CN114910540A - Detection method, control method and detection system for crystal crystallization process - Google Patents
Detection method, control method and detection system for crystal crystallization process Download PDFInfo
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 28
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 15
- 230000033116 oxidation-reduction process Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 11
- 230000007613 environmental effect Effects 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- -1 polydimethylsiloxane Polymers 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical class [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 7
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
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- UICQRVKPMFZOAJ-UHFFFAOYSA-L azanium dipotassium phosphate Chemical class [NH4+].[K+].[K+].[O-]P([O-])([O-])=O UICQRVKPMFZOAJ-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- 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
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The application relates to the technical field of crystal preparation, and provides a detection method for a crystal crystallization process, which comprises the following steps: preparing a sample solution, wherein the sample solution contains a solute capable of crystallizing under a preset condition; placing the interdigital electrode in a sample solution, then carrying out crystallization treatment under a preset condition, and then collecting an electric signal generated by the interdigital electrode to obtain a time-varying relation between current and voltage corresponding to solute crystallization; and determining the corresponding crystallization states of the solute at different time lengths during the crystallization according to the change relation of the current and the voltage along with the time. The detection method for the crystal crystallization process can detect the crystallization process of the solute in the solution in real time, and can obtain the concentration change of the ion clusters in the solution in real time, so that the crystallization state of the solute in the solution can be obtained in real time. The detection method has high sensitivity and can be widely applied to the detection and analysis of crystallization kinetics. In addition, the method also has the advantages of high detection flux, repeated utilization, low cost and the like.
Description
Technical Field
The application belongs to the technical field of crystal preparation, and particularly relates to a detection method, a control method and a detection system for a crystal crystallization process.
Background
Crystallization refers to the evolution of amorphous molecules in a dissolved or molten state to a crystalline state, and the whole crystallization process includes the dynamic evolution of ion clusters, nucleation and crystal growth. How to produce crystals of large size and desired crystal form by controlling the crystal formation process (nucleation and crystal growth) is the key to the widespread use of crystalline materials. However, the critical processes such as the change of the ion cluster state in the solution and nucleation lack real-time monitoring technology.
The existing nondestructive spectrum detection means comprise infrared spectrum, Raman spectrum and the like, and because the crystallization process involves two-phase change from liquid to solid, the spectrum detection can only roughly know the information of the crystallization surface and cannot deeply detect the change of the crystallization interface. In addition, the method is limited by the problems of spectral sensitivity and the like in the prior art, the changes of key steps in the crystallization process cannot be captured in real time, and the crystallization nucleation time cannot be captured in time, so that the steps of crystallization nucleation and the like cannot be interfered.
Therefore, there is an urgent need for a technique capable of monitoring the crystallization process of a crystal in real time.
Disclosure of Invention
The application aims to provide a detection method, a control method and a detection system for a crystal crystallization process, and aims to solve the problem that the existing detection method for the crystal crystallization process cannot detect the change of a crystallization interface in real time and cannot control the crystallization process.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for detecting a crystallization process of a crystal, the method comprising:
preparing a sample solution, wherein the sample solution contains a solute capable of crystallizing under a preset condition;
placing the interdigital electrode in a sample solution, then carrying out crystallization treatment under a preset condition, and then collecting an electric signal generated by the interdigital electrode to obtain a time-varying relation between current and voltage corresponding to solute crystallization;
and determining the corresponding crystallization states of the solute at different time lengths during the crystallization according to the change relation of the current and the voltage along with the time.
In a second aspect, the present application provides a method for controlling a crystallization process of a crystal, the method comprising:
according to the detection method, crystallization states of solutes in a sample solution corresponding to different crystallization durations are obtained;
determining a target growth condition of solute crystallization according to crystallization states of solutes in a sample solution corresponding to different crystallization durations;
and adjusting the environmental condition of the sample solution to a target growth condition, and controlling the crystallization of the solute.
In a third aspect, the present application provides a detection system for a crystal crystallization process, the detection system comprising: the system comprises an interface detector, electrochemical working equipment connected with the interface detector and an electric signal processor connected with the electrochemical working equipment;
the interface detector comprises an interdigital electrode, and the interdigital electrode is used for detecting an electric signal formed on the interface of the interdigital electrode when a solute in a sample solution is crystallized under a preset growth condition;
the electrochemical working equipment is used for collecting an electric signal;
the electric signal processor is used for processing the electric signals: and obtaining the change relation of the current and the voltage corresponding to the crystallization of the solute in the sample solution along with time according to the electric signal, thereby determining the crystallization state of the solute corresponding to different crystallization time lengths.
Compared with the prior art, the method has the following technical effects:
the method for detecting the crystal crystallization process includes the steps of preparing a sample solution containing a solute capable of crystallizing under a preset condition, placing an interdigital electrode in the sample solution, and then performing crystallization treatment under the preset condition, wherein under the condition that a voltage is applied to the interdigital electrode, a potential difference formed between the interdigital electrode and the solution can enable anions and cations in the solution to move directionally and perform redox reaction on an interface of the interdigital electrode, so that the interdigital electrode generates an electric signal, the change relation between corresponding current and voltage during crystallization along with time can be obtained by collecting the electric signal, finally the concentration change of an ion cluster in the solution can be determined according to the change relation between the current and the voltage along with time, and the corresponding crystallization states of the solute during crystallization under different durations can be determined according to the concentration change of the ion cluster. Therefore, the detection method can detect the crystallization process of the solute in the solution in real time, and can obtain the concentration change of the ion clusters in the solution in real time, so that the crystallization state of the solute in the solution can be obtained in real time. The detection method has high sensitivity and can be widely applied to the detection and analysis of crystallization kinetics. In addition, the method also has the advantages of high detection flux, repeated utilization, low cost and the like.
According to the control method for the crystal crystallization process provided by the second aspect of the application, the crystallization states of the solute in the sample solution corresponding to different crystallization time lengths are obtained according to the detection method, then the target growth condition of solute crystallization is determined according to the crystallization states of the solute in the sample solution corresponding to different crystallization time lengths, and finally the solute crystallization is controlled by adjusting the environmental condition of the sample solution to the target growth condition. Therefore, the control method can determine the target growth condition of solute crystallization according to the crystallization states of the solute in the solution corresponding to different crystallization time lengths, can control the crystallization process of the solute in the solution by adjusting the environmental condition to the target growth condition, can keep higher crystal growth speed, and can realize the rapid preparation of crystals with low defects, excellent grain size, appearance and other properties. Therefore, the control method controls the crystallization of the solute in the solution to obtain the crystals with good quality and higher utilization value.
The detection system for the crystal crystallization process provided by the third aspect of the application comprises an interface detector, electrochemical working equipment and an electrical signal processor, wherein an interdigital electrode contained in the interface detector is used for detecting an electrical signal formed on an interdigital electrode interface when a solute in a sample solution is crystallized under a preset growth condition, the electrochemical working equipment is used for collecting the electrical signal, and the electrical signal processor is used for obtaining a change relation between current and voltage along with time when the solute in the sample solution is crystallized according to the electrical signal, so that the crystallization states of the solute corresponding to different crystallization durations are determined. Therefore, the detection system can detect the crystallization process of the solute in the solution in real time, so that the crystallization state of the solute in the solution can be obtained in real time. The detection system has high sensitivity and can be widely applied to the detection and analysis of crystallization kinetics. In addition, the method also has the advantages of high detection flux, repeated utilization, low cost and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a detection flow chart of a detection method of a crystal crystallization process provided in an embodiment of the present application;
FIG. 2 is a control flow chart of a method for controlling a crystallization process of a crystal according to an embodiment of the present application;
FIG. 3 is a schematic diagram of a detection system for a crystal crystallization process provided in an embodiment of the present application;
FIG. 4 is a graph of electrochemical cyclic voltammetry for the saturated potassium dihydrogen phosphate crystallization process provided in example A1 of the present application;
FIG. 5 is a graph of electrochemical cyclic voltammetry for the saturated ammonium dihydrogen phosphate crystallization process provided in example A2 of the present application;
FIG. 6 is an electrochemical cyclic voltammogram of a potassium dihydrogen phosphate crystallization process at a concentration of 0.5mol/L as provided in example A3 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In a first aspect, an embodiment of the present application provides a method for detecting a crystal crystallization process, where the method includes:
s11: preparing a sample solution, wherein the sample solution contains a solute capable of crystallizing under a preset condition;
s12: placing the interdigital electrode in a sample solution, then carrying out crystallization treatment under a preset condition, and then collecting an electric signal generated by the interdigital electrode to obtain a time-varying relation between current and voltage corresponding to solute crystallization;
s13: and determining the corresponding crystallization states of the solute at different time lengths during the crystallization according to the change relation of the current and the voltage along with the time.
The method for detecting the crystal crystallization process includes the steps of preparing a sample solution containing a solute capable of crystallizing under a preset condition, placing an interdigital electrode in the sample solution, and then performing crystallization treatment under the preset condition, wherein under the condition that a voltage is applied to the interdigital electrode, a potential difference formed between the interdigital electrode and the solution can enable anions and cations in the solution to move directionally and perform redox reaction on an interface of the interdigital electrode, so that the interdigital electrode generates an electric signal, the change relation between corresponding current and voltage during crystallization along with time can be obtained by collecting the electric signal, finally the concentration change of an ion cluster in the solution can be determined according to the change relation between the current and the voltage along with time, and the corresponding crystallization states of the solute during crystallization under different durations can be determined according to the concentration change of the ion cluster. Therefore, the detection method can detect the crystallization process of the solute in the solution in real time, and can obtain the concentration change of the ion clusters in the solution in real time, so that the crystallization state of the solute in the solution can be obtained in real time. The detection method has high sensitivity and can be widely applied to the detection and analysis of crystallization kinetics. In addition, the method also has the advantages of high detection flux, repeated utilization, low cost and the like.
In step S11, the solute refers to a substance dissolved in the sample solution. The preset conditions are conditions for crystallizing the solute in the sample solution, which are preset. In an embodiment, the preset condition may include at least one preset condition of magnetic field strength, ultrasonic strength, temperature, gravity. Specifically, the preset condition may be a preset temperature. The preset condition may be a preset ultrasonic intensity. The sample solution is a solution in which a solute capable of crystallizing under a predetermined condition is dissolved in a solvent to form a uniform and stable solution. The sample solution includes at least one of a potassium dihydrogen phosphate solution, an ammonium dihydrogen phosphate solution, a sodium chloride solution, a potassium chloride solution, a sodium nitrate solution, a potassium nitrate solution, a sodium hydroxide solution, and a potassium hydroxide solution. In a specific embodiment, the sample solution may be a potassium dihydrogen phosphate solution, and the sample solution may also be an ammonium dihydrogen phosphate solution.
In step S12, placing the interdigital electrode in a sample solution, and performing crystallization treatment under a preset condition, wherein when a voltage is applied to the interdigital electrode, a potential difference is formed between the interdigital electrode and the solution, so as to promote the directional movement of anions and cations in the solution and the redox reaction at the interface of the interdigital electrode, thereby generating an electrical signal by the interdigital electrode; then collecting the electric signal generated by the interdigital electrode, and obtaining the time-varying relation between the corresponding current and voltage when the solute is crystallized. Wherein, the anions and the cations in the solution are the anions and the cations of the solute in the solution.
In an embodiment, the step of collecting the electrical signal generated by the interdigital electrode comprises: and connecting the interdigital electrode with electrochemical working equipment, and reading an electric signal of the interdigital electrode by using the electrochemical working equipment. The electrochemical working equipment can be used for controlling and monitoring the current, potential and other electrochemical parameter changes of the electrochemical cell, and can be used for measurement such as cyclic voltammetry, current titration, potentiometric titration and the like. In a particular embodiment, the electrochemical work apparatus may be an electrochemical work station.
In an embodiment, the interdigital electrode is a flexible interdigital array electrode, and the interdigital electrode includes: the electrode comprises a flexible substrate and an electrode material layer combined on the surface of the flexible substrate. Wherein, the material of the flexible substrate comprises at least one of polyimide and polydimethylsiloxane. The material of the electrode material layer comprises at least one of gold, platinum and palladium. In a specific embodiment, the material of the flexible substrate may be polyimide, and may also be polydimethylsiloxane. The material of the electrode material layer can be gold, and can also be platinum.
In the embodiment, the thickness of the interdigital electrode is 100-1000 μm, the interdigital distance is 20-500 μm, the interdigital width is 20-800 μm, and the interdigital length is 0.1-500 mm.
In an embodiment, the relationship of current to voltage over time comprises: electrochemical cyclic voltammetry.
In step S13, the ion cluster is a cluster formed by combining several to several hundreds or even ten thousands of ions of solute together. With the progress of the crystallization process of the solute in the sample solution, ions in the solution are gradually combined to form ion clusters, so that the ion concentration and the ion cluster concentration in the sample solution are changed, and further, an electric signal generated by the interdigital electrode is changed, therefore, the ion cluster concentration in the sample solution can be determined according to the change relation between the corresponding current and voltage along with the time when the solute is crystallized, and the crystallization state of the solute can be determined according to the ion cluster concentration of the sample solution.
In an embodiment, the step of determining the crystallization states corresponding to different time periods when the solute is crystallized according to the relationship between the current and the voltage with time comprises: obtaining the ion cluster concentration of the sample solution according to the oxidation-reduction potential change of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve; and determining the crystallization state of the solute according to the ion cluster concentration of the sample solution.
A second aspect of the embodiments of the present application provides a method for controlling a crystallization process of a crystal, where the method includes:
s21: according to the detection method, crystallization states of solutes in a sample solution corresponding to different crystallization durations are obtained;
s22: determining a target growth condition of solute crystallization according to crystallization states of solutes in a sample solution corresponding to different crystallization durations;
s23: and adjusting the environmental condition of the sample solution to a target growth condition, and controlling the crystallization of the solute.
According to the control method for the crystal crystallization process, the crystallization states of the solute in the sample solution corresponding to different crystallization time lengths are obtained according to the detection method, then the target growth condition of solute crystallization is determined according to the crystallization states of the solute in the sample solution corresponding to the different crystallization time lengths, and finally the target growth condition is adjusted according to the environmental condition of the sample solution to control the solute crystallization. Therefore, the control method can determine the target growth condition of solute crystallization according to the crystallization states of the solute in the solution corresponding to different crystallization time lengths, can control the crystallization process of the solute in the solution by adjusting the environmental condition to the target growth condition, can keep higher crystal growth speed, and can realize the rapid preparation of crystals with low defects, excellent grain size, appearance and other properties. Therefore, the control method controls the crystallization of the solute in the solution to obtain the crystals with good quality and higher utilization value.
In step S21, the steps of the method for obtaining the crystallization states of the solute in the sample solution at different crystallization time lengths have been described above and are not repeated here.
In step S22, the target growth conditions refer to growth conditions set for crystallization of the solute in the sample solution to achieve a desired result. The target growth conditions include: at least one of magnetic field strength, ultrasonic strength, temperature, gravity. The process of solute crystallization in solution can include three stages of cluster formation, crystal nucleus generation and crystal nucleus growth. The crystallization state may refer to a form in which a solute in a sample solution is present at any time during crystallization. In an embodiment, when it is detected that the solute in the sample solution is in the nucleation stage, the target growth condition for the crystallization of the solute may be determined according to the number of the solute-generating nuclei in the sample solution. Specifically, the target growth conditions such as ultrasonic intensity and temperature can be determined according to the generation of a large number of crystal nuclei in the solution or the generation of a small number of crystal nuclei in the solution. Such as: a large number of crystal nuclei are generated in the solution, which is not beneficial to crystal growth, and the ultrasonic intensity can be reduced or the temperature can be reduced as target growth conditions.
A third aspect of the embodiments of the present application provides a detection system for a crystal crystallization process, as shown in fig. 3, the detection system includes: the device comprises an interface detector 1, an electrochemical working device 2 connected with the interface detector 1, and an electric signal processor 3 connected with the electrochemical working device 2.
The interface detector 3 comprises an interdigital electrode for detecting an electrical signal formed at an interdigital electrode interface when a solute in a sample solution is crystallized under a preset growth condition. The structure and material of the interdigital electrode have been described in detail above, and are not repeated here.
The electrochemical working device 2 is used to collect an electrical signal. In an embodiment, the electrochemical work apparatus may be an electrochemical work station.
The electrical signal processor 3 is used to process electrical signals: and obtaining the change relation of the current and the voltage corresponding to the crystallization of the solute in the sample solution along with time according to the electric signal, thereby determining the crystallization state of the solute corresponding to different crystallization time lengths. In an embodiment, the current versus voltage variation over time may comprise an electrochemical cyclic voltammetry curve. The electric signal processor 3 can obtain the ion cluster concentration of the sample solution according to the oxidation-reduction potential change of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve, and then determines the crystallization states of the solute corresponding to different crystallization durations according to the ion cluster concentration in the sample solution.
The detection system for the crystal crystallization process comprises an interface detector, electrochemical working equipment and an electric signal processor, wherein an interdigital electrode contained in the interface detector is used for detecting an electric signal formed on the interface of the interdigital electrode when a solute in a sample solution is crystallized under a preset growth condition, the electrochemical working equipment is used for collecting the electric signal, and the electric signal processor is used for obtaining a change relation between current and voltage corresponding to the crystallization of the solute in the sample solution along with time according to the electric signal, so that the crystallization states corresponding to different crystallization durations of the solute are determined. Therefore, the detection system can detect the crystallization process of the solute in the solution in real time, so that the crystallization state of the solute in the solution can be obtained in real time. The detection system has high sensitivity and can be widely applied to the detection and analysis of crystallization kinetics. In addition, the method also has the advantages of high detection flux, repeated utilization, low cost and the like.
The following description will be given with reference to specific examples.
Example 1A
The embodiment provides a detection method for a crystal crystallization process, which comprises the following steps:
s11: preparing saturated dipotassium phosphate ammonium solution and preparing an interdigital electrode;
the preparation method of the interdigital electrode comprises the following steps: providing a polyimide film of 3 x 3 cm, covering a mask plate on the surface of the polyimide film, and evaporating platinum with the thickness of 300 mu m on the surface of the polyimide film by using an evaporator to obtain an interdigital electrode with the interdigital spacing of 500 mu m, the interdigital length of 800 mu m and the interdigital width of 10000 mu m;
s12: electrically connecting the interdigital electrode with an electrochemical workstation, then placing the interdigital electrode at the bottom of a saturated potassium dihydrogen phosphate solution, setting the electrochemical workstation in a cyclic scanning mode, setting the scanning speed to be 50mV/s, and continuously scanning to obtain an electrochemical cyclic voltammetry curve of a monopotassium phosphate crystallization process;
s13: and obtaining the ion cluster concentration of the potassium dihydrogen phosphate solution according to the oxidation-reduction potential change of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve, and determining the crystallization state of the potassium dihydrogen phosphate according to the ion cluster concentration of the potassium dihydrogen phosphate solution.
Example 1B
The present embodiment provides a method for controlling a crystal crystallization process, the method comprising the steps of:
s21: according to the detection method provided in embodiment 1A, cyclic voltammetry data corresponding to different crystallization durations of potassium dihydrogen phosphate is obtained;
s22: determining the target temperature of potassium dihydrogen phosphate crystallization at the position with the maximum change of the oxidation-reduction potential of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve;
s23: adjusting the preset temperature of the potassium dihydrogen phosphate solution to a target temperature, and controlling the supersaturation degree of the potassium dihydrogen phosphate solution so as to control the crystallization of the potassium dihydrogen phosphate.
Example 2A
The embodiment provides a detection method for a crystal crystallization process, which comprises the following steps:
s11: preparing saturated ammonium dihydrogen phosphate solution and preparing an interdigital electrode;
the preparation method of the interdigital electrode comprises the following steps: providing a polyimide film of 3 x 3 cm, covering a mask plate on the surface of the polyimide film, and evaporating platinum with the thickness of 300 mu m on the surface of the polyimide film by using an evaporator to obtain an interdigital electrode with the interdigital spacing of 500 mu m, the interdigital length of 600 mu m and the interdigital width of 10000 mu m;
s12: electrically connecting the interdigital electrode with an electrochemical workstation, then placing the interdigital electrode at the bottom of a saturated ammonium dihydrogen phosphate solution, setting the electrochemical workstation in a cyclic scanning mode, setting the scanning speed to be 50mV/s, and continuously scanning to obtain an electrochemical cyclic voltammetry curve in the ammonium dihydrogen phosphate crystallization process;
s13: and obtaining the ion cluster concentration of the ammonium dihydrogen phosphate solution according to the oxidation-reduction potential change of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve, and determining the crystallization state of the ammonium dihydrogen phosphate according to the ion cluster concentration of the ammonium dihydrogen phosphate solution.
Example 2B
The present embodiment provides a method for controlling a crystal crystallization process, the method comprising the steps of:
s21: according to the detection method provided in the embodiment 2A, cyclic voltammetry data corresponding to different crystallization time lengths of ammonium dihydrogen phosphate is obtained;
s22: determining the magnetic field intensity of ammonium dihydrogen phosphate crystals at the position with the maximum change of the oxidation-reduction potential of cyclic voltammetry data in an electrochemical cyclic voltammetry curve;
s23: and adjusting the environmental condition of the ammonium dihydrogen phosphate solution to the applied magnetic field to control the crystallization of the ammonium dihydrogen phosphate.
Example 3A
The embodiment provides a detection method for a crystal crystallization process, which comprises the following steps:
s11: respectively preparing potassium dihydrogen phosphate solutions with the concentrations of 0.5mol/L, 1mol/L and 2mol/L and preparing interdigital electrodes;
the preparation method of the interdigital electrode comprises the following steps: providing a polyimide film with the thickness of 3 multiplied by 3 cm, covering a mask plate on the surface of the polyimide film, and evaporating platinum with the thickness of 400 mu m on the surface of the polyimide film by using an evaporator to obtain an interdigital electrode with the interdigital spacing of 300 mu m, the interdigital length of 500 mu m and the interdigital width of 15000 mu m;
s12: electrically connecting the interdigital electrodes with an electrochemical workstation, then respectively placing the interdigital electrodes at the bottoms of the potassium dihydrogen phosphate solutions with different molar concentrations, setting a cyclic scanning mode of the electrochemical workstation, setting the scanning speed to be 50mV/s, and continuously scanning to obtain electrochemical cyclic voltammetry curves of potassium dihydrogen phosphate crystallization processes with different molar concentrations;
s13: and obtaining the ion cluster concentration of the potassium dihydrogen phosphate solution according to the oxidation-reduction potential change of the cyclic voltammetry data in different electrochemical cyclic voltammetry curves, and determining the crystallization state of the potassium dihydrogen phosphate with different molar concentrations according to the ion cluster concentration of the potassium dihydrogen phosphate solution.
The present embodiment provides a method for controlling a crystal crystallization process, the method comprising the steps of:
s21: according to the detection method provided in the embodiment 3A, cyclic voltammetry data corresponding to potassium dihydrogen phosphate with the concentration of 0.5mol/L in different crystallization time lengths are obtained;
s22: determining the target temperature of potassium dihydrogen phosphate crystallization at the position with the maximum change of the oxidation-reduction potential of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve;
s23: adjusting the preset temperature of the potassium dihydrogen phosphate solution to a target temperature, and controlling the crystallization of the potassium dihydrogen phosphate.
And (4) analyzing related test results:
fig. 4 is an electrochemical cyclic voltammetry curve diagram of a saturated potassium dihydrogen phosphate crystallization process, and it can be seen from fig. 4 that the oxidation-reduction potential changes in real time, the ion cluster concentration of the potassium dihydrogen phosphate solution can be obtained in real time, and the change of the ion cluster in the saturated potassium dihydrogen phosphate solution from a disordered state to an ordered state can be judged from the potential increase to the maximum position, so that the crystallization state of the potassium dihydrogen phosphate can be determined. In addition, the saturation degree of the potassium dihydrogen phosphate solution can be controlled by adjusting the temperature of the solution at the position of the maximum potential (nucleation position) to control the potassium dihydrogen phosphate crystallization, and large-size potassium dihydrogen phosphate crystals can be quickly obtained.
Fig. 5 is an electrochemical cyclic voltammogram of a saturated ammonium dihydrogen phosphate crystallization process, from fig. 5, it can be seen that an oxidation-reduction potential changes in real time, and compared with the electrochemical cyclic voltammogram of the saturated potassium dihydrogen phosphate crystallization process provided in example 1, dynamic curves of the two are different, which illustrates that the detection method of the crystal crystallization process provided in the present application can be used for detecting crystallization processes of different solutes.
Fig. 6 is an electrochemical cyclic voltammetry graph of a potassium dihydrogen phosphate crystallization process with a concentration of 0.5mol/L, and from fig. 6, it can be seen that the oxidation-reduction potential changes in real time, and compared with the electrochemical cyclic voltammetry graph of a saturated potassium dihydrogen phosphate crystallization process provided in example 1, the dynamic curves of the two are different, which shows that the detection method of the crystal crystallization process provided by the present application has high sensitivity, and can be used for detecting the crystallization process of solutes with different molar concentrations.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method of detecting a crystallization process of a crystal, the method comprising:
preparing a sample solution, wherein the sample solution contains a solute capable of crystallizing under a preset condition;
placing the interdigital electrode in the sample solution, then carrying out crystallization treatment under the preset condition, and then collecting an electric signal generated by the interdigital electrode to obtain a time-varying relation between current and voltage corresponding to the crystallization of the solute;
and determining the corresponding crystallization states of the solute at different time lengths during the crystallization according to the change relation of the current and the voltage along with the time.
2. The detection method of claim 1, wherein the current versus voltage variation over time comprises: electrochemical cyclic voltammetry.
3. A method of detecting as claimed in claim 2 wherein the step of determining from the relationship of the current to voltage over time the corresponding crystallisation states for different durations during which the solute crystallises comprises:
obtaining the ion cluster concentration of the sample solution according to the oxidation-reduction potential change of the cyclic voltammetry data in the electrochemical cyclic voltammetry curve;
and determining the crystallization state of the solute according to the ion cluster concentration of the sample solution.
4. The probing method of claim 1, wherein said step of collecting electrical signals generated by said interdigitated electrodes comprises: and connecting the interdigital electrode with electrochemical working equipment, and reading an electric signal of the interdigital electrode by using the electrochemical working equipment.
5. The detection method according to any one of claims 1 to 4, wherein the interdigital electrodes are flexible interdigital array electrodes comprising: the flexible substrate comprises a flexible substrate and an electrode material layer combined on the surface of the flexible substrate.
6. A detection method according to claim 5, wherein the material of the flexible substrate comprises at least one of polyimide, polydimethylsiloxane; and/or
The material of the electrode material layer comprises at least one of gold, platinum and palladium.
7. A detection method according to any one of claims 1 to 4, wherein the sample solution includes at least one of a potassium dihydrogen phosphate solution, an ammonium dihydrogen phosphate solution, a sodium chloride solution, a potassium chloride solution, a sodium nitrate solution, a potassium nitrate solution, a sodium hydroxide solution, and a potassium hydroxide solution.
8. A method of controlling a crystallization process of a crystal, the method comprising:
the detection method according to any one of claims 1 to 7, obtaining crystallization states of the solute in the sample solution corresponding to different crystallization time lengths;
determining a target growth condition of the solute crystallization according to crystallization states of the solute in the sample solution corresponding to different crystallization durations;
adjusting the environmental condition of the sample solution to the target growth condition, and controlling the crystallization of the solute.
9. The control method according to claim 8, wherein the target growth condition includes: at least one of magnetic field strength, ultrasonic strength, temperature, gravity.
10. A detection system for a crystallization process of a crystal, the detection system comprising: the system comprises an interface detector, electrochemical working equipment connected with the interface detector, and an electric signal processor connected with the electrochemical working equipment;
the interface detector comprises an interdigital electrode, and the interdigital electrode is used for detecting an electric signal formed on the interface of the interdigital electrode when a solute in a sample solution is crystallized under a preset growth condition;
the electrochemical working device is used for collecting the electric signal;
the electric signal processor is used for processing the electric signals: and obtaining the change relation between the current and the voltage corresponding to the crystallization of the solute in the sample solution along with time according to the electric signal, thereby determining the crystallization state of the solute corresponding to different crystallization time lengths.
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