WO2022134000A1 - Method and system for continuous excitation of crystallization - Google Patents

Abstract

A method and system for continuous excitation of crystallization, comprising: controlling laser generators (60) to emit laser, and refracting and focusing the laser to a specified position of a test tube (40); averaging radiuses of bubbles in multiple frames of images acquired at the same time in two directions to obtain an average radius of the bubbles at this time; calculating an average radius of the frames of images from bubble generation to bubble disappearance, obtaining an array corresponding to the average radius of the bubbles with respect to the time, and fitting the array to obtain a function r=f(t) of the average radius of the bubbles and the time; and controlling the multiple laser generators (60) to emit the laser at intervals or circularly emit the laser at intervals to perform the continuous excitation, in the continuous excitation, when time t_x satisfies that f(t_x-t_x-1)=R, controlling the laser generators (60) to emit the laser, R being less than a maximum radius of bubble diffusion and greater than a system interval excitation duration multiplied by a bubble diffusion speed. The method and system use high-speed visual capture for feedback control of the multiple lasers after the fitting to perform the continuous excitation successively, thus forming an increasing supersaturation gradient in the local part of a solution, and facilitating discovery of a new crystal form.

Description

Method and system for continuous excitation crystallization technical field

The invention relates to crystallization experiments, in particular to a method and system for continuously exciting crystallization.

Background technique

An important goal of crystallization experimental research is to study the polymorphic behavior of the target, such as a compound molecule, which can form different crystal forms under different experimental conditions. Obtaining as many different crystal forms as possible, and studying the physical and chemical properties of these crystal forms, as well as the transformation relationship between them, plays a very important role in the later industrial production and commercialization of the target product.

At present, the conventional crystallization experimental equipment mainly controls different solvent environments, different temperatures, different cooling rates, and different stirring rates.

Laser is a means of effectively creating a crystallization environment with a surge of local supersaturation, thereby obtaining more crystal forms that cannot be obtained under conventional experimental conditions. At present, there is no small-scale special equipment for laboratory use using lasers for crystal formation research.

In the crystallization process, the degree of supersaturation is a very important condition. The size of the degree of supersaturation and the rate of change will affect what kind of crystal form is formed.

Conventional crystallization methods in the current laboratory, such as controlling the solvent, temperature and stirring rate, have a limited range of control over the degree of supersaturation. Many crystal forms that require extreme supersaturation conditions cannot be found by conventional experimental methods.

The laser mainly relies on instantaneously creating a single-point high temperature condition in a solvent environment, and locally generates air expansion, thereby generating highly supersaturated conditions around small air bubbles. However, using laser directly for single-point excitation, the time to form supersaturation is short, and the conditions for continuous increase of supersaturation cannot be created. Therefore, it is still relatively difficult to use laser to discover new crystal forms.

SUMMARY OF THE INVENTION

Based on this, it is necessary to provide a method for continuously excited crystallization that can improve the crystallization diversity.

At the same time, a continuous excitation crystallization system which can improve the crystallization diversity is provided.

A method of continuous excitation crystallization, comprising:

Laser emission: receive instructions, control the laser generator to emit laser, and refract and focus on the designated position of the test tube through the laser path;

Obtain the average radius of bubbles: collect the images of the bubbles in the test tube caused by laser focused irradiation, identify the edges of the bubbles in each frame of images, obtain the radii of the bubbles in the vertical and horizontal directions, and collect multiple images collected by multiple image acquisition devices at the same time. The radii of the bubbles in the two directions of the image frame are averaged to obtain the average radii of the bubbles at this moment;

Fitting function: Calculate the average bubble radius of each frame from the bubble generation to the disappearance of the bubble, obtain an array of the average bubble radius corresponding to time, and use the nonlinear least squares method to fit the array to obtain the function of the average bubble radius and time. r=f(t), t is the time, r is the average radius of the bubble, and f is the fitting function;

Continuous excitation: If a continuous excitation command is received, multiple laser generators are controlled to emit lasers at intervals or intervals to perform continuous excitation, and the continuous excitation is that at the moment t _x satisfies f(t _x -t _x-1 )=R When , control the laser generator to emit, R is less than the maximum radius of bubble diffusion, and greater than the value obtained by multiplying the minimum duration of the interval excitation controlled by the system multiplied by the speed of bubble diffusion.

In a preferred embodiment, the fitting function is f(t)=ae ^bt , where a and b are fitting parameters; the bubble diffusion speed is obtained according to the radius and time of each frame of the obtained bubble image, and the image The acquisition device includes: a first image acquisition device and a second image acquisition device arranged on different sides relative to the test tube, wherein the test tube is a glass test tube with a square section or a rectangular section.

In a preferred embodiment, the laser generator includes: a first laser generator located in the middle position, a second laser generator and a third laser generator located on both sides, and the continuous excitation includes: receiving After the continuous excitation command is reached, the first laser generator is controlled to emit, and the timing is started. When the time t ₀ satisfies f(t ₀ )=R, the second laser generator emits, and when the time t1 satisfies f(t ₁ -t ₀ )=R, the third laser generator emits,

Before the continuous excitation, it also includes focus adjustment: the focus of the second laser generator emitting laser refraction focusing is adjusted to be located at a distance R above the first laser generator emitting laser refraction focusing focal point, and the third laser generator emits The focal point of the laser refraction focusing is adjusted to be located at a distance R above the focal point of the laser refraction focusing emitted by the second laser generator.

In a preferred embodiment, the second laser generator is placed opposite to the right side, and the third laser generator is placed opposite to the left side, and the continuous excitation includes: after receiving the continuous excitation instruction, controlling the first laser to generate The generator emits and starts timing. When the time t ₀ satisfies f(t ₀ )=0.05 cm, the second laser generator emits, and when the time t1 satisfies f(t ₁ -t ₀ )=0.05 cm, the third laser generator generates launcher;

The focus adjustment: the focus of the second laser generator emitting laser refraction focusing is adjusted to be located at a distance of 0.05 cm above the first laser generator emitting laser refraction focusing focus, and the third laser generator is emitting laser light. The focus of refraction and focusing is adjusted to be located at a distance of 0.1 cm above the focus of refraction and focusing of the laser emitted by the first laser generator, and the laser light emitted by the first laser generator, the second laser generator, and the third laser generator is refracted and focused. The focus in the test tube solution is adjusted to be greater than 1 cm from the bottom of the test tube, the side wall of the test tube, and the surface of the test tube solution.

In a preferred embodiment, the continuous excitation includes: after the first laser generator emits and excites the bubbles, when the bubbles diffuse to the focus of the laser refraction and focus emitted by the second laser generator, the second laser generator emits laser light for excitation , generate new bubbles, when the bubbles diffuse to the focus of laser refraction emitted by the third laser generator, the third laser generator emits laser light for excitation, forming the effect of laser bubbles again on the edge of the bubbles excited by the previous laser, forming Continuous excitation, each laser generator is provided with a corresponding laser path, and each laser path is provided with a laser focusing head;

The focus adjustment: by adjusting the respective laser focusing heads, the lasers emitted by the first laser generator, the second laser generator, and the third laser generator are refracted and focused on the central axis of the test tube, and the first laser The focus of the laser emitted by the generator after being refracted and focused is located at 2 cm from the central axis of the test tube from the bottom of the test tube, the focus of the second laser generator's laser refraction focusing is located at 2.05 cm from the central axis of the test tube from the bottom of the test tube, and the third laser The focal point of the laser emitted by the generator after being refracted and focused is located at 2.1 cm from the central axis of the test tube from the bottom of the test tube. The first, second and third laser generators are fired in sequence to form a group of three bursts. The continuous excitation is set to one. Group or groups of three bursts, the interval between each group is set time.

A continuous excitation crystallization system, comprising: a plurality of controlled laser generators for laser emission, a laser path corresponding to the laser generators for refracting and focusing the laser light emitted by the laser generators, a test tube rack, A test tube on the test tube rack and corresponding to the laser passage to receive the focused laser light, an image acquisition device disposed on the test tube rack and corresponding to the test tube and controlled to collect the image of the test tube, and the laser generated The laser generator and the image acquisition device are communicatively connected and control a control system for their respective operations, and the laser path includes: a laser refraction path that refracts and guides the laser light emitted by the laser generator, and is connected to the laser refraction path and refracts the laser. After the laser is focused, the laser focusing head,

The control system includes:

Laser emission module: receive instructions, control the laser generator to emit laser light, and refract and focus on the designated position in the test tube through the laser path;

The module for obtaining the average radius of bubbles: collects the images of the bubbles in the test tube caused by laser focused irradiation, identifies the edges of the bubbles in each frame of images, obtains the radii of the bubbles in the vertical and horizontal directions, and collects multiple images collected by multiple image acquisition devices at the same time. Average the radii of the bubbles in the two directions of the image frames to obtain the average radius of the bubbles at this moment;

Fitting function module: Calculate the average bubble radius of each frame of image from the bubble generation to the bubble disappearance, obtain an array of the average bubble radius corresponding to time, and use the nonlinear least squares method to fit the array to obtain the difference between the average bubble radius and time. The function r=f(t), t is the time, r is the average radius of the bubble, and f is the fitting function;

Continuous excitation module: if a continuous excitation command is received, multiple laser generators are controlled to emit lasers at intervals or intervals to perform continuous excitation, and the continuous excitation is that the current time t _x satisfies f(t _x -t _x-1 )= When R, the laser generator is controlled to emit, and R is less than the maximum radius of bubble diffusion and greater than the value obtained by multiplying the minimum duration of the interval excitation controlled by the system multiplied by the speed of bubble diffusion.

In a preferred embodiment, the laser generator includes: a first laser generator located in the middle position, a second laser generator and a third laser generator located on both sides, and the laser path includes: A laser refraction path that refracts and guides the laser light emitted by the laser generator, and a laser focusing head that is connected to the laser refraction path and focuses the refracted laser light, the laser refraction path includes: The first laser refraction path corresponding to and guiding the refraction of the laser light emitted by the first laser generator, the second refraction path corresponding to the second laser generator and guiding the refraction of the laser light emitted by the second laser generator, and the The third laser generator is correspondingly arranged and guides a third refraction path for refracting the laser light emitted by the third laser generator, and the laser focusing head includes: A first laser focusing head for focusing the laser light of a laser generator, a second laser focusing head corresponding to the second laser refraction path and focusing the refracted laser light of the second laser generator, and a second laser focusing head for focusing the refracted laser light of the second laser generator The third laser refraction path is correspondingly arranged and the third laser focusing head for focusing the refracted laser light of the third laser generator, the first laser focusing head or the second laser focusing head or the third laser focusing head It includes: a laser path connection part that is connected to the first laser refraction path or the second laser refraction path or the third laser refraction path and adjusts the upper and lower positions; a head gimbal shaft, and a focusing head lens arranged at the end of the focusing head gimbal shaft and adjusting the angle through the focusing head gimbal shaft and corresponding to the test tube, the first laser refraction path or the second laser refraction The passage or the third refraction passage is provided with a refraction prism that refracts the parallel light emitted by the first laser generator or the second laser generator or the third laser generator into vertical rays; the continuous excitation module includes: receiving the continuous excitation After the instruction, control the first laser generator to emit, start timing, when the time t ₀ satisfies f(t ₀ )=R, the second laser generator emits, and when the time t1 satisfies f(t ₁ -t ₀ )=R , the third laser generator is fired.

In a preferred embodiment, the laser refraction path is arranged in a right-angle or inflection-shaped structure, the refraction prism is arranged at the corner, the laser focusing head is screwed with the laser refraction path, and the laser path connection part is a threaded head , the focal length of the focusing head lens is 5-50 cm, and the focal length of the first laser generator, the second laser generator, and the third laser generator to emit laser light is refracted and focused in the test tube solution from the bottom of the test tube, the side of the test tube The surface of the wall and the test tube solution is greater than 1 cm, the focus of the second laser generator emission laser refraction focusing is located at a distance R above the focus after the first laser generator emission laser is refracted and focused, and the third laser generator The focal point of the refracting and focusing of the emitted laser light is located at a distance R above the focal point after the refracting and focusing of the emitted laser light of the second laser generator.

In a preferred embodiment, the image acquisition device includes: a first image acquisition device and a second image acquisition device that are relatively arranged on different sides of the test tube, and the module for obtaining the average radius of bubbles includes: identifying the bubbles in each frame of image Edge, obtain the vertical and horizontal radii of the bubbles in the picture, and average the radii of the bubbles in the two directions of the image frames collected by the first image acquisition device and the second image acquisition device at the same time to obtain the bubble at the current moment. Average radius; the front side and left side of the test tube rack are set as semi-open structures, the bottom of the test tube rack is also provided with a fill light connected to the control system, and the inner wall of the test tube rack is painted or set to be white , the test tube is a glass test tube with a square cross-section or a rectangular cross-section, the photographing field of view of the first image acquisition device or the second image acquisition device does not exceed the side wall of the test tube, and the upper and lower sides do not exceed the test tube solution; the second laser generator The third laser generator is placed opposite to the left side, and the continuous excitation module includes: after receiving the continuous excitation instruction, controlling the first laser generator to emit, and starting timing, when the time t ₀ satisfies When f(t ₀ )=0.05 cm, the second laser generator emits, and when time t1 satisfies f(t ₁ -t ₀ )=0.05 cm, the third laser generator emits, and the second laser generator emits laser light The focal point of the refraction focusing is located at a distance of 0.05 cm above the focal point of the first laser generator emitting laser refraction focusing, and the focal point of the third laser generator emitting laser refraction focusing is located above the focal point of the first laser generator emitting laser refraction focusing 0.1 cm away.

In a preferred embodiment, the test tube is a glass test tube with a square cross-section or a rectangular cross-section, the length or width of the test tube is not less than 2.5 cm, and the height is not less than 4 cm, and the continuous excitation module includes: the first After a laser generator emits and excites bubbles, when the bubbles diffuse to the focus of the laser refraction and focus emitted by the second emitter, the second laser generator emits lasers for excitation to generate new bubbles, and when the bubbles diffuse to the third laser to generate When the laser emitted by the laser is refracted and focused, the third laser generator emits laser light for excitation, forming the effect of laser bubbles on the edge of the bubble excited by the previous laser, forming continuous excitation. Each laser passage is provided with a laser focusing head. By adjusting the laser focusing head, the lasers emitted by the first laser generator, the second laser generator and the third laser generator are refracted and focused on the central axis of the test tube. The focus of the laser emitted by the generator after being refracted and focused is located at 2 cm from the center axis of the test tube from the bottom of the test tube, the focus of the second laser generator emitted laser refraction and focusing is located at 2.05 cm from the center axis of the test tube from the bottom of the test tube, and the third The focal point of the laser emitted by the laser generator after being refracted and focused is located at 2.1 cm from the central axis of the test tube from the bottom of the test tube; the first, second and third laser generators are fired in sequence to form a group of three bursts, and the continuous excitation module Set one or more groups of three bursts, and the interval between each group is set time.

The above-mentioned continuous excitation crystallization method and system use an image acquisition device for high-speed visual capture, and after fitting, feedback control of multiple lasers to successively excite successively, forming a gradually increasing supersaturation gradient locally in the solution, which is helpful for discovering conventional experimental methods and single crystals. New crystal forms that are difficult to find by the point laser method.

Description of drawings

1 is a partial structural schematic diagram of a continuous excitation crystallization system according to an embodiment of the present invention;

2 is a partial structural schematic diagram of a certain laser path according to an embodiment of the present invention;

FIG. 3 is a partial flowchart of a method for continuously excited crystallization according to an embodiment of the present invention.

Detailed ways

As shown in FIG. 1 to FIG. 2 , a continuous excitation crystallization system 100 according to an embodiment of the present invention includes: a test tube rack 20 , a test tube 40 arranged on the test tube rack 20 , a plurality of laser generators 60 for controlled laser emission, Corresponding to the laser generator 60, a laser path 80 is provided for refracting and focusing the laser light emitted by the laser generator 60 on a designated position in the test tube, and an image acquisition device is arranged on the test tube rack 20 and corresponding to the test tube 40 and is controlled to collect the image of the test tube. 90. A control system 50 that is communicatively connected to the laser generator 60 and the image acquisition device 90 and controls their respective operations.

Since the image taken from the side of the conventional cylindrical test tube will be deformed due to the curved glass, the internal image size cannot be accurately calculated. Further, preferably, in order to ensure the shooting quality and ensure that the image is not deformed during shooting, the test tube in this embodiment adopts a square section. or glass test tubes of rectangular cross section.

Further, preferably, the test tube rack of this embodiment is a square frame with a square opening at the top, which can be inserted into the special square glass test tube of this embodiment.

Further, preferably, the image capturing device 90 in this embodiment includes: a first image capturing device 92 and a second image capturing device 94 that are oppositely disposed on different sides of the test tube. In this embodiment, the image acquisition device 90 uses a camera to perform image acquisition. The first image acquisition device is a first camera, and the second image acquisition device is a second camera.

Preferably, the front side and the left side of the test tube rack in this embodiment are semi-open, and the camera rack and the camera are installed at the height of the middle position of the test tube, preferably 10 cm from the top of the test tube rack, and the horizontal position of the camera is located on the side. Face the middle, the camera is facing inward, facing the glass test tube.

Further, preferably, relative to the use direction, the first camera is installed on the front side of the test tube rack, and the second camera is installed on the left side of the test tube rack. The first camera and the second camera in this embodiment are preferably high-speed cameras with 1000 frames per second. Preferably, in order to improve the quality of image acquisition, the inner wall of the test tube rack in this embodiment is set to be white, or painted white. The right side and the rear side of the test tube rack in this embodiment are closed, and the interior is painted white, so that the background of the glass test tube photographed by the camera is pure white.

Further, a white light fill light 25 is installed at the bottom of the test tube rack 20 in this embodiment. When the whole system is working, the fill light 25 fills the light from bottom to top to ensure the clarity of the pictures taken by the camera.

Further, other areas on the top and bottom of the test tube rack 20 in this embodiment are also painted in white to ensure sufficient reflection and pure white for the shooting background.

Further, the control system 50 in this embodiment is connected to the bottom of the test tube rack 20 , and the camera and the fill light 25 on the test tube rack 20 have lines connected to the control system. The control system 50 supplies power to the camera and the fill light 25 through the line, and receives the images captured by the camera in real time.

Further, the laser generator of this embodiment is arranged on the top of the control system. The laser generator of this embodiment includes three laser generators. Three laser generators are mounted on top of the control system. The laser generator is wired to the main board inside the control system. The control system can send commands to the laser generator through the wire to turn the laser generator on or off.

Further, the control system 50 of this embodiment includes a hardware part and a software part. The hardware part of the control system 50 includes: a motherboard, a computing chip, a memory, a hard disk, and a power supply; the software part runs the Android system to run the software part of the entire system.

Further, there are four buttons on the control system 50 of this embodiment, which are respectively the control buttons of three laser generators and an automatic continuous excitation button.

The laser generator control button can manually control the switch of the laser generator. Press the switch to start the laser emission, and release the laser to turn off the laser. After the automatic continuous excitation button is clicked, the system will start to execute the continuous excitation function of the software module.

The laser generator 60 in this embodiment is preferably a carbon dioxide laser generator. Further, preferably, the laser generator 60 in this embodiment includes: a first laser generator 62 positioned opposite to the middle position, a second laser generator 64 and a third laser generator 66 positioned opposite to both sides. Referring to the direction of use, further, preferably, the second laser generator 64 is relatively arranged on the right side of the first laser generator 62 , and the third laser generator 66 is relatively arranged on the left side of the first laser generator 62 .

The CO2 laser generator emits CO2 laser light. A carbon dioxide laser is a molecular laser. The main substance is carbon dioxide molecules. It can manifest various energy states depending on its vibration and rotation patterns. The gas mixture in carbon dioxide is a plasma of low pressure gas (usually 30-50 Torr) due to the release of electrons. As the Maxwell-Boltzmann distribution law states, in a plasma, molecules exhibit a variety of excited states. Some will exhibit a high energy state (00o1) which behaves as an asymmetrically oscillating state. The molecule also occasionally loses energy when colliding with a hollow wall or emanating naturally. By naturally emitting this high-energy state drops to a symmetrical wiggle form (10o0) and emits photons (a beam of 10.6 μm wavelength) that may travel in any direction. Occasionally, one of these photons will travel down the cavity along the optical axis and will also wiggle in the resonance mirror.

The carbon dioxide laser generator is a gas laser with _CO2 gas as the working substance. The discharge tube is usually made of glass or quartz material, which is filled with CO ₂ gas and other auxiliary gases (mainly helium and nitrogen, and generally a small amount of hydrogen or xenon); the electrode can be a hollow nickel cylinder; resonance One end of the cavity is a gold-coated total reflection mirror, and the other end is a partially reflecting mirror ground with germanium or gallium arsenide.

When a high voltage (usually DC or low-frequency AC) is applied to the electrode, a glow discharge is generated in the discharge tube, and one end of the germanium mirror has a laser output with a wavelength of the mid-infrared band near 10.6 microns; about one meter long The discharge area can obtain a continuous output power of 40 to 60 watts. CO2 laser generators have the following advantages:

First, it has relatively large power and relatively high energy conversion efficiency. The general closed-tube CO ₂ laser can have a continuous output power of several tens of watts, which is far more than other gas lasers, and the lateral-flow electro-excited CO ₂ laser can have a continuous output of hundreds of thousands of watts. In addition, the transverse atmospheric pressure CO ₂ laser has also reached a high level in terms of energy and power output from the pulse, which is comparable to that of solid-state lasers. The energy conversion efficiency of CO ₂ lasers can reach 30-40%, which also exceeds the general gas lasers.

Second, it utilizes the transition between the vibrational and rotational energy levels of CO ₂ molecules, and has relatively abundant spectral lines, with a laser output of dozens of spectral lines around 10 microns. High-pressure CO ₂ lasers can even achieve continuously tunable output from 9 to 10 microns.

Third, its output band is exactly the atmospheric window (that is, the transmittance of the atmosphere to this wavelength is high). In addition, it also has the advantages of high optical quality of the output beam, good coherence, narrow line width, and stable operation.

The continuous excitation crystallization system of the present invention refracts and focuses the laser light emitted by the laser generator 60 to a designated position in the test tube 40 through the laser path 80 .

Further, the laser path 80 in this embodiment includes: a laser refraction path 82 that refracts and guides the laser light emitted by the laser generator, and a laser focusing head 84 that is connected to the laser refraction path 82 and focuses the refracted laser light.

The front end of the laser refraction passage 82 is located just above the glass test tube, and a refractive prism is built in the end, which can refract horizontal laser light into vertical laser light and irradiate it into the glass test tube. The back end is attached to the laser generator.

A laser focusing head is installed at the lower part of the front end of the laser refraction passage. The focusing head has a built-in focusing convex lens. Preferably, the focusing convex lens can be a convex lens with a focal length of 5 cm to 50 cm, which can focus the parallel laser light on a focal point with a focal length away from the lens. Further, preferably, the focusing convex lens is a convex lens with a focal length of 30 cm, which can focus the parallel laser light on a focal point at a distance of 30 cm from the lens.

The laser focusing head 84 includes: a laser path connecting portion 842 connected with the laser refraction path 82 and adjusting the upper and lower positions, a focusing head universal shaft 844 connected with the laser path connecting portion 842 and adjusting the focal position of the emitted laser, and a setting A focusing head lens 846 at the end of the focusing head gimbal shaft 844 and through which the focusing head gimbal shaft 844 adjusts the angle.

Further, preferably, the laser path connecting portion 842 in this embodiment adopts a screw head structure. The laser focusing head 84 can adjust the height of the focusing head lens 846 up and down by rotating the laser passage connecting part 842 of the screw head structure. By adjusting the universal shaft 844 of the focusing head, the inclination of the symmetry axis of the focusing head lens 846 can be changed, so that the coordinate position of the laser focus in space can be controlled.

Further, preferably, the laser paths in this embodiment are set according to the laser generators, and each laser generator is equipped with a set of laser paths, so that three laser paths are set, and the operation of three consecutive excitations can be completed. If it is necessary to support more continuous excitation operations, this can be done by adding laser generators and laser paths. The laser path 80 is arranged corresponding to the emission port 602 of the laser generator 60 . Further, the laser refraction path 82 is arranged corresponding to the emission port 602 of the laser generator 60, and converts the parallel laser light 605 emitted by the laser generator 60 into vertical light.

The laser refraction path 82 in this embodiment is a right-angled or corner-shaped structure. The corner of the laser refraction path 82 is provided with a refraction prism 89 that refracts the parallel light emitted by the laser generator into vertical light.

The laser refraction path 82 in this embodiment includes: a first laser refraction path 822 corresponding to the first laser generator 62 and guiding to refract the parallel laser light emitted by the first laser generator 62 into vertical light, and a second laser generator 64 is correspondingly arranged and guided to refract the parallel laser light emitted by the second laser generator 64 into a second refraction path 824 of vertical light, and the third laser generator 66 is correspondingly arranged and guided to refract the parallel laser light emitted by the third laser generator as The third refraction path 826 for vertical light.

The laser focusing head 84 is provided with a plurality of laser focusing heads 83 according to the laser generator, including: a first laser focusing head 83 arranged corresponding to the first laser refraction path 822 and focusing the emitted laser light of the first laser generator 62 after refracting, and a second laser focusing head 83 . The refraction passage 824 is correspondingly arranged and the second laser focusing head 85 is arranged to focus the refracted laser light of the second laser generator 64, and the third laser refraction passage 826 is arranged corresponding to the refracted laser light of the third laser generator 64. Focused third laser focusing head 87 .

As shown in FIG. 3 , the method for continuously excited crystallization according to an embodiment of the present invention includes:

Step S101, emitting laser light: receiving an instruction, controlling the laser generator to emit laser light, and refracting and focusing on the designated position of the test tube through the laser path;

Step S103, obtaining the average radius of the bubbles: collecting images of the bubbles in the test tube due to laser focused irradiation, identifying the edges of the bubbles in each frame of the image, obtaining the radii of the bubbles in the vertical and horizontal directions, and collecting multiple image acquisition devices at the same time. Average the radii of the bubbles in the two directions of the multiple image frames to obtain the average radii of the bubbles at this moment;

Step S105, fitting function: calculate the average radius of the bubbles in each frame of images from the generation of the bubbles to the disappearance of the bubbles, obtain an array of the average radius of the bubbles corresponding to time, and fit the array with the nonlinear least squares method to obtain the average radius of the bubbles and The function of time r=f(t), t is the time, r is the average radius of the bubble, and f is the fitting function;

Step S107, continuous excitation: if a continuous excitation instruction is received, control multiple laser generators to emit lasers at intervals or intervals to perform continuous excitation, and the continuous excitation is that the time t _x satisfies f(t _x -t _x-1 )=R, control the laser generator to emit, and R is smaller than the maximum radius of bubble diffusion and greater than the value obtained by multiplying the minimum duration of the interval excitation controlled by the system multiplied by the speed of bubble diffusion.

In this embodiment, in step S101, laser light is emitted, and any one of a plurality of laser generators may be used for laser emission. Preferably, the first laser generator located in the middle position is used for laser emission. In this step, the laser path is refracted and focused on the designated position of the test tube, the designated position is located in the solution of the test tube, and the distance from the bottom of the test tube, the side wall of the test tube, and the surface of the test tube solution is greater than the focal distance and the test tube is greater than 0.1 cm. Preferably, the distance between the solution in the test tube and the side wall of the test tube and the surface of the solution in the test tube is greater than 1 cm by refracting and focusing on the solution through the laser channel.

The laser is focused on a point in the solution in the glass test tube, and a bubble is formed locally because of the instantaneously high temperature. If the bubbles are formed in the field of view of the camera, the camera will capture the entire picture from the absence of the bubbles to the formation and disappearance of the bubbles. Two cameras on the front and left side capture 1,000 frames per second from both angles.

Preferably, in this embodiment, an image edge recognition algorithm is used to recognize the bubble edge in each frame of image. This gives the vertical and horizontal radii of the bubble in the picture. The average radius of the bubble at the current moment is obtained by averaging the radii of the bubbles in the two directions of the image frames collected by the front and left cameras at the same moment.

The image edge recognition algorithm of the present invention utilizes the algorithm module of OpenCV to complete the edge recognition function. Edge detection supports Canny operator, Sobel operator, Laplace operator, Roberts operator, Krisch operator, and Prewitt operator. In this embodiment, the Laplace operator is preferably used.

Calculate the average bubble radius of each frame of image from the bubble generation to the bubble disappearance, and obtain an array of the average bubble radius corresponding to time, and then use the nonlinear least squares method to fit the array to obtain the function of the average bubble radius and time r= f(t). t is the current time, r is the average radius of the bubble at the current time, and f is the fitting function. The fitting function is adopted as an exponential function, that is, f(t)=ae ^bt , where a and b are fitting parameters.

Further, the bubble diffusion speed in this embodiment is obtained according to the radius and time of each frame of the obtained bubble image.

Further, preferably, the laser generator 60 in this embodiment includes: a first laser generator 62 positioned opposite to the middle position, a second laser generator 64 and a third laser generator 66 positioned opposite to both sides. Referring to the direction of use, further, preferably, the second laser generator 64 is relatively arranged on the right side of the first laser generator 62 , and the third laser generator 66 is relatively arranged on the left side of the first laser generator 62 .

Further, preferably, the continuous excitation in this embodiment includes: after receiving the continuous excitation instruction, controlling the first laser generator to emit, and starting timing, when the time t ₀ satisfies f(t ₀ )=R, the second laser is generated When the time t1 satisfies f(t ₁ -t ₀ )=R, the third laser generator emits.

Further, preferably, before the continuous excitation, it also includes focus adjustment: adjust the focus of the second laser generator to emit laser refraction and focus at a distance R above the focus of the first laser generator to emit laser refraction; adjust the third laser generator to emit laser refraction The focused focal point is located at a distance R above the focused focal point of the second laser generator emitting laser refraction. The focus adjustment can only be set before continuous excitation.

The controller controls the laser generator to emit laser light at a certain time interval, so as to form the effect of re-exciting the bubble at the edge of the bubble excited by the previous laser, so as to obtain a more extreme supersaturation condition.

Through the calculation of the bubble diffusion velocity, the function of the bubble diffusion radius and time can be obtained under the current solution environment and the current laser power.

Further, preferably, the first laser generator 62, the second laser generator 64, and the third laser generator 66 in this embodiment emit lasers that are refracted and focused in the test tube solution. surface greater than 1 cm.

Further, preferably, after the first laser generator 62 in this embodiment emits and excites the bubbles, when the bubbles diffuse to the focus of the laser refraction and focus emitted by the second emitter, the second laser generator 64 emits laser light for excitation to generate new When the bubble diffuses to the focusing focus of laser refraction emitted by the third laser generator 66, the third laser generator 66 emits laser light for excitation, forming the effect of laser bubbles again on the edge of the bubble excited by the previous laser, forming a continuous excitation.

The interval between the refracted and focused focal point of the laser light emitted by the second laser generator and the refracted and focused focal point of the laser light emitted by the first laser generator, and the difference between the refracted and focused focal point of the laser light emitted by the third laser generator 66 The interval between the foci of the laser emitted by the second laser generator after being refracted and focused, the lower limit of the interval is the time between two excitations that can be controlled by the system multiplied by the bubble diffusion speed, and the upper limit of the interval is the maximum radius of bubble diffusion. Among them, the interval time between two excitations is a built-in property of the control system. The two laser generators can be controlled by a program, and their excitation times can be recorded and then obtained by subtracting them from each other. The bubble diffusion speed is captured by a camera. The maximum radius of bubble diffusion can be Obtained with the maximum radius of all frames captured by the camera. After the range interval is obtained by the above method, the focal point of the second laser generator on the right is separated from the upper and lower intervals of the focal point of the first laser generator in the middle, and the focal point of the third laser generator on the left is separated from the second laser on the right side. The upper and lower intervals of the generator's focal point need to be kept within this range.

Set the focal points of the three-way lasers at different positions for continuous excitation, that is, the first laser generator in the middle needs to be excited again at the edge of the excited bubble in a short period of time after laser emission. At this time, the second laser on the right is generated. The laser can be fired when the bubble diffuses to its focal point, creating a new bubble, which is then fired again when it diffuses to the laser focus of the left-hand laser generator.

Further, preferably, the continuous excitation includes: after receiving the continuous excitation instruction, controlling the first laser generator to emit, starting timing, and when the time t ₀ satisfies f(t ₀ )=0.05 cm, the second laser generator emits, When the time t1 satisfies f(t ₁ -t ₀ )=0.05 cm, the third laser generator emits. The experimental ability to achieve continuous excitation in test-tube solutions and continuously obtain more extreme supersaturation conditions is achieved.

Further, the focus adjustment is further preferably: the focus of adjusting the second laser generator to emit laser refraction focusing is located at a distance of 0.05 cm above the first laser generator to emit laser refraction focusing focus; to adjust the focus of the third laser generator to emit laser refraction focusing It is located at a distance of 0.1 cm above the focal point of the refracting focus of the first laser generator.

Each laser generator 60 is correspondingly provided with a laser channel, and each laser channel is provided with a laser focusing head.

Further, the focus adjustment is further preferably as follows: by adjusting the respective laser focusing heads, the lasers emitted by the first laser generator 62, the second laser generator 64, and the third laser generator 66 are refracted and focused on the central axis of the test tube 40. The focal point of the laser light emitted by the first laser generator 62 after being refracted and focused is located at 2 cm from the center axis of the test tube 40 from the bottom of the test tube. The second laser generator 64 emits a refracted and focused focal point of the laser light at a position 2.05 cm from the central axis of the test tube from the bottom of the test tube. The focal point of the laser light emitted by the third laser generator 66 after being refracted and focused is located at 2.1 cm from the central axis of the test tube 40 from the bottom of the test tube 40 .

That is, the focal point of the refraction and focusing of the laser emitted by the second laser generator 64 is located 0.05 cm above the focal point of the laser beam emitted by the first laser generator 62 after refraction and focusing, and the focal point of the laser beam emitted by the third laser generator 66 after refraction and focusing is located at 0.05 cm. The laser light emitted by the first laser generator 62 is 0.1 cm above the focal point after being refracted and focused. Since the radius of the formed bubble will usually be within 0.1 cm,

After the first laser generator 62 in the middle position excites the bubble, the bubble spreads to the focus of the second laser generator 64, where the laser is refracted and focused. After the second laser generator 64 is controlled to be excited again, the bubble spreads to the third laser generator 64. The laser light emitted by the laser generator 66 is refracted and focused at the focal point.

The first laser generator 62 , the second laser generator 64 , and the third laser generator 66 fire in sequence to form a group of three bursts. After the three bursts, the time interval for the next group of laser emission can be manually activated according to the experimental situation. You can also set the interval time and the number of groups to launch in the control system, for example, set the interval time to 1 second and launch 5 groups. Then the system will repeat the three-shot operation 5 times, with an interval of 1 second each time.

Further, preferably, in order for the user to directly see what happens inside, the front side and left side of the test tube rack 20 in this embodiment are set in a semi-open form. The semi-open state means that except for the position where the camera is installed, other positions are set to the open state. The specific camera is installed and fixed on the test tube rack, and other scopes can be open except for the brackets and lines necessary for the installation.

Further, preferably, in order to further improve the shooting quality, the upper edge of each frame of pictures taken by the first image acquisition device or the second image acquisition device, that is, the first camera or the second camera camera, needs to be controlled below the level of the solution inside the test tube, and the lower edge It needs to be controlled above the bottom of the test tube, the left and right edges of the picture do not exceed the left and right walls of the test tube, and the center of the picture is located on the central axis of the test tube, that is, the entire field of view of each frame of pictures captured by the camera is the solution environment in the test tube. The first camera located on the front side and the second camera located on the left side should be at the same level. The entire field of view is the solution environment in the test tube, and the center of the field of view is located on the central axis of the test tube.

A control system according to an embodiment of the present invention includes:

Laser emission module: receive instructions, control the laser generator to emit laser light, and refract and focus on the designated position of the test tube through the laser path;

The module for obtaining the average radius of bubbles: collects the images of the bubbles in the test tube caused by laser focused irradiation, identifies the edges of the bubbles in each frame of images, obtains the radii of the bubbles in the vertical and horizontal directions, and collects multiple images collected by multiple image acquisition devices at the same time. Average the radii of the bubbles in the two directions of the image frames to obtain the average radius of the bubbles at this moment;

Fitting function module: Calculate the average bubble radius of each frame of image from the bubble generation to the bubble disappearance, obtain an array of the average bubble radius corresponding to time, and use the nonlinear least squares method to fit the array to obtain the difference between the average bubble radius and time. The function r=f(t), t is the time, r is the average radius of the bubble, and f is the fitting function;

Continuous excitation module: If a continuous excitation command is received, multiple laser generators are controlled to emit lasers at intervals or intervals to perform continuous excitation. The continuous excitation is when the time tx satisfies f(tx-tx-1)=R, The laser generator is controlled to emit, and R is smaller than the maximum radius of bubble diffusion and greater than the value obtained by multiplying the minimum duration of the interval excitation controlled by the system multiplied by the speed of bubble diffusion.

Further, preferably, the fitting function in this embodiment is an exponential function f(t)=ae ^bt , where a and b are fitting parameters.

Further, preferably, the bubble diffusion speed in this embodiment is obtained according to the radius and time of each frame of the obtained bubble image.

Further, the image acquisition device of this embodiment includes: a first image acquisition device and a second image acquisition device disposed on different sides relative to the test tube.

Further, preferably, the first image acquisition device in this embodiment is a first camera disposed on the front side of the test tube rack 20 . The second image acquisition device in this embodiment is a second camera disposed on the left side of the test tube rack 20 .

Further, preferably, the test tube in this embodiment is a glass test tube with a square cross-section or a rectangular cross-section. Preferably, the length or width of the inner cavity of the test tube 40 is not less than 2.5 cm, and the height is not less than 4 cm. Further, preferably, the test tube 40 in this embodiment is a glass test tube with a square cross section. Further, preferably, the length and width of the inner cavity of the test tube 40 in this embodiment is 3.8 cm, the length and width of the outer wall is 4 cm, and the height is 20 cm. In order to conveniently hang the test tube 40 on the test tube rack 20 , the upper edge of the test tube is also provided with a flange edge of 1 cm wide and 1 cm high to hang on the test tube rack 20 .

Further, preferably, the second laser generator 64 in this embodiment is placed opposite to the right side; the third laser generator 66 is placed opposite to the left side.

The laser refraction path 82 in this embodiment includes: a first laser refraction path 822 corresponding to the first laser generator 62 and guiding to refract the parallel laser light emitted by the first laser generator 62 into vertical light, and a second laser generator 64 is correspondingly arranged and guided to refract the parallel laser light emitted by the second laser generator 64 into a second refraction path 824 of vertical light, and the third laser generator 66 is correspondingly arranged and guided to refract the parallel laser light emitted by the third laser generator as The third refraction path 826 for vertical light.

The laser focusing head 84 includes: a first laser focusing head 83 arranged corresponding to the first laser refraction path 822 and focusing the emitted laser light of the first laser generator 62 after refraction; The second laser focusing head 85 for focusing the laser light of the second laser generator 64 and the third laser focusing head 87 corresponding to the third laser refraction path 826 and focusing the laser light of the third laser generator after refracting .

The first laser focusing head 83 or the second laser focusing head 85 or the third laser focusing head 87 in this embodiment includes: connecting and adjusting the first laser refraction path 822 or the second laser refraction path 824 or the third laser refraction path 826 The laser path connecting part 842 in the upper and lower positions, the focusing head universal shaft 844 which is connected to the laser path connecting part and adjusts the focal position of the emitted laser light, and is arranged at the end of the focusing head universal shaft 844 and adjusted by the focusing head universal shaft 844 The focusing head lens 846 is set at an angle and corresponding to the test tube 40 .

The first laser refraction path 822 or the second laser refraction path 824 or the third refraction path 826 is respectively provided with a device to refract the parallel light emitted by the first laser generator 62 or the second laser generator 64 or the third laser generator 66 as Refracting prism 89 for vertical rays.

The laser refraction paths include the first laser refraction path 822 or the second laser refraction path 824 or the third laser refraction path 826, which are arranged in a right-angle or inflection-shaped structure. Refractive prisms 89 are provided at the corners. The laser focusing head 84 is screwed to the laser refraction passage 82 . The laser path connection portion 842 is a screw head.

Further, the focal length of the focusing head lens of this embodiment is 5-50 cm. Further, preferably, the focal length of the focusing head lens in this embodiment is 30 cm.

Further, the first laser generator 62, the second laser generator 64, and the third laser generator 66 in this embodiment emit lasers that are refracted and focused in the test tube solution. centimeter.

Further, in this embodiment, the focal point of the laser refraction and focusing of the second laser generator 64 is located at a distance R above the focal point of the first laser generator 62 after the laser is refracted and focused; The second laser generator 64 emits laser light at a distance R above the focal point after being refracted and focused.

Further, the front side and the left side of the test tube rack 20 in this embodiment are set as semi-open structures. The bottom of the test tube rack 20 is also provided with a supplementary light 25 which is connected to the control system and is controlled to perform supplementary light. Preferably, the inner wall of the test tube rack 20 in this embodiment is painted or set in white.

Further, the photographing field of view of the first image acquisition device or the second image acquisition device in this embodiment does not exceed the side wall of the test tube from left to right, and does not exceed the solution of the test tube from top to bottom.

Further, the module for obtaining the average radius of bubbles in this embodiment includes: identifying the edge of the bubble in each frame of image, obtaining the radius of the bubble in the vertical and horizontal directions in the picture, and comparing the first image acquisition device and the second image at the same time The radii of the bubbles in the two directions of the image frames collected by the collecting device are averaged to obtain the average radius of the bubbles at the current moment.

Further, the continuous excitation module of this embodiment includes: after receiving the continuous excitation instruction, controlling the first laser generator to emit, and starting timing, and when the time t ₀ satisfies f(t ₀ )=R, the second laser generator emits , when the time t1 satisfies f(t ₁ -t ₀ )=R, the third laser generator emits.

Further, preferably, the continuous excitation module of this embodiment includes: after receiving the continuous excitation instruction, controlling the first laser generator to emit, and starting timing, when the time t ₀ satisfies f(t ₀ )=0.05 cm, the second laser generator The laser generator emits, and when the time t1 satisfies f(t ₁ -t ₀ )=0.05 cm, the third laser generator emits.

Further, preferably, in this embodiment, the focus of the second laser generator emitting laser refraction focusing is located at a distance of 0.05 cm above the focal point of the first laser generator emitting laser refraction focusing, and the third laser generator emitting laser refraction focusing The focal point is located at a distance of 0.1 cm above the focused focal point of the first laser generator emitting laser refraction.

Further, preferably, the continuous excitation module of this embodiment includes: after the first laser generator emits and excites the bubble, when the bubble diffuses to the focus of the laser refraction and focusing emitted by the second emitter, the second laser generator emits laser light for excitation , generate new bubbles, when the bubbles diffuse to the focus of laser refraction emitted by the third laser generator, the third laser generator emits laser light for excitation, forming the effect of laser bubbles again on the edge of the bubbles excited by the previous laser, forming continuous excitation.

Further, preferably, each laser generator in this embodiment is provided with a corresponding laser path. Each laser path is provided with a laser focus head. By adjusting the laser focusing head, the laser light emitted by the first laser generator 62 , the second laser generator 64 and the third laser generator 66 is refracted and focused on the central axis of the test tube 40 . Preferably, after the laser light emitted by the first laser generator 62, the second laser generator 64, and the third laser generator 66 is refracted, the focus is kept at the same height as the camera.

Further, preferably, the focus of the laser light emitted by the first laser generator 62 in this embodiment after being refracted and focused is located at a distance of 2 cm from the central axis of the test tube 40 from the bottom of the test tube 40 . The second laser generator 64 emits a laser refracted and focused focal point located at 2.05 cm from the central axis of the test tube 40 from the bottom of the test tube 40 . The focal point of the laser light emitted by the third laser generator 66 after being refracted and focused is located at 2.1 cm from the central axis of the test tube 40 from the bottom of the test tube 40 .

The first, second and third laser generators are fired in sequence to form a group of three bursts. The continuous excitation module sets one or more groups of three bursts, and the interval between each group sets the time.

The test tube 40 is a square glass test tube with an outer wall of 3 cm in length and width, an inner wall of 3.8 cm in length and width, and a height of 20 cm. superior.

When operating the continuous excitation crystallization system of the present invention, 1. Add the experimental sample and experimental solvent to be crystallized into the special glass test tube of this embodiment;

2. Put the special glass test tube on the test tube rack;

3. Adjust the height of the focusing head in the middle laser path, for example, adjust the focus to 10 cm from the bottom of the test tube, keep the same height as the first camera on the front side and the second camera on the left, and select the focal length of the focusing head lens 846 It is preferably 30 cm. By rotating the focusing head and adjusting the height of the laser focusing head to 20 cm from the mouth of the test tube, the focus can be kept at the same height as the camera;

4. Press the button of the middle laser generator, the laser will generate bubbles at the focus position. At this time, the system will call the bubble diffusion speed calculation function in the software module to calculate the bubble diffusion under the current solution environment and current laser power. speed;

5. Adjust the height of the focusing head to 12 cm from the mouth of the test tube, and the focus is 2 cm from the bottom of the test tube.

6. Press the automatic continuous excitation button to start the continuous excitation function, turn on the laser generators in the middle, right and left respectively, and continuously excite bubbles during the dissolution, forming a crystallization environment with a third-order elevated supersaturation.

The invention utilizes a high-speed visual capture system to feedback-control multiple lasers to continuously excite successively, thereby forming a gradually increasing supersaturation gradient locally in the solution, which is helpful for discovering new crystal forms that are difficult to discover by conventional experimental methods and single-point laser methods.

The invention can be widely used in the related fields of crystallization engineering research and development and production. In particular, solid-state R&D and production in the fields of drugs, materials, and energy have very important applications.

Taking the above-mentioned ideal embodiments according to the present application as inspiration, and through the above-mentioned description contents, the relevant staff can make various changes and modifications within the scope of not departing from the technical idea of the present application. The technical scope of the present application is not limited to the content in the description, and the technical scope must be determined according to the scope of the claims.

As will be appreciated by those skilled in the art, the embodiments of the present application may be provided as a method, a system, or a computer program product. Accordingly, the present application may take the form of an entirely hardware embodiment, an entirely software embodiment, or an embodiment combining software and hardware aspects. Furthermore, the present application may take the form of a computer program product embodied on one or more computer-usable storage media (including, but not limited to, disk storage, CD-ROM, optical storage, etc.) having computer-usable program code embodied therein.

The present application is described with reference to flowchart illustrations and/or block diagrams of methods, apparatus (systems), and computer program products according to embodiments of the present application. It will be understood that each process and/or block in the flowchart illustrations and/or block diagrams, and combinations of processes and/or blocks in the flowchart illustrations and/or block diagrams, can be implemented by computer program instructions. These computer program instructions may be provided to the processor of a general purpose computer, special purpose computer, embedded processor or other programmable data processing device to produce a machine such that the instructions executed by the processor of the computer or other programmable data processing device produce Means for implementing the functions specified in a flow or flow of a flowchart and/or a block or blocks of a block diagram.

These computer program instructions may also be stored in a computer-readable memory capable of directing a computer or other programmable data processing apparatus to function in a particular manner, such that the instructions stored in the computer-readable memory result in an article of manufacture comprising instruction means, the instructions The apparatus implements the functions specified in the flow or flow of the flowcharts and/or the block or blocks of the block diagrams.

These computer program instructions can also be loaded on a computer or other programmable data processing device to cause a series of operational steps to be performed on the computer or other programmable device to produce a computer-implemented process such that The instructions provide steps for implementing the functions specified in the flow or blocks of the flowcharts and/or the block or blocks of the block diagrams.

Claims (10)

1. A method for continuous excitation crystallization, comprising:

   Laser emission: receive instructions, control the laser generator to emit laser, and refract and focus on the designated position of the test tube through the laser path;

   Obtain the average radius of bubbles: collect the images of the bubbles in the test tube generated by the laser focus irradiation, identify the edges of the bubbles in each frame of images, obtain the radii of the bubbles in the vertical and horizontal directions, and collect multiple images collected by multiple image acquisition devices at the same time. Average the radii of the bubbles in the two directions of the image frame to obtain the average radii of the bubbles at this moment;

   Fitting function: Calculate the average bubble radius of each frame from the bubble generation to the disappearance of the bubble, obtain an array of the average bubble radius corresponding to time, and use the nonlinear least squares method to fit the array to obtain the function of the average bubble radius and time. r=f(t), t is the time, r is the average radius of the bubble, and f is the fitting function;

   Continuous excitation: If a continuous excitation command is received, multiple laser generators are controlled to emit lasers at intervals or intervals to perform continuous excitation, and the continuous excitation is that at the moment t _x satisfies f(t _x -t _x-1 )=R When , control the laser generator to emit, R is less than the maximum radius of bubble diffusion, and greater than the value obtained by multiplying the minimum duration of the interval excitation controlled by the system multiplied by the speed of bubble diffusion.
2. The method for continuous excitation crystallization according to claim 1, wherein the fitting function is f(t)=ae ^bt , wherein a and b are fitting parameters; the bubble diffusion speed is based on the obtained bubble image The radius and time of each frame are obtained. The image acquisition device includes: a first image acquisition device and a second image acquisition device arranged on different sides relative to the test tube. The test tube is a glass test tube with a square section or a rectangular section.
3. The method for continuous excitation crystallization according to claim 1 or 2, wherein the laser generator comprises: a first laser generator placed opposite to a middle position, a second laser generator placed opposite to both sides, The third laser generator, the continuous excitation includes: after receiving the continuous excitation instruction, controlling the first laser generator to emit, and starting timing, when the time t ₀ satisfies f(t ₀ )=R, the second laser generator emission, when the time t1 satisfies f(t ₁ -t ₀ )=R, the third laser generator emits;

   Before the continuous excitation, it also includes focus adjustment: adjusting the focal point of the refraction and focusing of the laser emitted by the second laser generator to be located at a distance R above the focus of refraction and focusing of the laser emitted by the first laser generator, and adjusting the focus of the third laser The focal point of the refracting focus of the laser emitted by the generator is adjusted to be located at a distance R above the focal point of the refracting focus of the emitted laser light of the second laser generator.
4. The method for continuously exciting crystallization according to claim 3, wherein the second laser generator is placed opposite to the right side, the third laser generator is placed opposite to the left side, and the continuous exciting comprises: receiving After the continuous excitation command is reached, the first laser generator is controlled to emit, and the timing is started. When the time t ₀ satisfies f(t ₀ )=0.05 cm, the second laser generator emits, and when the time t1 satisfies f(t ₁ -t ₀ )=0.05 cm, the third laser generator emits;

   The focus adjustment: the focus of the second laser generator emitting laser refraction focusing is adjusted to be located at a distance of 0.05 cm above the first laser generator emitting laser refraction focusing focus, and the third laser generator is emitting laser light. The focal point of the refraction focusing is adjusted to be located at a distance of 0.1 cm above the refracting and focusing focal point of the laser emitted by the first laser generator, and the laser light emitted by the first laser generator, the second laser generator and the third laser generator is refracted and focused on The focal point in the test tube solution is more than 1 cm from the bottom of the test tube, the side wall of the test tube, and the surface of the test tube solution.
5. The method for continuously exciting crystallization according to claim 3, wherein the continuous exciting comprises: after the first laser generator emits excited bubbles, waiting for the bubbles to diffuse to the focal point of laser refraction and focusing emitted by the second laser generator When the second laser generator emits laser light for excitation, new bubbles are generated, and when the bubbles diffuse to the focus of laser refraction emitted by the third laser generator, the third laser generator emits laser light for excitation, forming a bubble in the previous laser The edge of the excited bubble has the effect of laser bubble again to form continuous excitation. Each laser generator is provided with a corresponding laser path, and each laser path is provided with a laser focusing head;

   The focus adjustment includes: by adjusting the respective laser focusing heads, the lasers emitted by the first laser generator, the second laser generator and the third laser generator are refracted and focused on the central axis of the test tube, and the first laser The focus of the laser emitted by the generator after being refracted and focused is located at 2 cm from the center axis of the test tube from the bottom of the test tube, the focus of the second laser generator emitted laser refraction and focusing is located at 2.05 cm from the center axis of the test tube from the bottom of the test tube, and the third The focal point of the laser emitted by the laser generator after being refracted and focused is located at 2.1 cm from the central axis of the test tube from the bottom of the test tube. The first, second and third laser generators are fired in sequence to form a group of three bursts. The continuous excitation is set One or more groups of three bursts, the interval between each group is set time.
6. A continuous excitation crystallization system is characterized in that it comprises: a plurality of controlled laser generators for laser emission, a laser path corresponding to the laser generators for refracting and focusing the laser light emitted by the laser generators, a test tube rack, A test tube disposed on the test tube rack and corresponding to the laser passage to receive the focused laser light, an image acquisition device disposed on the test tube rack and corresponding to the test tube and controlled to capture the image of the test tube, and The laser generator and the image acquisition device are communicatively connected and control a control system that works respectively, and the laser path includes: a laser refraction path that refracts and guides the laser light emitted by the laser generator, and a laser refraction path that refracts and guides the laser light emitted by the laser generator. A laser focusing head that connects and focuses the refracted laser light,

   The control system includes:

   Laser emission module: receive instructions, control the laser generator to emit laser light, and refract and focus on the designated position in the test tube through the laser path;

   The module for obtaining the average radius of bubbles: collects the images of the bubbles in the test tube caused by laser focused irradiation, identifies the edges of the bubbles in each frame of images, obtains the radii of the bubbles in the vertical and horizontal directions, and collects multiple images collected by multiple image acquisition devices at the same time. Average the radii of the bubbles in each image frame in two directions to obtain the average radius of the bubbles at this moment;

   Fitting function module: Calculate the average bubble radius of each frame of image from the bubble generation to the bubble disappearance, obtain an array of the average bubble radius corresponding to time, and use the nonlinear least squares method to fit the array to obtain the difference between the average bubble radius and time. The function r=f(t), t is the time, r is the average radius of the bubble, and f is the fitting function;

   Continuous excitation module: if a continuous excitation command is received, multiple laser generators are controlled to emit lasers at intervals or intervals to perform continuous excitation, and the continuous excitation is that the current time t _x satisfies f(t _x -t _x-1 )= When R, the laser generator is controlled to emit, and R is less than the maximum radius of bubble diffusion and greater than the value obtained by multiplying the minimum duration of the interval excitation controlled by the system multiplied by the speed of bubble diffusion.
7. The continuous excitation crystallization system according to claim 6, wherein the laser generator comprises: a first laser generator located in the middle position opposite to each other, a second laser generator located opposite to both sides, a third laser generator The laser path includes: a laser refraction path that refracts and guides the laser light emitted by the laser generator, a laser focusing head that is connected to the laser refraction path and focuses the refracted laser light, and the laser refraction path It includes: a first laser refraction path corresponding to the first laser generator and guiding and refracting the laser light emitted by the first laser generator; a second refraction path of the laser light, a third refraction path corresponding to the third laser generator and guiding and refracting the laser light emitted by the third laser generator, and the laser focusing head includes: corresponding to the first laser refraction path A first laser focusing head for setting and focusing the refracted laser light of the first laser generator, corresponding to the second laser refraction path and focusing the refracted laser light of the second laser generator the second laser focusing head, the third laser focusing head that is set corresponding to the third laser refraction path and focuses the refracted laser light of the third laser generator, the first laser focusing head or the second laser focusing head The laser focusing head or the third laser focusing head includes: a laser path connecting part which is connected with the first laser refraction path or the second laser refraction path or the third laser refraction path and adjusts the upper and lower positions, and is connected with the laser path connecting part A focusing head gimbal shaft that adjusts the focal position of the emitted laser, and a focusing head lens arranged at the end of the focusing head gimbal shaft and adjusting the angle through the focusing head gimbal shaft and corresponding to the test tube. A laser refraction path or a second laser refraction path or a third refraction path is provided with a refraction prism that refracts the parallel light emitted by the first laser generator or the second laser generator or the third laser generator into vertical rays; the The continuous excitation module includes: after receiving the continuous excitation instruction, it controls the first laser generator to emit, and starts timing. When the time t ₀ satisfies f(t ₀ )=R, the second laser generator emits, and when the time t1 satisfies f When (t ₁ -t ₀ )=R, the third laser generator emits.
8. The continuous excitation crystallization system according to claim 7, wherein the laser refraction path is arranged in a right-angle or corner-shaped structure, the refraction prism is arranged at the corner, and the laser focusing head is screwed with the laser refraction path , the connecting part of the laser path is a threaded head, the focal length of the focusing head lens is 5-50 cm, and the first laser generator, the second laser generator, and the third laser generator emit laser light and focus on the test tube through refraction The focal point in the solution is greater than 1 cm from the bottom of the test tube, the side wall of the test tube, and the surface of the test tube solution, and the focal point of the second laser generator emitting laser refraction and focusing is located at the distance above the focal point after the first laser generator emits laser light that is refracted and focused At R, the focal point of the refraction and focusing of the laser emitted by the third laser generator is located at a distance R above the focal point after the laser emitted by the second laser generator is refracted and focused.
9. The continuous excitation crystallization system according to claim 7, wherein the image acquisition device comprises: a first image acquisition device and a second image acquisition device which are relatively arranged on different sides of the test tube, and the module for acquiring the average radius of bubbles It includes: identifying the edge of the bubble in each frame of image, obtaining the radius of the bubble in the vertical direction and the horizontal direction in the picture, and comparing the two directions of the bubble in the image frames collected by the first image acquisition device and the second image acquisition device at the same time The average radius of the test tube rack is averaged to obtain the average radius of the bubble at the current moment; the front side and the left side of the test tube rack are set as semi-open structures, and the bottom of the test tube rack is also provided with a fill light connected to the control system, so The inner wall of the test tube rack is painted or set to be white, the test tube is a glass test tube with a square section or a rectangular section, and the shooting field of view of the first image acquisition device or the second image acquisition device does not exceed the side wall of the test tube, and does not exceed the upper and lower sides of the test tube. test tube solution; the second laser generator is placed opposite to the right side, the third laser generator is placed opposite to the left side, and the continuous excitation module includes: after receiving the continuous excitation instruction, controlling the first laser generator to perform Launch, start timing, when time t ₀ satisfies f(t ₀ )=0.05 cm, the second laser generator emits, and when time t1 satisfies f(t ₁ -t ₀ )=0.05 cm, the third laser generator emits , the focus of the second laser generator's laser refraction focusing is located at a distance of 0.05 cm above the first laser generator's laser refraction focus, and the third laser generator's laser refraction focus is located at the first laser generator. A laser generator emits laser light refracted at a distance of 0.1 cm above the focused focal point.
10. The continuous excitation crystallization system according to claim 7 or 8, wherein the test tube is a glass test tube with a square cross section or a rectangular cross section, and the length or width of the test tube is not less than 2.5 cm and the height is not less than 4 cm , the continuous excitation module includes: after the first laser generator emits and excites the bubble, when the bubble diffuses to the focus of the laser refraction and focusing emitted by the second emitter, the second laser generator emits laser light for excitation, generating a new When the bubble diffuses to the focusing focus of the laser refraction emitted by the third laser generator, the third laser generator emits a laser to excite, forming the effect of re-lasing the bubble on the edge of the bubble excited by the previous laser, forming continuous excitation. Each laser generator is provided with a corresponding laser path, and each laser path is provided with a laser focusing head. By adjusting the laser focusing head, the lasers emitted by the first laser generator, the second laser generator and the third laser generator are refracted and focused. On the central axis of the test tube, the focus of the laser emitted by the first laser generator after being refracted and focused is located at 2 cm from the central axis of the test tube from the bottom of the test tube, and the focus of the second laser generator emitted laser refraction and focusing is located at the central axis of the test tube. At 2.05 cm from the bottom of the test tube, the focus of the laser emitted by the third laser generator after being refracted and focused is located at 2.1 cm from the central axis of the test tube from the bottom of the test tube; the first, second and third laser generators are fired in turn to form One group of three bursts, the continuous excitation module sets one or more groups of three bursts, and the interval between each group is set by time.

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