KR900002160B1 - Method of thermal diffusion alloy plating for steel wire - Google Patents

Abstract

A method of continuously electrolytical coating of steel wire with alloys consists of coating the wire with at least two different metals in two different electrolytic processes and then subjecting the coated wire to a thermal diffusion stage. To control the amount of each metal in the coating and coating compsn. gradient or orientation the X-ray characteristic of each metal is established by an energy distribution X-ray fluorescent analyser which via a computer converts any deviation from an optional value into a control signal which is specifically fed to the two baths and/or the thermodiffusion device to alter the electrolytic current and/or the diffustion heat values.

Description

Thermal Diffusion Alloy Plating Method on Ship Body

1 is a schematic diagram of a manufacturing process of Example (1).

(A) (b) is a correlation chart which shows the analytical curve of the fluorescence X-ray analysis in the brass plating plated with Fe.

Fig. 3 (a) is a correlation diagram showing a result of fluorescence X-ray analysis by the amount of heating in thermal diffusion brass plating on a steel wire.

(B) X-ray analysis diagram which shows the change of the alloy state of the plating in 3rd (a), respectively.

4A is a correlation diagram showing the distribution of plating composition ratio according to Example (1).

Fig. 4 (b) is a correlation diagram showing the distribution of plating composition ratio by the conventional method.

5 is a schematic view of the manufacturing process of Example (2).

6 (a) is a correlation diagram showing the distribution of the diffusion state according to the embodiment (2).

6 (b) is a correlation diagram showing a distribution of diffusion states by a conventional method.

7 is a schematic view of the manufacturing process of Example (3).

8 is a schematic view of the manufacturing process of Example (4).

9 is a correlation diagram showing the relationship between the amount of diffused heating and the characteristic X-ray intensity ratio.

10 is a curve diagram showing composition gradients of the inside and outside of plating.

11 is an X-ray analysis showing the degree of diffusion and the change of alloy state.

Fig. 12 (a) is a correlation diagram showing the relationship between the Cu concentration and the adhesiveness and freshness of rubber.

Fig. 12 (b) is a correlation diagram showing the relationship between the amount of diffused heating and the adhesiveness and freshness of rubber.

* Explanation of symbols for main parts of the drawings

5: thermal diffusion device 6: energy dispersive X-ray analyzer

7: current control device 10: microcomputer

11: ship body 13: thermal diffusion control device

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for plating a thermal diffusion alloy onto a wire body in which a thermal diffusion alloy is plated by continuously plating two or three or more different metals on a wire body in a two-layer or multi-layer shape and then thermally diffusing.

In the case of conventional alloy plating consisting of two or three or more metals on a linear body, alloy plating is formed by thermally diffusing the metals of the linear body in a layered order one after another. However, in the above-described method, the plating deposition rate and plating alloy composition ratio (alloy plating constituted by the plating current efficiency, diffusion voltage, and current change such as the change of the concentration of the plating liquid, the change of the plating voltage, the reduced state of the electrode, the state of the electrode plate, etc. There is an error in the weight ratio (%) of the various metals to be made or the plating composition gradient (the degree of change in the alloy composition ratio between the inside and outside of the alloy plating), so that the target alloy plating has a good precision or a length with respect to the ship body. It was very difficult to get uniform in the long direction. Particularly in the case of a ship body used for rubber reinforcement such as automobile tires or conveyor belts, the strength and adhesion to rubber are required as the most important quality, and the precision required for this type of alloy plating is extremely strict. .

In other words, the alloy plating on the linear body is strictly limited in the amount of plating adhesion and the composition of the plating alloy (for example, the weight ratio between Cu and Zn) under the influence of the adhesiveness with the rubber, and the value is subtly depending on the type of rubber. It is changing.

In order to make this adhesion better, the present condition has been required to make the composition ratio incline (composition inclination) by showing a change in the inside (center side) and the outside (outer side) of alloy plating. . In addition, these coating weights, plating alloy composition ratios, and plating composition inclinations do not affect the kind of rubber, and the same degree of rubber is affected by the state in which they are used.

For example, when used at a high temperature, the composition gradient is greatly affected, and for moist, the composition ratio is greatly affected.

Therefore, there is a problem that the plating adhesion amount, the plating alloy composition ratio, and the plating composition gradient must be combined in order to obtain the desired alloy plating depending on the type of rubber, its use, and the like.

Moreover, these precisions greatly influence the freshness in the drawing process performed after alloy plating.

In particular, the plating alloy composition ratio is a problem related to disconnection in the drawing process.

In response to such a requirement, the conventional method of obtaining the desired coating weight, plating alloy composition ratio or plating composition inclination with good accuracy and uniformly in the longitudinal direction with respect to the linear body is actually performed by the thermally diffusion alloy plated linear body. A part of the sample is cut for analysis, and the cut sample is used for various analyzes such as atomic absorption or fluorescence X-ray method, and the plating current in the plating tank for various metal platings according to the analysis result obtained therefrom. By modifying the value, an alloy plating having a desired plating deposition amount and plating composition ratio is obtained. Alternatively, in order to uniformly obtain a desired compositional test, a predetermined amount of heat is given to the ship body to maintain a constant diffusion temperature of the ship body, so that a current flows directly through the ship body to increase the temperature by Joule heating. Indirect heating method by the method or the passage inside a diffusion furnace is performed.

However, even when a predetermined amount of heat is obtained to obtain a desired composition gradient, the temperature of the ship body itself does not rise to a predetermined temperature, or a change in heating amount, a change in retention time of the temperature rise, or a layer of metal composed of an alloy component. There was a drawback that the composition gradient remarkably changed depending on the variation in the thickness of the state and the metal weight ratio.

As described above, it is sufficient to sample and analyze as much as possible to continuously obtain a uniform linear body of alloy plating accuracy, but there is a drawback that it is not practical when continuity is required such as the linear body.

Moreover, even if it is going to manufacture the brass plating steel wire of 65% of Cu density | concentration by the conventional method mentioned above, it is a limit to suppress as much as 62-68%, and it was inevitable to generate the error of +/- 3% in Cu concentration. .

However, the relationship between the Cu concentration (Cu / Cu + Zn × 100 (weight ratio)) and the adhesiveness and freshness of the rubber is as shown in FIG. 12 (a).

Rubber adhesion after the adhesion test in this figure indicates the amount of rubber adhering to the surface of the steel wire after leaving the copper plated steel wire by thermal diffusion for 2 weeks at 80 ° C 95% RH. Moreover, the relationship between the diffusion heating amount and the adhesiveness and freshness of the rubber when the Cu concentration can be made constant is as shown in FIG. 12 (b).

In this figure, the rubber adhesion after the adhesion test indicates the amount of rubber adhering to the surface of the steel wire by leaving it at 80 ° C 95 RH for two weeks after drawing the Cu concentration 65% brass plated steel wire.

As is apparent from each of the above drawings, the adhesiveness to rubber and freshness are in the opposite relationship, and an error of ± 3% in Cu concentration as in the conventional method is produced. If you can't do that, you know the cause

In such a method of thermal diffusion alloy plating on a linear body, it is important to manage the plating deposition amount, the plating alloy composition ratio, and the plating composition gradient to reduce the error thereof.

According to the present invention, when the plating deposition amount of the thermal diffusion alloy plating, the plating alloy composition ratio or the plating composition gradient, or a plurality of them, which are continuously carried out on the ship body, are detected at an instant with an energy dispersive fluorescence X-ray analyzer, the values thereof change, The control signal is transmitted to the controller to automatically correct the plating current or diffusion heating amount of each plating diffusion process, so that the target coating weight, plating alloy composition ratio, and plating composition gradient can be roughly uniform in the direction of the length of the ship body. The present invention provides a method of thermal diffusion alloy plating on shipboards.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described in detail.

Example 1

As shown in FIG. 1, the linear body 11 withdrawn from the derivation rail 1 passes through the whole processing apparatus 2, such as degreasing, washing with water, and pickling. Two-layer plating is carried out through the first-layer metal plating apparatus 3 and the second-layer metal plating apparatus 4, and then thermally diffused after post-treatment in the washing apparatus 8 and the drying apparatus 9. The device 5 is thermally diffused to form an alloy plated linear body 11 which is continuously wound onto the winding take-up rail 12.

As described above, in the thermal diffusion alloy plating step, an energy dispersive fluorescent X-ray analyzing apparatus 6 is disposed after the drying apparatus 9, and the energy dispersive fluorescent X-ray analyzing apparatus 6 causes the linear body ( 11) Simultaneously detect characteristic X-rays from each metal plated on two layers on the surface of 2), and detect variations in the coating weight and the weight ratio of the metal in the two-layer state by the variation in the intensity ratio. 10) is transmitted as a control signal to the current controller 7 so that the characteristic X-ray intensity ratio is always constant through the metal plating so that the target coating weight and the weight ratio of the metal are uniformly obtained in the longitudinal direction of the ship body. The plating current of the apparatus (3) (4) is automatically controlled.

In this embodiment, the plating deposition amount and the ratio of each metal of the plating layer is measured as the layer state before thermal diffusion without stopping the operation, and the measurement results are fed back to each plating process to adjust the plating current. A linear body which has been subjected to good alloy plating can be obtained continuously.

Next, a description will be given of the case of brass plating on steel wire as a specific example. When measuring as a state of linear body directly by energy dispersive fluorescence X-ray analysis, Cu, Zn in brass plating obtained by measuring several kinds of brass plating steel which knows plating amount and alloy composition beforehand, and Fe of prepared steel wire In terms of its ratio, i.e. thickness,

ICu / IFe + IZn / IFe

ICu: Secondary X-ray intensity from Cu (cps), IZn: Secondary X-ray intensity from Zn, IFe: Secondary X-ray intensity from Fe (cps)

Here, cps means Count per second. In the composition ratio, an analytical curve as shown in Figs. 2A and 2B is prepared from ICu / (ICu + IZn) and their actual plating amount and composition ratio, and the intensity of each secondary X-ray obtained as an unknown sample measurement from this. The method of knowing the plating thickness and composition ratio (here Cu concentration) is taken from the. However, in the actual thermal diffusion brass plated wire, when the composition ratio, ie, the difference in concentration of Cu-Zn, occurs in the inside and outside of the plating as described above, the secondary X-rays generated from the inside or the prepared steel wire are absorbed outside the plating. The method of receiving is different from the case of completely uniform brass, so that an error occurs in the measured value.

Fig. 3 shows the case of fluorescence X-ray analysis using a calibration curve obtained from a standard sample in a uniform layer state when the degree of thermal diffusion is changed by plating Cu as the first layer on the steel wire and Zn on the second layer. The composition ratio is shown as an example.

That is, in this embodiment, in order to avoid measurement errors caused by such fluctuations in the diffusion state, the calibration curve described above is prepared for a sample which knows the deposition amount and the metal ratio of each of the platings in the state of the layer before thermal diffusion. By measuring the unknown sample before thermal diffusion during the actual continuous operation, the error is successfully avoided.

Next, the distribution state of the plating composition in the case where a brass plated steel wire having a Cu concentration of 65% is manufactured as a conventional method in this example is shown in FIGS. 4A and 4B.

As is apparent from this figure, in the conventional method, while having a large error of ± 3%, in this embodiment, it succeeded in suppressing with a small error of ± 1%.

Example 2

5 shows an embodiment (2), in which the energy dispersive fluorescent X-ray analyzer 6 is disposed after the heat diffusion device 5 in the same heat diffusion alloy plating process as in the embodiment (1).

According to this embodiment, by the energy dispersive fluorescence X-ray analyzer 6, the characteristic X-rays from the metal of the alloy plating component coated on the surface of the linear body 11 are simultaneously detected, and the intensity ratio thereof. By detecting the variation in the diffusion degree of the alloying plating due to the variation of, the transmission is transmitted as a control signal to the thermal diffusion control device 13 so that the characteristic X-ray intensity ratio is always constant via the microcomputer 10 for the purpose. The amount of heat of diffusion of the heat spreader 5 is automatically controlled so that the degree of diffusion can be uniformly obtained in the longitudinal direction and the length of the ship body.

In addition, the method of simultaneously detecting the characteristic X-rays of the plating component metals made of the alloy by the fluorescent X-ray analyzer 6 and determining the degree of diffusion at each of the ratios is characterized by the characteristic X-rays generated in the respective metals in the alloy plating. These are absorbed by the metals of each other, and the degree of absorption is changed by the degree of diffusion. If enough heat is supplied to the metal plated in two layers, the final diffusion degree, that is, the composition ratio of each metal of the alloy plating is uniform inside and outside the plating, and if less calorie value is given, the incomplete diffusion degree, The alloy composition ratio at the inside and outside of the plating has a slope.

However, here, the high ratio outside the plating is the second layer in the two-layer plating before diffusion, that is, the metal plated on the outside, and the high inside is the first layer, that is, inside Plated metal.

In this manner, in the diffusion process generated by heating the two-layer plating on the ship body, the abundance ratio of the metal in the second layer before diffusion existing outside the plating gradually decreases, and finally, the inside and outside of the plating. When the characteristic X-rays were detected from the metals by the energy dispersive fluorescence X-ray analysis, the characteristic X-rays generated in the metals of the first layer were the same as those of the second layer. The rate absorbed by the metal gradually decreases. In other words, absorption is maximized in the two-layer state before diffusion, and least in the complete diffusion degree.

Therefore, although the intensity ratio of the characteristic X-rays from protons obtained by fluorescent X-rays does not change, the total amount ratio of the two-layer metal in the plating present on the linear body remains unchanged even before diffusion and after alloying. It depends on the degree of diffusion. That is, as the degree of diffusion progresses, the intensity ratio of the characteristic X-rays from the plated metal applied to the first layer increases, and conversely, the characteristic X-ray intensity ratio from the plated metals from the second layer decreases.

In this embodiment, the degree of diffusion is determined by using the relationship between their degree of diffusion and the characteristic X-ray intensity ratio. That is, in the linear body plated in a two-layer state so as to have a predetermined alloy ratio, a sample in which the degree of diffusion was changed in advance was prepared, and the characteristic X-ray intensity ratio of the plated component metal by fluorescence X-ray analysis was prepared. In the energy dispersive fluorescence X-ray analyzer 6 in the thermal diffusion alloy plating step of the continuous production described above by obtaining the data and inputting the above data into the microcomputer 10, it is measured under the same conditions. For the linear body plated with the same alloy composition ratio, the degree of diffusion can be determined from the characteristic X-ray intensity ratio.

The measurement results of the energy dispersive fluorescence X-ray analyzing apparatus can be automatically corrected by knowing the actual degree of diffusion of the fluctuation for the purpose of thermal diffusion through the microcomputer 10 and during the continuous operation.

Next, in this Example (2) and the conventional method, distributions of the diffusion state of the alloy plating when the brass plated steel wire is manufactured are shown in Figs. 6 (a) and 6 (b).

는 에너지분산형 형광 X선 분석장치에 의하여 측정된 놋쇠의

상(相)(111)의 피이크의 높이, β는 동일하게 측정된 놋쇠의 β상(110)의 피이크의 높이를 표시한다. 또

/

+β는 확산정도의 파라미터이다.In this drawing

Of the brass measured by the energy dispersive fluorescence X-ray analyzer.

The height of the peak of the phase 111, β indicates the height of the peak of the β phase 110 of brass, which was measured in the same manner. In addition

Of

+ β is a parameter of the degree of diffusion.

As apparent from this figure, in the conventional method, the error of ± 7-9 was found at the parameter 10 of interest, and in this embodiment, it succeeded in suppressing it with a small error of ± 4.

Example 3

7 shows Example (3), in which the energy dispersive fluorescence X-ray analyzer (6) is placed after the drying apparatus (9) in the same thermal diffusion alloy plating process as Example (1), and this is a microcomputer. It connects to the thermal-diffusion control apparatus 13 via (10).

However, when a change occurs in the plating composition rate itself during continuous production, that is, when the plating deposition amount of the metal is changed in two-layer state prior to entering the thermal diffusion apparatus 5 of the foregoing process, Since the amount of metal is changing, a difference may arise in the relationship between the spreading degree and characteristic X-ray intensity ratio demonstrated in Example (2). However, it is considered that the characteristic X-ray intensity ratio also fluctuates relative to the variation of the overall metal composition ratio.

Therefore, even in such a case, in order to correct the difference, as shown in FIG. 7, the energy dispersive fluorescent X-ray apparatus 6 is arranged in a two-layer state after plating and before thermal diffusion. Each characteristic X-ray of the plated metal is obtained, and these fluctuation values are sometimes corrected via the microcomputer 10, and the corrected data is transmitted as a control signal to the diffusion calorific control device 13 in the next step. By controlling the amount of thermal diffusion, it is possible to obtain the target diffusion degree with higher precision.

Example 4

8 shows an embodiment (4), in which the energy dispersive fluorescence X-ray analyzer (6) is followed by the drying device (9) and the heat diffusion device (5) in the same thermal diffusion alloy plating process as in Example (1). (6), and the two energy dispersive fluorescence X-ray analyzers (6) and (6) were connected to the current control device 7 and the diffusion calorific control device 13 via the microcomputer 10, respectively. will be.

According to this embodiment, when a variation occurs in the deposition amount of the plating and the diffusion of the alloy plating during the continuous production, the variation value obtained by the energy dispersive fluorescence X-ray analyzer (6) (6) is interposed through the microcomputer (10). The correction is sometimes performed, and the corrected data is converted into a control signal and transmitted to the current control device 7 and the diffusion calorific control device 13 so that the precision of the plating deposition amount, the plating alloy composition ratio and the plating composition gradient is extremely small. It is possible to perform good alloy plating substantially uniformly in the longitudinal direction of the linear body 11.

By the way, each embodiment described above has been described with respect to the plating method consisting of two-component metal, but even in the case of three or more components, in the method of thermal diffusion after plating in a multi-layered form, the spreading ratio is determined by the degree of diffusion. Since a difference is generated, it can be performed similarly to two-layer plating.

The fluorescence X-ray analyzer used in the present invention may be a wavelength dispersion type in addition to an energy dispersion type. However, two or more kinds of characteristic X-rays must be detected at the same place at the same time. The same number of spectral crystals and detectors as needed are required, and there are geometrical limitations on the location of installation.

On the other hand, in the energy dissipation type, characteristic X-rays of the entire energy range can be detected at the same time, and since the positional limitation is small, it is more effective for the linear body like the present invention.

정도의 가늘은 선상체로서 미소한 진동을 수반하는 연속제조중에도 좋은 정밀도로서 분석이 가능하게 되었다.In addition, if the energy dispersion type is used, the diameter of the line is 1mm

As a linear body, the precision of the precision can be analyzed with good precision even during continuous production accompanied by a slight vibration.

The characteristic X-rays to be detected may be any of the energy levels of the Ka line and the La line, but may be appropriately selected according to the coating weight, the alloy plating component, and the like in the absorption relationship.

9 is a relational diagram showing the characteristic X-ray intensity ratio with respect to the diffusion heating amount of the thermal diffusion brass plated steel wire used for automobile tire steel cord. The composition ratio of Cu and Zn is 65%: 35% and 67%: 33%. The amount of diffusion heat is changed to A ₁ , A ₂ , A ₃ , and A ₄ for the steel wire coated with Cu plating on the first layer and Zn plating on the second layer such that Cu and Zn characteristics by energy dispersive fluorescence X-ray spectrometer obtained from another brass Cu characteristic to sum of X-ray intensity X-ray intensity ratio The characteristic from Cu plated on the first layer with increasing heating amount X-ray intensity ratio is large.

In the case where the copper ratio of brass plating with different diffusion degrees was 65%, the plating was dissolved on the surface of the plating one by one, and the composition ratio was measured internally by atomic absorption, and the energy dispersive fluorescent X-ray analyzer was applied to the same sample. The measurement of the alloy state is shown in FIGS. 10 and 11.

In this figure, if the thermal diffusion amount is controlled so that the characteristic X-ray intensity ratio of Cu and Zn corresponding to the desired diffusion degree among A ₁ , A ₂ , A ₃ , and A ₄ is always constant, the presence of Cu near the surface after diffusion It is possible to produce the tire cord wire arbitrarily and continuously without varying the amount.

According to the method of the present invention, the variation of the layer state of the linear body and the state of the alloy plating during continuous production is analyzed and corrected by an energy dispersive fluorescence X-ray analyzer and a microcomputer, and the corrected data is transferred to the control unit. Since metal plating and thermal diffusion are performed by automatically adjusting the plating current and diffusion heating amount by transmission, it is possible to minimize alloying amount, plating alloy composition ratio, and plating composition inclination, and to make alloy plating with good precision of arbitrary plating composition inclination. The length of the upper body can be substantially uniform in the longitudinal direction.

In addition, in terms of adhesiveness and freshness with rubber, the accuracy of plating adhesion amount, plating alloy composition ratio and plating composition gradient is strictly required, and the tire tire cord for automobiles having various combinations of the above values according to the type and application of rubber. It is most suitable for the manufacture of steel wire.

In addition, in the related art, much effort has been put into plating tank management, current management, diffusion calorie management, and various analyzes, and the operation rate of the ship body of alloy plating is also badly reduced.

Claims (5)

In the linear body continuous alloy plating method in which two or three or more different metals are successively plated in various layers for each of various metals and subsequently thermally diffused to form an alloy while feeding and running the linear body 11. The distributed fluorescence X-ray analyzer 6 detects the characteristic X-rays of various metals and continuously measures the amount of plating deposition, the plating alloy composition ratio, the plating composition gradient, or a plurality thereof, and the measured value is measured by a microcomputer ( And converting the control signal into the control signal in step 10) and transmitting the control signal to the control unit. The energy dispersive fluorescence X-ray analyzer (6) is arranged after metal plating, and the measured values obtained therefrom are converted into control signals by the microcomputer (10) and transmitted to the plating control unit to provide various metals. A method for plating a thermal diffusion alloy on a ship body, the method comprising: plating a metal while automatically controlling a plating current of a plating tank. The energy dissipation type fluorescent X-ray analyzer (6) is arranged after thermal diffusion, and the measured value obtained is converted into a control signal by the microcomputer (10) and transmitted to the diffusion calorific control unit to diffuse heating amount. A thermal diffusion alloy plating method on a ship body, characterized in that thermal diffusion is carried out while controlling the temperature automatically. An energy dispersive fluorescence X-ray analyzer (6) is arranged after metal plating and prior to thermal diffusion, and the measured value obtained therefrom is converted into a control signal by the microcomputer (10) for diffusion calorific control. A method of thermally diffusing alloy plating onto a ship body, characterized in that thermal diffusion is carried out while the heat transfer is carried out and the diffusion heating is automatically controlled. 2. The energy dispersive X-ray analyzer (6) (6) is arranged after the metal plating and thermal diffusion, and the measured values are converted into control signals by the microcomputer (10). A method for plating a thermal diffusion alloy onto a ship body, characterized in that the metal plating and thermal diffusion are performed while automatically transmitting the plating current and the diffusion heating amount to the plating control unit and the diffusion heat control unit.

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