KR101679351B1 - Mixed solution analysis sensor and mixed solution management system using the sensor - Google Patents

Mixed solution analysis sensor and mixed solution management system using the sensor Download PDF

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KR101679351B1
KR101679351B1 KR1020150082304A KR20150082304A KR101679351B1 KR 101679351 B1 KR101679351 B1 KR 101679351B1 KR 1020150082304 A KR1020150082304 A KR 1020150082304A KR 20150082304 A KR20150082304 A KR 20150082304A KR 101679351 B1 KR101679351 B1 KR 101679351B1
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mixed solution
branch valve
measuring
sensor
measurement
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KR1020150082304A
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전성욱
김익범
김정일
이동광
김희섭
공정식
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와이엠티 주식회사
주식회사에이치티엔씨
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K13/00—Thermometers specially adapted for specific purposes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
    • G01N27/4165—Systems checking the operation of, or calibrating, the measuring apparatus for pH meters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4166—Systems measuring a particular property of an electrolyte
    • G01N27/4167—Systems measuring a particular property of an electrolyte pH
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N2021/3129—Determining multicomponents by multiwavelength light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/121—Correction signals
    • G01N2201/1211—Correction signals for temperature

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Abstract

The present invention relates to a mixed solution analysis sensor and a mixed solution management system using the same, wherein the concentration of a specific component contained in the mixed solution is measured to supply an additive to the mixed solution, It is possible to maintain the state of the mixed solution at the optimum state at all times by making it possible to correct the measured value in consideration of the change.

Description

TECHNICAL FIELD The present invention relates to a mixed solution analysis sensor and a mixed solution management system using the same,

The present invention relates to a mixed solution analysis sensor and a mixed solution management system using the same. More specifically, the concentration of a specific component contained in a mixed solution is measured to supply an additive to the mixed solution. The present invention relates to a technique for maintaining a state of a mixed solution in an optimal state by making it possible to correct a measured value in consideration of a change in a state of a mixed solution.

Electroplating (electroplating) refers to a surface treatment method in which metal ions are reduced and precipitated on the surface of a product by electrolytic dissolution to form a thin film. For example, electrolytic nickel plating is a plating method in which nickel or an alloy thereof is used for a positive electrode in a plating solution mainly composed of a nickel salt, ammonium chloride or boric acid, and nickel is plated using a product such as iron, brass or zinc die cast as a negative electrode.

However, if the plating process is continued, the nickel ions in the plating solution may be reduced, which may lower the plating efficiency and cause defective products. For this purpose, a technique has been developed to grasp the state of the plating liquid and to fill in the main component when the main component is insufficient.

Methods for analyzing the plating solution include various methods such as using a measured impedance value by applying a potential to the plating solution or using light. However, the measured values of the plating solution may vary depending on the surrounding environment. In other words, if the state of the plating liquid is measured without considering the surrounding environment, it is possible to introduce the wrong additive due to the error of the measured value.

On the other hand, Korean Patent Laid-Open Publication No. 10-2011-0110462 and the like are known as prior art related to the analysis of the plating solution.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems of the prior art as described above, and it is an object of the present invention to measure the concentration of a specific component contained in a mixed solution by sampling a mixed solution in which various components such as a plating solution are mixed, And it is an object of the present invention to provide a mixed solution analysis sensor capable of accurately deriving a concentration value in consideration of the environment.

In addition, the present invention provides a mixed solution management system capable of analyzing the state of a mixed solution and then supplying necessary additives, and using the reference solution to accumulate data to be used for correction of a concentration value according to the surrounding environment, .

According to an aspect of the present invention, there is provided a mixed solution analyzing sensor including: a flow cell through which a mixed solution flows; A light emitting unit emitting light of a specific wavelength toward the mixed solution flowing in the flow cell; A light receiving unit for receiving the light emitted from the light emitting unit and transmitted through the mixed solution, and outputting a light receiving signal corresponding to the received light to the control unit; And a temperature measuring unit measuring the temperature of the mixed solution flowing in the flow cell and outputting a temperature signal corresponding to the measured temperature to the control unit.

Here, the controller may derive the concentration value of the specific component included in the mixed solution through the light receiving signal, and derive the concentration value of the specific component according to the temperature signal.

According to another aspect of the present invention, there is provided a mixed solution management system comprising: a sampling pump for generating circulating power; A mixed solution analysis sensor for analyzing the mixed solution sampled according to the operation of the sampling pump and outputting an analysis signal; A controller for deriving a concentration value of a specific component contained in the mixed solution according to an analysis signal output from the mixed solution analysis sensor and outputting a driving signal corresponding to the concentration value of the specific component; And a driving driver for driving the supply pump so that the additive stored in the additive storage tank is supplied to the mixed solution storage tank in which the mixed solution is stored according to the drive signal outputted from the control unit, A flow cell through which the mixed solution flows; A light emitting unit emitting light of a specific wavelength toward the mixed solution flowing in the flow cell; A light receiving unit for receiving the light emitted from the light emitting unit and transmitted through the mixed solution, and outputting a light receiving signal corresponding to the received light to the control unit side; And a temperature measuring unit measuring the temperature of the mixed solution flowing in the flow cell and outputting a temperature signal corresponding to the measured temperature to the control unit side, The concentration value of the specific component may be derived, and the concentration value of the specific component may be corrected according to the temperature signal.

Here, the pH measurement vessel for temporarily storing the sampled mixed solution according to the operation of the sampling pump; PH measuring means for measuring a pH level of the mixed solution stored in the pH measuring container; And a temperature measuring means for measuring a temperature of the mixed solution stored in the pH measuring container, wherein the controller derives a pH level of the mixed solution according to a measurement result of the pH measuring means, And the driving driver outputs a driving signal corresponding to the pH level derived from the correction, and the driving driver outputs the driving signal in response to the pH level output from the control unit The supply pump may be driven so that the additive stored in the additive storage tank is supplied to the mixed solution storage tank.

And a merging portion having an inlet portion 1, an inlet portion 2 and a discharge portion for discharging the mixed solution flowing through the inlet portion 1 and the inlet portion 2 to the sampling pump side through the outlet portion, One end of the mixed solution analyzing sensor is connected to one end of the outlet port 2 of the pH measuring container, and the other end of the mixed solution analyzing sensor is connected to the outlet port 1 And the other end is connected to the inlet 1 of the merging unit and the outlet 1 of the pH measuring vessel is connected to the inlet 2 of the merging unit so that circulating power is generated according to the operation of the sampling pump, When the stored mixed solution is discharged, the mixed solution is simultaneously discharged through the discharge port 1 and the discharge port 2, and the combined solution is merged at the merged portion, To be able to flow, a bubble generating in the mixed solution that flows into the mixed solution detection sensor can be suppressed.

The branch valve (1) further includes a branch valve (1) having a connection portion (a), a connection portion (b) and a connection portion (c) and communicating the selected two connection portions between the connection portions The connection part b of the branch valve 1 is connected to the inlet of the pH measurement container, the connection part c of the branch valve 1 is connected to the reference solution, the connection part a of the branch valve 2 is connected to the sampling pump , The connection portion b of the branch valve 2 is connected to the mixed solution storage tank and the connection portion c of the branch valve 2 is connected to the reference solution or drain so that the connection portion a of the branch valve 1 is connected to the connection portion b, In the state in which the connection portion a of the valve 2 is in communication with the connection portion b, the mixed solution stored in the mixed solution storage tank is supplied to the branch valve 1, the pH measurement container, A sampling pump, and a branch valve 2, and the connection portion b of the branch valve 1 and the connection portion c are communicated. In a state where the connection portion a of the branch valve 2 and the connection portion c are in communication with each other The reference solution is discharged through the branch valve 1, the pH measurement container, the mixed solution analysis sensor, the sampling pump, and the branch valve 2 according to the operation of the sampling pump, Data can be accumulated.

The present invention has the following effects.

First, the mixed solution management system according to the present invention samples the mixed solution, derives the pH level and the concentration value of a specific component contained in the mixed solution, and supplies the mixed solution with the mixed solution according to the analyzed result, Can always be maintained in a constant state. For example, in the case of the plating solution used in the nickel-tungsten alloy plating process, if the plating process is performed for a long time, the nickel ion or tungsten ion may be deteriorated and the pH level may be lowered. It is possible to continuously supply the necessary additives after monitoring in real time (or at predetermined time intervals), thereby continuously performing the plating process without deteriorating the quality.

Here, a sensor (a pH measuring means and a mixed solution analyzing sensor) is used for detecting a pH level or a specific component of the mixed solution. However, if the surrounding state of the mixed solution is changed, the measured value in the sensor may be changed. For example, the concentration of nickel in the mixed solution is 5 g / L, but if the temperature of the mixed solution is higher or lower than the reference value, the concentration of nickel can be measured differently. Likewise, the pH level can also be measured differently depending on the temperature. To this end, in the present invention, it is possible to accurately determine the state of the mixed solution by measuring the pH at the time of measuring the pH and the temperature of the components of the mixed solution, and correcting the pH level and the concentration value of the specific component according to the measured temperature. .

In addition, correction of the pH level and the concentration value of a specific component is possible by the control unit accumulating data while circulating the reference solution. That is, the branch valve 1 is provided at the front end of the pH measurement vessel for measuring the pH level, and the branch valve 2 is provided at the downstream end of the sampling pump, so that the mixed solution is circulated according to the state of the branch valves, It is possible to accumulate data in the control section while changing the state of the branch valves and circulating the reference solution. For example, the pH level and the nickel concentration are measured in a sensor (a pH measuring means and a mixed solution analyzing sensor) while circulating a reference solution having a pH level of 7 and a nickel concentration of 5 g / L, (PH level 7, nickel concentration 5 g / L), the control unit can store the measured value, the corresponding temperature, and the actual value (pH level 7, nickel concentration 5 g / L) It can be used as data for the measurement value correction. In this way, since the measurement value is corrected by the data accumulation using the reference solution, accurate analysis can be performed even if the ambient environment of the mixed solution is variously changed.

In addition, the mixed solution analysis sensor is capable of analyzing a specific component of the mixed solution by providing a light emitting portion and a light receiving portion around the flow cell. However, depending on the state of the light emitting portion and the light receiving portion, the light may be refracted or distorted, have. However, this can also be corrected by correcting the measured values through data accumulation using the reference solution.

Further, in the mixed solution analyzing sensor used in the present invention, since the two light emitting units and the two light receiving units are provided, even if any one of the light emitting units and the light receiving units can not be used due to a failure, measurement using the remaining light emitting units and the light receiving units is possible. It is, of course, also possible to detect the concentration of a plurality of components contained in the mixed solution when the plurality of light emitting parts are made to emit light of different wavelengths.

On the other hand, in this mixed solution analysis sensor, an optical analysis method is used. In order to minimize the scattering or distortion of light and to perform accurate measurement, the mixed solution flowing in the flow cell must have no bubbles. For this purpose, the mixed solution analysis sensor is designed to minimize the upper and lower tolerances and to prevent foreign matter or air from flowing into the flow cell by using rubber packing, and furthermore, So that it can be introduced. That is, in the pH measurement vessel, the mixed solution is simultaneously discharged through the discharge port 1 and the discharge port 2, and the mixed solution discharged from the discharge port 1 is directly introduced into the sampling pump through the confluent part. By introducing it into the analysis sensor, bubble formation is suppressed when the mixed solution is discharged from the pH measurement vessel. Therefore, when analyzing the mixed solution in the mixed solution analyzing sensor, analysis error due to the bubble does not occur.

1 is a perspective view for explaining a mixed solution management system according to an embodiment of the present invention;
FIG. 2 is a block diagram for explaining an internal configuration of the mixed solution management system shown in FIG. 1. FIG.
3 is an exploded perspective view illustrating a configuration of a mixed solution analysis sensor applied to the mixed solution management system shown in FIG.
FIG. 4 is a conceptual view for explaining the operation principle of the mixed solution analysis sensor shown in FIG. 3; FIG.
5 is a view for explaining analysis of nickel components.
6 is a view for explaining analysis of a tungsten component.
FIG. 7 is a view for explaining an example of screen output through a display in the mixed solution management system shown in FIG. 1; FIG.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, some configurations which are not related to the gist of the present invention may be omitted or compressed, but the configurations omitted are not necessarily those not necessary in the present invention, and they may be combined by a person having ordinary skill in the art to which the present invention belongs. .

FIG. 1 is a perspective view for explaining a mixed solution management system according to an embodiment of the present invention, and FIG. 2 is a block diagram for explaining an internal configuration of the mixed solution management system shown in FIG. 1, a mixed solution management system 100 according to an embodiment of the present invention includes a main body 101, a beacon 103, a display 104, and an operation unit 105.

Various components for analyzing the mixed solution are mounted on the main body 101. The respective components are protected through the cover 102 on the front surface of the main body 101. On the rear surface of the main body 101, The storage tank 107 and the oil line are connected.

The beacon light 103 is provided to notify the manager promptly of an error or an urgent situation according to the analysis result.

The display 104 outputs an analysis result of the mixed solution, or outputs a user interface for system setting. An example of screen output through the display 104 is shown in Fig.

The operation unit 105 is provided for receiving a user command. The operation unit 105 may be a keyboard, a button, or the like, but may be a touch screen, which is integrally formed with the display 104.

2, the interior of the body 101 includes components for analyzing the mixed solution, that is, the cooling unit 107, the filter 108, the branch valve 1 109, the pH measuring container 113, the pH measuring unit 117 The temperature measurement means 118, the control unit 119, the mixed solution analysis sensor 120, the auxiliary valve 141, the merging unit 142, the sampling pump 143, the branch valve 2 144, 148 and pipes 150 for connecting the respective components.

The cooling means 107 is provided to lower the temperature of the mixed solution introduced from the mixed solution storage tank 106 provided outside the main body 101 to a certain level or less through the pipe 150. The cooling means 107 may be cooled by air or water, and the cooling means 107 may be omitted.

The filter 108 is provided to filter the foreign substances and bubbles of the mixed solution whose temperature has been lowered through the cooling means 107.

The branch valve 1 (109) allows the mixed solution to flow into the pH measuring vessel 113 at the downstream or allows the reference solution to flow. That is, the branch valve 1 (109) may be a solenoid valve that operates by receiving a signal from the controller 119, and includes a connection portion 110 connected to the filter 108 side, an inlet 114 of the pH measurement container 113, A connecting portion b 111 connected to the reference solution, and a connecting portion c 112 connected to the reference solution. Therefore, by connecting the connection part a 110 and the connection part b 111 according to the valve setting, the mixed solution passing through the filter 108 can be introduced into the pH measurement container 113, or the connection part c 112 and the connection part b 111 To allow the reference solution to flow into the pH measurement vessel 113. [

An inlet port 114 and an outlet port 115 are formed on the side surface of the pH measuring container 113 and an outlet port 116 is provided on the bottom. When the mixed solution flows into the pH measurement vessel 113 through the inlet 114, the solution is temporarily stored at a predetermined height.

The pH measuring means 117 and the temperature measuring means 118 are provided for measuring the pH level and the temperature of the mixed solution temporarily stored in the pH measuring vessel 113. The results measured by the pH measuring means 117 and the temperature measuring means 118 are transmitted to the controller 119.

the outlet 1 115 of the pH measuring vessel 113 is connected to the inlet 2 142b of the merging portion 142 through the auxiliary valve 141 and the outlet 2 116 is connected to the bottom of the mixed solution analyzing sensor 120 Lt; / RTI > The auxiliary valve 141 may be omitted according to the embodiment.

The upper portion of the mixed solution analysis sensor 120 is connected to the inlet portion 142a of the merging portion 142. In addition, the discharge portion 142c of the merging portion 142 is connected to the sampling pump 143. When the sampling pump 143 is operated, the inlet portion 142a and the inlet portion 142b of the merging portion 142, So that the mixed solution is simultaneously discharged from the outlet 1 (115) and the outlet 2 (116) of the pH measuring vessel (113). Of course, the mixed solution discharged simultaneously from the two outlets 115 and 116 of the pH measuring vessel 113 is then merged at the merging portion 142. [

The reason why the mixed solution is discharged through the two paths when discharging the mixed solution in the pH measuring container 113 is that the phenomenon of bubbles being generated in the process of discharging the mixed solution is suppressed, This is to make it possible. The description will be made later.

The mixed solution analyzing sensor 120 is for analyzing the concentration of a specific component contained in the mixed solution, and provides an analysis signal obtained by using light to the controller 119.

3 is a schematic exploded perspective view illustrating the configuration of the mixed solution analysis sensor 120. As shown in FIG. 3, the mixed solution analyzing sensor 120 includes an upper frame 121, a lower frame 122, a flow cell 121a, an upper substrate 123, a light emitting substrate 124, a light receiving substrate 127, A temperature measurement substrate 130, a central substrate 132, and a lower substrate 134.

The upper frame 121 and the lower frame 122 support other substrates and are mounted at the center of the upper frame 121 and the lower frame 122 and have a cylindrical flow cell 121a. Therefore, the mixed solution flowing into the lower frame 122 passes through the flow cell 121a and is discharged to the confluence portion 142 side via the upper frame 121. [ Of course, the flow direction of the mixed solution in the flow cell 121a is not important.

The upper and lower frames 121 and 122 are designed to minimize the upper and lower tolerances at the portion where the upper frame 121 and the lower frame 122 are connected to the outer pipe 150 and the portion connected to the flow cell 121a, So that foreign matter and air can be prevented from entering.

The upper substrate 123, the central substrate 132, and the lower substrate 134 are formed in a substantially donut shape, and the flow cell 121a penetrates through the center. A light emitting substrate 124, a light receiving substrate 127, and a temperature measuring substrate 130 are installed between the upper substrate 123 and the central substrate 132 in a standing state.

The light emitting substrate 124 is provided with a first light emitting portion 125 and a second light emitting portion 126 that emit light of a specific wavelength and the first light receiving portion 128 and the second light receiving portion 129 ). A temperature measuring unit 131 is provided on the temperature measuring board 130.

A power supply and a control signal are transmitted to the light emitting units 125 and 126 and the light receiving units 128 and 129 and the temperature measuring unit 131 and a signal for transmitting the analyzed signal to the control unit 119 is transmitted between the central substrate 132 and the lower substrate 134 A connecting means 133 is provided.

The components of the mixed solution analyzing sensor 120 described above are mounted in a separate case (not shown) after the assembly is completed, so that external light can be introduced or the light from the light emitting parts 125 and 126 can be prevented from escaping to the outside have.

4 is a conceptual diagram for explaining the operation principle of the mixed solution analysis sensor shown in FIG. 4, when the mixed solution analyzing sensor 120 is assembled, the first light emitting portion 125 and the second light emitting portion 126 are positioned on one side of the flow cell 121a, The first light receiving portion 128 and the second light receiving portion 129 are located on the opposite sides. The temperature measuring unit 131 is located at another point of the flow cell 121a. Accordingly, when the light of a specific wavelength is emitted from the first light emitting part 125 according to the signal of the controller 119, the light of the first light emitting part 125 transmits the mixed solution flowing in the flow cell 121a, The light is received by the first light-receiving portion 128 of the light-receiving element. At this time, the transmittance of the specific wavelength light differs depending on the concentration of the specific component material contained in the mixed solution. Therefore, the concentration value of a specific component can be calculated according to the amount of light received by the first light receiving unit 128. [ For example, the nickel component reacts sensitively to light having a wavelength of approximately 410 nm or approximately 660 nm. Accordingly, when the first light emitting portion 125 emits light having a wavelength of 410 nm or 660 nm, the nickel concentration can be grasped through the voltage level output according to the amount of light received by the first light receiving portion 128. FIG. 5 shows an example in which light in the 410 nm and 660 nm wavelength bands is measured differently in the light receiving units 128 and 129 according to the concentration of the nickel component contained in the mixed solution, and FIG. 6 shows an example in which light in the 310 nm wavelength band And the light receiving portions 128 and 129 are measured differently from each other.

However, in spite of the same concentration, the amount of light received by the light receiving units 128 and 129 may be different depending on the ambient environment such as the temperature, and accordingly, the control unit 119 may possibly misdetect the concentration value. To this end, the mixed solution analyzer 120 according to the present embodiment is provided with a temperature measuring unit 131. When the light receiving unit 128 or 129 transmits a light receiving signal to the controller 119, the temperature measuring unit 131 And transmits the measured temperature signal to the control unit 119 together. Accordingly, the control unit 119 can derive the concentration value of the specific component through the analysis signal including the temperature signal and the light receiving signal. The description will be made later.

In the present embodiment, two light emitting portions 125 and 126 and two light receiving portions 128 and 129 are provided. Therefore, even if any one of the light emitting units 125 and 126 and the light receiving units 128 and 129 is broken and can not be used, the measurement using the remaining light emitting units 125 and 126 and the light receiving units 128 and 129 can be performed. It is also possible to detect the concentration of a plurality of components contained in the mixed solution if the light emitting units 125 and 126 emit light of different wavelengths. For example, the first light emitting unit 125 emits light in a wavelength band of 660 nm for analyzing nickel components, and the second light emitting unit 126 emits light in a wavelength band of 310 nm for tungsten component analysis.

Referring again to FIG. 2, the mixed solution having passed through the mixed solution analysis sensor 120 flows into the sampling pump 143 through the merging portion 142. The mixed solution passing through the mixed solution analyzing sensor 120 is introduced into the sampling pump 143. However, the mixed solution may be circulated by the power generated from the sampling pump 143 The mixed solution is pulled up from the mixed solution storage tank 106.

The mixed solution having passed through the sampling pump 143 flows into the connecting portion a 145 of the branch valve 2 144. The branch valve 2 144 may be a solenoid valve that receives a signal from the control unit 119 in the same manner as the branch valve 1 109. The branch valve 2 144 may include a connection part 145 connected to the sampling pump 143, A connection portion b 146 connected to the connection portion 106, and a connection portion c 147 connected to the reference solution or drain pipe. Accordingly, when the connection part a 145 and the connection part b 146 are communicated with each other according to the valve setting, the mixed solution having passed through the sampling pump 143 is discharged again to the mixed solution storage tank 106, and the connection part a 145 and the connection part c (147) is communicated, the reference solution is again discharged to the reference solution storage tank or discarded.

The driving driver 148 drives the supply pump 149 so that the additive stored in the additive storage tank 107 is supplied to the mixed solution storage tank 106 in accordance with the drive signal outputted from the control unit 119. The additive storage tank 107 provided outside the main body 101 of the mixed solution management system 100 may be provided with a plurality of different additives so as to store different additives, 149 and a drive driver 148 may be prepared.

The control unit 119 derives a concentration value of a specific component included in the mixed solution according to the analysis signal (light receiving signal, temperature signal) output from the mixed solution analysis sensor 120 and outputs a corresponding driving signal to the driving driver 148 . That is, when the specific component measured by the mixed solution analyzing sensor 120 is analyzed, when the material falls below a predetermined level, the driving signal is outputted to the driving driver 148 to operate the supply pump 149, So that the additive is supplied to the mixed solution. The control unit 119 derives the pH level of the mixed solution according to the result of the measurement by the pH measuring unit 117. When the pH level falls below a certain level, the controller 119 outputs a driving signal to the driving driver 148, ) So that additives such as a pH adjusting agent are supplied to the mixed solution.

Here, when deriving the concentration value of a specific component according to the light receiving signal of the mixed solution analyzing sensor 120, the controller 119 derives the concentration value based on the temperature signal transmitted from the temperature measuring unit 131. Further, when the pH level is derived, the control unit 119 corrects the pH level of the mixed solution according to the measurement result of the temperature measuring unit 118 and derives it. That is, even if the same concentration and the same pH level, the measured value may be changed if the ambient environment such as temperature changes. To this end, the control unit 119 corrects the measurement value (light reception signal, pH level) by utilizing the data constructed through the reference solution. Specific examples of this will be described later.

On the other hand, the control unit 119 displays on the display 104 the status of the entire system, the analysis result of the mixed solution (concentration of specific components, pH level, temperature, etc.), setting interface, Analysis result, etc. can be transmitted to the outside. In addition, if an error occurs in the system or if it is urgently required to notify the administrator according to the analysis result, the warning light 103 can be operated.

The mixed solution management system 100 according to the embodiment of the present invention described above will be further detailed from the description of the operation process of the mixed solution management system 100 hereinafter.

<Example of data accumulation process with reference solution>

For the analysis through the sampling of the mixed solution, the data accumulation process is required before the reference solution. This process is intended to correct the error that the measured value changes according to the change of the surrounding environment.

That is, referring to FIG. 2, when the user activates the calibration mode through the operation unit 105, the control unit 119 changes the valve connection state of the branch valve 1 109 and the branch valve 2 144. That is, the connection portion b 111 of the branch valve 1 109 is connected to the connection portion c 112, and the connection portion a 145 of the branch valve 2 144 is connected to the connection portion c 147. When the sampling pump 143 is operated in this state, the reference solution is discharged to the connecting portion b 111 through the connecting portion c 112 of the branching valve 1 109, and the pH measuring container 113, The sample solution is returned to the container in which the reference solution is stored, or is discarded, via the first valve 120, the merging portion 142, the sampling pump 143, and the branch valve 2 144. [ Therefore, the pH measuring unit 117 and the mixed solution analyzing sensor 120 can perform the measurement on the reference solution, and the result is transmitted to the control unit 119.

For example, it is possible to measure the pH level and the nickel concentration while circulating a reference solution having a pH level of 7 and a nickel concentration of 5 g / L. At this time, the measurement is performed while changing the temperature of the reference solution. In this case, the pH level measuring unit 117 and the mixed solution analyzing sensor 120 may measure the pH level or the nickel concentration differently. The controller 119 may measure the measured value, the corresponding temperature, and the actual value (pH level 7, nickel Concentration 5 g / L) is stored as the data for calibration of the measurement value at the time of sampling for later analysis.

Meanwhile, the mixed solution analyzing sensor 120 measures the concentration of a specific component using light. Depending on the installation state of the light emitting units 125 and 126 and the light receiving units 128 and 129, the light may be refracted or distorted, have. However, if the data is accumulated through the calibration process using the reference solution, it is possible to calibrate the measured value even in actual analysis in the future, so that accurate concentration measurement is possible.

<Example of analysis process by mixed solution sampling>

When the user sets the analysis mode through sampling via the operation unit 105, the control unit 119 changes the valve connection state of the branch valve 1 109 and the branch valve 2 144 as shown in Fig. The connection portion a 110 of the branch valve 1 109 and the connection portion b 111 communicate with each other and the connection portion a 145 of the branch valve 2 144 and the connection portion b 146 communicate with each other. When the sampling pump 143 operates in this state, the mixed solution stored in the mixed solution storage tank 106 is drawn up through the pipe 150.

The mixed solution is first cooled to a certain temperature or lower while passing through the cooling means 107, and the foreign matter and air are filtered by passing through the filter 108. The mixed solution flowing into the pH measurement vessel 113 through the branch valve 1 (109) is temporarily stored in the pH measurement vessel 113.

The pH measurement unit 117 and the temperature measurement unit 118 measure the pH level and the temperature of the mixed solution stored in the pH measurement vessel 113 in real time (or at predetermined time intervals) and output the result to the control unit 119 .

The control unit 119 derives the pH level of the mixed solution according to the measurement result of the pH measuring unit 117. At this time, the pH level is corrected according to the measurement result of the temperature measuring unit 118 and is derived. When the pH level is corrected, the data accumulated through the reference solution is utilized. Further, the control unit 119 outputs a driving signal corresponding to the adjusted pH level to the driving driver 148, so that the supply pump 149 is driven so that the additive stored in the additive storage tank 107 is mixed with the mixed solution And is supplied to the storage tank 106. For example, when the adjusted pH level drops to 6 or less, a certain amount of the pH adjusting agent is supplied to the mixed solution storage tank 106.

The mixed solution stored in the pH measurement container 113 is discharged to the mixed solution analysis sensor 120 side along the pipe 150. Here, the mixed solution analysis sensor 120 uses an optical analysis method. If bubbles are included in the mixed solution, scattering or distortion of light may occur, thereby causing errors in the accurate measurement values. For this, in the present invention, bubble generation can be minimized by simultaneously discharging the mixed solution at two points of the pH measurement vessel 113.

That is, when negative pressure is generated in the discharge portion 142c of the merging portion 142 according to the operation of the sampling pump 143, the outlet 1 of the pH measuring container 113 connected to the inlet portion 142a and the inlet portion 142b The mixed solution is simultaneously sucked from the outlet 115 and the outlet 2 (116). Accordingly, as the pressure and the flow rate of the mixed solution flowing into the mixed solution analysis sensor 120 are lowered, the possibility of bubble formation becomes extremely low.

Generally, when the pressure of the moving fluid is high and the flow velocity is high, the reactivity increases together, thereby increasing the bubble generation rate. For example, when the carbonated beverage is sucked by using a straw, if the sucking force is increased and the sucked sucked quickly, the reactivity of the carbonic acid dissolved in the beverage is increased and the bubbles are rapidly generated. When the sucking is slow, relatively little air bubbles are generated, I feel less.

That is, if the pressure generated by the operation of the sampling pump 143 is applied to both the front and rear ends of the mixed solution analyzing sensor 120 and the mixed solution is discharged only through the outlet 2 116 of the pH measuring container 113, In this embodiment, the pressure generated in the sampling pump 143 is dispersed so that the outlet 1 115 of the pH measuring vessel 113 is separated from the outlet 115 of the pH measuring vessel 113. In this case, And the outlet 2 (116), the pressure and the flow rate of the mixed solution flowing into the mixed solution analyzing sensor 120 are low, and the possibility of bubble formation is greatly suppressed. Therefore, concentration analysis using light in the mixed solution analysis sensor 120 can be performed smoothly.

The control unit 119 may derive a concentration value of a specific component contained in the mixed solution based on the received light signal and output the received concentration signal to the control unit 119. [ And the drive signal corresponding thereto is transmitted to the drive driver 148, thereby operating the supply pump 149 to supply necessary additives to the mixed solution. For example, if the nickel component falls below the reference value, additives such as nickel salts are supplied to the mixed solution.

In addition, the control unit 119 corrects the concentration value based on the temperature signal output from the temperature measuring unit 131 of the mixed solution analyzing sensor 120 and derives the corrected concentration value. When the concentration value is corrected, the data accumulated through the reference solution is utilized.

The mixed solution introduced into the inlet portion 142a of the merging portion 142 through the mixed solution analyzing sensor 120 is mixed with the mixed solution introduced into the inlet portion 142b of the merging portion 142 via the auxiliary valve 141, And then flows into the sampling pump 143 through the discharge portion 142c and then returns to the mixed solution storage tank 106 via the branch valve 2 144. [

As described above in detail, the mixed solution management system 100 according to the present invention has the following effects.

First, the mixed solution management system 100 according to the present invention samples the mixed solution, derives the pH level and the concentration value of the specific component included in the mixed solution, and supplies the added solution to the mixed solution according to the analyzed result , The mixed solution can always be maintained in a constant state. For example, in the case of the plating solution used in the nickel-tungsten alloy plating process, if the plating process is performed for a long time, the nickel ion or tungsten ion may be deteriorated and the pH level may be lowered. It is possible to continuously supply the necessary additives after monitoring in real time (or at predetermined time intervals), thereby continuously performing the plating process without deteriorating the quality.

Here, the sensors (the pH measuring means 117 and the mixed solution analyzing sensor 120) are used to detect the pH level or specific components of the mixed solution. However, if the ambient state of the mixed solution is changed, have. For example, the concentration of nickel in the mixed solution is 5 g / L, but if the temperature of the mixed solution is higher or lower than the reference value, the concentration of nickel can be measured differently. Likewise, the pH level can also be measured differently depending on the temperature. To this end, in the present invention, it is possible to accurately determine the state of the mixed solution by measuring the pH at the time of measuring the pH and the temperature of the components of the mixed solution, and correcting the pH level and the concentration value of the specific component according to the measured temperature. .

In addition, correction of the pH level and the concentration value of the specific component is possible by the control section 119 accumulating data while circulating the reference solution. That is, the branch valve 1 (109) is provided at the front end of the pH measurement vessel 113 for pH level measurement and the branch valve 2 (144) is provided at the rear end of the sampling pump 143, And the data can be accumulated in the controller 119 while circulating the reference solution by changing the state of the branch valves 109 and 144. [ For example, the pH level and the nickel concentration are measured in the sensors (the pH measuring means 117 and the mixed solution analysis sensor 120) while circulating the reference solution having a pH level of 7 and a nickel concentration of 5 g / L, If the pH level or the nickel concentration is measured differently at the sensor, the measured value, the corresponding temperature, and the actual value (pH level 7, nickel concentration 5 g / L) By matching and storing it, it can be utilized as data for the measurement value correction at the time of sampling for later analysis. In this way, since the measurement value is corrected by the data accumulation using the reference solution, accurate analysis can be performed even if the ambient environment of the mixed solution is variously changed.

The light emitting units 125 and 126 and the light receiving units 128 and 129 are disposed in the vicinity of the flow cell 121a in the mixed solution analyzing sensor 120 to analyze specific components of the mixed solution. The light emitting units 125 and 126 and the light receiving units 128 and 129 ), The light may be refracted or distorted, resulting in different measured values. However, this can also be corrected by correcting the measured values through data accumulation using the reference solution.

The mixed solution analyzing sensor 120 used in the present invention includes two light emitting portions 125 and 126 and two light receiving portions 128 and 129 so that any one of the light emitting portions 125 and 126 and the light receiving portions 128 and 129 The measurement using the remaining light emitting units 125 and 126 and the light receiving units 128 and 129 can be performed. It is also possible to detect the concentration of a plurality of components contained in the mixed solution when the plurality of light emitting portions 125 and 126 emit light of different wavelengths.

Meanwhile, in the present mixed solution analysis sensor 120, an analysis method using light is used. In order to minimize the scattering or distortion of light and to perform accurate measurement, the mixed solution flowing in the flow cell 121a must have no air bubbles do. For this purpose, the mixed solution analyzing sensor 120 is designed to minimize the upper and lower tolerances and to block the introduction of foreign matter or air into the flow cell 121a by using a rubber packing. Further, So that the mixed solution can be introduced into the analysis sensor 120. That is, the mixed solution is simultaneously discharged through the outlet 1 (115) and the outlet 2 (116) in the pH measurement vessel 113, and the mixed solution discharged from the outlet 1 (115) The mixed solution discharged from the outlet 2 116 flows into the mixed solution analyzing sensor 120 so that bubble generation is suppressed when the mixed solution is discharged from the pH measuring container 113 . Therefore, when analyzing the mixed solution in the mixed solution analyzing sensor 120, analysis error due to bubbles does not occur.

Although it has been described above that the additive is supplied to the mixed solution storage tank 106 based on the measured value, the controller 119 may determine that a specific additive such as a reducing agent is mixed at a predetermined time interval, And may be periodically supplied to the storage tank 106.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And additions should be considered as falling within the scope of the claims of the present invention.

100: mixed solution management system
101: Body
102: Cover
103: warning light
104: Display
105:
107: cooling means
108: Filter
109: Branch valve 1
110: connection a
111: connection b
112: connection c
113: pH measuring container
114: inlet
115: Outlet 1
116: Outlet 2
117: pH measuring means
118: Temperature measuring means
119:
120: mixed solution analysis sensor
121: upper frame
121a: Flow cell
122: Lower frame
123: upper substrate
124: light emitting substrate
125:
126:
127: light receiving substrate
128: First light receiving section
129: Second light receiving section
130: Temperature measurement substrate
131: Temperature measuring unit
132: central substrate
133: Connection means
134: Lower substrate
141: Auxiliary valve
142:
142a: inlet 1
142b: inlet 2
142c:
143: Sampling pump
144: Branch valve 2
145: connection a
146: connection b
147: connection c
148: Driving driver
149: Feed pump
150: Piping
106: mixed solution storage tank
107: Additive storage tank

Claims (6)

delete delete A sampling pump for generating circulating power;
A mixed solution analysis sensor for analyzing the mixed solution sampled according to the operation of the sampling pump and outputting an analysis signal;
A controller for deriving a concentration value of a specific component contained in the mixed solution according to an analysis signal output from the mixed solution analysis sensor and outputting a driving signal corresponding to the concentration value of the specific component; And
And a driving driver for driving the supply pump so that the additive stored in the additive storage tank is supplied to the mixed solution storage tank in which the mixed solution is stored according to the drive signal output from the controller,
The mixed solution analyzing sensor comprises:
A cylindrical flow cell through which the sampled mixed solution flows;
A light emitting unit emitting light of a specific wavelength toward the mixed solution flowing in the flow cell;
A light receiving unit for receiving the light emitted from the light emitting unit and transmitted through the mixed solution, and outputting a light receiving signal corresponding to the received light to the control unit side; And
And a temperature measuring unit measuring the temperature of the mixed solution flowing in the flow cell and outputting a temperature signal corresponding to the measured temperature to the control unit side,
Wherein the control unit derives a concentration value of a specific component contained in the mixed solution through the light receiving signal and corrects the concentration value of the specific component according to the temperature signal,
A pH measurement vessel for temporarily storing the sampled mixed solution according to the operation of the sampling pump;
PH measuring means for measuring a pH level of the mixed solution stored in the pH measuring container; And
And a temperature measuring means for measuring a temperature of the mixed solution stored in the pH measuring container,
Wherein the control unit derives the pH level of the mixed solution according to the measurement result of the pH measuring unit and derives the pH level of the mixed solution according to the measurement result of the temperature measuring unit to derive the corrected pH value, Outputs a driving signal corresponding to the level,
The driving driver drives the supply pump so that the additive stored in the additive storage tank is supplied to the mixed solution storage tank in accordance with the drive signal output corresponding to the pH level output from the controller,
And a merging portion having an inlet portion 1, an inlet portion 2 and a discharge portion, and discharging the mixed solution flowing through the inlet portion 1 and the inlet portion 2 to the sampling pump side through the outlet portion,
An inlet port through which the mixed solution flows is provided at one point of the pH measurement container and an outlet port 1 and an outlet port 2 through which the mixed solution is discharged are provided at other points,
One side of the mixed solution analyzing sensor is connected to the outlet 2 of the pH measuring container and the other side is connected to the inlet portion 1 of the merging portion. The outlet 1 of the pH measuring container is connected to the inlet portion 2 of the merging portion,
When circulating power is generated according to the operation of the sampling pump and the mixed solution stored in the pH measurement container is discharged, the mixed solution is simultaneously discharged through the discharge port 1 and the discharge port 2, So that the generation of bubbles in the mixed solution flowing into the mixed solution analysis sensor is suppressed,
Further comprising a branch valve (1) and a branch valve (2) having a connecting portion (a), a connecting portion (b) and a connecting portion (c)
The connection portion a of the branch valve 1 is connected to the mixed solution storage tank, the connection portion b of the branch valve 1 is connected to the inlet of the pH measurement container, the connection portion c of the branch valve 1 is connected to the reference solution,
The connection portion a of the branch valve 2 is connected to the sampling pump, the connection portion b of the branch valve 2 is connected to the mixed solution storage tank, and the connection portion c of the branch valve 2 is connected to the reference solution or drain,
In the state where the connection portion a of the branch valve 1 and the connection portion b communicate with each other and the connection portion a of the branch valve 2 is in communication with the connection portion b, the mixed solution stored in the mixed solution storage tank, 1, a pH measuring vessel, a mixed solution analyzing sensor, a sampling pump and a branch valve 2 to be discharged again into the mixed solution storage tank,
The reference solution is supplied to the branch valve 1, the pH measurement vessel, and the pH measurement vessel in accordance with the operation of the sampling pump in a state where the connection part b of the branch valve 1 and the connection part c communicate, The mixed solution analyzing sensor, the sampling pump, and the branch valve 2, the control unit is capable of accumulating data for the measurement value correction through the reference solution.
delete delete delete
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114778773A (en) * 2022-04-21 2022-07-22 国网重庆市电力公司 Fire very early warning equipment, fire very early warning control system and fire very early warning control method for energy storage system
WO2023101764A1 (en) * 2021-11-30 2023-06-08 Applied Materials, Inc. Electrochemical deposition systems with enhanced crystallization prevention features

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002513861A (en) 1998-05-01 2002-05-14 ディージェー パーカー カンパニー インコーポレイテッド Chemical mixing, replenishment and waste management systems

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002513861A (en) 1998-05-01 2002-05-14 ディージェー パーカー カンパニー インコーポレイテッド Chemical mixing, replenishment and waste management systems

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023101764A1 (en) * 2021-11-30 2023-06-08 Applied Materials, Inc. Electrochemical deposition systems with enhanced crystallization prevention features
CN114778773A (en) * 2022-04-21 2022-07-22 国网重庆市电力公司 Fire very early warning equipment, fire very early warning control system and fire very early warning control method for energy storage system
CN114778773B (en) * 2022-04-21 2023-11-14 国网重庆市电力公司 Fire disaster extremely early warning equipment, control system and method of energy storage system

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