JP4533223B2 - How to make hot-dip galvanized steel sheet and alloyed hot-dip galvanized steel sheet separately in the same bath - Google Patents

Description

  The present invention relates to a method for producing a hot-dip galvanized steel sheet and an alloyed hot-dip galvanized steel sheet by the pre-Ni method, and more specifically, hot-dip galvanized steel sheet and alloyed hot-dip zinc in the same bath without adjusting the bath of the hot-dip plating bath. The present invention relates to a method for separately producing plated steel sheets.

Hot-dip galvanized steel sheet (hereinafter abbreviated as “GI”) and alloyed hot-dip galvanized steel sheet (hereinafter abbreviated as “GA”) are both used for automobiles, home appliances, building materials, etc. Manufactured. In either case, Al is added to the hot dip galvanizing bath.
Al forms an alloy layer at the base iron interface, and in the case of GI, it plays an important role of suppressing the formation of Fe-Zn intermetallic compounds that are inferior in workability and controlling alloying in GA. ing.

  Here, when manufacturing GI, Al is normally used at a concentration of about 0.14% or more. This is to ensure adhesion of the hot dip galvanized film. On the other hand, in the case of GA, Al is usually about 0.11% or less. This is because when Al is high, alloying is too delayed, so it is necessary to increase the alloying time by lowering the plate passing speed, or to increase the furnace length, which is not acceptable in terms of manufacturing cost. .

  As described above, since the optimum Al concentration differs between GI and GA, bath concentration adjustment is required each time an attempt is made to make the same equipment separately. That is, when shifting from GI manufacturing to GA manufacturing, it is necessary to lower the Al concentration. In this case, a method of pumping a part of the bath and replacing it, a method of passing through a conditioner or a material whose quality requirements are not strict, and waiting for a gradual decrease in Al are taken. Time is required and the manufacturing cost increases.

  Patent Document 1 discloses a method of reducing the transition time by adding a predetermined concentration of Ni to a bath and recovering Al as Ni-Al-based dross. There is no change in the necessity of this work, and there is a concern about quality defects due to dross that could not be recovered.

On the other hand, when shifting from GA production to GI production, if Al is additionally added, the Al concentration can be easily increased in a short time. However, in this case, there is a problem that the so-called bottom dross of ZnFe type generated at the time of GA production reacts with Al and the so-called top dross of FeAl type rapidly increases. For this reason, it is difficult to increase the Al concentration rapidly from the viewpoint of quality, resulting in an increase in manufacturing cost due to an increase in work time.
As described above, when manufacturing GI and GA with the same equipment, making them separately in the same bath without the need for adjusting the bath concentration has not been put into practical use in spite of the great merit.

By the way, the manufacturing method of GI or GA by the pre Ni method which this invention makes object is disclosed by patent documents 2-5. Although both of these provide guidelines for the production of GI or GA alone, the GI and GA can be produced in substantially the same bath without adjusting the bath of the hot dipped bath, which is the object of the present invention. The knowledge about the method of dividing is not disclosed, and there is no knowledge about the method of separately making GI and GA in the same bath while satisfying strict quality requirements in recent appearance and workability.
Japanese Patent No. 2978947 Japanese Patent Publication No.46-19282 Japanese Patent Publication No.61-9386 Japanese Patent No. 2517169 Japanese Patent No. 2784352

  An object of the present invention is to provide a method of separately producing GI and GA of good quality in the same bath without adjusting the bath of the hot dipping bath by the pre-Ni method.

  As a result of the study by the present inventors, if the pretreatment, bath Al concentration, pre-Ni deposition amount, alloying conditions, etc. are optimized using the pre-Ni method, the quality can be maintained in the same bath without adjusting the bath. It was found that good GI and GA can be made separately.

That is, the gist of the present invention is as follows.
(1) After degreasing and pickling treatment on a cold rolled and annealed ultra-low carbon steel plate, Ni pre-plating is performed, and a plate temperature of 430 to 500 ° C. in a non-oxidizing or reducing atmosphere is 30 ° C./sec or more. In the method of hot-plating in a Zn plating bath after rapid heating at a rate of temperature increase, the Al concentration in the Zn plating bath is 0.14 to 0.2% by mass,
1) When manufacturing a hot dip galvanized steel sheet, the Ni pre-plating amount is set to 0.05 to 0.3 g / m ^2, and no reheating treatment is performed after hot dipping and wiping or a heat treatment at 450 ° C. or less is performed.
2) When producing galvannealed steel sheet, the amount of Ni pre-plating is 0.2-2.0 g.
/ m ² , after hot dipping and wiping, rapidly heat to 470-600 ° C. at a temperature rising rate of 30 ° C./sec or more, and cool without taking a soaking time, or keep soaking for less than 15 seconds After cooling,
A method of separately producing a hot-dip galvanized steel sheet and an alloyed hot-dip galvanized steel sheet in the same hot-dip galvanizing bath .
(2) when producing the alloyed hot-dip galvanized steel sheet is characterized in that Ni Puremekki weight of 0.2 to 1.0 g / m ^2, the same galvanizing bath according to (1) The method of making galvanized steel sheet and galvannealed steel sheet separately.
(3) The ultra-low carbon steel sheet that has been cold-rolled and annealed is an Nb- and Ti-added ultra-low carbon steel sheet, and is melted in the same hot-dip galvanizing bath as described in (1) or (2) above A method of making a galvanized steel sheet and an alloyed hot-dip galvanized steel sheet separately.

  According to the pre-Ni method of the present invention, it is possible to separately produce GI and GA of good quality in the same bath without adjusting the bath of the hot dipping bath. In this method, not only the working time can be shortened, but also there is no increase in dross accompanying the bath adjustment, so that quality defects caused by dross can be greatly reduced.

The present invention is described in detail below.
The steel plate as the plating original plate in the present invention is a cold-rolled and annealed ultra-low carbon steel plate .
First, it is necessary to clean the surface of the steel sheet and remove the dirt and oxide film on the surface. If this treatment is inadequate, the subsequent Ni pre-plating will be non-uniform, and in the case of GI production, alloying will partly progress and adhesion will deteriorate, and in the case of GA production, appearance unevenness and alloying will occur. Unevenness may occur.

As the cleaning treatment, it is necessary to carry out a degreasing treatment with an alkaline aqueous solution and a pickling treatment with an acid aqueous solution in this order. As the degreasing treatment with an alkaline aqueous solution, any of spraying, dipping, electrolysis and the like can be used, and it can be used in combination with mechanical degreasing such as a brush.
As the pickling treatment, any of spraying, dipping, electrolysis and the like can be used using an aqueous solution of sulfuric acid, hydrochloric acid or the like. After the pickling treatment, it is desirable to perform the next Ni pre-plating without washing and drying.

In the present invention, it is necessary to make the range of the Ni pre-plating amount different between GI and GA. First, in GI production, the Ni pre-plating amount is set to 0.05 to 0.3 g / m ² . If it is less than the lower limit, the wettability of the plating is insufficient and the appearance of the plating becomes abnormal. If the upper limit is exceeded, partial alloying proceeds at the interface of the ground metal plating, resulting in loss of plating adhesion and appearance uniformity.
Further, the preferable range of the Ni pre-plating amount is slightly different depending on the type of the original plate, its surface condition, the above-mentioned surface cleaning treatment conditions, and the like. In an ultra-low carbon steel sheet that has been cold-rolled and annealed, alloying at the iron-plating interface is more likely to proceed, so the upper limit of the Ni pre-plating amount is 0.3 g / m ² .

Next, in the GA production, the Ni pre-plating amount is set to 0.2 to 2.0 g / m ² . If it is less than the lower limit, alloying is insufficient, and if it exceeds the upper limit, plating adhesion deteriorates. Also in this case, the preferable range of the Ni pre-plating amount is slightly different depending on the type of the original plate and the surface state thereof, the conditions for the surface cleaning treatment described above, and the like in the cold rolled and annealed ultra-low carbon steel plate. 1.0 g / m ² is desirable. This depends on the Al concentration in the hot dip galvanizing bath later, but if it exceeds 1.0 g / m ² , the Γ layer after alloying tends to increase and the plating adhesion deteriorates.

The conditions for Ni pre-plating are not particularly limited, and plating may be performed by a known method such as a sulfuric acid bath or a watt bath.
After the Ni pre-plating, rapid heating is performed at a temperature increase rate of 30 ° C./sec or more at a plate temperature of 430 to 500 ° C. in a non-oxidizing or reducing atmosphere. This treatment is necessary in order to ensure wettability of the molten plating and plating adhesion. In addition, the upper limit of a temperature increase rate is not specifically limited.

As the hot dip galvanizing bath, a bath composed of Al: 0.14 to 0.2%, unavoidable impurities, and the balance Zn is used. If Al is less than the lower limit, quality will be poor during GI production, and if it exceeds the upper limit, alloying in GA production will be significantly delayed. In particular, steel sheets to which P or the like is added are slow to alloy, making it impossible to produce GA. If it is in the range of Al: 0.14 to 0.2%, GI and GA can be produced in the same bath.
Here, the same bath means that there is no need to positively adjust the bath concentration when switching from GI to GA, or from GA to GI, and the bath concentration changes as a result of the passage of time. However, in the meantime, if the bath concentration is not adjusted, the same bath is used.

  After plating, after adjusting the basis weight by wiping, alloying is performed in the case of GA production. In the case of GI production, the alloying treatment is naturally not performed. However, when heating is unavoidable due to equipment restrictions (furnace controllability), the quality is not affected at temperatures up to 450 ° C. In the alloying process of GA, in order to ensure high plating adhesion, rapid heating is performed at a temperature increase rate of 30 ° C./sec or more to 470 to 600 ° C., and cooling is performed without taking a soaking time, or 15 It is necessary to cool after soaking for less than a second. In addition, the upper limit of a temperature increase rate is not specifically limited.

Hereinafter, the present invention will be described in detail by way of examples.
Table 1 shows the components of the original plate used in the test. Here, cold-rolled and annealed materials were used. As a pretreatment Ni Puremekki, after performing the processing by the conditions shown in Table 2 or Table 3, electroplating (bath temperature 60 ° C., a current density of 30A / dm ²⁾ at the plating bath shown in Table 4. Ni Puremekki at I did it.

After that, it is heated to 450 ° C. in a 3% H ₂ + N ₂ atmosphere at a heating rate of 50 ° C./sec, immediately immersed in a molten Zn plating bath kept at 450 ° C., held for 3 sec, and then wiped to form. Adjusted. In the case of GI, alloying was not performed, and in the case of GA, alloying was performed immediately above the wiping at a predetermined heating rate, temperature, and soaking time. The cooling was performed by slow cooling at 2 ° C./sec for 10 seconds and then rapidly cooling at 20 ° C./sec. Both GI and GA were temper rolled at 0.5%.

Table 5 shows sample manufacturing conditions. In Examples 1 to 4, 6 to 9, and Comparative Examples 1 to 5, the Al concentration in the plating bath was set to 0.16%. In Examples 11 , 12, and 14, the Al concentration was 0.14%. In Examples 15 to 18 and Comparative Example 6, the Al concentration was 0.2%. In Comparative Example 7, the Al concentration was 0.11%, and in Comparative Examples 9 and 10, 0.25%.

The results of performance evaluation for each sample are also shown in Table 5. The performance evaluation was performed as follows.
(1) Plating appearance (common to GI and GA): Visually observed and evaluated as “◯” for those with no defects such as non-plating, “△” for certain, and “×” for severe. In addition, even if the unevenness is so small that it is not noticeable at the time of plating, it may come out after coating, so trication conversion treatment for automobiles (SD5000 manufactured by Nippon Paint Co., Ltd.), cationic electrodeposition coating (Nippon Paint) Co., Ltd. PN120M: 20 μm) was applied and the appearance was similarly evaluated. Table 5 shows the evaluation of plating appearance, which is the worse of the evaluations without coating and after coating.
(2) Adhesion (GI evaluation): A ball impact test was conducted with a ball diameter of 1/2 inch and an overhang of 5 mm. Five-point evaluation was performed, and the rating 5 (no peeling) was evaluated as “◯”, the scores 3 to 4 as “Δ”, and the scores 1 and 2 as “x”.

(3) Degree of alloying (GA evaluation): The plating layer was dissolved in hydrochloric acid, and the Fe% in the plating layer was determined by wet chemical analysis. The case where 9% to 12% of Fe% was obtained was indicated by “◯”, and otherwise “x”.
(4) Adhesion (GA evaluation): Using a sample coated with rust-preventive oil, a 40 mmφ cylindrical press (drawing out) was performed under the condition of a drawing ratio of 2.2, and the side surface was taped off and blackened. Rated by degree. The degree of blackening of 0 to less than 20% was evaluated as “◯”, the degree of less than 20 to 30% was evaluated as “Δ”, and 30% or more was evaluated as “x”.

  As described above, those within the scope of the present invention have excellent characteristics, and GI and GA can be produced in the same bath without bath adjustment.

The present invention is extremely effective when GI and GA are separately produced in the same equipment. Particularly in line with the thermal control of a good alloying furnace such as an induction heater, even possible and will be produced GI and GA alternately, you can shorten the manufacturing chance constraints eliminates the working time. Furthermore, since there is no increase in dross accompanying current bath adjustment, quality defects due to dross can be greatly reduced. Thus, it is very useful industrially.

Claims (3)

After degreasing and pickling treatment on a cold rolled and annealed ultra low carbon steel plate, Ni pre-plating is performed, and the temperature rise rate is 30 ° C./sec or more at a plate temperature of 430 to 500 ° C. in a non-oxidizing or reducing atmosphere. In the method of performing hot plating in a Zn plating bath after rapid heating in step 1, the Al concentration in the Zn plating bath is 0.14 to 0.2% by mass,
1) when producing the galvanized steel sheet, the Ni Puremekki amount with 0.05~ 0.3 g / m ^2, subjected to hot-dip plating, or not a reheating treatment after wiping, or 450 ° C. or less heat treatment ,
2) When producing galvannealed steel sheet, the amount of Ni pre-plating is 0.2-2.0 g.
/ m ² , after hot dipping and wiping, rapidly heat to 470-600 ° C. at a temperature rising rate of 30 ° C./sec or more, and cool without taking a soaking time, or keep soaking for less than 15 seconds After cooling,
A method of separately producing a hot-dip galvanized steel sheet and an alloyed hot-dip galvanized steel sheet in the same hot-dip galvanizing bath. When producing alloyed hot-dip galvanized steel sheet, the Ni pre-plating amount is 0.2 to 1.0 g.
characterized in that it is a / m ^2, a method of dividing build galvanized steel sheets and alloyed hot-dip galvanized steel sheets under the same galvanizing bath according to claim 1.   The cold-rolled and annealed ultra-low carbon steel sheet is an Nb- and Ti-added ultra-low carbon steel sheet and alloyed with a hot-dip galvanized steel sheet in the same hot-dip galvanizing bath according to claim 1 or 2. A method for making hot-dip galvanized steel sheets.