CN108380148B - droplet gyration solidification reaction system of simulation microgravity - Google Patents
droplet gyration solidification reaction system of simulation microgravity Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00824—Ceramic
- B01J2219/00826—Quartz
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00925—Irradiation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00925—Irradiation
- B01J2219/00934—Electromagnetic waves
- B01J2219/00936—UV-radiations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00925—Irradiation
- B01J2219/00934—Electromagnetic waves
- B01J2219/00945—Infrared light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J2219/0095—Control aspects
- B01J2219/00952—Sensing operations
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a droplet rotation solidification reaction system simulating microgravity. The system comprises a rotary evaporator, an annular rotary bracket, a curing reaction container, a reaction control chamber and an observation part; the simulated microgravity effect is obtained by regulating and controlling the internal flow field of the cavity of the simple gyrator device, so that emulsion droplets are cured and formed in situ under a controllable condition, and millimeter-scale large particles with regular geometric shapes are prepared in batches; compared with the turbulent flow field of the traditional common rotary bottle partial liquid filling technology, the full liquid filling technology and the speed control rotation technology in the system can form a more stable and controllable laminar flow field, emulsion liquid drops are self-adaptively suspended and restrained into spheres with extremely small ellipticity under the condition of zero gravity, the damage of a gas-liquid interface and supersaturated air to the emulsion is avoided, all the emulsion liquid drops survive and disperse well, the emulsion system polymerization and solidification are more efficient and controllable, the yield and the quality of product spheres are improved, and the system can be widely used for preparing large-diameter polymer microspheres.
Description
Technical Field
The invention belongs to the field of application of droplet microreactor and emulsion template method microsphere/capsule forming technology, and particularly relates to a droplet rotary curing reaction system for simulating microgravity.
Background
In the fields of microreactors, drug controlled release, catalyst carriers, bioactive species loading, laser Inertial Confinement Fusion (ICF) targets and the like, microspheres/capsules with particle sizes of hundreds of microns to several millimeters are widely applied. In particular, the polymer hollow sphere is used as a core shaft material of a laser fusion target and a fusion energy target fuel container, so that the demand is high, and the requirement on the quality of the sphere is extremely high. With the increasing power of laser drivers, the batch preparation of polymer microspheres with regular geometric shapes from millimeter level to centimeter level becomes one of the bottlenecks in the targeting field. The traditional top-down (top-to-down) methods such as mechanical stirring, ultrasonic, spraying, membrane emulsification and the like are difficult to prepare large particles/spheres with high monodispersity and controllable structures in batches, and the methods are often more in steps and time-consuming and labor-consuming. In recent years, the technology of forming micro-/milli-fluidic droplets from bottom to top has unique advantages for controlling the particle size and the geometric structure of particles/microspheres. In either method, the emulsion droplets are used as a template to be solidified and molded to produce microspheres/capsules. Wherein, the double/multiple emulsion in-situ solidification forming process is complex and difficult to control, the emulsion survival rate is low, the sphericity and concentricity (wall thickness uniformity) of the product are difficult to improve, and the preparation and application of the ICF fusion target pellet are restricted.
Compared with micro-nano-scale droplets, the droplets with millimeter-scale or even larger particle size have complex self-rheological property and more obvious gravity sedimentation and buoyancy effect. The double/multiple emulsion system is more complex, the thermodynamics is extremely unstable, the density layering effect and the like cause huge risks and uncontrollable property, and great challenges are brought to the preparation of millimeter-magnitude or even larger-particle-size polymer hollow microspheres and microcapsules. Therefore, the density matching liquid drop neutral suspension technology and the physical property parameter regulation and control technologies such as emulsion system viscosity, interfacial tension and the like are researched at the earliest. On the basis, the Qinghua university adopts a partial liquid-filled round-bottom flask which rotates obliquely at an angle of 30 degrees as a curing reaction container, and Polystyrene (PS) hollow spheres with the particle size of about 2mm are prepared by heating and curing in a water bath, but the flow field is limited by the shape of the container and is not suitable for large-particle-size emulsion dispersion. The American national center and the laser fusion research center of China institute of engineering and physics adopt a horizontal rotating part liquid-filled cylindrical curing reaction vessel to prepare Polydivinylbenzene (PDVB) foam hollow spheres with the particle size of about 3mm, Polystyrene (PS) hollow spheres with the particle size of 2mm and poly-alpha-methylstyrene (PAMS) hollow spheres by a thermosetting technology. In addition, the American national center for Point and Rochester university, et al, used an electrophoretic centering technique to obtain resorcinol-formaldehyde (RF) and polyhydroxy methyl methacrylate (TMPTA) hollow spheres having a particle size of about 2 mm. At present, the electrophoresis centering technology is limited by the dielectric constant of a system, is mainly used for preparing hollow microspheres with the thickness of less than 2mm, and introduces more complex control parameters in the process. Research shows that the external flow field disturbance effect is an effective way to optimize the emulsion curing process based on the density matching technology and the physical properties of the emulsion system. However, the liquid filling technology of the rotary part often obtains a turbulent flow field, emulsion droplets do random and violent movement under the action of vortex, the emulsion is greatly deformed, heat and mass transfer is intensified, the density of the system is mismatched, emulsion breaking is serious, the emulsion is not suitable for stable dispersion of the emulsion with millimeter magnitude and larger particle size, and in addition, most colloidal particles are agglomerated in the later period of the curing process, so that the microsphere yield is extremely low, and the method is particularly unfavorable for a system with longer polymerization time. At the same time, supersaturated air can also attack the emulsion due to the presence of a gas-liquid interface. Compared with the research on biological tissues under the condition of microgravity simulated by a rotary bioreactor (RCCS) used by the American aerospace agency, the rotary full-liquid-filling technology of the research on the biological tissues usually obtains a laminar flow field, so that the hidden danger of partial liquid-filling technology can be avoided, and the efficiency is higher. Unfortunately, the art has not received sufficient attention in the field of target making where the demand for large particles/balls is extremely high, and the development and application of high quality target balls has been greatly delayed.
Therefore, it is necessary to develop a droplet revolving solidification reaction system suitable for millimeter-scale or even larger scale and capable of simulating microgravity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a droplet rotary curing reaction system simulating microgravity.
The invention relates to a droplet rotary curing reaction system simulating microgravity, which is characterized by comprising a rotary evaporator, an annular rotary bracket, a curing reaction container, a reaction control chamber and an observation part; the rotary evaporator comprises a controller, a lifting rod and a hollow rotating shaft, the curing reaction container comprises a bottle opening and a bottle body, the annular rotating support comprises a neck part and a main body which are matched with the curing reaction container, the neck part of the annular rotating support is clamped on the hollow rotating shaft, the curing reaction container is clamped in the annular rotating support, and the controller controls the lifting rod to lift and the hollow rotating shaft to rotate;
The reaction control chamber comprises a cylindrical cover, a temperature controller and an infrared heating lamp tube; the cylindrical cover is horizontally placed and covers the outer side of the annular rotating support body, the two ends of the cylindrical cover are respectively an open end and a closed end, the neck of the annular rotating support extends out of the open end, and a gap is reserved at the outlet; the inner wall of the cylindrical cover is uniformly distributed with an infrared heating lamp tube and a temperature sensor probe, and the temperature controller measures the temperature in the cylindrical cover through the temperature sensor probe and controls the temperature in the cylindrical cover based on temperature feedback; the upper part and the lower part of the cylindrical cover are provided with a hole I and a hole II, and the closed end is provided with a hole III;
The observation part comprises a sheet laser, a camera and a particle imaging speed measurement system, the camera observes the state of liquid drops in the curing reaction vessel from the hole III, and an obtained image signal is transmitted to the particle imaging speed measurement system for processing;
The external irradiation light source and the lamp holder of the sheet laser respectively extend into the cylindrical cover from the hole I or the hole II.
the inner wall of the cylindrical cover is made of a reflective material or is polished.
the cylindrical cover is provided with a heat insulation material layer.
The curing reaction vessel is in the shape of a cylindrical bottle or a round-bottom flask and is made of quartz glass.
the controller of the rotary evaporator utilizes the stepping motor to drive the hollow rotating shaft to rotate in an infinitely variable speed mode according to the set rotating time, intensity and direction.
The main body of the annular rotating bracket can be opened and closed up and down so as to be convenient for assembling and disassembling the curing reaction vessel.
The annular rotating support should cover the curing reaction vessel as little as possible.
The solidification reaction vessel is used as a vessel for containing particles such as liquid drops, emulsion, multiple emulsion, microspheres and the like after being filled with liquid, and provides an external flow field effect in the process of liquid drop solidification reaction.
The cylindrical cover can be opened and closed up and down so as to be convenient for assembling and disassembling the annular rotating bracket and the curing reaction container.
The reaction control chamber is used for providing a numerical control constant temperature air bath device.
the core of the droplet rotary curing reaction system for simulating microgravity is to obtain the effect of simulating microgravity/low gravity by regulating and controlling the internal flow field of the cavity of the simple gyrator device, so that emulsion droplets are cured and formed in situ under a controllable condition, and millimeter-scale large particles with regular geometric shapes are prepared in batches; compared with the turbulent flow field of the traditional common rotary bottle partial liquid filling technology, the full liquid filling technology and the speed control rotation technology can form a more stable and controllable laminar flow field, liquid drops rotate to the other direction when the gravity action is not in time, the gravity action is almost counteracted, emulsion liquid drops are self-adaptively suspended and restrained into spheres with extremely small ellipticity under the micro/low gravity condition, the damage of a gas-liquid interface and supersaturated air to emulsion is avoided, all the emulsion liquid drops are alive and well dispersed, the solidification reaction conditions (light, irradiation and heat) and a process monitoring and controlling device are integrated, the polymerization and solidification of an emulsion system are more efficient and controllable, the yield and the quality of product spheres are improved, and the method can be widely used for preparing large-diameter polymer microspheres, and particularly can meet the requirement of preparing laser Inertial Confinement Fusion (ICF) experiment target spheres.
Drawings
FIG. 1 is a schematic structural diagram of a microgravity-simulated liquid drop rotation solidification reaction system according to the present invention;
in the figure, 1, a microfluidic droplet generator 2, a lifting rod 3, a hollow rotating shaft 4, an annular rotating support 5, a curing reaction container 6, a cylindrical cover 7, a camera 8, a rotary evaporator 9, a temperature controller 10, an infrared heating lamp tube 11, a hole I12, a hole II 13, a hole III 14 and a particle imaging speed measurement system are arranged.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
As shown in fig. 1, the droplet revolution curing reaction system simulating microgravity of the present invention includes a rotary evaporator 8, an annular rotary support 4, a curing reaction vessel 5, a reaction control chamber, and an observation part; the rotary evaporator 8 comprises a controller, a lifting rod 2 and a hollow rotating shaft 3, the curing reaction container 5 comprises a bottle opening and a bottle body, the annular rotary support 4 comprises a neck part and a main body which are matched with the curing reaction container 5, the neck part of the annular rotary support 4 is clamped on the hollow rotating shaft 3, the curing reaction container 5 is clamped in the annular rotary support 4, and the controller controls the lifting rod 2 to lift and the hollow rotating shaft 3 to rotate;
The reaction control chamber comprises a cylindrical cover 6, a temperature controller 9 and an infrared heating lamp tube 10; the cylindrical cover 6 is horizontally arranged and covers the outer side of the annular rotating support 4 main body, two ends of the cylindrical cover 6 are respectively an open end and a closed end, the neck of the annular rotating support 4 extends out of the open end, and a gap is reserved at the outlet; the inner wall of the cylindrical cover 6 is uniformly distributed with an infrared heating lamp tube 10 and a temperature sensor probe, and the temperature controller 9 measures the temperature in the cylindrical cover 6 through the temperature sensor probe and controls the temperature in the cylindrical cover 6 based on temperature feedback; the upper part and the lower part of the cylindrical cover 6 are provided with a hole I11 and a hole II 12, and the closed end is provided with a hole III 13;
The observation part comprises a sheet laser, a camera 7 and a particle imaging speed measurement system 14, the camera 7 observes the state of liquid drops in the curing reaction vessel 5 from a hole III 13, and an obtained image signal is transmitted to the particle imaging speed measurement system 14 for processing;
An external irradiation light source and a lamp cap of the sheet laser respectively extend into the cylindrical cover 6 from the hole I11 or the hole II 12.
the inner wall of the cylindrical cover 6 is made of a reflective material or is polished.
The cylindrical cover 6 is provided with a heat insulation material layer.
The curing reaction vessel 5 is in the shape of a cylindrical bottle or a round-bottom flask and is made of quartz glass.
The working process of the droplet rotation solidification reaction system simulating the microgravity is as follows:
a. Install rotary evaporator 8 and reaction control room respectively on horizontal laboratory bench, relative position and effect refer to figure 1, and according to cylindrical cover 6's position adjustment lifter 2 make hollow rotating shaft 3 high position and cylindrical cover 6 highly adapt to adjust annular runing rest 4 to the level on hollow rotating shaft 3 to ensure that annular runing rest 4 can normally rotate.
b. The toroidal rotating support 4 is opened and a partially filled curing reaction vessel 5 (e.g., a pre-filled aqueous solution of PVA, more than 1/3, less than 1/2) is installed in the toroidal rotating support 4.
c. The bent end of a guide pipe with one bent end extends into a curing reaction container 5, the other end extends out of a hollow rotating shaft 3 and extends into a liquid drop outlet channel connected to a microfluidic liquid drop generator 1, so that the microfluidic liquid drop generator 1 works, emulsion liquid drops are prepared in batches continuously, the emulsion passes through the hollow rotating shaft 3 through a glass pipeline and is transported, the emulsion enters the curing reaction container 5 which rotates at a speed controlled by a rotary evaporator 8, and the collection is stopped after the emulsion liquid drops are collected to a required number.
d. And (3) filling the curing reaction container 5, sealing the bottle mouth, enabling the curing reaction container 5 to rotate at a controlled speed through a rotary evaporator 8 under the driving of the annular rotating support 4, and closing the cylindrical cover 6.
e. a sheet laser lamp holder is arranged at a hole I11, an irradiation light source (UV) lamp holder is arranged at a hole II 12, a camera 7 is arranged at a hole III 13, and the emulsion state is observed on line by adjusting a particle imaging speed measurement system 14. After the emulsion finishes self-repairing, the emulsion is in a more ideal spherical shape and well dispersed.
f. Heating, or irradiating, or heating and irradiating simultaneously, setting and adjusting temperature via temperature controller 9, and keeping the temperature or irradiating with Ultraviolet (UV) lamp; in the curing process, the rotation mode can be properly adjusted through the rotary evaporator 8 according to the state of the emulsion, the color change of the emulsion is observed on line through adjusting the particle imaging speed measuring system 14, the emulsion is continuously illuminated until the emulsion is completely cured, and the product ball is obtained after transferring and drying.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
example 1
And finishing the assembly work in the steps a, b and c.
The volume ratio of 100: 32 pure water (H)2O) and heavy water (D)2O) is the internal water phase W1; mixing a Divinylbenzene (DVB) monomer and a solvent dibutyl phthalate (DBP) according to a volume ratio of 1: 5, and 0.4wt% of sorbitan oleate (SPAN 80) is used as the mass fractionAn emulsifier, wherein 3% by mass of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (BAPO) is used as a photoinitiator, the mixture is stirred for 10 minutes and uniformly mixed under the protection of argon, and the obtained mixed solution is an intermediate oil phase O; polyvinyl alcohol (PVA, M) at a mass fraction of 5%w= 88000 g/mol) aqueous solution is external aqueous phase W2. Three-phase flow rate (Q) control with a microfluidic droplet generator 1 with an outlet channel of 5.5mmW1=3.33uL/S,QO=0.88uL/S,QW2=20.83 uL/S), continuous batch preparation to double emulsion (W)1/O/W2) The emulsion is conveyed to a partial liquid-filled solidification reaction vessel 5 which horizontally rotates at the speed of 5rpm through a glass pipeline by penetrating through the hollow rotating shaft 3, no less than 200 particles are collected, the outer diameter is 5.172mm, the wall thickness is 356 mu m, and the standard deviation of the size is less than 5 per thousand.
The collection was stopped, the curing reaction vessel 5 was filled with the aqueous PVA solution, the mouth of the vessel was closed, the curing reaction vessel 5 was rotated horizontally by the rotary evaporator 8 at a rate of 8 to 12rpm by the ring-shaped rotary holder 4, and the cylindrical cap 6 was closed. A sheet laser lamp holder is arranged at a hole I11, an irradiation light source (UV) lamp holder is arranged at a hole II 12, a camera 7 is arranged at a hole III 13, and the emulsion state is observed on line by adjusting a particle imaging speed measurement system 14. After about 5 minutes, the emulsion finishes self-repairing, is in a more ideal spherical shape and is well dispersed.
Heating, setting and adjusting the temperature through a temperature controller 9, and keeping the temperature at 50 ℃; simultaneously irradiating the liquid drops by using an Ultraviolet (UV) lamp with the wavelength of 365nm and the illumination intensity of 3.7W/cm 3; the rotating speed can be properly adjusted through the rotary evaporator 8 according to the state of the emulsion in the curing process, the double emulsion is changed into milk white from transparent through online observation by adjusting the particle imaging speed measuring system 14, the double emulsion is continuously illuminated for 45 minutes to be completely cured to obtain wet gel balls, and the survival rate reaches 100 percent; transferring the wet gel balls into an ethanol solution for replacement; and (3) placing the displaced wet gel balls into CO2 supercritical drying equipment for drying to obtain Polydivinylbenzene (PDVB) foam hollow balls, wherein the outer diameter of the foam hollow balls is 5.111mm, the wall thickness of the ball shells is 351 mu m, the standard deviation of the sizes of the balls of the same batch of products is less than 5 per thousand, and the sphericity and the concentricity are both higher than 99%.
the present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make various modifications without creative efforts from the above-described conception, and fall within the scope of the present invention.
Claims (4)
1. A droplet rotation solidification reaction system simulating microgravity is characterized in that: comprises a rotary evaporator (8), an annular rotary bracket (4), a curing reaction container (5), a reaction control chamber and an observation part; the rotary evaporator (8) comprises a controller, a lifting rod (2) and a hollow rotating shaft (3), the curing reaction container (5) comprises a bottle opening and a bottle body, the annular rotary support (4) comprises a neck part and a main body which are assembled with the curing reaction container (5), the neck part of the annular rotary support (4) is clamped on the hollow rotating shaft (3), the curing reaction container (5) is clamped in the annular rotary support (4), and the controller controls the lifting rod (2) to lift and the hollow rotating shaft (3) to rotate;
The reaction control chamber comprises a cylindrical cover (6), a temperature controller (9) and an infrared heating lamp tube (10); the cylindrical cover (6) is horizontally arranged and covers the outer side of the main body of the annular rotating support (4), the two ends of the cylindrical cover (6) are respectively an open end and a closed end, the neck of the annular rotating support (4) extends out of the open end, and a gap is reserved at the outlet; the inner wall of the cylindrical cover (6) is uniformly distributed with an infrared heating lamp tube (10) and a temperature sensor probe, and a temperature controller (9) measures the temperature in the cylindrical cover (6) through the temperature sensor probe and controls the temperature in the cylindrical cover (6) based on temperature feedback; the upper part and the lower part of the cylindrical cover (6) are provided with a hole I (11) and a hole II (12), and the closed end is provided with a hole III (13);
The observation part comprises a sheet laser, a camera (7) and a particle imaging speed measurement system (14), the camera (7) observes the state of liquid drops in the curing reaction container (5) from the hole III (13), and an obtained image signal is transmitted to the particle imaging speed measurement system (14) for processing; an external irradiation light source extends into the cylindrical cover (6) from the hole II (12), and an external sheet-shaped laser lamp holder extends into the cylindrical cover (6) from the hole I (11).
2. A microgravity-simulating drop rotation solidification reaction system as claimed in claim 1, wherein: the inner wall of the cylindrical cover (6) is made of a reflective material or is polished.
3. A microgravity-simulating drop rotation solidification reaction system as claimed in claim 1, wherein: the cylindrical cover (6) is provided with a heat insulation material layer.
4. A microgravity-simulating drop rotation solidification reaction system as claimed in claim 1, wherein: the curing reaction vessel (5) is in the shape of a cylindrical bottle or a round-bottom flask and is made of quartz glass.
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