CN109444245A - A kind of calibration system and its calibration method of cyclic voltammetric analyzer - Google Patents
A kind of calibration system and its calibration method of cyclic voltammetric analyzer Download PDFInfo
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- CN109444245A CN109444245A CN201811588343.9A CN201811588343A CN109444245A CN 109444245 A CN109444245 A CN 109444245A CN 201811588343 A CN201811588343 A CN 201811588343A CN 109444245 A CN109444245 A CN 109444245A
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Abstract
The present invention provides the calibration systems and its calibration method of a kind of cyclic voltammetric analyzer, belong to field of electroplating.In order to solve there is no the standards such as special vertification regulation, calibrating standard to the metering performance of cyclic voltammetric analyzer in current industry, the technical issues of being accurately unable to effective guarantee surely, its meter characteristic can not be evaluated of its magnitude tracing is caused.The present invention provides the calibration systems and its calibration method of a kind of cyclic voltammetric analyzer, and the parameter that can remove analyzer to cyclic voltammetric is calibrated, and carries out thoroughly evaluating to its meter characteristic.
Description
Technical field
The present invention relates to field of electroplating, calibration system and its calibration side more particularly to a kind of cyclic voltammetric analyzer
Method.
Background technique
Electroplate liquid additive analyzer uses cyclic voltammetry, i.e. cyclic voltammetric (CVS) analyzer, Ke Yiyong substantially at present
To realize the analysis to organic matter in plating and pollutant.Additive in tank liquor finally will affect prolonging for circuit board gold category coating
Malleability, pulling force or even final solderability.It analyzes and tests for electroplating additive (photo etching, leveling agent), be mainly used for electroplating bath
Analysis is widely used in requiring plating control relatively high wiring board, semiconductor, accuracy electroplate, solar energy plating etc..It is right
The normalization inspection of organic additive is to guarantee the important means of product quality.
Electrolytic cell is the place being electroplated, it can convert electrical energy into a device of chemical energy, by additional power source,
Electrolyte solution, the electrode for participating in work are constituted:
Its cathode: obtaining electronics, reduction reaction, which is connected with power cathode；
Anode: betatopic occurs oxidation reaction, is connected with positive pole；
In electrolytic cell, electric current flows to cathode by anode.
If electrode reaction is O+e- → R, reaction particle O is contained only in solution before reacting, and O, R are solvable in solution, control
System scanning onset potential at than system standard equilibrium potential (φ flat) onset potential (φ i) just much gesture make positive electricity
Scanning, current-responsive curve are then as shown in Fig. 1.
When electrode potential is gradually negative moves on to (φ is flat) nearby, O starts to restore on the electrode, and has i faraday to pass through.By
More and more negative in potential, the concentration of electrode surface reactant O is gradually reduced, therefore is just increased to the flow of electrode surface and electric current
Add.It is bordering on zero when the surface concentration of O drops to, electric current is also added to maximum value Ipc, then electric current is gradually reduced.When potential reaches
After (φ r), and it is changed to reverse scan.
As electrode potential gradually becomes just, the concentration of oxidable R particle is larger near electrode, approaches and passes through in potential
When (φ is flat), the electrochemical equilibrium on surface should develop towards the direction for being increasingly conducive to generate R.Then R starts by oxygen
Change, and electric current increases to peak oxidation current Ipa, then cause electric current to decline drop due to significant consume of R again.Entire curve
Referred to as " cyclic voltammetry curve ".
Cyclic voltammetric analyzer is manufacturing electroplating solution Additive analysis important equipment, can be environment-friendly and green
Manufacture provides strong technical support, and market is widely used, but at present in industry to its metering performance do not have special vertification regulation,
The standards such as calibrating standard are accurately unable to effective guarantee to its magnitude tracing surely, can not evaluate its meter characteristic, so, having must
Study the measurement and calibration of cyclic voltammetric analyzer.
Summary of the invention
The object of the present invention is to provide the calibration systems and its calibration method of a kind of cyclic voltammetric analyzer, for solution
The problem of cyclic voltammetric analyzer magnitude can not trace to the source.
To solve the above problems, the present invention provides a kind of calibration systems of cyclic voltammetric analyzer.
A kind of calibration system recycling analyzer of bending over the desk, including computer, single-chip microcontroller, voltage measurement module, the first impedance
Module, the second impedance module, multicircuit switch module, terminals 1, terminals 2 and terminals 3.Wherein:
Terminals 1 are to connect by the working electrode of school cyclic voltammetric analyzer, and the first end with the first impedance module
Mouth is connected；
Terminals 2 are to connect by the reference electrode of school cyclic voltammetric analyzer, and the second end with the first impedance module
Mouth is connected with the first port of the second impedance module；
Terminals 3 are to connect by the reference electrode of school cyclic voltammetric analyzer, and the second end with the second impedance module
Mouth is connected；
Multicircuit switch module is connected with voltage measurement module, single-chip microcontroller, terminals 1, terminals 2 and terminals 3,
The variable connector module can make voltage measurement module detect the first impedance module or the second impedance under the control of single-chip microcontroller
The potential difference at module both ends；
Computer is connected with single-chip microcontroller, and single-chip microcontroller realizes the control to variable connector module under control of the computer；
Computer receives the measurement data of the voltage measurement module sampled via single-chip microcontroller, and computer is to measurement data
It is handled and generates final Calibration Report.
The present invention is in the calibration system, it is also proposed that the calibration method of cyclic voltammetric analyzer can obtain circulation volt
The voltage of dutiful analyzer is with respect to the error of indication, electric current with respect to the error of indication, wherein the step of voltage of acquisition is with respect to the error of indication
Are as follows:
It disconnects by the working electrode, reference electrode and auxiliary electrode of school cyclic voltammetric analyzer；
The terminals 1 of calibration system are connected by the working electrode of school cycle analysis instrument；The terminals 2 of calibration system connect quilt
The reference electrode of school cycle analysis instrument；The terminals 3 of calibration system are connected by the auxiliary electrode of school cycle analysis instrument；
And computer is sent into control instruction to single-chip microcontroller, MCU driving multiplexing module enables voltage measurement module
Enough measure the potential difference at the first impedance module both ends；
Setting uniformly chooses no less than 5 by school cyclic voltammetric analyzer voltage output in the voltage range of its measurement
Calibration point is recorded by the voltage value U of school cyclic voltammetric analyzerXWith the voltage reading numerical value U of voltage measurement moduleS, computer passes through
The test data of single-chip microcontroller recording voltage test module；
Voltage is calculated with respect to the error of indication:
Wherein: ΔUIt is voltage with respect to the error of indication；UXFor by school cyclic voltammetric analyzer voltage indicating value；USFor voltage measurement
The voltage indicating value of module.
On the other hand, the step of electric current is with respect to the error of indication is obtained are as follows:
It disconnects by the working electrode, reference electrode and auxiliary electrode of school cyclic voltammetric analyzer；
The terminals 1 of calibration system are connected to by the working electrode of school cycle analysis instrument；By the terminals 2 of calibration system
It is connected to by the reference electrode of school cycle analysis instrument；The terminals 3 of calibration system are connected to the auxiliary electricity of school cycle analysis instrument
Pole；
Computer sends control instruction to single-chip microcontroller, and MCU driving multiplexing module enables voltage measurement module to survey
The potential difference at two impedance module both ends of flow control；
It is arranged by school cyclic voltammetric analyzer voltage output Ub(generally output 1V), change the first impedance module to extrernal resistance
Anti- R1, the second normal impedance module to external impedance R2, to change the electric current for passing through working electrode and auxiliary electrode, record quilt
The current value I of school cyclic voltammetric analyzerXWith the voltage reading numerical value U of voltage measurement moduleS, computer is recorded electric by single-chip microcontroller
Press the test data of test module.
Calculating current is with respect to the error of indication:
Wherein: ΔIIt is electric current with respect to the error of indication；IXFor by school cyclic voltammetric analyzer electric current indicating value；R2For the second impedance
The resistance value of module；USFor the voltage indicating value of voltage measurement module.
Further, according to above-mentioned calibration method obtain as a result, to the linearity error of cyclic voltammetric analyzer with can weigh
Renaturation is further assessed.
In the following, introducing the calibration method of the linearity error of cyclic voltammetric analyzer:
Each parameter of cyclic voltammetric analyzer is adjusted to normal operating conditions, according to cyclic voltammetric analyzer by step 21)
The 10mL/L series standard solution that specification uses according to the preparation of other concentration (if should use the standard of intermediate concentration point molten
Liquid) it is calibrated；
Step 22) records measurement result using the series standard solution that cyclic voltammetric analyzer measures other concentration respectively
ci；
Step 23), linearity error calculated as described below:
Wherein: ΔiFor the linearity error of i-th of concentration measurement；ciFor the apparatus measures of i-th of concentration standard solution
Value；csiFor the standard value of i-th of concentration standard solution；Maximum linearization error value take absolute value as cyclic voltammetric analyzer
Linearity error.
In the following, introducing the calibration method of the repeatability of cyclic voltammetric analyzer:
Each parameter of cyclic voltammetric analyzer is adjusted to normal operating conditions by step 31), executes step 21), step every time
22) the dense of 3 10mL/L series standard solution (if Cmin standard solution should be measured by preparing according to other concentration), is measured
Degree；
Measurement reproducibility is calculated as follows in step 32):
Wherein: δ is measurement reproducibility；cmax、cminMaximum value, minimum value for 3 measurement results；For 3 measurements knot
The average value of fruit.
The calibration system and its calibration method of the above-mentioned cyclic voltammetric analyzer proposed according to the present invention can be realized to following
The calibration of the electrical parameter of ring analysis instrument, such as voltage are proposed with respect to the error of indication, electric current with respect to the error of indication, line style error
Cyclic voltammetric analyzer is evaluated by repeatability verification.It is final to realize to cyclic voltammetric analyzer magnitude tracing, relatively
In the prior art, the present invention can the electrical parameter to cyclic voltammetric analyzer carry out calibration and comprehensive evaluation.
Detailed description of the invention
Fig. 1 is the sweep current response curve of cyclic voltammetry；
Fig. 2 is the calibration system of cyclic voltammetric analyzer of the present invention；
Fig. 3 is the voltage calibration connection figure of calibration system of the present invention；
Fig. 4 is the correcting current connection figure of calibration system of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
Cyclic voltammetric analyzer is manufacturing electroplating solution Additive analysis important equipment, can be environment-friendly and green
Manufacture provides strong technical support, and market is widely used.But in current industry to its metering performance do not have special vertification regulation,
The standards such as calibrating standard are accurately unable to effective guarantee to its magnitude tracing surely, can not evaluate its meter characteristic.
Present applicant proposes a kind of cyclic voltammetric analyzer calibration systems.
Attached drawing 2 is the connection figure of cyclic voltammetric analyzer calibration system proposed by the present invention.Wherein:
A kind of calibration system recycling analyzer of bending over the desk, it is characterised in that: including computer, single-chip microcontroller, voltage measurement mould
Block, the first impedance module, the second impedance module, multicircuit switch module, terminals 1, terminals 2 and terminals 3.Wherein:
Terminals 1 are to connect by the working electrode of school cyclic voltammetric analyzer, and the first end with the first impedance module
Mouth is connected；
Terminals 2 are to connect by the reference electrode of school cyclic voltammetric analyzer, and the second end with the first impedance module
Mouth is connected with the first port of the second impedance module；
Terminals 3 are to connect by the reference electrode of school cyclic voltammetric analyzer, and the second end with the second impedance module
Mouth is connected；
Multicircuit switch module is connected with voltage measurement module, single-chip microcontroller, terminals 1, terminals 2 and terminals 3,
The variable connector module can make voltage measurement module detect the first impedance module or the second impedance under the control of single-chip microcontroller
Potential difference in module；
Computer is connected with single-chip microcontroller, and single-chip microcontroller realizes the control to variable connector module under control of the computer；
Computer receives the measurement data of the voltage measurement module sampled via single-chip microcontroller, and computer is to measurement data
It is handled and generates final Calibration Report.
Wherein, the first impedance module and the second impedance module can connect for multi-channel gating switch with measuring resistance array
Made of module: at this point, the multi-channel gating switch is connected with the single-chip microcontroller, the multi-channel gating switch is in single-chip microcontroller
Under control, only gate electric resistance array in a specific criteria resistance, make the impedance module to external impedance and the specific criteria
The resistance value of resistance is identical.
First impedance module and the second impedance module can also be single variable resistance.
Preferably, the range of the change in resistance of variable resistance is 10K Ω~20K Ω；Measuring resistance array is comprising resistance value
The measuring resistance of 10K Ω, 12K Ω, 14K Ω, 16K Ω, 18K Ω, 20K Ω；Measuring resistance array includes N number of resistance, minimum
Value is 10K Ω, maximum value is 20K Ω, and the measuring resistance of arithmetic progression that the impedance of N number of resistance is constituted.
Wherein, the first impedance module and the second impedance module are denoted as R to external impedance respectively1、R2。
In order to realize that the characteristic to voltammetric analyzer is comprehensively evaluated, the calibration system based on above-mentioned voltammetric analyzer
System, respectively from voltage with respect to the error of indication, electric current with respect to the error of indication, the repeatability of linearity error and cyclic voltammetric analyzer into
Row verification, has carried out comprehensive analysis and calibration to the electrical parameter of voltammetric analyzer.
Firstly, introducing the voltage of calibration system with respect to error of indication calibration steps:
Step 1) is disconnected by the working electrode, reference electrode and auxiliary electrode of school cyclic voltammetric analyzer；
The terminals 1 of step 2), calibration system are connected by the working electrode of school cycle analysis instrument；The terminals of calibration system
2 connections are by the reference electrode of school cycle analysis instrument；The terminals 3 of calibration system are connected by the auxiliary electrode of school cycle analysis instrument；
Its connection type is referring to attached drawing 3；
Step 3), and computer is sent into control instruction to single-chip microcontroller, MCU driving multiplexing module surveys voltage
Amount module can measure the potential difference at the first impedance module both ends；
Step 4), setting are uniformly chosen not in the voltage range of its measurement by school cyclic voltammetric analyzer voltage output
Less than 5 calibration points are recorded by the voltage value U of school cyclic voltammetric analyzerXWith the voltage reading numerical value U of voltage measurement moduleS, meter
Calculation machine passes through the test data of single-chip microcontroller recording voltage test module；
Step 5) calculates voltage with respect to the error of indication by formula (1):
Wherein: ΔUIt is voltage with respect to the error of indication；UXFor by school cyclic voltammetric analyzer voltage indicating value；USFor voltage measurement
The voltage indicating value of module.
Then, calibration method of the electric current with respect to the error of indication of calibration system is introduced:
Step 11) is disconnected by the working electrode, reference electrode and auxiliary electrode of school cyclic voltammetric analyzer；
The terminals 1 of calibration system are connected to by the working electrode of school cycle analysis instrument by step 12)；By calibration system
Terminals 2 be connected to by the reference electrode of school cycle analysis instrument；The terminals 3 of Barebone are connected to school cycle analysis instrument
Auxiliary electrode；Its connection type is referring to attached drawing 4；
Step 13), computer send control instruction to single-chip microcontroller, and MCU driving multiplexing module makes voltage measurement mould
Block can measure the potential difference at the second impedance module both ends；
Step 14) is arranged by school cyclic voltammetric analyzer voltage output Ub(generally output 1V), changes the first impedance module
To external impedance R1, the second normal impedance module to external impedance R2, to change the electricity for passing through working electrode and auxiliary electrode
Stream is recorded by the current value I of school cyclic voltammetric analyzerXWith the voltage reading numerical value U of voltage measurement moduleS, computer passes through monolithic
The test data of machine recording voltage test module.
Step 15), by formula (2) calculating current with respect to the error of indication:
Wherein: ΔIIt is electric current with respect to the error of indication；IXFor by school cyclic voltammetric analyzer electric current indicating value；R2For the second impedance
The resistance value of module；USFor the voltage indicating value of voltage measurement module.
Preferably, the tandem of voltage error of indication calibration steps opposite with electric current with respect to error of indication calibration steps can
With reverse.
Using it is above-mentioned the voltage for obtaining cyclic voltammetric analyzer with respect to the error of indication and electric current with respect to the error of indication it
Afterwards, the concentration of particular solution can be obtained according to the cyclic voltammogram of the particular solution of known standard；And then to cyclic voltammetric
The linearity error and its repeatability of analyzer are assessed.
In the following, introducing the calibration method of the linearity error of cyclic voltammetric analyzer:
Each parameter of cyclic voltammetric analyzer is adjusted to normal operating conditions, according to cyclic voltammetric analyzer by step 21)
The 10mL/L series standard solution that specification uses according to the preparation of other concentration (if should use the standard of intermediate concentration point molten
Liquid) it is calibrated；
Step 22) records measurement result using the series standard solution that cyclic voltammetric analyzer measures other concentration respectively
ci；
Step 23) calculates linearity error by following equation (3):
Wherein: ΔiFor the linearity error of i-th of concentration measurement；ciFor the apparatus measures of i-th of concentration standard solution
Value；csiFor the standard value of i-th of concentration standard solution；Maximum linearization error value take absolute value as cyclic voltammetric analyzer
Linearity error.
In the following, introducing the calibration method of the repeatability of cyclic voltammetric analyzer:
Each parameter of cyclic voltammetric analyzer is adjusted to normal operating conditions by step 31), executes step 21), step every time
22) the dense of 3 10mL/L series standard solution (if Cmin standard solution should be measured by preparing according to other concentration), is measured
Degree；
Step 32) calculates measurement reproducibility by formula (4):
Wherein: δ is measurement reproducibility；cmax、cminMaximum value, minimum value for 3 measurement results；For 3 measurements knot
The average value of fruit.
Using above-mentioned reperformance test, can reduce due to influence of the uncontrollable factor to calibration result in operating process.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and replacement can also be made, these are improved and replacement
Also it should be regarded as protection scope of the present invention.
Claims (10)
- The calibration system of analyzer 1. a kind of circulation is bent over the desk, it is characterised in that: including computer, single-chip microcontroller, voltage measurement module, First impedance module, the second impedance module, multicircuit switch module, terminals 1, terminals 2 and terminals 3；Terminals 1 are to connect by the working electrode of school cyclic voltammetric analyzer, and the first port phase with the first impedance module Connection；Terminals 2 to connect by the reference electrode of school cyclic voltammetric analyzer, and with the second port of the first impedance module and The first port of second impedance module is connected；Terminals 3 are to connect by the reference electrode of school cyclic voltammetric analyzer, and the second port phase with the second impedance module Connection；Multicircuit switch module is connected with voltage measurement module, single-chip microcontroller, terminals 1, terminals 2 and terminals 3, described Variable connector module can make voltage measurement module detect the first impedance module or the second impedance module under the control of single-chip microcontroller The potential difference at both ends；Computer is connected with single-chip microcontroller, and single-chip microcontroller realizes the control to variable connector module under control of the computer；Computer receives the measurement data of the voltage measurement module sampled via single-chip microcontroller, and computer carries out measurement data It handles and generates final Calibration Report.
- 2. calibration system as described in claim 1, it is characterised in that: the first impedance module and the second impedance module are single Variable resistance.
- 3. calibration system as claimed in claim 2, it is characterised in that the range of the resistance value of variable resistance is 10K Ω~20K Ω.
- 4. calibration system as described in claim 1, it is characterised in that: the first impedance module and the second impedance module are multichannel Module made of gating switch is connected with measuring resistance array:The multi-channel gating switch is connected with the single-chip microcontroller；The multi-channel gating switch only gates a specific criteria resistance in electric resistance array, makes this under the control of single-chip microcontroller Impedance module it is identical as the resistance value of the specific criteria resistance to external impedance.
- 5. calibration system as claimed in claim 2 or claim 3, it is characterised in that: measuring resistance array includes that resistance value is 10K Ω, 12K The measuring resistance of Ω, 14K Ω, 16K Ω, 18K Ω, 20K Ω.
- 6. a kind of calibration method of calibration system as claimed in claims 1-5, it is characterised in that: missed including voltage with respect to indicating value The obtaining step of difference:Step 1) is disconnected by the working electrode, reference electrode and auxiliary electrode of school cyclic voltammetric analyzer；The terminals 1 of calibration system are connected to by the working electrode of school cycle analysis instrument by step 2)；By the wiring of calibration system End 2 is connected to by the reference electrode of school cycle analysis instrument；The terminals 3 of calibration system are connected to by the auxiliary of school cycle analysis instrument Help electrode；Step 3), computer send control instruction to single-chip microcontroller, and MCU driving multiplexing module enables voltage measurement module Enough measure the potential difference at the first impedance module both ends；Step 4), setting uniformly choose no less than 5 by school cyclic voltammetric analyzer voltage output in the voltage range of its measurement A calibration point is recorded by the voltage value U of school cyclic voltammetric analyzerXWith the voltage reading numerical value U of voltage measurement moduleS, computer is logical Cross the test data of single-chip microcontroller recording voltage test module；Step 5), voltage is with respect to the error of indication according to the following formula:Wherein: ΔUIt is voltage with respect to the error of indication；UXFor by school cyclic voltammetric analyzer voltage indicating value；USFor voltage measurement module Voltage indicating value.
- 7. a kind of electric current of calibration system as claimed in claim 6 is with respect to the calibration method of the error of indication, it is characterised in that: institute Voltage is stated with respect to the obtaining step for after the obtaining step of the error of indication further including the opposite error of indication of electric current:Step 11) is disconnected by the working electrode, reference electrode and auxiliary electrode of school cyclic voltammetric analyzer；The terminals 1 of calibration system are connected to by the working electrode of school cycle analysis instrument by step 12)；By connecing for calibration system Line end 2 is connected to by the reference electrode of school cycle analysis instrument；The terminals 3 of Barebone are connected to the auxiliary of school cycle analysis instrument Electrode；Step 13), computer send control instruction to single-chip microcontroller, and MCU driving multiplexing module enables voltage measurement module Enough measure the potential difference at the second impedance module both ends；Step 14) is arranged by school cyclic voltammetric analyzer voltage output Ub, change the first impedance module to external impedance R1, second Normal impedance module to external impedance R2, to change the electric current for passing through working electrode and auxiliary electrode, record is recycled by school and is lied prostrate The current value I of dutiful analyzerXWith the voltage reading numerical value U of voltage measurement moduleS, computer by single-chip microcontroller recording voltage test mould The test data of block；Step 15), following formula calculating currents are with respect to the error of indication:Wherein: ΔIIt is electric current with respect to the error of indication；IXFor by school cyclic voltammetric analyzer electric current indicating value；R2For the second impedance module Resistance value；USFor the voltage indicating value of voltage measurement module.
- 8. a kind of calibration method of calibration system as claimed in claim 7, it is characterised in that: the electric current is obtained with respect to the error of indication Take step before obtaining step of the electric current with respect to the error of indication.
- 9. a kind of calibration method of calibration system as claimed in claim 7 or 8, it is characterised in that: further include linearity error point Analyse step:Each parameter of cyclic voltammetric analyzer is adjusted to normal operating conditions, according to the explanation of cyclic voltammetric analyzer by step 21) Book, the 10mL/L series standard solution used are calibrated；Step 22) records measurement result c using the series standard solution that cyclic voltammetric analyzer measures other concentration respectivelyi；Step 23), following formula calculate linearity error:Wherein: ΔiFor the linearity error of i-th of concentration measurement；ciFor the instrument measurements of i-th of concentration standard solution；csi For the standard value of i-th of concentration standard solution；Maximum linearization error value take absolute value as the linear of cyclic voltammetric analyzer Error.
- 10. a kind of calibration method of calibration system as claimed in claims 6 or 7, feature also with: further include cyclic voltammetric The calibration method of the repeatability of analyzer:Each parameter of cyclic voltammetric analyzer is adjusted to normal operating conditions by step 31), executes step 21), step 22) every time, Measure the concentration of 3 10mL/L series standard solution；Step 32), measurement reproducibility according to the following formula:Wherein: δ is measurement reproducibility；cmax、cminMaximum value, minimum value for 3 measurement results；For 3 measurement results Average value.
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| CN110749848A (en) * | 2019-09-25 | 2020-02-04 | 西安航天计量测试研究所 | Current parameter calibration system and method based on current channel switching instrument |
| CN110823976A (en) * | 2019-11-28 | 2020-02-21 | 河南省计量科学研究院 | Microbial membrane electrode method BOD analyzer calibration method |
| CN113774471A (en) * | 2021-09-06 | 2021-12-10 | 吉林江机特种工业有限公司 | Current and voltage parameter online calibration method based on electroplating automatic production line |
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Address after: No. 8 Qishan Road, Shiqi Town, Panyu District, Guangzhou City, Guangdong Province, 510000, 150 Patentee after: Radio and TV Measurement and Testing Group Co.,Ltd. Patentee after: GRGT METERING DETECTION (NANNING) Co.,Ltd. Address before: 510630 Xiping Road, Whampoa Road, Tianhe District, Guangzhou, Guangdong 163 Patentee before: GUANGZHOU GRG METROLOGY & TEST Co.,Ltd. Patentee before: GRGT METERING DETECTION (NANNING) Co.,Ltd. |
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