• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 法律状态
  • 优先权
    • 专利摘要:
    In the present invention, in order to maintain uniform appearance quality of the electrogalvanized steel sheet produced from the chloride bath, the organic additive in the plating solution is developed with a color developing agent, and then the absorbance at a specific wavelength is measured. It relates to a method for quantifying organic additives. In the present invention, in particular, when polyethylene glycol is used as the organic additive, first, a mixed solution of ferric chloride and thiocyanate is added to the plating solution to develop color, extract the organic layer colored with 2-ethylene chloride, and then absorbance at a specific wavelength. Indirectly quantify the concentration of the organic additive. According to the method of the present invention, the time required for the analysis of the concentration of the organic additive is greatly shortened and the accuracy is improved, and thus it is possible to measure and adjust the concentration of the organic additive at any time during the electrogalvanizing operation, thereby producing a chloride bath. The appearance quality of the galvanized steel sheet can be greatly improved.
    公开号:KR20020022255A
    申请号:KR1020000054958
    申请日:2000-09-19
    公开日:2002-03-27
    发明作者:김영근；김종호；정진환；유승준
    申请人:이구택；포항종합제철 주식회사；
    IPC主号:
    专利说明:

    Quantitative Method of the Organic Additives in Chloride Bath
    [5] The present invention relates to a method for quickly and accurately quantitating the concentration of an organic additive in a chloride-based galvanized electrolytic solution used in the manufacture of galvanized steel sheet, and more particularly, to maintain uniform appearance quality of the galvanized steel sheet produced from a chloride bath. To this end, the present invention relates to a method for quantitating an organic additive in a chloride-based zinc electrolytic solution, characterized by measuring the absorbance at a specific wavelength after developing an organic additive, particularly polyethylene glycol, in a plating solution with a color developing agent.
    [6] Electro-galvanized steel sheet has been used for household appliances or automotive steel plates for a long time because of its beautiful surface and excellent sacrificial anticorrosion ability. Zinc chloride bath and zinc sulfate bath are mainly adopted in the manufacture of galvanized steel sheet. Zinc chloride bath has the advantage of large electrical conductivity of solution compared to zinc sulfate bath, which greatly reduces the power cost. Therefore, the crystal grain of the plating layer is coarse, and the crystal surface has a characteristic that the base surface (0002) is preferentially oriented. Therefore, the plated steel sheet obtained from a zinc chloride bath surface brightness is high, but the gloss is poor, because it is a disadvantage that the coating layer hardness of the steel sheet scratching (scratch) caused well in handling low, usually as a main component the polyethylene glycol in order to compensate, A small amount (0.1 to 3.0 ml / l) of an organic additive containing a small amount of benzoic acid is added to the plating liquid. The organic additive is adsorbed on the surface of the steel sheet, which is the cathode during the precipitation reaction, thereby inhibiting the reduction reaction of the ions, thereby inhibiting the growth of the crystals and preventing the growth of the base surface, resulting in fine grains and irregular crystal surfaces.
    [7] At this time, since the surface appearance of the plating layer and the physical properties of the plating layer are determined according to the amount of the organic additive added, proper concentration control of the additive is very important for appearance quality control of the galvanized steel sheet. 1 is a graph showing the effect of the organic additive concentration in the plating solution on the whiteness of the plating surface, it can be seen that the whiteness decreases as the additive concentration increases. On the other hand, Figure 2 is a graph showing the effect of the concentration of the organic additive in the plating solution on the hardness of the plating layer, the hardness of the plating layer increases as the additive concentration is increased, the hardness tends to decrease rather than 0.5ml / ℓ or more.
    [8] As such, since the concentration of the organic additive in the plating liquid determines the surface appearance of the galvanized steel sheet, the concentration of the organic additive should be measured quickly while minimizing an analytical error. However, until now, the weight of the beaker is directly measured by the human hand, and the organic additive in the plating solution is repeatedly extracted from the beaker with chloroform, the chloroform is evaporated, and the weight of the organic additive remaining in the beaker is measured manually. Because of the various steps, the analysis error reaches 50% and when the analysis results are transferred to the plating work, it is already a long time of more than 6 hours, so that the uniform surface quality of the electroplated steel sheet could not be obtained. The left bar graph of Figure 3 shows the difference in whiteness between the coils working while adjusting the concentration by analyzing the concentration of the organic additive in the plating solution once every six hours by the conventional extraction weight method, it can be seen that the difference in whiteness between the coils is about 5 have. Therefore, a great deal of dissatisfaction has been raised from the demands, and it is acting as an important problem of not having an advantage even in competition with other products.
    [9] Accordingly, the present invention has been made to solve the above problems, an object of the present invention is to add an organic additive in the chloride-based electro-zinc plating solution to obtain an electro-galvanized steel sheet having a uniform surface appearance and excellent plating layer properties from the chloride bath In particular, the present invention provides a method for quickly and accurately quantifying the concentration of polyethylene glycol.
    [1] 1 is a graph showing the effect of the organic additive concentration in the plating solution on the whiteness of the plating surface.
    [2] 2 is a graph showing the effect of the concentration of the organic additive in the plating solution on the hardness of the plating layer.
    [3] Figure 3 is a bar graph showing the difference in whiteness (δL) between the coils produced by analyzing the concentration of the organic additive in the plating solution by the conventional extraction weight method and ultraviolet-visible light spectroscopy of the present invention, respectively.
    [4] 4 is a calibration curve for absorbance at 510 nm for each organic additive concentration in a plating solution.
    [10] Hereinafter, the present invention will be described in detail.
    [11] In order to achieve the above object, the method of quantifying the organic additives in the chloride-based zinc electroplating solution of the present invention is to first develop a plating solution containing an organic additive with a colorant, extract the colorant organic layer, and then measure the absorbance of the extracted organic layer to a specific wavelength. It is characterized by indirectly quantifying the concentration of the organic additive by measuring in.
    [12] Since certain materials absorb only light of a specific wavelength, most organic materials can be easily quantified using conventional ultraviolet-visible spectroscopy (hereinafter referred to as "UV method"). When organic matters are dissolved in water, as in zinc plating solutions, absorbance analysis of pure organic matters is impossible because water and organic absorption wavelengths overlap each other. However, in the present invention, first, the organic material to be quantified is developed, and then the absorbed color is measured by extracting and separating the colored organic layer. Therefore, it is possible to quickly and accurately analyze the concentration of the organic additive in the plating solution every 30 minutes and the analysis error is 3%. Lowers within. As a result, the difference in whiteness between the coils produced from the chloride bath can be reduced to 1 or less (see FIG. 3). Hereinafter, the method for quantifying the organic additive, particularly polyethylene glycol, in the chloride-based zinc electrolytic solution of the present invention will be described in detail.
    [13] An aliquot of a zinc chloride solution containing polyethyleneglycol as an organic additive was added at different concentrations, and then, 5 ml of a mixed solution of ferric chloride and thiocyanate were added, followed by coloring. After 20 ml of ethylene were mixed, the organic layer was separated by centrifugation, and then the absorbance at 510 nm was measured to obtain a calibration curve. Subsequently, after 1 ml of the zinc-based zinc plating solution to be analyzed and color development and extraction are carried out in the same manner as above, the absorbance at 510 nm is measured and substituted into the calibration curve to confirm the concentration of the organic additive.
    [14] The content of ferric chloride in the mixed solution of ferric chloride and thiocyanate used as a coloring agent is 0.5 to 3.0 mol, and the thiocyanate is potassium, ammonium, sodium, calcium, lithium, magnesium, aluminum or barium Any salt is preferable, but the content thereof should be 0.05 to 1.0 mole relative to ferric chloride in molar ratio. The reason for limiting the content of ferric chloride as described above is that if the content of ferric chloride is 0.5 mol or less, sufficient color cannot be exhibited. . In addition, the reason for limiting the content of thiocyanate as described above is that if the content of thiocyanate is 0.05 mole or less or 1.0 mole or more in a molar ratio of ferric chloride, the color can not be measured by the UV method. to be.
    [15] Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples according to the gist of the present invention.
    [16] Example 1
    [17] A conventional organic additive containing polyethylene glycol as a main component was divided into 1 ml each of four chloride-based electro zinc plating solutions added at concentrations of 0, 1, 2, and 3 ml / l, and ferric chloride and thiocyanate 5 ml of each of the color developing agents mixed in a molar ratio of 1: 0.5 was added thereto, and 20 ml of 2-ethylene chloride was mixed thereto. Subsequently, the organic layer was separated by a centrifugal separator, and then absorbance at 510 nm was measured to prepare a calibration curve (see Fig. 4). As can be seen in Figure 4, as the concentration of the organic additive in the plating solution increases the absorbance was shown to increase proportionally, the analysis accuracy was nearly 100%, the time required for analysis was possible within 10 minutes.
    [18] Several calibration curves were prepared by the same method as above except that the concentrations of organic additives were different. Only 3% of the additives were found to be less than 0.05 ml / l. Accuracy of over% was shown.
    [19] Example 2
    [20] Electro zinc plating was performed with the plating solution under the conditions as shown in Table 1 below.
    [21] TABLE 1
    [22] Zn 2+ concentration70 to 90 g / l Cl - concentration210 to 230 g / l Organic additive management concentration0.1 to 0.3 ml / l Solution temperature57 to 63 ° C Solution pH5 to 6
    [23] At this time, the specimen of electro-galvanized steel sheet when working with the concentration of the organic additive mainly composed of polyethylene glycol every 8 hours by the conventional extraction weight method and analyzed every 1 hour by the UV method of the present invention The results of conducting the surface analysis by collecting one minute each week one coil each day are shown in Table 2 below.
    [24] TABLE 2
    [25] Analysis methodAnalysis dateGlossinessWhitenessPlating layer hardness Extraction gravimetric methodDay 13.588.549 Day 25.890.075 Day 36.287.468 Day 44.685.055 Day 52.688.377 Day 63.086.763 Day 77.084.965 UV methodDay 15.687.470 Day 25.787.072 Day 35.387.875 Day 46.288.074 Day 55.988.272 Day 65.087.973 Day 76.087.769
    [26] In order to analyze the surface of the coated steel sheet, the glossiness was measured with a glossmeter and the whiteness was measured with a color difference meter, and the hardness of the plated layer was measured with a Knoop hardness at a load of 2 g using an ultra-micrometer.
    [27] As can be seen in Table 2, when working while analyzing the concentration of the organic additives in the conventional extraction weight method, the gloss exhibits a two-fold deviation in the range of 3.5 to 7.0, the whiteness to 84.9 to 90.0, and the coating layer hardness is The deviation of Hk 20 or more is shown by Hk 49-77. In contrast, when the organic additive concentration was analyzed by the UV method of the present invention, glossiness 5.0 to 6.2, whiteness 87.0 to 88.2, and hardness represented Hk 69 to 75, maintaining a uniform surface appearance with almost no quality deviation. It can be seen that. Figure 3 shows the difference in the whiteness of the coils produced while managing the organic additive concentration by the extraction weight method and the UV method, respectively, it can be seen that the difference in whiteness between the coils is significantly reduced when the UV method of the present invention is applied.
    [28] As described in detail above, according to the method for quantifying the organic additive in the chloride-based zinc electrolytic solution of the present invention, the time required for the analysis of the concentration of the organic additive is greatly shortened and the accuracy is improved. Since it is possible to measure and adjust the concentration, it is possible to uniformly maintain the surface appearance of the galvanized steel sheet, especially the anti-fingerprint steel sheet produced from the chloride bath, and the physical properties of the plating layer.
    权利要求:
    Claims (4)
    [1" claim-type="Currently amended] A method of quantifying an organic additive in a chloride-based zinc oxide solution comprising the step of developing a chloride-based zinc oxide solution containing an organic additive with a colorant, extracting the colored organic layer with an organic solvent, and then measuring the absorbance of the extracted organic layer.
    [2" claim-type="Currently amended] The method of claim 1,
    The organic additive is a polyethylene glycol as a main component, the coloring agent is a mixed solution of ferric chloride and thiocyanate, the organic solvent is a two-ethylene chloride, characterized in that the organic additive in the electrolytic zinc plating solution .
    [3" claim-type="Currently amended] The method of claim 2,
    The content of ferric chloride in the mixed solution of ferric chloride and thiocyanate is 0.5 to 3.0 moles, and the content of thiocyanate is 0.05 to 1.0 mole compared to ferric chloride. Method of quantifying organic additives in water.
    [4" claim-type="Currently amended] The method of claim 2,
    The thiocyanate is a salt of potassium, ammonium, sodium, calcium, lithium, magnesium, aluminum or barium.
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    同族专利:
    公开号 | 公开日
    KR100474418B1|2005-03-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-09-19|Application filed by 이구택, 포항종합제철 주식회사
    2000-09-19|Priority to KR20000054958A
    2002-03-27|Publication of KR20020022255A
    2005-03-08|Application granted
    2005-03-08|Publication of KR100474418B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR20000054958A|KR100474418B1|2000-09-19|2000-09-19|Quantitative Method of the organic additives in chloride bath|
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