytic ion water generated in the B electrode chamber with the cleaning waste liquid, and further neutralization treatment is unnecessary.

1 reel 1a metal strip (copper strip)
21 Surface treatment chamber 100 Self-generated two-fluid generating means 101 Self-generated two-fluid nozzle 120 Water pressure heating supply means

Claims (9)

An oily substance on the surface of a metal member is removed using a gas-liquid 2 fluid (self-generated 2 fluid) obtained by boiling heated and pressurized electrolytic ion water under normal pressure. A method for surface treatment of a metal member.   The surface treatment method for a metal member according to claim 1, wherein the pressure of the heated and pressurized water is 0.45 MPa or less.   The surface treatment method for a metal member according to claim 1, wherein the temperature of the gas-liquid 2 fluid is 40 ° C. or higher.   The surface treatment method for a metal member according to any one of claims 1 to 3, wherein the gas-liquid 2 fluid is composed of water vapor and water and has a water droplet diameter of 1 µm to 100 µm. A metal member surface treatment apparatus for removing oily substances on the surface of a metal member, which generates two gas-liquid fluids (self-generated two fluids) by boiling heated and pressurized water under normal pressure. A generation 2 fluid generating means, and a surface treatment chamber for performing a surface treatment by bringing the gas-liquid 2 fluid (self-generated 2 fluid) into contact with the metal member ,
The self-generated two-fluid generating means is connected to a water pressurizing and heating supply means for pressurizing and heating water, and a self-generated two fluid that is connected to the water pressurizing and heating supply means and generates gas-liquid two fluid (self-generated two fluid). Comprising an electrolytic cell that electrolyzes a liquid mainly composed of water, and selected one of electrolytic ionic water selected from the anode side or the cathode side generated by electrolysis in the electrolytic cell. A mixer that supplies the self-generated two-fluid nozzle and mixes and discharges the other electrolytic ionic water and the other electrolytic ionic water after contacting the metal member and performing the surface treatment. A surface treatment apparatus for a metal member. The self-generated two-fluid generating means is a water-heated and pressurized water jetted by the self-generated two-fluid nozzle when the water heated and pressurized by the water pressurizing and heating supply means is jetted and the boiling accompanying the pressure drop. The metal member surface treatment apparatus according to claim 5, wherein a self-generated two-fluid is generated from the steam generated by the gas and sprayed onto the surface of the metal member. The self-generated two-fluid nozzle includes an injection unit that injects pressurized and heated water, and a rectifying wall nozzle that regulates expansion of an injection pattern of the gas-liquid two fluid (self-generated two fluid) injected by the injection unit. The surface treatment apparatus according to claim 5 or 6 . The surface treatment apparatus for a metal member according to any one of claims 5 to 7 , wherein the pressure of the water to be heated and pressurized by the water pressure heating supply means is 0.45 MPa or less. The surface treatment apparatus for a metal member according to any one of claims 5 to 8 , wherein the temperature of the gas-liquid 2 fluid sprayed onto the surface of the metal member is 40 ° C or higher.

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