JPH031396B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a heat diffusion alloy plating device for rubber reinforcing linear bodies, which continuously forms an alloy plating layer made of two or more metals on the linear bodies. It is something.

(Prior art and problems to be solved by the invention) Conventionally, as an apparatus for continuously applying alloy plating made of two or more metals to a linear body, a device that simultaneously coats the linear body with a target alloy metal component is used. A device that performs plating as an alloy without heat diffusion in a plating bath, or a device that performs alloy plating by sequentially arranging two or more types of plating baths and a thermal diffusion heating device that sequentially plate metals that are alloy components in layers. It was hot.

Then, the thickness or alloy composition ratio of the alloy plated on the above-mentioned linear body is non-destructively analyzed during the production process, and based on the results, feedback is provided to the process in real time, and the plating current etc. are automatically adjusted. Various studies have been made to improve the quality and accuracy of plating by providing control means.

For example, as shown in Japanese Patent Application Laid-Open No. 54-29843, in alloy plating by simultaneous electrodeposition, a method has been established to conduct a non-destructive and accurate analysis after complete alloy plating, and this method can be used in actual equipment. However, in the latter type of alloy plating equipment obtained by the thermal diffusion method, plating changes such as changes in the concentration of the plating solution, changes in the plating voltage, wear and tear of the electrode rod, and condition of the electrode plate, etc. Due to changes in electroplating conditions such as changes in current rate, diffusion voltage, and current, the amount of plating deposited, the plating alloy composition ratio (weight ratio (%) of various metals that make up the alloy plating), and the plating specific to the heat diffusion alloy plating method may change. Alloy composition gradient (alloy composition ratio changes from the inner layer of the plating layer to the middle layer,
(continuous changes to the surface layer), etc., and it is impossible to analyze with high precision using conventional equipment that analyzes after complete alloy plating. It was very difficult to obtain a good and uniform coating in the longitudinal direction of the linear body.

By the way, for linear bodies used to reinforce rubber in automobile tires, conveyor belts, etc., the most important qualities are required to have strength as well as adhesion to the rubber, and the precision required for this type of alloy plating is There are some extremely tough ones.

In other words, the amount of plating and plating alloy composition ratio (for example, the weight ratio of Cu and Zn) in alloy plating on the above-mentioned linear bodies is strictly limited due to the influence of adhesion with the rubber, and the value also depends on the type of rubber. It changes slightly depending on the situation.

Furthermore, these precisions greatly affect the wire drawability in the wire drawing process performed after alloy plating.
In particular, the plating alloy composition ratio is a problem related to wire breakage in the wire drawing process. Furthermore, in recent years, due to pollution problems, devices that use a cyanide bath or the like and simultaneously perform alloy plating by diffusion have come to be used more frequently than devices that perform alloy plating by electrodeposition. However, even if an attempt is made to manufacture a brass-plated steel wire with a Cu concentration of 65% using the above-mentioned conventional heat diffusion alloy plating equipment, the limit is at most 62 to 68%, and the variation in Cu concentration is ±3%. It was inevitable that this would happen.

(Means for Solving the Problems) The present invention has been made in order to eliminate the above-mentioned problems, and it is possible to continuously apply alloy plating to a rubber reinforcing linear body by heat diffusion, depending on the thickness of the plating and the alloy composition ratio. The purpose of this system is to accurately apply the metal to the desired value, and it is equipped with a wire feeding device, a plating pre-treatment device, and multiple electroplating baths for individually plating two or more types of metals. , a plating post-processing device, a thermal diffusion heating device, and a linear object winding device are arranged in sequence, and further, at a predetermined position between the above-mentioned plating post-processing device and the thermal diffusion heating device, a heating device is placed on the surface of the linear object. It has a detection means for detecting secondary X-rays from each metal plated in a layer, and an analysis means for analyzing the amount of each metal deposited or the ratio of the amount of metal deposited from the intensity ratio of the secondary X-rays. an energy-dispersive fluorescent X-ray analyzer having an energy-dispersive fluorescent The present invention provides an apparatus for plating a rubber reinforcing linear body with a heat diffusion alloy, characterized in that it is connected to a control means that continuously provides feedback to the means and controls the plating conditions.

(Function) In the plating device of the present invention, the energy dispersive X-ray fluorescence analyzer is placed at a predetermined position in front of the thermal diffusion heating device, that is, at a position where the plating is in the state of multilayer plating before being alloyed. The reason for this is that when alloying is done by thermal diffusion, the alloy layer is not uniform from the inner layer to the surface layer of the plating layer due to the way the heat is applied, that is, the alloy composition ratio is different from that of the plating layer. From the inner layer to the middle layer,
In most cases, the difference occurs in the surface layer (so-called composition gradient), and if the above phenomenon occurs when the amount of heating for diffusion is unstable or when the amount of heating is intentionally changed, the fluorescence When measuring the alloy plating layer due to thermal diffusion in line analysis,
This is because large errors occur in the measurement results, especially in the alloy composition ratio.

For example, if a steel wire is plated with brass, in order to directly measure the linear body using fluorescent X-ray analysis, several types of brass-plated steel wire with known thickness and alloy composition must be used. The ratio of the secondary X-ray intensity from Cu, Zn in the brass plating and Fe of the underlying steel wire, that is, the thickness, is Icu/IFe + Izn/IFe Icu: Secondary X-ray from Cu Linear intensity (cps) Izn: Secondary X-ray intensity from Zn (cps) IFe: Secondary X-ray intensity from Fe (cps) (cps) = Count per second In terms of composition ratio, Icu/(Icu+Izn) From the actual plating thickness and composition ratio, a calibration curve is created as shown in Figure 2 A and B, and from this, the plating thickness and composition ratio (here, A method is used to find out the Cu concentration). However, in actual heat-diffusion brass-plated steel wire, a difference in composition ratio, that is, concentration of Cu-Zn, may occur inside the plating layer as described above. The Cu composition ratio is sometimes set to 61%, 65%, 69%, etc. (the average composition ratio is 65%). In this case, due to the characteristics of fluorescent X-ray measurement, the amount of secondary X-rays generated from the entire plating layer is not the same as the irradiated X-ray dose, but the secondary X-rays generated from the inner layer of the plating are detected as shown in Figure 3 C. Since a large amount of secondary X-rays, which serve as information sources, are absorbed and attenuated inside the metal plate before reaching the container, most of the secondary X-rays are reflected from the outermost surface.For example, in this case, the Cu composition ratio is 63%. This will result in an analysis result value that is different from the actual Cu composition ratio.

However, the above-mentioned phenomenon is almost never observed when using a device that applies brass plating with a completely uniform Cu-Zn concentration in each part of the plating layer, such as conventional simultaneous electrodeposition alloy plating. be.

Figure 3 shows Cu as the first layer on the steel wire,
The following is an example of the composition ratio when the second layer is plated with Zn and the degree of thermal diffusion is changed and fluorescent X-ray analysis is performed using a calibration curve obtained in advance from a standard sample in a uniform layer state. was measured by changing the degree of heating during diffusion and using an energy dispersive X-ray fluorescence analyzer.

For example, when the amount of heating to the steel wire surface for heat diffusion is small (e.g. 400℃ x 4 seconds) as in case a, the diffusion is insufficient and the surface layer of the plating layer
The Cu composition ratio is low, and the Cu content is low in the intermediate layer and inner layer.
Brass has a high composition ratio, and even if the Cu composition ratio of the entire plating layer is 65%, when a steel wire is subjected to direct fluorescent X-ray analysis, it is affected by the concentration gradient of this Cu composition ratio. The analysis result has an error of about 63%. Furthermore, in the case of c, uniform diffusion can be obtained with a sufficient amount of heat (for example, 500° C. x 4 seconds), resulting in an analysis result that is almost close to the actual value. In addition,
b is a case of an intermediate state of heat (for example, 450° C. x 4 seconds).

When such plating of a, b, and c is measured using an X-ray diffraction device, it is found that the less heat is required for diffusion in brass, the more the β phase appears, and the lower the Cu composition ratio in the surface layer of the alloy plating layer. is supported.
Moreover, FIG. 3B is a diagram showing that the α phase and β phase of the above a, b, and c are measured using an X-ray analysis standard, and that they change.

As described above, in the plating device of the present invention,
An energy dispersive fluorescent X-ray spectrometer is installed in front of the thermal diffusion heating device to perform analytical measurements, and feeds back to the plating condition setting means for automatic control, eliminating the influence of compositional gradients and reducing the attenuation of X-ray analysis as described above. Although it occurs in the same way, since the attenuation is within the plating of Cu alone or Zn alone, the attenuation rate can be easily calculated in advance, making it possible to perform highly accurate analytical measurements.

Furthermore, since the thermal diffusion heating device is placed after the analysis device, even if the amount of diffusion heat is freely changed, it will not affect the measurement results at all.

(Example) An example of the present invention will be described below based on the drawings.

As shown in FIG. 1, a plating pretreatment device 2 that performs pretreatment such as degreasing, water washing, pickling, etc. on the linear body is disposed in succession to the feeding device 1 that feeds the linear body 11,
Next, a Cu plating bath 3 and a Zn plating bath 4 equipped with a plating condition control means 7 for controlling the plating current etc. of each plating bath are arranged, and further plating post-processing devices such as a water washing device 8 and a drying device 9 are installed. A thermal diffusion heating device 5 and a winding device 12 for winding up the alloy-plated linear body 11 are arranged in sequence.

Then, an energy dispersive X-ray fluorescence analyzer 6 having an X-ray generating tube 13 is installed near the linear body 11 between the plating post-processing device and the thermal diffusion heating device 5, and a layered structure is formed on the surface of the linear body. It constitutes a detection and analysis means that detects and separates secondary X-rays from each plated metal.

Furthermore, by connecting the X-ray analysis device 6 and the plating condition control means 7 via a microcomputer 10, a correction value is calculated by comparing the detected and analyzed values with a preset reference value. a calculation means, and a plating condition control means 7 that continuously feeds back the modified values to the plating condition setting means for each metal plating and controls the plating conditions.
An apparatus for plating a rubber reinforcing linear body with a heat diffusion alloy according to the present invention is comprised of the following.

Note that the drying device 9 may be omitted as the plating post-processing device, and the water washing device 8 may be replaced with a hot water washing device.

Next, a method of plating a linear body using the apparatus of the present invention will be explained.

As shown in FIG. 1, a linear body 11 drawn out from a feeding device 1 consisting of a feeding reel or the like passes through a plating pre-treatment device 2 such as degreasing, water washing, pickling, etc.
The Cu plating bath 3 for the first layer and the Cu plating bath 3 for the second layer in which the plating current is set by the plating condition control means 7
The linear body 11 is plated in two layers through a plating bath 4 for Zn plating, further passed through a washing device 8 and a drying device 9, and then subjected to a thermal diffusion treatment through a thermal diffusion heating device 5 and alloy plated. The film is continuously wound onto the take-up reel 12.

In the heat diffusion alloy plating process arranged as described above, an energy dispersive fluorescent X-ray analyzer 6 is disposed near the linear body at a predetermined position after the metal plating process is completed and before the heat diffusion process, and the fluorescent The generation tube 13 irradiates the surface of the linear body 11 with X-rays, simultaneously detecting the characteristic X-rays from each metal plated in two layers on the surface of the linear body, and detecting the characteristics of each metal detected by the detection means. Analyze the layer condition of the two-layer plating (plating adhesion amount or metal adhesion amount ratio) from the X-ray intensity ratio, compare the detected value with a preset reference value, and calculate a correction value on the computer 10, The above correction values are continuously fed back to the plating condition setting means for each metal plating, and the plating of the plating baths 3 and 4 is performed so that the desired plating amount or metal adhesion amount ratio is uniformly obtained in the longitudinal direction of the linear body. Automatically controls plating conditions such as current.

The linear body plated in two layers as described above is alloy-plated by the heat diffusion device 5, but in this alloy-plated state, the plating thickness and alloy composition ratio have already been adjusted to the desired values. There is.

In this way, the desired alloy plating can be uniformly and precisely obtained continuously without stopping operation, and even if the plating current efficiency changes over time.

(Effects of the Invention) The heat diffusion alloy plating device for rubber reinforcing linear bodies of the present invention has the above-mentioned configuration, and the heat diffusion alloy plating device for rubber reinforcing linear bodies has the above-mentioned configuration. Since it uses characteristic X-rays as a means of detection and analysis, it is possible to analyze with high accuracy even when the wire is a thin wire with a diameter of about 1 mmφ and is continuously operated with minute vibrations.

In addition, for linear bodies for reinforcing rubber such as steel tire cords, the plating thickness of the alloy plating applied to the linear body and the accuracy of the plating alloy ratio are more strictly required than the adhesion with the rubber. For example, to obtain a Cu concentration of 65% in brass-plated steel wire, conventional continuous plating equipment requires at most 62% to 68% Cu concentration.
Although the accuracy is about 64%, in the device of the present invention, the detection and analysis means are placed at a predetermined position in front of the heat diffusion heating device, and the plating conditions are automatically controlled by the calculation means, plating condition setting means, etc. Brass plating with an accuracy within 66% can be obtained, and alloy plating with good accuracy can be obtained.

Furthermore, conventionally, a great deal of effort was required for plating bath management, current control, various analyses, etc., but the device of the present invention performs automatic control, improving the operation rate of alloy plating linear bodies and increasing yield. This invention has excellent effects such as improving productivity and greatly improving productivity.

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram showing one embodiment of the present invention, FIGS. 2A and 2B are correlation diagrams showing the calibration curve of fluorescent X-ray analysis for brass plating plated with Fe, and FIG. 1 is a correlation diagram showing the results of fluorescent X-ray analysis depending on the amount of heating in the heat diffusion brass plating on the steel wire, B is an X-ray analysis diagram showing the change in the alloy state of each plating in A, and C is the fluorescent FIG. 3 is an action diagram showing the degree of attenuation of a calibration curve in line analysis. 1... Feeding device, 2... Plating pretreatment device,
3, 4...Metsuki bathtub, 5...Thermal diffusion heating device,
6...Energy dispersive X-ray fluorescence analyzer, 7...
... Plating condition control means, 8... Water washing device, 9...
Drying device, 10...Microcomputer, 11
... Linear body, 12 ... Winding device, 13 ... X-ray generating tube.

Claims (1)

[Claims] 1. A linear body feeding device, a plating pre-treatment device, a plurality of electroplating baths for individually plating two or more metals, a plating post-treatment device, a thermal diffusion heating device, and a linear body winding device. Place the devices in sequence,
Furthermore, at a predetermined position between the plating post-processing device and the thermal diffusion heating device, there is provided a detection means for detecting secondary X-rays from each metal plated in layers on the surface of the linear body, and An energy-dispersive fluorescent X-ray analyzer is provided which has an analysis means for analyzing the amount of each metal attached or the ratio of the amount of attached metal based on the intensity ratio of the rays, and the value detected by the above-mentioned analyzer is compared with a preset reference value. Rubber reinforcement characterized in that it is connected to a calculation means for comparing and calculating a modification value, and a control means for continuously feeding back the modification value to a plating condition setting means for each metal plating and controlling the plating conditions. Heat diffusion alloy plating device for linear objects.