WO2020095939A1 - 溶融めっき方法 - Google Patents
溶融めっき方法 Download PDFInfo
- Publication number
- WO2020095939A1 WO2020095939A1 PCT/JP2019/043454 JP2019043454W WO2020095939A1 WO 2020095939 A1 WO2020095939 A1 WO 2020095939A1 JP 2019043454 W JP2019043454 W JP 2019043454W WO 2020095939 A1 WO2020095939 A1 WO 2020095939A1
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- Prior art keywords
- hot
- plating
- bath
- dip
- vibration
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
- C23C2/51—Computer-controlled implementation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
- C23C2/52—Controlling or regulating the coating processes with means for measuring or sensing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
Definitions
- the present invention relates to a hot-dip plating method for metal materials, and more particularly to a hot-dip plating method for steel materials.
- hot-dip plating methods are roughly classified into continuous hot-dip plating methods and immersion plating methods.
- a steel material will be exemplified as a representative of metal materials, and a hot-dip plating method for steel material will be described.
- the continuous hot-dip plating method is a method in which a coil-shaped steel material (metal strip) is continuously passed (immersed and passed) through a hot-dip plating bath to plate the steel material.
- the immersion plating method is a so-called “dough pickling plating", which is a method of depositing a flux on a preformed steel material and then immersing the steel material in a hot dip bath to perform plating. ..
- the equipment (continuous hot-dip plating equipment) used for carrying out the continuous hot-dip plating method usually includes a pretreatment equipment, a reduction heating furnace, a hot-dip galvanizing bath (molten metal pot), and a post-treatment equipment.
- a pretreatment facility a treatment for removing rolling oil and dirt adhering to the steel material is performed.
- the reduction heating furnace the steel material is heated in an atmosphere containing H 2 to reduce the Fe oxide existing on the surface of the steel material.
- the hot dip bath part the steel material treated in the reduction heating furnace is immersed in and passed through the hot dip bath while being held in a reducing atmosphere or in an atmosphere that prevents reoxidation of the steel surface, thereby Is subjected to hot dip coating.
- various treatments are performed on the hot-dipped steel material depending on the application.
- the equipment used to carry out Dobu-zuke plating is a degreasing equipment that removes oil and dirt from preformed steel materials, and an Fe oxide layer (called rust or black skin).
- a flux equipment for applying a flux to the pickled steel material, and a hot dip bath section for performing hot dip plating on the steel material after drying the flux is a degreasing equipment that removes oil and dirt from preformed steel materials, and an Fe oxide layer (called rust or black skin).
- a flux equipment for applying a flux to the pickled steel material, and a hot dip bath section for performing hot dip plating on the steel material after drying the flux is a post-treatment equipment may be attached to the dobu-zuke plating equipment as in the case of the continuous hot dip plating equipment.
- the flux is used to improve the reactivity between the steel material and the hot dip bath.
- the problem of occurrence of plating defects (called non-plating or pinholes) on the surface of a plated product (semi-finished product) after hot-dip plating may occur.
- the plating defect is a portion in which the molten metal does not adhere to the steel material and the plated metal does not exist on the surface of the steel material.
- countermeasures have been taken for many years.
- a technique of performing hot-dip plating in a state where ultrasonic vibration is applied to a metal strip after heat treatment (reduction treatment) in a continuous hot-dip plating method Patent Documents 1 and 2). See).
- a technique has been proposed for performing Dobuzuke plating using ultrasonic waves to solve the problem of non-plating caused by burns (exposed alloy layer) (Patent Document 3). See).
- the annealing treatment of the material of the metal strip and the reduction treatment of the oxide film existing on the surface of the metal strip are performed by the reduction heating furnace in the previous step of immersing the metal strip in the molten metal pot. ..
- the metal band is heat-treated in a mixed atmosphere of, for example, nitrogen and hydrogen in order to reduce the oxide film.
- the heating temperature of the metal strip is set according to the intended use of the plated product, and in order to improve the reactivity between the metal strip and the hot dip bath, the metal strip must be at least at the temperature of the hot dip bath or higher. Be heated.
- the oxide film on the surface of the metal strip is removed by the treatment in the reduction heating furnace, the reactivity between the metal strip and the hot dip bath is improved in the hot dip bath. Therefore, it is possible to stably produce the hot-dipped metal strip.
- JP-A-2-125850 Japanese Unexamined Patent Publication “JP-A-2-28456” Japanese Patent Laid-Open Publication "JP 2000-064020”
- plating defects may occur on the surface of plated products.This is not only the case of continuous hot dip plating but also of dobuzuke plating. The same applies when a plated product is manufactured.
- the reduction heating furnace in continuous hot dip coating equipment requires a very large amount of heat and consumes a large amount of nitrogen and hydrogen used as atmospheric gases. This also applies to the techniques described in Patent Documents 1 and 2. In the conventional continuous hot dip plating method, it is not easy to reduce the energy consumption while satisfying the requirements for hot dip plated products (small plating defects, etc.).
- the dobu-zuke plating facility is usually provided with a flux facility to ensure good plating properties.
- a flux facility to ensure good plating properties.
- chloride including ZnCl 2 , NH 4 Cl, etc.
- One aspect of the present invention has been made in view of the above-mentioned conventional problems, and an object thereof is good plating wettability between a metal material and a hot dip plating bath, and a reduction in energy consumption as compared with the related art.
- Another object of the present invention is to provide a hot dip plating method capable of improving the working environment.
- the hot-dip plating method is such that a metal material is introduced into a plating bath that is a hot-melt metal, and the hot-melt metal is in contact with the hot-melt metal.
- a plating step of coating the molten metal on the metal material while applying vibration in the plating bath the frequency of the vibration applied to the plating bath as a fundamental frequency, in the plating step, in the plating bath.
- the above-mentioned vibration is applied so that the measured acoustic spectrum satisfies the relationship of the following formula (1).
- IB-NB Average value of sound pressure over the entire measurement frequency band
- IB (i) Between sound pressure peak at the fundamental frequency and sound pressure peak at the second overtone frequency, and (ii) sound pressure at a plurality of overtone frequencies Of the sound pressure in a specific frequency band between adjacent peaks of the peaks of NA: NA: the average value of the sound pressure of the entire measurement frequency band when the vibration is not applied
- NB Specified with respect to the IB It is an average value of sound pressure in the specific frequency band when the vibration is not applied).
- the intensity ratio obtained by (IB-NB) / (IA-NA) as described above may be referred to as a characteristic intensity ratio.
- the present inventors have found that the hot-dip plating under the condition that the characteristic strength ratio is larger than 0.2 improves the plating property of the metal material.
- a hot-dip plating method that has good plating wettability between a metal material and a hot-dip galvanizing bath, and that can reduce energy consumption and improve the working environment more than ever before. be able to.
- FIG. 1 is a schematic diagram showing a state in which a steel sheet is introduced into a hot dip bath under an air atmosphere
- FIG. 2 is an enlarged schematic diagram showing a region (A1) in the diagram shown in (a).
- FIG. It is an acoustic spectrum observed when a hot dip bath is vibrated by using an ultrasonic oscillator with an output of 380 W.
- hot dip bath metal various kinds of molten metal (molten metal) forming the hot dip bath
- the material and shape of the steel material to be subjected to hot dip plating using the hot dip bath are not particularly limited unless otherwise specified.
- steel plate may be read as “steel band” as long as there is no inconvenience.
- platability means both the wettability of the metal material and the hot-dip plating bath, and the adhesion between the metal material and the plating layer formed on the surface of the metal material. Is sometimes referred to as platability. However, in the present specification, the term “platability” is used to mean plating wettability.
- FIG. 13A is a schematic diagram showing a state in which a steel sheet is allowed to enter a hot dip bath under an air atmosphere.
- FIG. 13B is a partially enlarged view schematically showing a region (A1) shown in FIG. 13A in an enlarged manner.
- the steel plate 100 that has not been subjected to the reduction treatment is allowed to enter the hot dip bath 110 in the atmosphere.
- An oxide film is formed on the surface of the steel plate 100.
- a bath surface oxide 112 exists at the boundary (that is, the surface of the hot dip coating bath 110) between the hot dip bath metal 111 inside the hot dip bath 110 and the atmosphere (atmosphere) outside the hot dip bath 110. To do.
- the steel sheet 100 includes (i) the bath surface oxide 112 and (ii) the air entrainment layer 120 formed by the atmospheric gas (air) on the surface of the hot dip bath 110. As it is rolled in, it enters the hot-dip plating bath 110. As a result, inside the hot dip bath 110, the reaction inhibiting portion 130 is formed between the hot dip bath metal 111 and the oxide film 101 of the steel plate 100. The reaction inhibiting portion 130 is formed by the bath surface oxide 112 and the air entrainment layer 120 in a composite manner.
- the reaction between the steel sheet 100 and the hot dip bath metal 111 is hindered by the oxide film 101 and the reaction inhibiting portion 130, the surface of the plated product after being pulled out from the hot dip bath 110 is plated with defects (pin holes or non-plating). Etc.) easily occur.
- the steel sheet obtained by reducing the oxide film on the steel sheet surface using the heating furnace is introduced into the hot-dip plating bath through the snout held in the reducing atmosphere ( See, for example, Patent Documents 1 and 2.
- Patent Documents 1 and 2 See, for example, Patent Documents 1 and 2.
- the reaction between the steel sheet and the hot dip bath metal rapidly progresses.
- the present inventors have diligently studied a hot-dip plating method that can reduce energy consumption by a new method different from the above-mentioned conventional technology.
- the vibration activation effect produced by applying vibration under the specific conditions to the hot dip coating bath can enhance the reactivity between the steel material and the hot dip coating metal.
- the plating property of the steel material can be improved.
- Such a phenomenon is a phenomenon that was not expected at all in the prior art, as can be seen from the structure in which the reduction heating furnace was arranged in the previous stage of the hot dip coating section in the conventional hot dipping equipment.
- FIG. 14 is an acoustic spectrum observed when vibration is applied to the hot-dip plating bath using an ultrasonic oscillator with an output of 380 W.
- the cavitation effect of high power ultrasonic irradiation to the hot dip bath is used to physically remove the oxide film existing on the steel plate surface (or the oxide film remaining on the steel plate surface after the reduction treatment). By breaking, the plateability of the steel sheet was improved.
- the inventors of the present invention have found that the vibration activation effect of the present invention is recognized even when a low-power ultrasonic transducer is used, and that the plateability of the steel sheet is effectively improved. I found it. In this case, a peak characteristic of the acoustic spectrum is observed, which will be specifically described later.
- the present inventors consider the following vibration activation effect, which is different from the conventional technique and which is exhibited even at a low sound pressure, as follows.
- the hot dip of the hot-dip galvanized metal vibrates due to sound waves, and this pressure vibration causes Bubbles are generated. It is considered that a shock wave is generated toward the periphery of the bubble when the generated bubble is crushed due to the pressure vibration. Further, it is considered that the bubbles repeatedly expand and contract due to the pressure vibration, and this expansion and contraction may cause a local flow of the hot-dip metal around the bubbles. Due to the action of the shock wave and the local flow based on the acoustic energy, the mass transfer is promoted at the interface between the steel material and the plating bath, and the effect of reducing the thickness of the boundary layer or increasing the mass transfer speed is brought about. As a result, a mechanism is considered in which the plating wettability between the steel material and the hot dip bath is secured.
- the reaction in which the steel material is dissolved in the hot dip plating bath is that the concentration of the components of the steel material such as iron (Fe) in the hot dip plating bath is increased, and as a result, the occurrence of dross is likely to occur.
- concentration of the components of the steel material such as iron (Fe) in the hot dip plating bath is increased, and as a result, the occurrence of dross is likely to occur.
- erosion of members (ultrasonic horns) and the like that are immersed in the bath for imparting vibration with high sound pressure to the hot dip bath is likely to occur, which makes maintenance of these members complicated.
- a hot-dip plating method (hereinafter sometimes simply referred to as the hot-dip plating method) according to an embodiment of the present invention based on the findings found by the present inventors. That is, (i) ultrasonic vibration is applied to the steel material, or (ii) ultrasonic vibration is applied to the hot-dip galvanizing bath using, for example, a vibration plate, so that vibration with a low sound pressure is applied to the hot-dip galvanizing bath. Give. Then, the acoustic spectrum is measured using an acoustic measuring device immersed in the hot dip bath.
- the ultrasonic vibration is applied to the hot dip bath so that the acoustic spectrum satisfies a predetermined condition.
- the ultrasonic vibration applied to the steel material or the diaphragm causes a vibration activation effect in the hot dip plating bath.
- the above-mentioned predetermined condition is defined to indirectly specify the degree of the vibration activation effect by using the acoustic spectrum in the hot dip bath so that the vibration activation effect above a certain level is generated.
- a plate-shaped steel material (steel plate) among metal materials is used, and the steel plate is immersed in a hot dip bath and then pulled up to perform hot dip plating on the steel plate (so-called dobu-zuke plating). Will be described. Further, in the hot-dip plating method of the present embodiment, the above-mentioned dobu-zuke plating is performed in the atmosphere. Note that the hot-dip plating method in one embodiment of the present invention is not necessarily limited to this. The present hot-dip plating method can be applied to various metallic materials that are generally objects of hot-dip plating.
- the present hot dip plating method can be applied to a continuous hot dip plating method in which a steel strip is used as a steel material and the steel strip is continuously subjected to hot dip plating.
- the hot-dip plating method can also be applied to the case where a steel wire is used as a steel material and the steel wire is subjected to doppling plating or continuous hot-dip plating.
- the steel plate used in the hot-dip plating method of the present embodiment may be appropriately selected from various known steel plates according to the application, and examples of the steel type constituting the steel plate include carbon steel (common steel, high-strength steel ( High Si / high Mn steel)), stainless steel, and the like.
- the plate thickness of the steel plate is not particularly limited, but may be, for example, 0.2 mm to 6.0 mm.
- the shape of the steel sheet is not particularly limited, but may be rectangular, for example.
- Steel plates generally used for hot dip plating can be used for the hot dip plating method of the present embodiment.
- the steel sheet does not need to be subjected to reduction heat treatment or the like before hot dipping treatment. Therefore, the steel sheet may have an oxide film on its surface at the time of being put into the hot dip plating bath.
- the thickness of the oxide film is, for example, about several tens nm to several hundreds nm although it depends on the type of steel constituting the steel plate.
- the temperature of the steel sheet before entering the hot dip bath may be room temperature.
- the temperature of the steel sheet may be, for example, room temperature to 700 ° C.
- the steel sheet may be subjected to a heat treatment, a reduction treatment, a flux treatment, or the like, if necessary, before the hot dipping treatment.
- hot dip plating bath As the hot dip plating bath in the present embodiment, various known hot dip plating baths can be used. Examples of the hot-dip plating bath include a zinc (Zn) -based plating bath, a Zn-aluminum (Al) -based plating bath, a Zn-Al-magnesium (Mg) -based plating bath, and a Zn-Al-Mg-silicon (Si) -based plating.
- Zn zinc
- Al Zn-aluminum
- Mg Zn-Al-magnesium
- Si Zn-Al-Mg-silicon
- Examples thereof include a bath, an Al-based plating bath, an Al-Si-based plating bath, a Zn-Al-Si-based plating bath, a Zn-Al-Si-Mg-based plating bath, and a tin (Sn) -Zn-based plating bath.
- the temperature of the hot dip bath in this hot dip plating method may be the same as the temperature of the hot dip bath used in the known hot dip plating method.
- FIG. 1 is a schematic diagram showing a hot dipping apparatus 1 for carrying out the hot dipping method in the present embodiment.
- the hot-dip galvanizing apparatus 1 includes an ultrasonic horn (vibration generator) 10, an ultrasonic power source device D1, a hot-dip galvanizing bath 20, and a measuring device 30.
- the ultrasonic horn 10 is provided with an ultrasonic transducer 11.
- the steel plate 2 is fixed to the tip of the ultrasonic horn 10 with bolts 12.
- the ultrasonic power supply device D1 includes an oscillator 13, a power amplifier 14, and a power meter 15.
- the oscillator 13 generates an AC signal having an arbitrary frequency
- the power amplifier 14 amplifies the AC signal to generate an ultrasonic signal.
- the ultrasonic horn 10 receives the ultrasonic signal supplied via the power meter 15. As a result, the ultrasonic transducer 11 vibrates ultrasonically.
- the steel plate 2 connected to the ultrasonic horn 10 vibrates due to the vibration of the ultrasonic vibrator 11.
- the vibration of the steel sheet 2 causes a vibration activation effect in the hot-dip galvanizing bath 20, and a vibration activation region 23 is formed inside the hot-dip galvanizing bath 20 near the steel sheet 2.
- Hot-dip plating bath 20 is stored in pot 24 and contains hot-dip plating bath metal 21 and bath surface oxide 22.
- the vibration activation region 23 occurs in both the hot dip bath metal 21 and the bath surface oxide 22 in the hot dip bath 20.
- a waveguide rod 31 is inserted in the hot dip bath 20.
- One end of the waveguide rod 31 is arranged at an appropriate position inside the molten plating bath 20 so that the frequency of vibration of the molten plating bath metal 21 can be acquired, and the other end is connected to the vibration sensor 32.
- the vibration sensor 32 is a device that converts the vibration of the waveguide rod 31 into an electric signal using a piezoelectric element.
- the electrical signal transmitted from the vibration sensor 32 is amplified by the amplifier 33 and then transmitted to the spectrum analyzer 34.
- the spectrum analyzer 34 includes a display unit 34a. In this embodiment, the case where the spectrum analyzer 34 includes the display unit 34a will be described, but the display unit 34a may be replaced by an external device connected to the spectrum analyzer 34.
- the frequency of the ultrasonic oscillator 11 is set to 20 kHz, the output of the ultrasonic oscillator 11 is reduced, and vibration with a low sound pressure is applied to the hot dip bath 20.
- an acoustic spectrum as shown in FIG. 2 is displayed on the display unit 34a.
- the distance L1 between the waveguide rod 31 and the steel plate 2 was 10 mm, and the depth (distance from the tip to the bath surface of the hot dip plating bath 20) D1 of the waveguide rod 31 was 30 mm.
- FIG. 2 is a graph showing an example of an acoustic spectrum measured by the spectrum analyzer 34 included in the hot dipping apparatus 1. In the graph of FIG.
- the horizontal axis represents frequency and the vertical axis represents power value measured by the spectrum analyzer 34.
- the unit of the power value dBm (more accurately, dBmW: decibel milliwatt) represents the power in decibel value with reference to 1 mW.
- dBmW decibel milliwatt
- Such a power value can be used as an index representing the intensity of the acoustic spectrum.
- the magnitude of the value of the intensity (vertical axis in FIG. 2) in the acoustic spectrum corresponds to the magnitude of the sound pressure in the hot dip bath 20. Therefore, the peak of intensity in the acoustic spectrum corresponds to the peak of sound pressure.
- a peak showing a fundamental tone (frequency: 20 kHz) corresponding to the vibration applied to the hot dip bath 20 and a peak showing a harmonic (frequency that is an integral multiple of the fundamental tone) are mainly present.
- the frequency of the fundamental tone is defined as the fundamental frequency f
- the range (width) of the frequencies at which the acoustic spectrum is measured is defined as the measurement frequency band.
- the intermediate frequency (specifically, 3 / 2f, 5 / 2f, 7 / 2f, 9 / 2f) of each of the fundamental frequency f and a plurality of overtone frequencies (integer overtones: 2f, 3f, 4f, 5f) is determined.
- the range of the width of is the overtone band (specific frequency band).
- a range of a predetermined width from the intermediate frequency between the fundamental frequency f and the overtone frequency 2f is also referred to as an overtone band.
- the predetermined width of the inter-harmonic band is set to a range of 1 / 3f centering on the intermediate frequency.
- this predetermined width is not necessarily limited to this, and is appropriately set so as to be the frequency band between adjacent peaks among the main peaks in the acoustic spectrum (peaks at the fundamental frequency and peaks at the overtone frequency). do it.
- FIG. 3 is a graph showing an example of an acoustic spectrum measured by the spectrum analyzer included in the hot dipping apparatus 1 when the ultrasonic wave output is changed.
- the horizontal axis represents frequency (Hz) and the vertical axis represents intensity (dBm).
- the fundamental frequency is set to 20 kHz and the ultrasonic output is changed to 0.1 W to 30 W.
- the output of the ultrasonic transducer 11 when the output of the ultrasonic transducer 11 was changed from 0.1 W to 30 W, the higher the output, the more the intensity of the acoustic spectrum increased over the entire frequency range. Further, when vibration is not applied to the hot dip bath 20 (the output of the ultrasonic transducer 11 is 0 W), the intensity of the acoustic spectrum measured by the spectrum analyzer can be regarded as noise. In this measurement system, the level (noise level) when no ultrasonic vibration was applied was ⁇ 100 dBm.
- the acoustic spectrum measured by the spectrum analyzer has a peak at the fundamental frequency (20 kHz) and a peak at the overtone frequency, and the intensity between these peaks (interharmonic band). Increase and decrease.
- the intensity between these peaks (interharmonic band).
- the inter-harmonic band there were some peaks with relatively small intensity, and the peak frequencies of these peaks varied variously depending on the output.
- the present inventors have found that there is a relationship between the strength (increase and decrease in strength) in the interharmonic band and the plateability of the steel sheet immersed in the hot dip plating bath 20. Specifically, it is as follows.
- the average value of the intensities in the inter-harmonic band may be referred to as inter-harmonic average intensity.
- FIG. 4 is a graph showing the influence of ultrasonic output on the average intensity of the entire measurement frequency band in the acoustic spectrum and the average intensity between overtones.
- the horizontal axis represents the ultrasonic wave output and the vertical axis represents the average intensity.
- the ultrasonic wave output is 10 W or less
- the inter-harmonic average intensity is smaller than the average intensity in the entire measurement frequency band.
- the ultrasonic wave output is 20 W or more
- the average intensity in the entire measurement frequency band and the interharmonic average intensity become equal to each other.
- the above noise level was evaluated as a reference. That is, the average intensity of the entire measurement frequency band and the inter-harmonic average intensity are evaluated as the signal intensity ratio with respect to the noise level. Then, the relationship between the ratio of the average intensities and the output was summarized. The result will be described below with reference to FIG.
- FIG. 4 (b) is a graph showing the influence of ultrasonic output on the intensity ratio of the interharmonic average intensity (noise standard) to the average intensity (noise standard) of the entire measurement frequency band in the acoustic spectrum.
- the ultrasonic output is plotted on the horizontal axis and the intensity ratio is plotted on the vertical axis.
- the intensity ratio (equation (1) described later) may be referred to as a characteristic intensity ratio.
- the above characteristic intensity ratio increased as the ultrasonic output increased from 0.1 W to 20 W.
- the characteristic intensity ratio became about 1 and became almost constant.
- the present inventors performed hot-dip plating of the steel sheet 2 by using the hot-dip galvanizing apparatus 1 while changing the ultrasonic output in various ways. As a result, it has been found that when hot-dip plating is performed under the condition that the characteristic strength ratio is larger than 0.2, the plateability of the steel sheet 2 is improved. That is, the reactivity between the surface of the steel sheet 2 and the hot-dip bath metal 21 can be improved by applying the vibration in the hot-dip bath 20 to satisfy the above condition. Specifically, the non-plating rate on the surface of the plated product after hot dipping can be less than 10%.
- the hot dip plating method is to allow a steel material to enter a plating bath which is a hot metal and to apply vibration to the hot metal while the steel material is in contact with the hot metal.
- the method includes a plating step of coating the steel material with the molten metal.
- the frequency of the vibration applied to the plating bath is the fundamental frequency.
- the vibration is applied so that the acoustic spectrum measured in the plating bath satisfies the relationship of the following formula (1): (IB-NB) / (IA-NA)> 0.2 (1) here, IA: Average value of sound pressure in the entire measurement frequency band IB: (i) Between sound pressure peak at the fundamental frequency and sound pressure peak at the second overtone frequency, and (ii) integer overtone frequencies (2 or more) Of the sound pressure peaks adjacent to each other among the peaks of the sound pressure in the specific frequency band NA: the average value of the sound pressure when the vibration is not applied in the entire measurement frequency band NB: It is the average value of the sound pressure in the specific frequency band defined with respect to the IB when the vibration is not applied.
- IA Average value of sound pressure in the entire measurement frequency band
- IB (i) Between sound pressure peak at the fundamental frequency and sound pressure peak at the second overtone frequency, and (ii) integer overtone frequencies (2 or more) Of the sound pressure peaks adjacent to each other among the peaks of the sound pressure in the specific
- the ultrasonic horn 10 imparts the vibration of the frequency of 20 kHz to the steel plate 2 by vibrating the ultrasonic transducer 11.
- the ultrasonic horn 10 may apply vibration of a frequency of 15 kHz to 150 kHz to the steel plate 2, for example.
- the intensity of vibration applied to the steel plate 2 by the ultrasonic horn 10 is set so that an acoustic spectrum satisfying the relationship of the above formula (1) is generated in the hot dip plating bath.
- what is the output of the ultrasonic transducer 11 and whether the acoustic spectrum satisfying the relationship of the above formula (1) is generated in the hot dip bath is determined for each condition such as the steel plate and the hot dip bath 20. You should check it beforehand.
- the predetermined condition is satisfied (the relationship of the above formula (1) is satisfied) while the steel sheet 2 and the hot-dip bath 20 are in contact with each other.
- the vibration is applied to the steel plate 2.
- the bath surface oxide 22 and the atmosphere caught in the hot-dip galvanizing bath 20 are dispersed in the bath. That is, the reaction inhibiting part is dispersed in the bath.
- mass transfer is promoted at the interface between the steel plate 2 and the hot-dip galvanizing bath 20, and the effect of reducing the thickness of the boundary layer or increasing the mass transfer speed is brought about. This ensures the wettability of the plating between the steel plate 2 and the hot dip bath 20.
- the hot-dip plating method according to the aspect of the present invention, it is not necessary to perform the flux treatment. Therefore, the running cost can be reduced and the work environment can be improved.
- the hot-dip plating method in one aspect of the present invention when a new hot-dip plating facility is newly introduced, the cost and materials for installing the heating furnace are unnecessary, and the introduction cost can be reduced. Further, since the heating furnace has a long furnace length, it is not necessary to install the heating furnace, so that the total length of the hot dip plating equipment can be shortened.
- either the heat treatment or the reduction treatment before the hot-dip plating treatment (plating step) may be omitted, or both of them may be omitted.
- the steel plate 2 may be subjected to a heat treatment and a reduction treatment that are lighter than conventional ones before the plating step. In this case, energy consumption in both of those treatments is reduced. The amount can be reduced.
- the steel plate 2 may be subjected to various pretreatments before the hot dip plating treatment. For example, it does not matter if a reduction treatment is performed as a pretreatment for the plating step. If necessary, the steel plate 2 may be subjected to degreasing treatment or pickling treatment, or both of them may be performed. In the present hot dipping method, degreasing treatment and pickling treatment may be performed on the steel sheet 2 as pretreatment for the plating step, and at least degreasing treatment is particularly preferable. A pickling treatment may be performed subsequent to the degreasing treatment.
- the measurement frequency band may include the fundamental frequency and have a frequency width that is four times or more the fundamental frequency.
- the measurement frequency band may be 10 kHz or more and 90 kHz or less.
- a vibration generator (ultrasonic horn 10) is used to apply the vibration to the plating bath, and the output of the vibration generator may be 0.5 W or more.
- the output of the vibration generator may be 0.5 W or more and 30 W or less, and the frequency of vibration applied to the hot dip bath 20 via the steel plate 2 may be 15 kHz or more and 150 kHz or less.
- the vibration generator applies vibration with a frequency of 15 kHz or more and 150 kHz or less to the hot dipping bath 20, and the output may be 1 W or more and 30 W or less, or may be 5 W or more and 30 W or less.
- the time for applying the vibration in the plating bath using the vibration generator may be 2 seconds or more and 90 seconds or less.
- the steel plate 2 may have a temperature (inlet temperature) immediately before being immersed in the hot dip bath 20 at room temperature, for example, 100 ° C. or lower, or 50 ° C. or lower. May be.
- the acoustic spectrum in the plating bath is measured using a vibration detection device (eg, vibration sensor 32, amplifier 33, spectrum analyzer 34).
- the distance between the vibration detection point and the steel plate 2 in the plating bath may be 1 mm or more and 10 mm or less. The distance is measured in a state in which the steel plate 2 is immersed in the hot dip bath 20 before the vibration of the ultrasonic horn 10 is started.
- Example 1 An example of the hot dipping method according to the first embodiment of the present invention will be described below.
- FIG. 5 is a schematic diagram showing an example of a hot-dip plating apparatus used when the hot-dip plating method according to an aspect of the present invention is applied to dobu-zuke plating under an air atmosphere.
- the hot dipping apparatus 40 has a carbon crucible 42 housed inside a crucible furnace 41, and heats the carbon crucible 42 by causing resistance heating in a heating zone 43.
- the molten plating bath metal 21 is stored in the carbon crucible 42, and the bath surface oxide 22 is formed on the surface of the molten plating bath metal 21.
- the surface of the hot dip bath metal 21 is in the atmosphere.
- the hot dipping apparatus 40 includes the ultrasonic horn 10, and the steel plate 2 is fixed to the tip of the ultrasonic horn 10.
- the ultrasonic transducer 11 of the ultrasonic horn 10 receives the ultrasonic signal supplied from the ultrasonic power supply device D1 (including the oscillator 13, the power amplifier 14, and the wattmeter 15), and the ultrasonic power supply device D1 operates to receive the ultrasonic signal. Vibration is applied to the steel plate 2 with the set output.
- ultrasonic oscillator 11 a commercially available bolted Langevin type oscillator can be used.
- ultrasonic horn 10 an ultrasonic horn made of aluminum, titanium, ceramics, or the like can be used.
- the hot dipping apparatus 40 has a waveguide rod 51, an acoustic emission sensor (hereinafter, may be referred to as an AE sensor) 52, and a measuring apparatus 50 (corresponding to the measuring apparatus 30 in FIG. 1) for measuring an acoustic spectrum.
- the measuring unit 53 is provided.
- the measuring unit 53 includes a spectrum analyzer and an amplifier.
- One end of the waveguide rod 51 is immersed in the molten plating bath metal 21, and the other end is connected to the AE sensor 52.
- the various equipment used for the hot dipping apparatus 40 in this embodiment is specifically as follows.
- Ultrasonic vibration supply system ⁇ Ultrasonic transducer 11: Honda Electronics, bolted Langevin type transducer ⁇ Ultrasonic horn 10: Material ⁇ Aluminum alloy A2024A> -Oscillator 13: 33220A, manufactured by Agilent Technology Co., Ltd. ⁇ Power amplifier 14: M-2141, manufactured by Mestec Co., Ltd. ⁇ Electricity meter 15: PW-3335 manufactured by Hioki Electric Co., Ltd. (Ultrasonic vibration measurement system) -Waveguide 51: Material ⁇ SUS430>, ⁇ 6mm x 300mm ⁇ AE sensor 52: AE-900M, manufactured by NF Circuit Design Block Co., Ltd. ⁇ Amplifier: AE9922 manufactured by NF Circuit Design Block Co., Ltd. Spectrum analyzer: E4408B manufactured by Agilent Technologies, Inc.
- steel plate 2 (plating base material)
- carbon steel steel (steel type A and steel type B) shown in Table 1 below or stainless steel (steel type C to steel type F) shown in Table 2 below was used.
- Steel types A to F are all annealed materials.
- Example 1-1 Using Zn-Al-Mg type hot dip bath species
- the steel plates A to F shown in Table 1 and Table 2 were respectively subjected to a pre-treatment of alkali degreasing and pickling treatment using 10% hydrochloric acid.
- the pre-treated steel plates were attached to the tips of the ultrasonic horns 10 respectively, and were immersed in a Zn--Al--Mg-based hot dip bath at a depth of 60 mm (in other words, immersed in the bath in the depth direction of the plating bath).
- the length of the steel plate which is present was soaked, and the soaking time was set to 100 seconds to carry out dobu-zuke plating.
- the application of the vibration was started 10 seconds after the immersion of the steel sheet attached to the tip of the ultrasonic horn 10 into the hot dip plating bath, and the vibration was applied for 90 seconds.
- the composition of the hot dip plating bath was 6 mass% Al, 3 mass% Mg, 0.025 mass% Si, and the balance Zn.
- the temperature of the hot dip bath was 380 ° C. to 550 ° C., and when vibration was applied to the hot dip bath, the fundamental frequency and the output of the ultrasonic vibrator 11 were changed.
- dobuzuke plating was performed without applying vibration to the hot dip bath.
- FIG. 6 is a side view showing the state of the sample material 3 after plating. As shown in FIG. 6, the test material 3 after plating is provided with a hot-dip plated region 3a. Further, a non-plated portion 4 which is not subjected to hot dip plating may exist in a part of the plated region 3a.
- the depth of the portion immersed in the hot dip bath is L11, and the width of the sample material 3 is L12.
- L11 ⁇ L12 ⁇ 2 is an ideal plating area ⁇ .
- the area ⁇ of the unplated portion 4 is measured using a known area measuring means.
- the area ⁇ of the unplated portion 4 is an area measured on both plated surfaces (both plate surfaces) of the sample material 3.
- the non-plating rate was calculated by calculating ( ⁇ / ⁇ ) ⁇ 100.
- the plating property of the sample 3 was evaluated based on the following criteria, and the evaluation of ⁇ or more was regarded as acceptable.
- Non-plating rate is 0% ⁇ : Non-plating rate is more than 0% and less than 1% ⁇ : Non-plating rate is 1% or more and less than 10% X: Non-plating rate is 10% or more and less than 80% XX: Non-plating rate is 80% or more.
- the plating base material is a steel plate, and whether or not the plating base material is heated means whether or not the steel plate is heated before the hot dip plating. Further, the inlet temperature means the temperature of the steel sheet at the time of charging into the hot dip bath.
- the sound intensity (noise standard) in the table is obtained by IA-NA, and the average intensity between integer overtones (that is, the average intensity between noise overtones) is obtained by IB-NB.
- the ratio (characteristic intensity ratio) of is determined by (IB-NB) / (IA-NA) (for these symbols, see the above-mentioned mathematical expression (1)). The above is the same in the following in the present specification.
- the vibration applied to the hot dip coating bath is too weak (sound pressure is too low)
- the acoustic spectrum within the range of the present invention is not measured in the hot dip bath, and No. 3 in Table 3 is not measured.
- the non-plating rate of the plated product was 10% or more.
- the non-plating rate of the plated product was 80% or more.
- Example 1-2 Using Al-Si type hot dip bath type
- the hot dip plating bath As the hot dip plating bath, various steel plates shown in Table 1 and Table 2 were subjected to dobu-zuke plating.
- the temperature of the hot dip bath is 630 to 700 ° C.
- the dipping time of the steel plate in the hot dip bath is 12 seconds
- vibration is applied 10 seconds after the dipping of the steel plate into the hot dip bath is started.
- the fundamental frequency was set to 15 kHz
- the output of the ultrasonic transducer 11 was changed to 10 W or 0.05 W to 0.3 W.
- the conditions other than these were the same as in Example 1-1 above.
- the test results are summarized in Table 4.
- the vibration applied to the hot dip coating bath is too weak (sound pressure is too low)
- the acoustic spectrum within the range of the present invention is not measured in the hot dip bath, and No. 4 in Table 4 is not measured.
- the non-plating rate of the plated product was 10% or more.
- the non-plating rate of the plated product was 80% or more.
- Example 1-3 Various kinds of hot dipping bath are used
- Various hot-dip plating baths shown in Example 2 (Example 2-3) of the third embodiment were used as the hot-dip galvanizing baths, and various steel sheets A to F shown in Tables 1 and 2 were subjected to dobu-zuke plating. ..
- the compositions of the hot dip baths M1 to M10 are shown in Table 8 of Example 2, and the compositions of the hot dip bath M12 are shown in Table 9 of Example 2.
- the plating bath type M11 is an Al-2 mass% Fe-based plating bath, and the bath temperature is 700 ° C.
- the plating bath type M11 used in the test shown in Table 4 is Al-9 mass% Si- Unlike the 2 mass% Fe-based plating bath, Si is not added).
- the dipping time of the steel sheet in the hot dip coating bath was 12 seconds.
- the vibration was started 10 seconds after the dipping of the steel sheet in the hot dipping bath was started, and the vibration was given for 2 seconds.
- Example 1-3 the basic frequency was set to 15 kHz and the output of the ultrasonic vibrator 11 was kept constant at 20 W, and vibration was applied to the molten plating bath.
- the comparative example dobu-zuke plating was performed without applying vibration to the hot dipping bath.
- the steel plates A to F used had a plate thickness of 0.8 mm.
- the acoustic spectrum was measured while fixing the distance L1 between the tip of the waveguide rod 31 and the surface of the steel plate 2 in the hot dipping bath 20 to 10 mm. According to a further study by the present inventor, it has been found that the characteristic intensity ratio in the acoustic spectrum can change with a change in the position where the acoustic spectrum is measured.
- 7A to 7E are graphs showing acoustic spectra measured by changing the output of the ultrasonic transducer 11 at each distance L1, where FIG. 7A is a distance L1 of 1 mm, and FIG. 7B is a graph.
- the distance L1 is 5 mm
- the distance L1 is 10 mm in (c)
- the distance L1 is 30 mm in (d)
- the distance L1 is 80 mm in (e).
- FIG. 8 is a graph showing the relationship between the distance L1 and the characteristic strength ratio. As shown in FIG. 8, as the distance L1 increases, the characteristic intensity ratio tends to decrease, and this tendency is particularly remarkable when the output is weak (specifically, 0.1 W and 0.5 W). is there. From this, for example, when the output is 0.1 W or 0.5 W, it can be said that the distance L1 is preferably 10 mm or less in order to detect the acoustic spectrum.
- the output is 0.5 W or more and the distance L1 is 10 mm or less.
- the ultrasonic horn 10 is used to apply vibration to the steel plate 2 with the steel plate 2 attached to the tip of the ultrasonic horn 10.
- vibration is applied to the vibration plate using the ultrasonic horn 10, and the steel plate 2 is passed through the hot dip bath 20. The difference is that it indirectly gives a vibration to.
- FIG. 9 is a schematic diagram showing a hot dipping apparatus 60 for carrying out the hot dipping method in the present embodiment.
- the hot-dip galvanizing apparatus 60 includes a gas reduction heating zone 61, a hot-dip galvanizing section 62, an ultrasonic horn 10, and a measuring device 50 for measuring an acoustic spectrum.
- the gas reduction heating zone 61 is provided with an atmospheric gas introducing portion 61a and a heating portion 61b, and can heat-treat the steel sheet 2 in a desired atmosphere.
- the space above the crucible furnace 41 is isolated from the atmosphere by a port flange 64 and an O-ring 65.
- An atmosphere gas introduction portion 66 is provided in a part of the port flange 64 so that the atmosphere in the hot dip coating portion 62 can be controlled.
- a gate valve 63 is provided between the gas reduction heating zone 61 and the hot dip coating 62.
- the steel plate 2 processed in the gas reduction heating zone 61 opens the gate valve 63 and is transferred to the hot-dip galvanizing section 62 without being exposed to the atmosphere.
- the steel sheet 2 enters the plating bath 21 after undergoing pretreatment such as atmosphere control and heat treatment in the gas reduction heating zone 61 above the gate valve 63.
- the vibration plate 70 is fixed to the tip of the ultrasonic horn 10 instead of the steel plate 2.
- the vibrating plate 70 is made of ordinary steel (the same steel type as the steel plate A in Table 1) and has a length of 150 mm, a width of 50 mm, and a thickness of 0.8 mm.
- the vibration of the vibrating plate 70 applies vibration to the molten plating bath metal 21.
- the steel plate 2 is vibrated via the hot dip bath metal 21. That is, the hot dipping device 60 indirectly applies vibration to the steel plate 2.
- the diaphragm 70 is not limited to the above materials.
- the vibrating plate 70 is preferably made of a material that has strong erosion resistance when immersed in a hot dip plating bath and does not have good wettability with respect to the hot dipping bath. For example, ceramics can be used.
- measuring device 50 Other configurations of the measuring device 50 and the like are similar to those of the above-described hot dipping device 40 (see FIG. 5), and thus detailed description thereof will be omitted.
- the hot dipping apparatus 60 as described above can be applied to a continuous hot dipping method. That is, in the continuous hot dip coating method, it is difficult to directly apply vibration to the steel plate, but it is possible to indirectly apply vibration to the steel plate 2 as in the hot dipping apparatus 60. Therefore, the results demonstrated by using the hot dipping apparatus 60 as described above can be applied to the continuous hot dipping method. An example of application to the continuous hot dip plating method will be specifically described later.
- Example 2 An example of the hot-dip plating method according to the third embodiment of the present invention will be described below.
- the hot dip plating apparatus 60 shown in FIG. 9 was used.
- Example 1 Various steel plates A to F (see Tables 1 and 2) are used as in Example 1, and a Zn—Al—Mg-based hot dip plating bath or an Al-9 mass% Si-2 mass% Fe-based plating bath is used. Was used to perform hot dip plating under various conditions.
- Example 2-1 No heat treatment in gas reduction heating zone 61
- Alkaline degreasing treatment was applied to each of the various steel sheets as a pretreatment.
- the hot dip plating bath the Zn-Al-Mg based plating bath in Example 1-1 of Example 1 and the Al-9% Si based plating bath in Example 1-2 of Example 1 were used.
- the atmosphere in the hot dip section 62 was changed to an air atmosphere, a nitrogen atmosphere, a 3% hydrogen-nitrogen atmosphere, or a 30% hydrogen-nitrogen atmosphere. Atmosphere control and heat treatment in the gas reduction heating zone 61 were not performed.
- the dipping time of the steel sheet in the hot dip coating bath is 12 seconds, and when vibrating the vibrating plate 70 by using the ultrasonic horn 10 to apply vibration to the hot dip coating bath, start dipping the steel sheet in the hot dipping bath.
- the application of vibration was started 10 seconds after, and the vibration was applied for 2 seconds.
- the fundamental frequency was set to 15 kHz
- the output of the ultrasonic transducer 11 was kept constant at 30 W, and vibration was applied to the hot dip bath.
- the arrangement of the steel plate and the vibration plate in the hot dip plating bath was adjusted so that the distance (distance) between the vibration plate and the steel plate was 5 mm.
- the distance between the steel plate and the tip of the waveguide rod was 5 mm.
- Example 2-2 There is heat treatment in the gas reduction heating zone 61
- Example 2 described above except that the atmosphere control and heat treatment in the gas reduction heating zone 61 were performed, and the vibration was started for 2 seconds after starting the immersion of the steel sheet in the hot dip plating bath for 2 seconds. Hot-dip plating was performed in the same manner as in -1. The results of the test are summarized in Table 7.
- Hot-dip plating was performed in the same manner as in Example 2-1 except that the hot-dip bath having the composition shown in Tables 8 and 9 below was used and the atmosphere in the hot-dip coating section 62 was a 3% hydrogen-nitrogen atmosphere. ..
- the plating bath type M11 is an Al-2 mass% Fe-based plating bath, and the bath temperature is 700 ° C.
- the plating bath type M11 used in the test shown in Table 4 is Al-9 mass% Si-2 mass% Fe. Unlike the system-based plating bath, Si is not added). The results of the test are summarized in Table 10.
- the hot dip plated steel sheet produced by the hot dip plating method of the present invention may have a base chemical conversion treatment film formed on the surface of the plating layer for improving corrosion resistance and film adhesion.
- the base chemical conversion coating is preferably an inorganic coating, and more specifically, a coating containing a valve metal oxide or hydroxide and a valve metal fluoride.
- valve metal refers to a metal whose oxide exhibits high insulation resistance.
- the valve metal element is preferably one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W.
- the base chemical conversion treatment film may contain a soluble or sparingly soluble metal phosphate or complex phosphate.
- the base chemical conversion coating may contain an organic wax such as a fluorine-based, polyethylene-based or styrene-based wax, or an inorganic lubricant such as silica, molybdenum disulfide or talc.
- the base chemical conversion coating may be an organic coating based on urethane resin, acrylic resin, epoxy resin, olefin resin, polyester resin or the like.
- the hot-dip plated steel sheet produced by the hot-dip plating method of the present invention on the surface of the plating layer, a polyester-based, acrylic resin-based, fluororesin-based, vinyl chloride resin-based, urethane resin-based, epoxy resin-based resin system
- the paint can be applied by methods such as roll coating, spray coating, curtain flow coating, and dip coating. Alternatively, it can also be used as a base material for film lamination when laminating a plastic film such as an acrylic resin film.
- a part of the ultrasonic horn is immersed in the hot dip bath, and vibration is applied to the hot dip bath from the tip of the ultrasonic horn.
- the vibration is indirectly transmitted from the tip of the ultrasonic horn to the steel sheet through the hot dip plating bath, and the steel sheet is subjected to doppling plating.
- FIG. 10 is a schematic diagram showing a hot dipping apparatus 80 for carrying out the hot dipping method in the present embodiment.
- the hot dip coating device 80 includes an elevating device 81, an ultrasonic horn 10A, a measuring device 50 for measuring an acoustic spectrum, and a carbon crucible 42 in which the hot dip bath metal 21 is stored. ing.
- the steel plate 2 is immersed in the hot dip plating bath 20 in the air and without heating the steel plate 2.
- the elevating device 81 is a device capable of immersing the steel plate 2 in the hot dip plating bath 20 while holding the steel plate 2 and pulling the steel plate 2 out of the hot dip bath 20.
- a known device may be used as the lifting device 81, and detailed description thereof will be omitted.
- the ultrasonic horn 10A includes an ultrasonic transducer 11, a tip portion 17, and a connecting portion 16 that connects the ultrasonic transducer 11 and the tip portion 17 together.
- the ultrasonic transducer 11 is fixed by a transducer fixing stage 19.
- the connection portion 16 has a length that facilitates resonance according to the frequency of the vibration generated by the ultrasonic transducer 11.
- the connecting portion 16 may be a simple adapter or a booster that amplifies the amplitude generated by the ultrasonic transducer 11 and transmits the amplified amplitude to the tip portion 17.
- the ultrasonic transducer 11 receives the ultrasonic signal transmitted from the ultrasonic power supply device D1 and vibrates ultrasonically. To do. This ultrasonic vibration is transmitted to the tip portion 17 via the connection portion 16, and the tip portion 17 imparts vibration to the hot dip bath 20.
- a vibrating surface 17A is formed at an end of the tip portion 17 farther from the connecting portion 16 in the longitudinal direction so that the cross-sectional shape of the end portion becomes an isosceles triangular shape, and the vibrating surface 17A is melted. It faces the surface of the steel plate 2 immersed in the plating bath 20.
- the tip 17 is preferably made of ceramic. This is to reduce deterioration of the tip portion 17 that may occur due to ultrasonic vibration of the tip portion 17 in the hot dip bath 20.
- the hot dipping device 80 may use an integrated ultrasonic horn instead of the ultrasonic horn 10A.
- the tip of the ultrasonic horn may be made of ceramics.
- the distance L2 between the vibrating surface 17A of the tip portion 17 and the surface of the steel plate 2 may be 0 mm or may be greater than 0 mm and 50 mm or less.
- the distance L2 of 0 mm means that the vibrating surface 17A and the surface of the steel plate 2 are in contact with each other before the ultrasonic horn 10A vibrates ultrasonically (that is, at the time of setting).
- the lifting device 81 can move the steel plate 2 in the horizontal direction, and the distance L2 can be adjusted by moving the steel plate 2 in the horizontal direction using the lifting device 81.
- the distance L2 is preferably more than 0 mm and 5 mm or less.
- the frequency and output of the vibration applied to the hot dipping bath 20 using the ultrasonic horn 10A are the same as those described in the first embodiment.
- Example 3 An example of the hot-dip plating method according to the fifth embodiment of the present invention will be described below.
- the hot dipping apparatus 80 shown in FIG. 10 described above was used.
- the various equipment used for the hot dipping apparatus 80 in this embodiment is specifically as follows.
- Ultrasonic vibration supply system ⁇ Ultrasonic transducer 11: Hielscher, 20 kHz transducer ⁇ Connecting portion 16 (booster): Material ⁇ Ti>, amplification factor 2.2 times, 1/2 wavelength type, length 126 mm -Tip 17: Material ⁇ Ti>, 1/2 wavelength type, length 250 mm ⁇ Ultrasonic power supply device D1: Hielscher, 20 kHz, 2 kW power supply (ultrasonic vibration measurement system) -Waveguide 51: Material ⁇ SUS430>, ⁇ 6mm x 300mm ⁇ AE sensor 52: AE-900M, manufactured by NF Circuit Design Block Co., Ltd. ⁇ Measuring unit 53 Amplifier: AE9922 manufactured by NF Circuit Design Block Co., Ltd. Spectrum analyzer: E4408B manufactured by Agilent Technologies, Inc.
- Example 3-1 Using Zn-Al-Mg type hot dip bath species
- Various steel plates A to F were used in the same manner as in Example 1, and the Zn-Al-Mg based hot dip bath in Example 1-1 of Example 1 was used as the hot dip bath. Hot-dip plating was performed under various conditions.
- the distance L2 was set to 0 mm to 50 mm and the fundamental frequency was set to 20 kHz.
- the ultrasonic transducer 11 has a built-in amplitude sensor for monitoring the amplitude of the ultrasonic transducer 11.
- a display device was used to receive the output from the amplitude sensor and display the output with a full scale of 5V. Since the magnitude of the amplitude of the ultrasonic transducer 11 is reflected in the output displayed by the display device, 5V of full scale is set as 100% of the output in the following, and is an index indicating the magnitude of the amplitude of the ultrasonic transducer 11. "Output%" was used as.
- the load on the ultrasonic power source is considered to be the steel sheet itself.
- the load on the ultrasonic power source is the steel sheet and the hot dip bath. Therefore, the vibration applying condition is expressed not by using the output (W) itself from the ultrasonic power source but by using “output%” which is an index indicating the amplitude of the ultrasonic vibrator when resonating.
- vibration is applied to the hot dip bath using the ultrasonic horn 10A
- vibration is applied 10 seconds after the steel plate 2 is immersed in the hot dip bath and vibration is applied for 2 seconds to 60 seconds. ..
- each test material was subjected to dobu-zuke plating using the hot dipping device 80 without applying vibration to the hot dipping bath.
- the conditions other than the above were the same as in Example 1-1 above.
- the test results are summarized in Table 11.
- Example 3-2 Using Al-Si type hot dip bath type
- Various steel plates A to F were used in the same manner as in Example 1, and Al-9 mass% Si-2 mass% Fe in Example 1-2 of Example 1 was used as the hot dipping bath.
- Hot-dip plating was performed under various conditions using a system plating bath.
- the distance L2 was set to 0 mm to 5 mm and the fundamental frequency was set to 20 kHz.
- the vibration was applied to the hot dip bath using the ultrasonic horn 10A, the vibration was started 10 seconds after the steel plate 2 was soaked in the hot dip bath and the vibration was started for 2 seconds.
- the other conditions were the same as in Example 1-2 above.
- the test results are summarized in Table 12.
- Example 3-3 Various kinds of hot dipping baths are used
- Various steel plates A to F were used in the same manner as in Example 1, and various hot-dip baths shown in Example 2 (Example 2-3) of the third embodiment were used as hot-dip baths.
- Example 2-3 various hot-dip baths shown in Example 2 (Example 2-3) of the third embodiment were used as hot-dip baths.
- the hot-dip plating method in the present embodiment while using a continuous hot-dip galvanizing equipment to continuously pass the steel strip in the hot-dip galvanizing bath, a part of the ultrasonic horn is immersed in the hot-dip galvanizing bath to Place the tip of the ultrasonic horn in the vicinity. While applying vibration to the hot dip bath or the steel strip from the tip of the ultrasonic horn, the hot dip is continuously applied to the steel strip.
- FIG. 11 is a schematic diagram showing an example of hot-dip plating equipment 90A for carrying out the hot-dip plating method in the present embodiment.
- the hot-dip galvanizing equipment 90A has a configuration in which an ultrasonic horn 10B and a measuring device 50 are added to a general continuous hot-dip galvanizing equipment.
- 2 A of steel strips are immersed in the hot dip bath 20 through the snout 91.
- the steel strip 2A is passed through the hot-dip galvanizing bath 20 by a guide roll 92 and a support roll 93, then pulled up, and the amount of coating adhered is adjusted by gas blowing or the like.
- the steel strip 2A may be subjected to a pickling treatment or the like to remove the iron oxide layer on the surface of the steel strip 2A as a pretreatment for the plating process.
- the hot dip equipment 90A may be configured to heat the steel strip 2A to a temperature suitable for hot dip plating by a heating device (not shown) provided in the preceding stage of the snout 91.
- the hot-dip galvanizing equipment 90A does not have to be provided with a reduction heating device before the snout 91.
- ultrasonic vibration is applied to the hot-dip bath 20 using the ultrasonic horn 10B so that the wettability of the steel strip 2A can be reduced even if the surface of the steel strip 2A is not subjected to reduction treatment. Can be increased.
- the ultrasonic horn 10B is an integrated device including the ultrasonic transducer 11, the tip portion 17, and the connecting portion 16 in the ultrasonic horn 10A described in the fifth embodiment.
- the hot dip equipment 90A may use the ultrasonic horn 10A instead of the ultrasonic horn 10B.
- the ultrasonic horn 10B is arranged so that the tip of the ultrasonic horn 10B is immersed in the hot dip bath 20 and located near the steel strip 2A near the outlet of the snout 91. There is.
- the ultrasonic horn 10B preferably has a vibrating surface 17A formed by chamfering the end of the ultrasonic horn 10B closer to the steel strip 2A in the longitudinal direction.
- the vibrating surface 17A faces the surface of the steel strip 2A that passes through the hot dip bath 20. Thereby, the vibration can be efficiently transmitted from the ultrasonic horn 10B to the steel strip 2A while keeping the distance between the vibrating surface 17A and the surface of the steel strip 2A constant according to the passing direction.
- the hot-dip galvanizing equipment 90A in the hot-dip galvanizing bath 20, in the vicinity of the second surface of the steel strip 2A on the side opposite to the first surface of the steel strip 2A facing the vibrating surface 17A.
- the tip of the wavy rod 51 is arranged. It is preferable that the waveguide rod 51 is arranged along the passing direction of the steel strip 2A.
- the waveguide rod 51 may be provided with a protective tube or the like that covers a portion other than the tip of the hot dip bath 20 in order to reduce noise and the like in the acoustic spectrum.
- the distance L3 between the vibrating surface 17A and the surface of the steel strip 2A may be 0 mm, or may be greater than 0 mm and 50 mm or less.
- the distance L3 of 0 mm means that the vibrating surface 17A and the surface of the steel strip 2A are in contact with each other before the ultrasonic horn 10B vibrates ultrasonically (that is, at the time of setting).
- the steel strip 2A is vibrated at the same fundamental frequency as the ultrasonic horn 10B. It is possible to As a result, the plating wettability can be improved not only on the first surface of the steel strip 2A but also on the second surface.
- the frequency and output of the vibration applied to the hot dip bath 20 using the ultrasonic horn 10B are the same as those described in the first embodiment.
- FIG. 12 is the schematic which shows the hot-dip plating equipment 90B and hot-dip plating equipment 90C of a modification.
- the hot dip equipment 90B and the hot dip equipment 90C differ from the hot dip equipment 90A described above in that the ultrasonic horn 10B is disposed near the support roll 93.
- the ultrasonic horn 10B is arranged at a position after the steel strip 2A has been passed through the hot dip coating bath 20 and passed through the support roll 93. Even when the ultrasonic horn 10B is arranged in this manner, the ultrasonic wetness of the ultrasonic horn 10B to the molten plating bath 20 or the steel strip 2A can enhance the wettability of the plating of the steel strip 2A. ..
- the ultrasonic horns 10B in the hot dip equipment 90A to 90C may be combined so as to apply ultrasonic vibration to the hot dip bath 20 or the steel strip 2A using a plurality of ultrasonic horns 10B. .. It is sufficient to appropriately select a configuration that provides good plating properties of the steel strip 2A.
- the strip speed of the steel strip 2A is adjusted so that the plating property of the steel strip 2A becomes good. May be adjusted appropriately.
- Example 4 An example of the hot-dip plating method according to the sixth embodiment of the present invention will be described below.
- the hot dip plating equipment 90A shown in FIG. 11 was used.
- the various equipment used in the hot-dip plating equipment 90A in this embodiment is specifically as follows.
- Ultrasonic vibration supply system ⁇ Ultrasonic transducer 11: Hielscher, 20 kHz transducer ⁇ Connecting part 16 (adapter): material ⁇ Ti>, 1/2 wavelength type, length 126 mm -Tip 17: Material ⁇ Super Sialon>, dual wavelength type, length 500 mm ⁇ Ultrasonic power supply device D1: Hielscher, 20 kHz, 2 kW power supply (ultrasonic vibration measurement system) -Waveguide 51: Material ⁇ SUS430>, ⁇ 6mm x 300mm ⁇ AE sensor 52: AE-900M, manufactured by NF Circuit Design Block Co., Ltd. ⁇ Measuring unit 53 Amplifier: AE9922 manufactured by NF Circuit Design Block Co., Ltd. Spectrum analyzer: E4408B manufactured by Agilent Technologies, Inc.
- Example 4-1 No heat treatment before hot dipping process
- Various steel plates A to F are used as in Example 1, and a Zn—Al—Mg-based hot dip plating bath or an Al-9 mass% Si-2 mass% Fe-based plating bath is used. Was used to perform hot dip plating under various conditions.
- the atmosphere inside the snout was changed to an air atmosphere, a nitrogen atmosphere, a 3% hydrogen-nitrogen atmosphere, or a 30% hydrogen-nitrogen atmosphere.
- the distance L3 was 0 mm and the fundamental frequency was 20 kHz.
- the strip running speed of the steel strip in the hot dip plating bath was 20 m / min.
- Example 4-2 There is heat treatment before the hot dipping process
- Example 4-2 There is heat treatment before the hot dipping process
- Example 4-1 In the same manner as in Example 4-1, except that the steel strip was heat-treated in the air atmosphere, the nitrogen atmosphere, the 3% hydrogen-nitrogen atmosphere, or the 30% hydrogen-nitrogen atmosphere before the snout. Then, continuous hot dip plating was performed.
- Table 15 The test results are summarized in Table 15.
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Abstract
Description
(ここで、
IA:測定周波数帯域全体における音圧の平均値
IB:(i)上記基本周波数における音圧のピークと2倍音周波数における音圧のピークとの間、並びに、(ii)複数の倍音周波数における音圧のピークのうち隣り合うピーク間、の特定周波数帯域における音圧の平均値
NA:上記測定周波数帯域全体における、上記振動を付与していない場合の音圧の平均値
NB:上記IBに関して規定される上記特定周波数帯域における、上記振動を付与していない場合の音圧の平均値
である)。
本明細書において、溶融めっき浴を構成する各種の溶融された金属(溶融金属)を「溶融めっき浴金属」と称することがある。また、本明細書において、溶融めっき浴を用いて溶融めっきを施される対象としての鋼材の材質および形状は、格別の記載が無い限り特に限定されない。また、「鋼板」は、不都合の無い限り「鋼帯」と読み替えてもよい。
一般に、(i)還元処理を行っていない鋼板(鋼帯)を溶融めっき浴に進入させる、または(ii)スナウトを用いずに大気(酸素濃度の高い)雰囲気下にて鋼板を溶融めっき浴に進入させると、鋼板と溶融めっき浴金属との反応が阻害され、良好なめっき性が得られない。この理由について、図13を用いて詳細に説明すれば、以下のとおりである。図13の(a)は、大気雰囲気下にて鋼板を溶融めっき浴に進入させる様子を示す模式図である。図13の(b)は、(a)に示した図の領域(A1)について拡大して模式的に示した部分拡大図である。
以下、本発明の実施の形態について、詳細に説明する。
本実施形態の溶融めっき方法に用いられる鋼板は、公知の各種鋼板の中から用途に応じて適宜選択されてよく、鋼板を構成する鋼種としては、例えば、炭素鋼(普通鋼、高強度鋼(高Si・高Mn鋼))、ステンレス鋼、等が挙げられる。上記鋼板の板厚は、特に限定されないが、例えば0.2mm~6.0mmであってもよい。また、上記鋼板の形状は特に限定されるものではないが、例えば長方形であってもよい。一般に溶融めっきに用いられる鋼板を、本実施形態の溶融めっき方法に用いることができる。
本実施形態における溶融めっき浴としては、公知の各種溶融めっき浴を用いることができる。溶融めっき浴としては、例えば、亜鉛(Zn)系めっき浴、Zn-アルミニウム(Al)系めっき浴、Zn-Al-マグネシウム(Mg)系めっき浴、Zn-Al-Mg-シリコン(Si)系めっき浴、Al系めっき浴、Al-Si系めっき浴、Zn-Al-Si系めっき浴、Zn-Al-Si-Mg系めっき浴、錫(Sn)-Zn系めっき浴、等が挙げられる。
本実施形態における溶融めっき方法を実施する溶融めっき装置1について、図1および図2を用いて説明する。なお、溶融めっき装置1は一例であって、本溶融めっき方法を実施する装置は、特に限定されるものではない。図1は、本実施の形態における溶融めっき方法を実施する溶融めっき装置1を示す概略図である。
(IB-NB)/(IA-NA)>0.2 ・・・(1)
ここで、
IA:測定周波数帯域全体における音圧の平均値
IB:(i)上記基本周波数における音圧のピークと2倍音周波数における音圧のピークとの間、並びに(ii)複数の整数倍音周波数(2以上の整数)における音圧のピークのうち隣り合うピーク間、の特定周波数帯域における音圧の平均値
NA:上記測定周波数帯域全体における、上記振動を付与していない場合の音圧の平均値
NB:上記IBに関して規定される上記特定周波数帯域における、上記振動を付与していない場合の音圧の平均値
である。
上記の例では、超音波ホーン10は、超音波振動子11が振動することによって、20kHzの周波数の振動を鋼板2に付与していた。しかし、これに限定されず、超音波ホーン10は、例えば、15kHz~150kHzの周波数の振動を鋼板2に付与してもよい。また、超音波ホーン10によって鋼板2に付与する振動の強度(超音波振動子11の出力)は、上記式(1)の関係を満たす音響スペクトルが溶融めっき浴中に生じるように設定されればよい。例えば、超音波振動子11がどの程度の出力であれば、上記式(1)の関係を満たす音響スペクトルが溶融めっき浴中に生じるかを、鋼板および溶融めっき浴20等の各種の条件毎に予め調べておけばよい。
以上のように、本発明の一態様における溶融めっき方法によれば、鋼板2と溶融めっき浴20とが接触している間に、所定条件となる(上記式(1)の関係を満たす)ような振動を鋼板2に付与する。これにより、溶融めっき浴20内に巻き込んだ浴面酸化物22および大気が浴中で分散される。すなわち、反応阻害部が浴中で分散される。また、鋼板2と溶融めっき浴20との界面において物質移動が促進され、境界層の厚みが小さくなる、または物質移動速度が大きくなる等の効果をもたらす。これにより、鋼板2と溶融めっき浴20との間のめっき濡れ性が確保される。そのため、溶融めっき浴金属21と鋼板2との反応がスムーズに進行する。その結果、予め加熱処理(還元処理)を行っていない鋼板2を用いた場合であっても、鋼板2のめっき性を良好なものとすることができる。したがって、溶融めっき浴金属21と鋼板2とのめっき濡れ性が良好であるとともに、従来よりもエネルギー消費量の低減を図ることができる溶融めっき方法を提供することができる。
本実施形態の溶融めっき方法では、溶融めっき処理(めっき工程)前の加熱処理および還元処理のいずれかを省略してもよく、それらの両方を省略してもよい。また、本実施形態の溶融めっき方法では、めっき工程の前に、鋼板2に対して、従来よりも軽度の加熱処理および還元処理を行ってもよく、この場合、それらの両方の処理におけるエネルギー消費量を低減することができる。
本発明の一態様における溶融めっき方法では、上記測定周波数帯域は、上記基本周波数を含むとともに上記基本周波数の4倍以上の周波数幅であってもよい。例えば、上記測定周波数帯域は、10kHz以上90kHz以下であってもよい。
本発明の実施形態1における溶融めっき方法の一実施例について以下に説明する。
・超音波振動子11:本多電子製、ボルト締めランジュバン型振動子
・超音波ホーン10:材質<アルミ合金A2024A>
・発振器13:アジレント・テクノロジー(株)社製、33220A
・電力増幅器14:(株)メステック社製、M-2141
・電力計15:日置電機(株)社製、PW-3335
(超音波振動測定系統)
・導波棒51:材質<SUS430>、φ6mm×300mm
・AEセンサ52:(株)エヌエフ回路設計ブロック社製、AE-900M
・アンプ:(株)エヌエフ回路設計ブロック社製、AE9922
・スペクトラムアナライザ:アジレント・テクノロジー(株)社製、E4408B。
表1および表2に示す上記鋼板A~Fについて、それぞれ前処理としてアルカリ脱脂および10%塩酸を用いて酸洗処理を行った。前処理後の鋼板をそれぞれ超音波ホーン10の先端に取り付け、Zn-Al-Mg系の溶融めっき浴内に60mmの深さ(換言すれば、めっき浴の深さ方向における浴中に浸漬している鋼板の長さ)まで浸漬し、浸漬時間を100秒として、どぶ漬けめっきを行った。鋼板に振動を付与する場合、超音波ホーン10の先端に取り付けた鋼板を溶融めっき浴中へ浸漬開始してから10秒後に振動の付与を開始し、90秒間振動を付与した。
○:不めっき率が0%より大きく1%未満
△:不めっき率が1%以上10%未満
×:不めっき率が10%以上80%未満
××:不めっき率が80%以上。
溶融めっき浴としてAl-9質量%Si-2質量%Fe系めっき浴を用いて、表1および表2に示した各種の鋼板にどぶ漬けめっきを行った。溶融めっき浴の温度は630℃~700℃、溶融めっき浴への鋼板の浸漬時間は12秒とし、鋼板を振動させる場合、鋼板を溶融めっき浴中へ浸漬開始してから10秒後に振動の付与を開始し、2秒間振動を付与した。鋼板を振動させる場合、基本周波数は15kHzとし、超音波振動子11の出力を10Wまたは0.05W~0.3Wに変化させた。これら以外の条件は上記の例1-1と同様とした。試験の結果をまとめ、表4に示す。
溶融めっき浴として、実施形態3の実施例2(例2-3)に示す各種の溶融めっき浴を用いて、表1および表2に示した各種の鋼板A~Fにどぶ漬けめっきを行った。溶融めっき浴M1~M10の組成は実施例2の表8に示され、溶融めっき浴M12の組成は実施例2の表9に示されている。また、めっき浴種M11は、Al-2質量%Fe系めっき浴であり、浴温は700℃である(めっき浴種M11は、表4に示す試験にて用いたAl-9質量%Si-2質量%Fe系めっき浴と異なり、Siを添加していない)。
本発明の他の実施形態について、以下に説明する。なお、説明の便宜上、上記実施形態にて説明した部材と同じ機能を有する部材については、同じ符号を付記し、その説明を繰り返さない。
本発明の他の実施形態について、以下に説明する。なお、説明の便宜上、上記実施形態にて説明した部材と同じ機能を有する部材については、同じ符号を付記し、その説明を繰り返さない。
本実施形態における溶融めっき方法を実施する溶融めっき装置60について、図9を用いて説明する。なお、溶融めっき装置60は一例であって、本溶融めっき方法を実施する装置は、特に限定されるものではない。図9は、本実施の形態における溶融めっき方法を実施する溶融めっき装置60を示す概略図である。
本発明の実施形態3における溶融めっき方法の実施例について以下に説明する。本実施例では、上述の図9に示す溶融めっき装置60を用いた。
各種の鋼板にはそれぞれ前処理としてアルカリ脱脂処理を行った。溶融めっき浴として、前述の実施例1の例1-1におけるZn-Al-Mg系めっき浴、および実施例1の例1-2におけるAl-9%Si系めっき浴を用いた。溶融めっき部62における雰囲気を大気雰囲気、窒素雰囲気、3%水素-窒素雰囲気、または30%水素-窒素雰囲気に変化させた。ガス還元加熱帯61における雰囲気制御および加熱処理は行わなかった。溶融めっき浴への鋼板の浸漬時間は12秒とし、超音波ホーン10を用いて振動板70を振動させて溶融めっき浴中へ振動を付与する場合、鋼板を溶融めっき浴中へ浸漬開始してから10秒後に振動の付与を開始し、2秒間振動を付与した。振動板70を振動させる場合、基本周波数を15kHzとし、超音波振動子11の出力を30Wと、それぞれ一定にして、溶融めっき浴中へ振動を付与した。
ガス還元加熱帯61における雰囲気制御および加熱処理を行うとともに、鋼板を溶融めっき浴中へ浸漬開始してから2秒後に振動の付与を開始し、2秒間振動を付与したこと以外は上記の例2-1と同様にして、溶融めっきを行った。試験の結果をまとめ、表7に示す。
下記表8、表9に示す組成の溶融めっき浴を用い、溶融めっき部62における雰囲気を3%水素-窒素雰囲気としたこと以外は上記の例2-1と同様にして、溶融めっきを行った。めっき浴種M11は、Al-2質量%Fe系めっき浴、浴温は700℃である(めっき浴種M11は、表4に示す試験にて用いたAl-9質量%Si-2質量%Fe系めっき浴と異なり、Siを添加していない)。試験の結果をまとめ、表10に示す。
本発明の溶融めっき方法により製造された溶融めっき鋼板は、めっき層の表面に、耐食性および皮膜密着性を向上させる下地化成処理皮膜が形成されていてもよい。下地化成処理皮膜としては、無機系皮膜が好ましく、さらに具体的には、バルブメタルの酸化物または水酸化物と、バルブメタルのフッ化物とを含有するものが好ましい。ここで「バルブメタル」とは、その酸化物が高い絶縁抵抗を示す金属をいう。バルブメタル元素としては、Ti、Zr、Hf、V、Nb、Ta、MoおよびWから選ばれる1種または2種以上の元素が好ましい。また、下地化成処理皮膜は、可溶性または難溶性の金属リン酸塩または複合リン酸塩を含んでいてもよい。さらに、下地化成処理皮膜は、フッ素系、ポリエチレン系、スチレン系などの有機ワックス、または、シリカ、二硫化モリブデン、タルクなどの無機質潤滑剤などを含んでいてもよい。下地化成処理皮膜は、ウレタン樹脂、アクリル樹脂、エポキシ樹脂、オレフィン樹脂、ポリステル樹脂などをベースとする有機系皮膜であってもよい。
本発明の他の実施形態について、以下に説明する。なお、説明の便宜上、上記実施形態にて説明した部材と同じ機能を有する部材については、同じ符号を付記し、その説明を繰り返さない。
本実施形態における溶融めっき方法を実施する溶融めっき装置80について、図10を用いて説明する。なお、溶融めっき装置80は一例であって、本溶融めっき方法を実施する装置は、特に限定されるものではない。図10は、本実施の形態における溶融めっき方法を実施する溶融めっき装置80を示す概略図である。
本発明の実施形態5における溶融めっき方法の実施例について以下に説明する。本実施例では、上述の図10に示す溶融めっき装置80を用いた。
・超音波振動子11:hielscher社製、20kHz振動子
・接続部16(ブースター):材質<Ti>、増幅率2.2倍、1/2波長型、長さ126mm
・先端部17:材質<Ti>、1/2波長型、長さ250mm
・超音波電源装置D1:hielscher社製、20kHz、2kW電源
(超音波振動測定系統)
・導波棒51:材質<SUS430>、φ6mm×300mm
・AEセンサ52:(株)エヌエフ回路設計ブロック社製、AE-900M
・計測部53
アンプ:(株)エヌエフ回路設計ブロック社製、AE9922
スペクトラムアナライザ:アジレント・テクノロジー(株)社製、E4408B。
前記実施例1と同様に各種の鋼板A~F(表1および表2参照)を用いるとともに、溶融めっき浴として前記実施例1の例1-1におけるZn-Al-Mg系の溶融めっき浴を用いて、各種の条件にて溶融めっきを行った。
前記実施例1と同様に各種の鋼板A~F(表1および表2参照)を用いるとともに、溶融めっき浴として前記実施例1の例1-2におけるAl-9質量%Si-2質量%Fe系めっき浴を用いて、各種の条件にて溶融めっきを行った。
前記実施例1と同様に各種の鋼板A~F(表1および表2参照)を用いるとともに、溶融めっき浴として、実施形態3の実施例2(例2-3)に示す各種の溶融めっき浴を用いて、各種の条件にて溶融めっきを行った。
本発明の他の実施形態について、以下に説明する。なお、説明の便宜上、上記実施形態にて説明した部材と同じ機能を有する部材については、同じ符号を付記し、その説明を繰り返さない。
本実施形態における溶融めっき方法を実施する溶融めっき設備90Aについて、図11を用いて説明する。なお、溶融めっき装置90Aは一例であって、本溶融めっき方法を実施する装置は、特に限定されるものではない。図11は、本実施の形態における溶融めっき方法を実施する溶融めっき設備90Aの一例を示す概略図である。
図12は、一変形例の溶融めっき設備90Bおよび溶融めっき設備90Cを示す概略図である。
本発明の実施形態6における溶融めっき方法の実施例について以下に説明する。本実施例では、上述の図11に示す溶融めっき設備90Aを用いた。
・超音波振動子11:hielscher社製、20kHz振動子
・接続部16(アダプタ):材質<Ti>、1/2波長型、長さ126mm
・先端部17:材質<スーパーサイアロン>、2波長型、長さ500mm
・超音波電源装置D1:hielscher社製、20kHz、2kW電源
(超音波振動測定系統)
・導波棒51:材質<SUS430>、φ6mm×300mm
・AEセンサ52:(株)エヌエフ回路設計ブロック社製、AE-900M
・計測部53
アンプ:(株)エヌエフ回路設計ブロック社製、AE9922
スペクトラムアナライザ:アジレント・テクノロジー(株)社製、E4408B。
前記実施例1と同様に各種の鋼板A~F(表1および表2参照)を用いるとともに、Zn-Al-Mg系の溶融めっき浴またはAl-9質量%Si-2質量%Fe系めっき浴を用いて、各種の条件にて溶融めっきを行った。
スナウトの前段において、鋼帯に対して、大気雰囲気、窒素雰囲気、3%水素-窒素雰囲気、または30%水素-窒素雰囲気にて加熱処理を行ったこと以外は上記の例4-1と同様にして、連続式溶融めっきを行った。試験の結果をまとめ、表15に示す。
本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。
2A 鋼帯(金属材料)
20 溶融めっき浴(めっき浴)
Claims (2)
- 溶融金属であるめっき浴中に金属材料を進入させて、上記溶融金属に上記金属材料が接触している間に上記めっき浴中に振動を付与しつつ上記金属材料に上記溶融金属を被覆させるめっき工程を含み、
上記めっき浴に付与する上記振動の周波数を基本周波数として、
上記めっき工程では、上記めっき浴中にて測定される音響スペクトルが下記式(1)の関係を満たすように、上記振動を付与することを特徴とする溶融めっき方法。
(IB-NB)/(IA-NA)>0.2 ・・・(1)
(ここで、
IA:測定周波数帯域全体における音圧の平均値
IB:(i)上記基本周波数における音圧のピークと2倍音周波数における音圧のピークとの間、並びに、(ii)複数の倍音周波数における音圧のピークのうち隣り合うピーク間、の特定周波数帯域における音圧の平均値
NA:上記測定周波数帯域全体における、上記振動を付与していない場合の音圧の平均値
NB:上記IBに関して規定される上記特定周波数帯域における、上記振動を付与していない場合の音圧の平均値
である) - 上記めっき工程の前に、前処理として上記金属材料に脱脂処理または酸洗処理を実施することを特徴とする請求項1に記載の溶融めっき方法。
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CN201980071034.0A CN113166915A (zh) | 2018-11-06 | 2019-11-06 | 热浸镀方法 |
EP19881403.0A EP3878998A4 (en) | 2018-11-06 | 2019-11-06 | DIP COATING PROCESS |
MX2021004818A MX2021004818A (es) | 2018-11-06 | 2019-11-06 | Metodo de enchapado por inmersion en caliente. |
JP2019561340A JP6841349B2 (ja) | 2018-11-06 | 2019-11-06 | 溶融めっき方法 |
KR1020217016341A KR102548252B1 (ko) | 2018-11-06 | 2019-11-06 | 용융 도금 방법 |
US17/288,519 US11566315B2 (en) | 2018-11-06 | 2019-11-06 | Hot-dip plating method |
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EP4177363A4 (en) * | 2020-07-14 | 2023-07-05 | JFE Steel Corporation | DEVICE FOR CONTINUOUS ANNEALING, DEVICE FOR CONTINUOUS HOT GALVANIZING AND METHOD FOR MANUFACTURING A STEEL SHEET |
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- 2019-11-06 TW TW108140282A patent/TWI797393B/zh active
- 2019-11-06 CN CN201980071034.0A patent/CN113166915A/zh active Pending
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- 2019-11-06 WO PCT/JP2019/043455 patent/WO2020095940A1/ja active Application Filing
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JPS55100969A (en) * | 1979-01-23 | 1980-08-01 | Asahi Glass Co Ltd | Manufacture of hot galvanized metal plate |
JPS59145771A (ja) * | 1983-02-08 | 1984-08-21 | Sumitomo Electric Ind Ltd | 連続溶融めつき方法 |
JPH02125850A (ja) | 1988-11-02 | 1990-05-14 | Kawasaki Steel Corp | 連続溶融亜鉛めっき方法 |
JPH02282456A (ja) | 1989-04-21 | 1990-11-20 | Nisshin Steel Co Ltd | 金属帯の超音波照射連続溶融めっき法 |
JPH03229849A (ja) * | 1990-02-05 | 1991-10-11 | Furukawa Electric Co Ltd:The | Al又はAl合金線棒管材の表面被覆方法 |
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EP4177363A4 (en) * | 2020-07-14 | 2023-07-05 | JFE Steel Corporation | DEVICE FOR CONTINUOUS ANNEALING, DEVICE FOR CONTINUOUS HOT GALVANIZING AND METHOD FOR MANUFACTURING A STEEL SHEET |
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CN113166915A (zh) | 2021-07-23 |
KR102548252B1 (ko) | 2023-06-27 |
WO2020095940A1 (ja) | 2020-05-14 |
JP6841349B2 (ja) | 2021-03-10 |
US11566315B2 (en) | 2023-01-31 |
EP3878998A1 (en) | 2021-09-15 |
TWI797393B (zh) | 2023-04-01 |
KR20210080544A (ko) | 2021-06-30 |
TW202028492A (zh) | 2020-08-01 |
MX2021004818A (es) | 2021-06-15 |
TW202033792A (zh) | 2020-09-16 |
US20210388477A1 (en) | 2021-12-16 |
EP3878998A4 (en) | 2022-06-01 |
JP6841348B2 (ja) | 2021-03-10 |
JPWO2020095940A1 (ja) | 2021-02-15 |
JPWO2020095939A1 (ja) | 2021-02-15 |
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