HEAVY METAL DETECTOR
20230103375 · 2023-04-06
Assignee
Inventors
- Yifang ZHAN (Wuhan, CN)
- Jinwei HU (Wuhan, CN)
- Shaowen SUN (Wuhan, CN)
- Lihua WANG (Wuhan, CN)
- Qi YAO (Wuhan, CN)
- Mingjie CHEN (Wuhan, CN)
- Tingting LI (Wuhan, CN)
- Sijie ZHENG (Wuhan, CN)
- Changchang WANG (Wuhan, CN)
- Jinyan GUAN (Wuhan, CN)
- Zheng LI (Wuhan, CN)
- Xiangru BAI (Wuhan, CN)
- Jing Wei (Wuhan, CN)
- Baoxi LI (Wuhan, CN)
Cpc classification
G01N27/283
PHYSICS
International classification
Abstract
A heavy metal detector includes a housing composed of a top cover and a base, and a main machine and an electrolysis module arranged in the housing, wherein the main machine includes a main machine circuit, and the main machine circuit includes a main controller, a power supply module, a signal acquisition and processing module, an electrolysis module interface and a signal conversion module. The electrolysis module interface is configured to connect the electrolysis module and the signal acquisition and processing module; the signal acquisition and processing module is configured to receive a characteristic electrical signal output by the electrolysis module, and output a detection result to the main controller; and the main controller displays the detection result on a display module. Multiple electrolysis module interfaces are provided. The base is provided with a plurality of electrolysis module installation ports and stirring devices corresponding to the electrolysis module installation ports.
Claims
1. A heavy metal detector, comprising a housing having a top cover and a base, and a main machine and an electrolysis module both arranged in the housing, wherein the main machine comprises a main machine circuit, and the main machine circuit comprises a main controller, a power supply module, a signal acquisition and processing module, an electrolysis module interface and a signal conversion module; the main controller being electrically connected to the signal acquisition and processing module, the signal conversion module and the power supply module; the electrolysis module interface being configured to connect the electrolysis module and the signal acquisition and processing module; the signal acquisition and processing module being configured to receive a characteristic electrical signal output by the electrolysis module, and then output a detection result to the main controller; the main controller being configured to display the detection result on a display module; and wherein a plurality of electrolysis module interfaces are provided, and the base is provided with a plurality of electrolysis module installation ports and stirring devices arranged side by side with the electrolysis module installation ports.
2. The heavy metal detector according to claim 1, wherein the electrolysis module comprises an electrode mounting plug and a screen-printed electrode (SPE); the SPE being installed on the electrode mounting plug in a plug-in fashion and electrically connected to the electrolysis module, and the electrode mounting plug being installed on the base in a plug-in fashion and electrically connected to the main machine circuit.
3. The heavy metal detector according to claim 2, wherein the SPE is a double-sided electrode comprising a PET substrate and electrodes arranged in mirror on both sides of the PET substrate; and the electrodes comprising a reference electrode, a working electrode and an auxiliary electrode.
4. The heavy metal detector according to claim 2, wherein the SPE is a dual-working electrode comprising a reference electrode, a first working electrode, a second working electrode and an auxiliary electrode arranged on one side of the PET substrate, and the first working electrode, the second working electrode and the auxiliary electrode being all L-shaped.
5. The heavy metal detector according to claim 2, wherein the electrode mounting plug is provided with a plug interface for installing the SPE, a guide groove is vertically arranged on an outside of the plug interface, and upper and lower ends of the guide groove are open; and the SPE is installed in the plug interface, and partially disposed in the guide groove.
6. The heavy metal detector according to claim 5, wherein the guide groove comprises a first side, a second side and a groove bottom plate, the first side and the second side being respectively disposed on both sides of the groove bottom plate; upper edges of the first side, the second side and the groove bottom plate being flush; and a length of the first side being greater than a length of the groove bottom plate, and the length of the groove bottom plate being greater than a length of the second side.
7. The heavy metal detector according to claim 6, wherein the first side comprises a first side plate provided with a first limiting rib, the first side plate being perpendicular to the groove bottom plate, the first side plate being perpendicular to the first limiting rib, the groove bottom plate and the first limiting rib being parallel to each other and disposed on the same side of the first side plate, an upper end of the first side plate being flush with an upper end of the first limiting rib, and a length of the first side plate being greater than a length of the first limiting rib; the second side comprises a second side plate provided with a second limiting rib, the second side plate being perpendicular to the groove bottom plate, the second side plate being perpendicular to the second limiting rib, the groove bottom plate and the second limiting rib being parallel to each other and disposed on the same side of the second side plate, an upper end of the second side plate being flush with an upper end of the second limiting rib, and a length of the second side plate being greater than a length of the second limiting rib; and the first side plate, the first limiting rib, the groove bottom plate, the second side plate, and the second limiting rib form the guide groove.
8. The heavy metal detector according to claim 1, wherein the stirring device comprises a stirring barrel, a reaction cell and a drive motor, the drive motor being embedded in a housing of the main machine and disposed on the bottom of the stirring barrel, the drive motor being a rotating motor or an eccentric motor and configured to drive the stirring barrel to rotate or vibrate quickly, and the reaction cell being detachably disposed in the stirring barrel and configured to follow the rotation or vibration of the stirring barrel during detection.
9. The heavy metal detector according to claim 1, wherein the signal conversion module is connected to a voice prompt module and the display module, the voice prompt module being configured to receive an instruction of the main controller conveyed by the signal conversion module and perform voice broadcast, and the display module comprising a running indicator and an LCD touch screen.
10. The heavy metal detector according to claim 1, further comprising an external interface module, wherein the external interface module is disposed on a rear side of the base and comprises a RS232 serial interface, a USB interface, an Ethernet interface, a Mini USB interface and a power socket.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The appended drawings described here are intended to provide a further understanding of the embodiments of the present disclosure, which constitute a part of the present disclosure, and do not constitute a limitation to the embodiments of the present disclosure, in which:
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REFERENCES
[0040] 1. LCD touch screen [0041] 2. power switch button [0042] 3. housing [0043] 4. running indicator [0044] 5. top cover [0045] 6. function expansion module [0046] 7. base [0047] 8. stirring device [0048] 9. screen-printed electrode (SPE) [0049] 10. guide groove [0050] 11. electrode plug [0051] 12. movable flip [0052] 13. RS232 serial interface [0053] 14. USB interface [0054] 15. Ethernet interface [0055] 16. Mini USB interface [0056] 17. power socket [0057] 18. PET substrate [0058] 19. reference electrode [0059] 20. working electrode [0060] 21. auxiliary electrode [0061] 22. reaction cell [0062] 23. stirring barrel [0063] 24. rotating motor [0064] 101. first side [0065] 102. groove bottom plate [0066] 103. second side [0067] 101a. first side plate [0068] 101b. first limiting rib [0069] 103a. second side plate [0070] 103b. second limiting rib [0071] 20-1. first working electrode [0072] 20-2. second working electrode [0073] 25-1. first locating hole [0074] 25-2. second locating hole
DETAILED DESCRIPTION
[0075] The present disclosure is further described in detail below with reference to the embodiments and drawings. The exemplary embodiments and descriptions of the present disclosure are merely intended to explain the present disclosure, rather than a limitation of the present disclosure.
[0076] Before explaining the present disclosure in more detail, it may be helpful to understand the present disclosure by providing definitions of certain terms used herein.
[0077] The terms first, second, and the like are merely used for distinguishing description, and shall not be understood as indicating or implying relative importance. Although the terms first, second, and the like may be used herein to describe various units, these units should not be limited by these terms. These terms are merely intended to distinguish one unit from another. For example, a first unit may be referred to as a second unit, and the second unit may be similarly referred to as the first unit without departing from the scope of the exemplary embodiment of the present disclosure.
[0078] When a unit is referred to as being “connected to”, “connected with” or “coupled to” the other unit, it may be directly connected or coupled to the other unit, or intervening units may exist. In contrast, when a unit is referred to as being “directly connected to” or “directly coupled to” the other unit, no intervening unit exists. Other words used to describe the relationship between units should be interpreted in a similar way (e.g., “between” and “directly between”, “adjacent” and “directly adjacent”, and the like).
[0079] In the description of the present disclosure, it should also be noted that, unless otherwise clearly defined and limited, the terms “provide”, “install”, and “connect” should be understood in a broad sense. For example, it may be a fixed connection, a detachable connection, or an integral connection; it may be a mechanical connection or an electrical connection; and it may be a direct connection or an indirect connection through an intermediate medium, and it may be an internal communication between two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present disclosure can be understood in specific situations.
[0080] The terms used herein are merely intended to describe specific embodiments, rather than limiting the exemplary embodiments of the present disclosure. As used herein, singular forms “a”, “an” and “the” are intended to include plural forms unless the context clearly indicates the opposite. It should also be understood that the terms “include”, “including”, “comprise”, and/or “comprising” when used herein, specify the existence of the stated features, integers, steps, operations, units and/or components and do not exclude the existence or addition of one or more other features, quantities, steps, operations, units, components, and/or their combinations; the term “and/or” used herein is merely an association relationship describing related objects, which means that three relationships may exist, for example, A and/or B means that: A alone exists, B alone exists, and A and B exist at the same time. The term “/and” used herein describes another association relationship of objects, which means that two relationships may exist, for example, A/and B means that: A alone exists, and A and B alone exist. In addition, the character “/” used herein generally means that the associated objects before and after are of an “or” relationship.
[0081] The anodic stripping voltammetry (ASV) was invented in the 1820s, which refers to an electrochemical analysis method in which metal ions under test are partially reduced to metal at a certain potential and precipitated on a surface of an electrode, and then a reverse voltage is applied to the electrode such that the metal on the electrode oxidizes to generate an oxidation current, and analysis is performed according to a current-voltage curve of the oxidation process. This method has the advantages of fast measurement speed, low detection limit, and can be used for simultaneous qualitative and quantitative analysis of a plurality of metal elements.
[0082] Screen-printed electrode (SPE), also called as thick-film electrode, includes a working electrode, a reference electrode and an auxiliary electrode, which is an electrochemical sensor prepared by thick-film integrated circuit technology. Recognition molecules (such as enzymes, antibodies, or nucleic acids) are often immobilized on the surface of the working electrode. SPEs usually have a Ag/AgCl layer as a reference electrode. The main advantages of screen printing technology include: flexible design, easy automatic mass production in the printing process, convenient use, good reproducibility, easy modification, and suitability for various materials.
[0083] Specific details are set forth in the following description to facilitate a complete understanding of the exemplary embodiments. However, those of ordinary skill in the art should understand that the exemplary embodiments can be implemented without these specific details. For example, the system can be shown in a block diagram to avoid unnecessary details to make the example unclear. In other instances, well-known procedures, structures, and techniques may not be shown in unnecessary details to avoid making the example embodiments unclear.
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[0085] The function expansion module 6 is a reserved position, and exclusive function modules can be customized according to user needs, such as weighing module, for example, a high-precision balance may be added for sample weighing; printing module, for example, a small printer may be added for printing detection results; and pre-treatment module, for example, a corresponding equipment may be added according to pre-treatment process requirements.
[0086] In some embodiments, the electrolysis module includes an electrode plug (i.e., an electrode mounting plug) 11 and a SPE 9. The electrolysis module is connected to the base through an electrolysis module interface. A plurality of electrolysis modules with the same structure and a plurality of corresponding electrolysis module interfaces may be provided. The electrolysis module interface includes an electrolysis module installation port and the stirring device 8 that are arranged on the base, in which the stirring device 8 and the electrolysis module installation port are arranged side by side. As shown in
[0087] By providing a plurality of electrolysis module interfaces, a plurality of electrolysis modules may be connected, increasing the number of detection units of the detector, enabling a plurality of detections at the same time. Moreover, special docking is realized through the electrolysis module interface, which is convenient to use. The simultaneous use of a plurality of electrolysis modules improves the efficiency and can obtain a plurality of reference results, making the results more stable.
[0088] By providing the electrode mounting plug that is installed on the base in a plug-in fashion and electrically connected to the main machine circuit, it is convenient to remove the electrode mounting plug to install the SPE, avoiding the inconvenience caused by the operation on the entire instrument. At the same time, the SPE can be installed in place, improving the detection accuracy.
[0089] In some embodiments, a rear side of the base 7 is provided with an external interface module. The heavy metal detector communicates with the outside through the external interface module. As shown in
[0090]
[0091] In a possible embodiment, the SPE is a double-sided electrode. The double-sided electrode includes a PET substrate and electrodes arranged in mirror on both sides of the PET substrate. As shown in
[0092] In a possible embodiment, as shown in
[0093] In some embodiments, the above dual-working electrode is a single-sided dual-working electrode. When designing the single-sided dual-working electrode, the areas of the working electrodes are controlled to a certain proportion, and the proportion of the current signals of the two working electrodes is analyzed through a software to determine a validity of the results. During implementation, a channel for corresponding data is designed through instrument hardware, avoiding the influence of factors such as the effective contact area and angle change of the solution under test and the working electrode, during the enrichment processes of a plurality of measurement on the detection results, and removing abnormal values. When analyzing a double-electrode signal, a correction algorithm is introduced through a detection software.
[0094] In a possible embodiment, as shown in
[0095] Moreover, with the addition of the guide groove and the use of the plug-in connection, the stability of the instrument is further enhanced, and the stability of the detection results is better, such that the stability of the detection results of different testers is significantly enhanced. In other words, adding a locating device and adopting a plug-in connection can significantly improve the stability of the detection results, reduce personnel operating errors, and beneficially improve the on-site adaptability of the instrument.
[0096] In some embodiments, the guide groove 10 includes a first side 101, a second side 103 and a groove bottom plate 102. The first side 101 and the second side 103 are respectively disposed on both sides of the groove bottom plate 102. Upper edges of the first side 101, the second side 103 and the groove bottom plate 102 are flush. A length of the first side 101 is greater than a length of the groove bottom plate 102. The length of the groove bottom plate 102 is greater than a length of the second side 103. By setting the lengths of the first side, the groove bottom plate and the second side to be reduced sequentially, the electrode can be easily located and installed from the first side as the first position when installing the electrode, improving the accuracy and consistency of the installation position.
[0097] In some embodiments, the first side 101 includes a first side plate 101a. The first side plate 101a is provided with a first limiting rib 101b. The first side plate 101a and the groove bottom plate 102 are arranged perpendicularly. The first side plate 101a and the first limiting rib 101b are arranged perpendicularly. The groove bottom plate 102 and the first limiting rib 101b are arranged in parallel and disposed on the same side of the first side plate 101a. An upper end of the first side plate 101a is flush with an upper end of the first limiting rib 101b. A length of the first side plate 101a is greater than a length of the first limiting rib 101b. As shown in
[0098] The limiting ribs on the two side plates realize further limiting, such that the position is more accurate.
[0099] In some embodiments, as shown in
[0100] In some embodiments, as shown in
[0101] In some embodiments, the drive motor is a rotating motor. The rotating motor is embedded in the housing of the main machine and disposed at the bottom of a rotating seat of the stirring barrel. A certain offset exists between a rotating shaft of the rotating motor and an axis of the rotating seat. The rotating motor is configured to drive the rotating seat to rotate and swing rapidly. The reaction cell is detachably disposed in the rotating seat, and follows the rotation and swinging of the rotating seat around the axis during detection. This rotation mode helps to improve the stirring efficiency.
[0102] In some embodiments, the heavy metal detector adopts a dual-channel detection mode, and its core controls are distributed in a view layer, a controller, and a model layer. The view layer is composed of a touch screen and client software. The user can configure parameters of an upper computer in the view layer, change a detection mode, control a detection process and obtain a final result. The controller includes a master control module and a plurality of sub-control modules. The controller assigns work tasks to the model layer according to instructions issued by the view layer to be executed by a plurality of lower computers. The master control module completes a routing function in accordance with the serial communication protocol, and detection processes of the channels are individually controlled by specific sub-control modules without interfering with each other, ensuring that synchronous detection and asynchronous detection requirements are supported.
[0103] In some embodiments, the detection process of a dual-channel or multi-channel heavy metal detector is as follows:
[0104] Startup: the power switch button of the instrument is clicked, the running indicator lights up, the LCD touch screen displays an interactive interface, and it is prompted through voice that the instrument is on.
[0105] Detection initialization configuration: the reference limit, sample number, sample type, detection time, channel selection, detection mode selection, submission unit, detection personnel information and other parameters are set.
[0106] Electrode activation: the electrode activation mode is selected, the two electrode plugs are taken out, a SPE is placed in an electrode socket (i.e., a plug interface of the electrode plug) and the electrode plugs are returned to the original position, and at the same time a certain amount of activator is injected into the two reaction cells with the guarantee that the liquid level is above the reaction zone at the bottom of the SPE, the start button on the interactive interface is clicked, and the stirring device starts up.
[0107] Sample detection: a sample detection mode is selected, a certain amount of sample solution under test is injected into the two reaction cells, the start button on the interactive interface is clicked, and the stirring device starts up to enter the detection process.
[0108] Completion of detection: the sample solution under test undergoes an electrochemical reaction on the surface of the SPE, the online detection system draws the characteristic electrical signal curve output by the control system on the LCD touch screen so as to display various test results of the tested sample, and it is prompted through voice that the detection is complete.
[0109] The beneficial effects can be illustrated through following experimental data:
[0110] A guide groove is provided at the end of the electrode socket to limit the insertion position of the SPE in both the horizontal and vertical directions to ensure a constant position of the electrode reaction zone during detection, that is, it is always disposed in the central area of the reaction cell. The connection between the electrode plug and the instrument is changed to a separate plug-in connection, which fixes the electrode immersion depth and facilitates the plug-in operation of the electrode, improving the detection accuracy and stability as a whole.
[0111] Cadmium element detection data is used as an example in the following to compare and analyze the performance of the instrument before and after the improvement:
[0112] (1) Instrument stability test data before the improvement
[0113] Under the control of the same ambient temperature and humidity, testers A, B, C, and D use unimproved heavy metal detectors 1 #, 2 #, 3 #, 4 #, and 5 # to perform instrument stability test. The test method is to define various parameters for instruction detection and use the same batch of SPEs. Each tester tests a 5 ppb standard single element solution of cadmium 20 times, and calculates a relative standard deviation (RSD) of each group of 20 pieces of detection data. The results are shown in the following table:
TABLE-US-00001 TABLE 1 Detection data of instrument stability test before the improvement from tester A and B Current/μA Tester A Tester B Instrument No. Test No. 1# 2# 3# 4# 5# 1# 2# 3# 4# 5# 1 0.4401 0.5171 0.5521 0.5143 0.6644 0.5821 0.3974 0.4349 0.4686 0.4152 2 0.4215 0.4039 0.5120 0.4143 0.4363 0.5547 0.4320 0.3901 0.5124 0.5295 3 0.5401 0.5302 0.5152 0.5857 0.4165 0.6578 0.4726 0.5459 0.5238 0.3889 4 0.6013 0.6028 0.5321 0.5857 0.5355 0.5260 0.4337 0.4563 0.5043 0.6338 5 0.5975 0.5024 0.4607 0.4140 0.6843 0.5080 0.4695 0.4651 0.4784 0.5423 6 0.7204 0.5504 0.5312 0.5286 0.5851 0.4279 0.4939 0.4940 0.4524 0.6864 7 0.6653 0.5037 0.6107 0.4857 0.7140 0.4332 0.5025 0.4385 0.4232 0.3391 8 0.5298 0.6034 0.5429 0.5714 0.6545 0.4937 0.4807 0.4313 0.5076 0.6106 9 0.4936 0.6124 0.5624 0.5857 0.5156 0.4912 0.4093 0.4922 0.5238 0.6848 10 0.6452 0.5387 0.6546 0.6025 0.4165 0.4895 0.5081 0.5047 0.4054 0.4400 11 0.6578 0.5650 0.5034 0.5429 0.6148 0.6446 0.4601 0.4922 0.4643 0.4384 12 0.6042 0.4463 0.4513 0.5012 0.6744 0.3643 0.4869 0.4636 0.4800 0.3627 13 0.7034 0.4507 0.4508 0.4543 0.6545 0.7336 0.5354 0.4725 0.4654 0.7091 14 0.7012 0.5071 0.4937 0.5213 0.7339 0.5335 0.4286 0.4351 0.5027 0.5392 15 0.7608 0.5103 0.4819 0.5428 0.7141 0.3694 0.5114 0.4045 0.5075 0.4710 16 0.3901 0.4525 0.4582 0.5429 0.3570 0.3910 0.4347 0.4403 0.4422 0.4602 17 0.3804 0.4600 0.4801 0.4289 0.5950 0.7167 0.5203 0.4259 0.4765 0.7384 18 0.4947 0.4013 0.4919 0.4428 0.5454 0.3692 0.5132 0.4886 0.5676 0.5221 19 0.7031 0.4152 0.4138 0.4571 0.5851 0.5345 0.473 0.4361 0.5335 0.4493 20 0.6742 0.4702 0.4913 0.4286 0.7239 0.4507 0.5679 0.4349 0.4930 0.4897 AV 0.5862 0.5022 0.5095 0.5075 0.5910 0.5136 0.4766 0.4573 0.4866 0.5225 SD 0.1149 0.0631 0.0555 0.0616 0.1115 0.1080 0.0432 0.0366 0.0380 0.1164 RSD 19.6% 12.6% 10.9% 12.1% 18.9% 21.0% 9.1% 8.0% 7.8% 22.3%
TABLE-US-00002 TABLE 2 Detection data of instrument stability test before the improvement from tester C and D Current/μA Tester C Tester D Instrument No. Test No. 1# 2# 3# 4# 5# 1# 2# 3# 4# 5# 1 0.4084 0.4944 0.4049 0.3707 0.4429 0.3884 0.4533 0.4807 0.3911 0.4858 2 0.6564 0.4343 0.4599 0.3947 0.5269 0.3924 0.3839 0.4301 0.4245 0.6339 3 0.3746 0.5142 0.4551 0.5231 0.4867 0.6686 0.3567 0.5031 0.5091 0.5866 4 0.5068 0.5023 0.4810 0.4974 0.4314 0.4715 0.5145 0.5469 0.5613 0.4788 5 0.4137 0.4972 0.4637 0.4909 0.5392 0.7053 0.5268 0.5596 0.5964 0.5733 6 0.6169 0.4504 0.4211 0.4914 0.6825 0.6736 0.4906 0.5486 0.5626 0.5810 7 0.5538 0.4608 0.4901 0.5192 0.7349 0.5380 0.5023 0.5458 0.5598 0.3035 8 0.5934 0.4912 0.4457 0.4384 0.4483 0.6077 0.5004 0.4095 0.4851 0.3439 9 0.5038 0.5224 0.4083 0.5291 0.6810 0.4968 0.5267 0.5276 0.4056 0.4637 10 0.4694 0.4704 0.5136 0.4971 0.4476 0.7141 0.5178 0.4844 0.4957 0.4009 11 0.4347 0.5632 0.4768 0.5374 0.4561 0.4483 0.4377 0.5457 0.5524 0.4384 12 0.4436 0.4528 0.4799 0.5378 0.5593 0.4856 0.5144 0.5344 0.5120 0.5530 13 0.6360 0.4592 0.4813 0.4710 0.6902 0.4804 0.5298 0.5378 0.4821 0.5395 14 0.4128 0.4244 0.5406 0.5103 0.5361 0.7100 0.5136 0.3971 0.5032 0.4107 15 0.3804 0.4176 0.5468 0.4966 0.4684 0.3953 0.5462 0.3996 0.4154 0.6272 16 0.7168 0.4880 0.5053 0.4957 0.4576 0.3905 0.4388 0.4231 0.5177 0.5868 17 0.6414 0.4428 0.4208 0.5019 0.7372 0.5509 0.4521 0.4345 0.4904 0.4249 18 0.4310 0.4528 0.5435 0.4338 0.4992 0.5211 0.5123 0.5069 0.5629 0.5194 19 0.5345 0.4320 0.3987 0.4563 0.4468 0.5164 0.6112 0.4395 0.5022 0.4587 20 0.5993 0.4416 0.4461 0.4099 0.5146 0.5194 0.5708 0.4171 0.4647 0.3579 AV 0.5164 0.4706 0.4692 0.4801 0.5393 0.5337 0.4950 0.4836 0.4997 0.4884 SD 0.1019 0.0366 0.0445 0.0468 0.1027 0.1086 0.0586 0.0572 0.0563 0.0941 RSD 19.7% 7.8% 9.5% 9.8% 19.1% 20.3% 11.8% 11.8% 11.3% 19.3%
TABLE-US-00003 TABLE 3 Comparison list of instrument stability test data before the improvement Test instrument Tester 1# 2# 3# 4# 5# Average Tester A 19.6% 12.6% 10.9% 12.1% 18.9% 14.8% Tester B 21.0% 9.1% 8.0% 7.8% 22.3% 13.6% Tester C 19.7% 7.8% 9.5% 9.8% 19.1% 13.2% Tester D 20.3% 11.8% 11.8% 11.3% 19.3% 14.9%
[0114] From the above data, it is found that the relative standard deviations of the detection data measured by different testers using the 1 # and 5 # instruments are significantly higher than those of other instruments. After careful inspection, it is found that the electrode socket of the instrument is loose and the electrode inserted is easy to tilt. This situation has increased the influence of electrode insertion method and angle on the stability of test results. Comparing the relative standard deviations of the detection data measured by different testers using the 2 #, 3 # and 4 # instruments, it is found that the stability of the testers' detection results is: B>C>A and D.
[0115] (2) Analysis of Stability Test Data after Adding an Electrode Guide Groove to the Instrument
[0116] Under the same ambient temperature and humidity, testers A, B, C, D use heavy metal detectors 1 #, 2 #, 3 #, 4 #, and 5 # with an electrode socket (a locating device is added) to perform instrument stability test. The test method is to define various parameters for instrument detection and use the same batch of SPEs (electrode batch: NA07-1, round working electrode). Each tester tests a 5 ppb standard single element solution of cadmium 20 times, and calculates a relative standard deviation of each group of 20 pieces of detection data. The results are shown in the following table:
TABLE-US-00004 TABLE 4 Test data of instrument stability test after electrode locating from tester A and B Current/μA Tester A Tester B Instrument No. Test No. 1# 2# 3# 4# 5# 1# 2# 3# 4# 5# 1 0.4545 0.4395 0.4517 0.4380 0.4156 0.4483 0.4744 0.4556 0.4604 0.4573 2 0.4600 0.3954 0.4026 0.5946 0.4827 0.4742 0.4208 0.4848 0.4422 0.3858 3 0.4466 0.4195 0.4921 0.4318 0.4699 0.4564 0.4569 0.4615 0.4735 0.4271 4 0.4629 0.3868 0.3935 0.4521 0.4661 0.4564 0.4192 0.4651 0.4655 0.4001 5 0.4988 0.4287 0.4124 0.3317 0.3917 0.5132 0.4540 0.5042 0.4604 0.4414 6 0.5244 0.4607 0.4825 0.4257 0.3602 0.4778 0.4772 0.4849 0.4876 0.4430 7 0.4108 0.4923 0.5464 0.4114 0.3849 0.4689 0.4859 0.4753 0.4871 0.3137 8 0.4866 0.5293 0.4266 0.4162 0.3679 0.4671 0.4641 0.4345 0.4204 0.4938 9 0.4953 0.4389 0.4059 0.4537 0.3865 0.4493 0.4216 0.4552 0.4397 0.4398 10 0.5345 0.5399 0.4413 0.4396 0.4623 0.4671 0.4917 0.4126 0.4528 0.4482 11 0.5059 0.5319 0.4378 0.5085 0.4153 0.4796 0.4453 0.4354 0.4687 0.6558 12 0.5462 0.4590 0.5065 0.4306 0.6927 0.4403 0.4700 0.4453 0.4403 0.6654 13 0.4113 0.4140 0.4186 0.4772 0.6812 0.5295 0.5178 0.5044 0.4604 0.4779 14 0.3952 0.4169 0.4777 0.4475 0.6366 0.4439 0.4816 0.4552 0.4771 0.4587 15 0.3732 0.4489 0.5208 0.4103 0.4934 0.4635 0.4946 0.4175 0.4588 0.5589 16 0.4292 0.4145 0.4745 0.3865 0.5785 0.5027 0.5065 0.5047 0.4702 0.4752 17 0.5143 0.4989 0.4825 0.5473 0.6385 0.4760 0.5034 0.4849 0.4729 0.692 18 0.3981 0.5272 0.4586 0.4600 0.4933 0.4403 0.4961 0.4453 0.4765 0.7084 19 0.4111 0.4425 0.4506 0.4553 0.4168 0.4617 0.4670 0.4651 0.4604 0.4001 20 0.5093 0.4126 0.5640 0.5422 0.4143 0.4671 0.5083 0.4478 0.4638 0.4684 AV 0.4634 0.4549 0.4623 0.4530 0.4824 0.4692 0.4728 0.4620 0.4619 0.4906 SD 0.0509 0.0472 0.0466 0.0578 0.1037 0.0229 0.0289 0.0264 0.0163 0.1061 RSD 11.0% 10.4% 10.1% 12.8% 21.5% 4.9% 6.1% 5.7% 3.5% 21.6%
TABLE-US-00005 TABLE 5 Test data of instrument stability test after electrode locating from tester C and D Current/μA Tester C Tester D Instrument No. Test No. 1# 2# 3# 4# 5# 1# 2# 3# 4# 5# 1 0.5237 0.5201 0.5302 0.4822 0.4726 0.4884 0.4248 0.5152 0.4762 0.6237 2 0.5131 0.4627 0.5227 0.4658 0.5678 0.4902 0.4627 0.4563 0.4701 0.618 3 0.5331 0.4842 0.5013 0.483 0.5226 0.4964 0.4786 0.4495 0.4786 0.5745 4 0.4962 0.5235 0.4435 0.4414 0.6609 0.5113 0.4515 0.4592 0.4571 0.4413 5 0.4238 0.4634 0.4805 0.4521 0.6504 0.4658 0.5006 0.4594 0.4882 0.4065 6 0.4684 0.4529 0.4101 0.4517 0.4210 0.5130 0.5246 0.4588 0.4041 0.3772 7 0.5008 0.4553 0.3928 0.4215 0.4049 0.4195 0.4908 0.4671 0.4701 0.3731 8 0.4761 0.4834 0.4369 0.4508 0.4887 0.4833 0.4887 0.5017 0.4419 0.4261 9 0.4469 0.5017 0.5076 0.4828 0.4533 0.5342 0.4633 0.4317 0.4532 0.3998 10 0.4715 0.4484 0.4668 0.4847 0.4484 0.5233 0.4289 0.4557 0.4638 0.4231 11 0.4907 0.4623 0.5396 0.4633 0.4742 0.4568 0.4364 0.4812 0.4715 0.6602 12 0.4392 0.4911 0.4734 0.4708 0.4452 0.4740 0.4225 0.4400 0.4721 0.5015 13 0.4592 0.5087 0.4446 0.483 0.4194 0.4559 0.5211 0.4986 0.4679 0.4139 14 0.4607 0.3673 0.4964 0.4645 0.5975 0.4543 0.4798 0.4600 0.4614 0.5964 15 0.4530 0.4529 0.4372 0.4761 0.4855 0.4886 0.4564 0.5031 0.4646 0.3949 16 0.4546 0.4581 0.4451 0.4845 0.4162 0.4458 0.4223 0.5025 0.5162 0.4124 17 0.4838 0.3613 0.4709 0.4828 0.3952 0.4980 0.5442 0.4610 0.5093 0.5202 18 0.5051 0.4329 0.4868 0.4809 0.3984 0.4844 0.4877 0.4828 0.5490 0.5707 19 0.5855 0.5012 0.4667 0.4622 0.4145 0.4761 0.5407 0.4209 0.4803 0.4134 20 0.4375 0.5089 0.4742 0.5120 0.4807 0.5054 0.4759 0.4913 0.4406 0.4275 AV 0.4811 0.4670 0.4714 0.4698 0.4809 0.4832 0.4751 0.4698 0.4718 0.4787 SD 0.0378 0.0426 0.0377 0.0194 0.0785 0.0274 0.0373 0.0254 0.0292 0.0921 RSD 7.8% 9.1% 8.0% 4.1% 16.3% 5.7% 7.9% 5.4% 6.2% 19.2%
TABLE-US-00006 TABLE 6 Instrument stability test data list after electrode locating Test instrument Tester 1# 2# 3# 4# 5# Average Tester A 11.0% 10.4% 10.1% 12.8% 21.5% 11.0% Tester B 4.9% 6.1% 5.7% 3.5% 21.6% 5.0% Tester C 7.8% 9.1% 8.0% 4.1% 16.3% 7.2% Tester D 5.7% 7.9% 5.4% 6.2% 19.2% 6.3%
[0117] From the above data, it is found that after an electrode locating device is added, the relative standard deviations of the detection data measured by different testers except for the 5 # instrument are significantly reduced, but the relative standard deviations of the detection data measured by different testers using the 1 #, 2 #, 3 # and 4 # instruments are still different, and the stability of the detection results is: B>D>C>A. After inspection, it is found that compared with the other 4 instruments, the lifting operation of a lifting rod of an electrode socket in the 5 # instrument is not smooth, and there is a phenomenon of inconsistent pressing positions for a plurality of operations, resulting in a difference in the liquid immersion depth of the electrode working zone, which affects the stability of the test results.
[0118] (3) Analysis of stability test data after adding a locating device to the electrode socket and adopting a plug-in connection between the electrode plug and the instrument
[0119] The 1 #, 2 #, 3 #, 4 #, 5 # heavy metal detectors were further improved, and a locating device was added to the electrode socket while the electrode plug was connected to the instrument in a plug-in fashion. Testers A, B, C, and D carry out instrument stability test. The test method is to: under the control of the same ambient temperature and humidity, define various parameters for instrument detection and use the same batch of SPEs (electrode batch: NA07-1, round working electrode). Each tester tests a 5 ppb standard single element solution of cadmium 20 times, and calculates a relative standard deviation of each group of 20 pieces of detection data. The results are shown in the following table:
TABLE-US-00007 TABLE 7 Test data of instrument stability test with electrode locating and pluggable electrode plug from tester A and B Current/μA Tester A Tester B Instrument No. Test No. 1# 2# 3# 4# 5# 1# 2# 3# 4# 5# 1 0.4675 0.4709 0.4666 0.4317 0.4713 0.4661 0.4598 0.4467 0.4632 0.4576 2 0.5027 0.4761 0.4534 0.4499 0.5041 0.4803 0.5027 0.4992 0.4871 0.4843 3 0.4695 0.4801 0.4867 0.4737 0.4734 0.4719 0.4956 0.4786 0.4904 0.4642 4 0.4929 0.4981 0.5008 0.4976 0.4883 0.4744 0.4948 0.4574 0.5081 0.4815 5 0.4812 0.5094 0.4728 0.4782 0.4917 0.4689 0.4693 0.5013 0.4904 0.5246 6 0.5203 0.5046 0.4967 0.4979 0.4620 0.4411 0.4439 0.5025 0.5019 0.5344 7 0.5008 0.4782 0.4605 0.4803 0.4757 0.4828 0.4452 0.4904 0.4722 0.4854 8 0.4496 0.4856 0.4766 0.4897 0.4982 0.4803 0.4979 0.4423 0.4689 0.4870 9 0.4548 0.4386 0.4887 0.4703 0.4976 0.4729 0.4839 0.5059 0.4854 0.4382 10 0.4675 0.4377 0.4565 0.4675 0.4765 0.4835 0.4977 0.4508 0.4689 0.4985 11 0.4929 0.4794 0.4847 0.4634 0.4845 0.4937 0.4659 0.4831 0.4012 0.4821 12 0.4871 0.4959 0.4827 0.4906 0.4896 0.5041 0.4709 0.4778 0.4821 0.4691 13 0.4851 0.4653 0.4746 0.4917 0.4879 0.4979 0.4566 0.4857 0.4706 0.4625 14 0.4616 0.4856 0.4809 0.4731 0.4943 0.4524 0.4932 0.484 0.5035 0.4887 15 0.5242 0.4717 0.4908 0.4754 0.5019 0.4914 0.4979 0.4876 0.4706 0.4694 16 0.4988 0.5112 0.4037 0.4471 0.4861 0.5011 0.4945 0.5081 0.5052 0.5001 17 0.5360 0.5094 0.4706 0.4609 0.4859 0.4798 0.4984 0.4903 0.4986 0.4908 18 0.5223 0.4911 0.4947 0.4891 0.4878 0.5057 0.5068 0.4475 0.5003 0.4989 19 0.5086 0.4782 0.4928 0.4816 0.4735 0.4809 0.5034 0.4741 0.4706 0.4976 20 0.4988 0.4654 0.4729 0.4550 0.4927 0.4643 0.4836 0.4681 0.4408 0.4593 AV 0.4911 0.4816 0.4754 0.4732 0.4862 0.4797 0.4831 0.4791 0.4790 0.4837 SD 0.0237 0.0202 0.0210 0.0175 0.0108 0.0163 0.0195 0.0203 0.0246 0.0222 RSD 4.8% 4.2% 4.4% 3.7% 2.2% 3.4% 4.0% 4.2% 5.1% 4.6%
TABLE-US-00008 TABLE 8 Test data of instrument stability test with electrode locating and pluggable electrode plug from tester C and D Current/μA Tester C Tester D Instrument No. Test No. 1# 2# 3# 4# 5# 1# 2# 3# 4# 5# 1 0.5059 0.4532 0.4829 0.4716 0.5401 0.4909 0.4849 0.4611 0.4668 0.4409 2 0.4965 0.4933 0.5072 0.4864 0.5341 0.4676 0.4967 0.4469 0.4850 0.4654 3 0.4808 0.4491 0.4772 0.4677 0.5078 0.4926 0.5037 0.5109 0.5455 0.5164 4 0.4984 0.4944 0.4546 0.4521 0.5045 0.4909 0.4817 0.5008 0.4846 0.5061 5 0.4928 0.4757 0.4755 0.4783 0.5049 0.4776 0.5085 0.4830 0.4618 0.4883 6 0.4471 0.4907 0.4745 0.4865 0.5041 0.4859 0.4984 0.4871 0.4884 0.4676 7 0.4752 0.5353 0.4598 0.5165 0.4936 0.5159 0.5046 0.5352 0.4710 0.5001 8 0.5088 0.4648 0.5319 0.4939 0.4997 0.4543 0.5072 0.4613 0.4719 0.4809 9 0.4901 0.4808 0.4989 0.4744 0.5057 0.4793 0.4876 0.5356 0.4894 0.5053 10 0.4783 0.4895 0.4806 0.4931 0.4798 0.4776 0.5098 0.4884 0.4708 0.5001 11 0.4812 0.4852 0.4513 0.5053 0.4758 0.4714 0.5051 0.4796 0.4781 0.4509 12 0.4513 0.5136 0.4976 0.4735 0.4778 0.5057 0.4971 0.5054 0.4905 0.4839 13 0.4927 0.5094 0.4756 0.4888 0.4968 0.4743 0.4977 0.4895 0.4426 0.5075 14 0.4252 0.4811 0.5048 0.4973 0.4932 0.4476 0.5086 0.4792 0.4788 0.4897 15 0.4989 0.4916 0.5002 0.4811 0.4881 0.5049 0.4918 0.4938 0.4899 0.4735 16 0.5096 0.4764 0.4420 0.4925 0.4657 0.5026 0.5070 0.4856 0.4813 0.4824 17 0.5071 0.4776 0.5262 0.4716 0.4978 0.4593 0.4866 0.4712 0.4813 0.4705 18 0.4848 0.4878 0.4655 0.5063 0.4826 0.5043 0.5043 0.4492 0.4905 0.4513 19 0.4859 0.4854 0.4967 0.4648 0.4936 0.4851 0.4904 0.4768 0.4482 0.4587 20 0.4882 0.4897 0.4828 0.4101 0.4857 0.4743 0.4916 0.4551 0.4553 0.4898 AV 0.4849 0.4862 0.4843 0.4806 0.4966 0.4831 0.4982 0.4848 0.4786 0.4815 SD 0.0213 0.0189 0.0232 0.0223 0.0175 0.0179 0.0087 0.0241 0.0207 0.0207 RSD 4.4% 3.9% 4.8% 4.6% 3.5% 3.7% 1.7% 5.0% 4.3% 4.3%
TABLE-US-00009 TABLE 9 Test data list of instrument stability test with electrode locating and pluggable electrode plug Test instrument Tester 1# 2# 3# 4# 5# Average Tester A 4.8% 4.2% 4.4% 3.7% 2.2% 4.3% Tester B 3.4% 4.0% 4.2% 5.1% 4.6% 4.2% Tester C 4.4% 3.9% 4.8% 4.6% 3.5% 4.4% Tester D 3.7% 1.7% 5.0% 4.3% 4.3% 3.7%
[0120] From the above data, it is found that the stability of the instrument is further enhanced after the addition of the locating device and the use of the plug-in connection. The relative standard deviation of each group of data is basically controlled below 5.0%, preferably 1.7%, such instrument has good stability, and the different testers has no significant impact on the stability of the detection. This shows that the addition of the locating device and the use of the plug-in connection can significantly improve the stability of the detection results, reduce personnel operating errors, and advantageously improve the on-site adaptability of the instrument.
[0121] 2. The design of the shape and structure of the working zone of the SPE improves the sensitivity, stability and current signal strength of the detection.
[0122] 1 #, 2 #, 3 #, 4 #, and 5 # heavy metal detectors with electrode locating and pluggable electrode plug are adopted, SPEs with working electrodes optimized (electrode batch: NA08-1, square working electrode) are adopted, under the control of the same ambient temperature and humidity, a 5 ppb standard single element solution of cadmium is tested 20 times, and a relative standard deviation of each group of 20 pieces of detection data is calculated. The results are shown in the following table:
TABLE-US-00010 TABLE 10 Comparison of different working electrode patterns vs. current signal Working Results of this method/(μA) Coefficient of electrode shape 1 2 3 4 5 6 7 Average Variation/% Determination of lead (Pb) content Square 0.27 0.25 0.24 0.28 0.24 0.21 0.22 0.25 8.6 Circular 0.30 0.30 0.29 0.26 0.27 0.27 0.26 0.28 6.1 Rectangular 0.34 0.33 0.27 0.30 0.31 0.36 0.35 0.32 9.3 Determination of cadmium (Cd) content Square 0.49 0.46 0.56 0.43 0.48 0.56 0.42 0.49 10.7 Circular 0.55 0.57 0.51 0.62 0.50 0.51 0.51 0.55 7.2 Rectangular 0.67 0.79 0.68 0.62 0.55 0.59 0.78 0.67 12.5
TABLE-US-00011 TABLE 11 Comparison of different additions of carbon-based materials vs. current signal Adding amount of carbon-based material in Results of this method/(μA) Coefficient of working electrode 1 2 3 4 5 6 7 Average Variation/% Determination of lead (Pb) content <0.3% 0.21 0.21 0.21 0.20 0.21 0.20 0.25 0.21 7.3 0.3%-0.5% 0.30 0.29 0.30 0.29 0.28 0.27 0.30 0.29 3.6 >0.5% 0.21 0.20 0.18 0.19 0.19 0.19 0.19 0.19 4.3 Determination of cadmium (Cd) content <0.3% 0.40 0.41 0.42 0.42 0.41 0.40 0.42 0.40 2.0 0.3%-0.5% 0.52 0.55 0.54 0.52 0.51 0.53 0.51 0.52 2.8 >0.5% 0.39 0.40 0.40 0.39 0.40 0.39 0.41 0.39 1.7
[0123] 3. Standard Sample Test Data
[0124] An instrument with electrode locating and pluggable electrode plug is adopted, SPEs with working electrodes optimized (electrode batch: NA08-1, square working electrode) are adopted, and a trial instrument uses recommended parameters to detect the cadmium content in an actual brown rice sample to detect the accuracy and precision of the test instrument. The detection methods are as follows:
[0125] Accuracy detection method: the cadmium content in brown rice flour is detected, physical standard samples of 3 concentration levels are adopted, each concentration level is measured 3 times in parallel, and an average value is taken. A deviation between the detection result and the physical standard sample is calculated.
[0126] Calculation method: (Detection average−sample calibration value)/sample calibration value×100%
[0127] Precision Measurement Method:
[0128] The precision is expressed by a coefficient of variation, the same physical standard sample is measured no less than 6 times, and the coefficient of variation is calculated.
[0129] Calculation method of the coefficient of variation: Coefficient of variation=standard deviation/detection mean×100%.
TABLE-US-00012 TABLE 12 Detection results of cadmium in brown rice flour samples Standard value Test value Coefficient of Number (mg/kg) (mg/kg) Average Accuracy/% Variation/% MIETAL-DJTZK-014 0.704 ± 0.055 0.709 0.714 0.698 0.709 0.4 / GBW (E) 100377 0.261 ± 0.020 0.265 0.276 0.268 0.269 3.4 1.3 0.271 0.267 0.272 GBW (E) 100378 0.169 ± 0.015 0.171 0.170 0.169 0.170 0.6 /
[0130] The accuracy deviation range is between −10% and +10%, and the precision (coefficient of variation) is ≤10%.
[0131] In a possible embodiment, the dual or multi-channel heavy metal detector has a voice prompt function, and prompts a user to standardize the operation for detection abnormalities. Usual abnormal situations are as follows:
[0132] 1. Insufficient battery life of a heavy metal detector: a battery module cannot supply a circuit module to work normally, prompting the instrument to be charged in time.
[0133] 2. Abnormal loop: a SPE is not inserted into an electrode socket at the upper end of an electrode plug; a volume of the solution added in a reaction cell is not enough to completely submerge an electrode immersion area; and a hardware circuit connection is interrupted. In view of the above, the user is prompted to check the loop.
[0134] 3. Invalid detection: dual-channel synchronous accurate detection is applied to the same detection sample. The detection results of the two channels are quite different. If a set threshold is exceeded, it is considered that current detection is wrong and prompts to retest.
[0135] The specific embodiments described above further describe the objectives, technical solutions, and beneficial effects of the present disclosure in further detail. It should be understood that the above descriptions are only specific embodiments of the present disclosure, and are not intended to limit the scope of the present disclosure. Any modifications, equivalent replacements, improvements and the like made within a spirit and principle of the present disclosure shall be included in the scope of protection of the present disclosure.