Ceramic microsphere preparation method based on microflow regulation and control and ceramic microsphere

Abstract

The invention relates to the technical field of ceramic microspheres, in particular to a ceramic microsphere preparation method based on microflow regulation and control, which comprises the following steps: step 1, preparing raw material colloid for forming ceramic microspheres; step 2, putting the raw material colloid into a container, wherein the container is connected with a micro-flow dripping nozzle; 3, the extrusion amount of a micro-flow dripping nozzle is adjusted and controlled according to the size of the needed microspheres, a cylinder body containing oil is arranged, the micro-flow dripping nozzle is located above the cylinder body and is a certain distance away from the cylinder body, the extruded raw material colloid is dripped into the oil liquid in a free falling mode, the density of the selected oil liquid is smaller than that of the raw material colloid, and the micro-flow dripping nozzle is arranged in the cylinder body; enabling the raw material colloid dripped into the oil liquid to gradually descend in the oil liquid and form microspheres, and irradiating the raw material colloid with ultraviolet light to form a microsphere-shaped area in which the microspheres gradually descend, so as to obtain a ceramic microsphere prepolymer; 4, the ceramic microsphere prepolymer is degreased and sintered, and the ceramic microspheres are obtained.By means of the method, the ceramic microspheres uniform in size can be accurately, rapidly and flexibly produced, and the method has the advantage of being easy to operate.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic microspheres, and in particular to a method for preparing ceramic microspheres based on microfluidic regulation. Background Art

[0002] Ceramic microspheres are widely used in implants, photocatalysis, sensors and other fields. In the field of sensing, microsphere materials are usually used as spacer materials in liquid crystal displays. The particle size uniformity and size of the microspheres directly affect the display effects such as the image quality and contrast of the liquid crystal panel. In the field of implants, ceramic microspheres are usually used as bone defect filling materials and drug carriers, and the diameter, porosity and size consistency of the microspheres have a significant impact on the tissue repair effect after implantation. In the field of photocatalysis, catalysts are usually attached to microspheres, and the catalysts are conditionally released by placing microspheres with different porosities and diameters, which has a regulating effect on the photocatalytic reaction.

[0003] At present, the method for preparing microspheres with different porosities and diameters is to disperse the glue dropwise into hot silicone oil, and solidify the droplets in the silicone oil to obtain gel microspheres. Although hot silicone oil can make the glue form microspheres and solidify, the microspheres are prone to deformation before being formed. Therefore, the existing technology is to allow the glue to solidify naturally in silicone oil, which takes a long time to solidify and the microspheres are prone to collision, which affects the size control of the microspheres, thus also leading to the problem of poor uniformity of the size of the microspheres. Summary of the invention

[0004] The purpose of the present invention is to avoid the shortcomings of the prior art and provide a method for preparing ceramic microspheres based on microfluidic regulation. The method for preparing ceramic microspheres based on microfluidic regulation can accurately, quickly and flexibly produce ceramic microspheres of uniform size and has the advantage of easy operation.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A method for preparing ceramic microspheres based on microfluidic regulation is provided, comprising the following steps:

[0007] Step 1: preparing raw material colloid for forming ceramic microspheres;

[0008] Step 2, placing the raw material colloid into a container, wherein the container is connected to a micro-flow nozzle;

[0009] Step 3: adjusting the extrusion amount of the microfluidic nozzle according to the required microsphere size, setting a cylinder filled with oil, so that the microfluidic nozzle is located above the cylinder and at a certain distance, so that the extruded raw material colloid is dripped into the oil by free fall, the density of the selected oil is less than the density of the raw material colloid, so that the raw material colloid after dripping into the oil gradually descends in the oil and forms microspheres, and ultraviolet light is used to irradiate the area where the microspheres gradually descend after the raw material colloid forms microspheres, so as to obtain a ceramic microsphere prepolymer;

[0010] Step 4: degreasing and sintering the ceramic microsphere prepolymer to obtain ceramic microspheres.

[0011] In some embodiments, the raw material colloid is prepared by the following method: ceramic powder, photocurable resin, thickener, and plasticizer are subjected to ball milling and stirring to obtain a mixed material, and a pore-forming agent is added to the mixed material to obtain the raw material colloid.

[0012] A certain amount of corn starch was added into the colloid as a pore-forming agent.

[0013] In some embodiments, the extrusion amount of the raw material colloid is 5 g to 20 g, and the extrusion frequency is 30 s to 50 s / drop.

[0014] In some embodiments, the oil comprises kerosene, nitroglycerin, rapeseed oil, olive oil, peanut oil, soybean oil, or sunflower oil.

[0015] In some embodiments, an ultraviolet lamp is used to output ultraviolet light, and the ultraviolet lamp is disposed on a machine tool, and the machine tool drives the ultraviolet lamp in the X-axis direction and the Y-axis direction.

[0016] In some embodiments, the wavelength of the ultraviolet light is 405 nm and the power is 35 W.

[0017] In some embodiments, the cylinder is a transparent cylinder.

[0018] Beneficial effects of the ceramic microsphere preparation method based on microfluidic regulation of the present invention:

[0019] (1) The method for preparing ceramic microspheres based on microfluidic regulation of the present invention adopts a microfluidic nozzle to extrude the amount of raw material glue according to the required microsphere size, so as to accurately control the size of the microspheres. Then, the extruded raw material glue is liquefied and formed into microspheres during the descent process. Since the density of the oil liquid is less than that of the raw material glue, the microspheres can slowly descend. During the descent process, after the raw material glue is formed into the shape of microspheres, ultraviolet light is used to irradiate the microspheres to ensure that the shape of the raw material glue after solidification is microspheres, thereby effectively controlling the uniformity of the size of the microspheres. Then, during the descent of the microspheres, ultraviolet light is used to irradiate the raw material glue to accelerate the solidification of the microspheres, so that the microspheres that have descended to the bottom are all solidified and formed, thereby avoiding the problem that the traditional microspheres have not yet completed solidification when they descend to the bottom, resulting in the mutual influence between the microspheres and reducing the uniformity of the quality of the microspheres. This method can efficiently produce ceramic microspheres and is suitable for large-scale production and application.

[0020] (2) The present invention provides a method for preparing ceramic microspheres based on microfluidic regulation. The method uses microfluidic oil to liquefy colloids and implements a photocuring method to prepare ceramic microspheres. This method can achieve high-throughput and high-quality preparation of β-TCP / alumina semiconductor spheres, i.e., ceramic microspheres, which are suitable for large-scale production and application.

[0021] A ceramic microsphere is also provided, characterized in that it is prepared by the above-mentioned ceramic microsphere preparation method based on microfluidic regulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a schematic diagram of the process of preparing ceramic microspheres based on microfluidic regulation according to an embodiment of the present invention.

[0023] Figure 2 It is a working state diagram of the ceramic microsphere preparation method based on microfluidic regulation according to an embodiment of the present invention. DETAILED DESCRIPTION

[0024] The preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although the preferred embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided to make the present invention more thorough and complete, and to fully convey the scope of the present invention to those skilled in the art.

[0025] The terms used in the present invention are only for the purpose of describing specific implementation regulations, and are not intended to limit the present invention. The singular forms "a", "the" used in the present invention and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings. It should also be understood that the term "and / or" used in this article refers to and includes any or all possible combinations of one or more associated listed items.

[0026] It should be understood that although the terms "first", "second", "third", etc. may be used to describe various information in the present invention, such information should not be limited to these terms. These terms are only used to distinguish the same type of information from each other. For example, without departing from the scope of the present invention, the first information may also be referred to as the second information, and similarly, the second information may also be referred to as the first information. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0027] Example 1

[0028] The method for preparing ceramic microspheres based on microfluidic regulation disclosed in this embodiment includes the following steps:

[0029] Step 1: preparing raw material colloid for forming ceramic microspheres;

[0030] Exemplarily, the raw material colloid is prepared in the following manner: a photosensitive resin is used, and thickener PE and plasticizer DOP are added to perform ball milling and stirring mixing to obtain a mixed material, and a pore-forming agent is added to the mixed material to obtain a raw material colloid.

[0031] The semiconductor ball material to be prepared is used to prepare the ceramic-photocurable adhesive material of the required ceramic powder + photocurable adhesive colloid system and prepare the raw material colloid, wherein the raw materials include but are not limited to: raw material ceramic powder, photocurable resin, thickener, plasticizer, etc.; for semiconductor balls with different porosity requirements, a certain amount of pore-forming agent is added to the prepared raw material colloid.

[0032] Exemplarily, it includes aluminum oxide powder, ethoxylated pentaerythritol tetraacrylate, epoxy resin, and the photosensitive resin may also be other resins. In practical applications, it can be selected according to actual conditions.

[0033] Exemplarily, the pore former is corn starch.

[0034] Step 2, placing the raw material colloid into a container, wherein the container is connected to a micro-flow nozzle;

[0035] The raw material colloid is introduced into a colloid container connected to a microfluidic microfluidic nozzle, and the raw material colloid of the required pore size weight is extruded; the microfluidic nozzle can be connected to a controller to intelligently control the extrusion amount according to the input of the required microsphere size.

[0036] Step 3: adjusting the extrusion amount of the microfluidic nozzle according to the required microsphere size, setting a cylinder body filled with oil, so that the microfluidic nozzle is located above the cylinder body and at a certain distance, so that the extruded raw material colloid is dripped into the oil, the density of the selected oil is less than the density of the raw material colloid, so that the raw material colloid after dripping into the oil gradually descends in the oil and forms microspheres, and using ultraviolet light to irradiate the area where the microspheres gradually descend after the raw material colloid forms microspheres, so as to obtain a ceramic microsphere prepolymer;

[0037] A micro-flow nozzle is used to extrude the amount of raw material glue according to the required microsphere size, so that the size of the microsphere can be accurately controlled, and then the extruded raw material glue is liquefied and formed into a microsphere during the descent process. Since the density of the oil liquid is less than that of the raw material glue, the microsphere can slowly descend. During the descent process, after the raw material glue is formed into the shape of a microsphere, ultraviolet light is used to irradiate the microsphere to ensure that the shape of the raw material glue after solidification is a microsphere, which effectively controls the uniformity of the size of the microsphere. Subsequently, ultraviolet light is used to irradiate the raw material glue during the descent of the microsphere to accelerate the solidification of the microsphere, so that the microspheres that have descended to the bottom have been solidified and formed, avoiding the problem that traditional microspheres have not completed solidification when they descend to the bottom, resulting in mutual influence between the microspheres and reducing the uniformity of the quality of the microspheres. This method can efficiently produce ceramic microspheres and is suitable for large-scale production and application.

[0038] Step 4: degreasing and sintering the ceramic microsphere prepolymer to obtain ceramic microspheres.

[0039] In this embodiment, the extrusion amount of the raw material colloid is 5g to 20g, and the extrusion frequency is 30s to 50s / drop. The specific extrusion amount can be selected according to actual conditions.

[0040] In this embodiment, the oil includes kerosene, nitroglycerin, rapeseed oil, olive oil, peanut oil, soybean oil, and sunflower oil. The specific type of oil can be selected according to the density of the raw material glue.

[0041] In this embodiment, an ultraviolet lamp is used to output ultraviolet light. The ultraviolet lamp is arranged on a machine tool, and the machine tool drives the ultraviolet lamp in the X-axis direction and the Y-axis direction.

[0042] The moving path of the UV lamp is controlled by the machine tool. UV light is arranged around the oil to irradiate the inside of the cylinder, and the falling colloid droplets are gradually solidified after being irradiated by the UV light.

[0043] In this embodiment, the wavelength of the ultraviolet light is 405nm and the power is 35w.

[0044] This UV wavelength can cure the microspheres better.

[0045] In this embodiment, the cylinder body is a transparent cylinder body.

[0046] The transparent cylinder makes it easy to observe the microsphere forming process.

[0047] The solidified ceramic microsphere samples sink to the bottom of the cylinder, and then the samples are taken out and degreased and sintered.

[0048] To further illustrate the implementation effect of the present invention, the following test examples are carried out:

[0049] Test Example 1

[0050] Preparation of Alumina Microfluidic Photocatalytic Beads

[0051] like Figures 1-2 As shown, after high-purity alumina powder is blended with photosensitive resins such as PPTTA and epoxy resin, thickener PE and plasticizer DOP are added and ball milled and stirred to obtain alumina raw material colloid;

[0052] A certain amount of corn starch is added to the colloid as a pore-forming agent;

[0053] The microfluidic drip nozzle was adjusted to extrude 15 g of colloid per drop, and the flow rate was set to 45 s per drop. The rubber container was placed 1 m above the kerosene cylinder, and the raw material colloid poured into the rubber container was squeezed out to make the raw material colloid fall freely.

[0054] When the colloid contacts the kerosene, the X-axis and Y-axis of the machine tool coordinates are turned on to output continuous ultraviolet light at the same time. The wavelength of the ultraviolet light is 405nm and the power is 35w.

[0055] During the curing process, the UV light output is maintained continuously until the ball falls to the bottom of the cylinder.

[0056] The photocatalytic beads at the bottom were taken out and degreased and sintered in a muffle furnace to obtain alumina microfluidic photocatalytic beads.

[0057] Test Example 2

[0058] Preparation of porous implant pellets

[0059] like Figures 1-2 As shown, after high-purity β-tricalcium phosphate powder is blended with photosensitive resins such as HDDA and polyurethane, thickener PE and plasticizer DOP are added and ball milled to stir and mix to obtain a raw material colloid;

[0060] A certain amount of liquid paraffin is added to the colloid as a pore-forming agent;

[0061] The microfluidic drip nozzle was adjusted to extrude 25 g of colloid per drop, and the flow rate was set to 70 s per drop. The rubber container was placed 1.5 m above the kerosene cylinder, and the raw material colloid poured into the rubber container was squeezed out to make the raw material colloid fall freely.

[0062] When the colloid contacts kerosene, the X-axis and Y-axis of the machine tool coordinates are turned on to output continuous ultraviolet light at the same time. The wavelength of the ultraviolet light is 405nm and the power is 40w.

[0063] During the curing process, the UV light output is maintained continuously until the ball falls to the bottom of the cylinder.

[0064] The photocatalytic beads at the bottom are taken out and degreased and sintered in a muffle furnace to obtain porous implant beads.

[0065] Test Example 3

[0066] Silica Sensor Spacer Microspheres

[0067] like Figures 1-2 As shown, after high-purity silica powder is blended with photosensitive resins such as polyurethane and epoxy resin, thickener PE and plasticizer DOP are added and ball milled and stirred to obtain silica raw material colloid;

[0068] A certain amount of diatomaceous earth is added to the colloid as a pore-forming agent;

[0069] Adjust the microfluidic drip nozzle to squeeze out 5g of colloid per drop, and set the flow rate to 20s per drop. Place the glue container 0.5m above the kerosene cylinder, squeeze out the raw material colloid poured into the glue container and let it fall freely.

[0070] When the colloid contacts kerosene, the X-axis and Y-axis of the machine tool coordinates are turned on to output continuous ultraviolet light at the same time. The wavelength of the ultraviolet light is 405nm and the power is 15w.

[0071] During the curing process, the UV light output is maintained continuously until the ball falls to the bottom of the cylinder.

[0072] The sensor spacer microspheres at the bottom are taken out and degreased and sintered in a muffle furnace to obtain silicon dioxide sensor spacer microspheres.

[0073] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing ceramic microspheres based on microfluidic regulation, characterized in that: The following steps are included: Step 1: preparing raw material colloid for forming ceramic microspheres; Step 2, placing the raw material colloid into a container, wherein the container is connected to a micro-flow nozzle; Step 3: adjusting the extrusion amount of the microfluidic nozzle according to the required microsphere size, setting a cylinder filled with oil, so that the microfluidic nozzle is located above the cylinder and at a certain distance, so that the extruded raw material colloid is dripped into the oil by free fall, the density of the selected oil is less than the density of the raw material colloid, so that the raw material colloid after dripping into the oil gradually descends in the oil and forms microspheres, and ultraviolet light is used to irradiate the area where the microspheres gradually descend after the raw material colloid forms microspheres, so as to obtain a ceramic microsphere prepolymer; Step 4: degreasing and sintering the ceramic microsphere prepolymer to obtain ceramic microspheres.

2. The method for preparing ceramic microspheres based on microfluidic regulation according to claim 1, characterized in that: The raw material colloid is prepared in the following manner: ceramic powder, light-curing resin, thickener and plasticizer are ball-milled and stirred to obtain a mixed material, and a pore-forming agent is added to the mixed material to obtain the raw material colloid. A certain amount of corn starch was added into the colloid as a pore-forming agent.

3. The method for preparing ceramic microspheres based on microfluidic regulation according to claim 1, characterized in that: The extrusion amount of the raw material colloid is 5g-20g, and the extrusion frequency is 30s-50s / drop.

4. The method for preparing ceramic microspheres based on microfluidic regulation according to claim 1, characterized in that: The oil includes kerosene, nitroglycerin, rapeseed oil, olive oil, peanut oil, soybean oil and sunflower oil.

5. The method for preparing ceramic microspheres based on microfluidic regulation according to claim 1, characterized in that: An ultraviolet lamp is used to output ultraviolet light. The ultraviolet lamp is arranged on a machine tool. The machine tool drives the ultraviolet lamp in the X-axis direction and the Y-axis direction.

6. The method for preparing ceramic microspheres based on microfluidic regulation according to claim 5, characterized in that: The wavelength of the ultraviolet light is 405nm and the power is 35w.

7. The method for preparing ceramic microspheres based on microfluidic regulation according to claim 1, characterized in that: The cylinder body is a transparent cylinder body.

8. A ceramic microsphere, characterized in that: The ceramic microspheres are prepared by the method for preparing ceramic microspheres based on microfluidic regulation as described in any one of claims 1 to 7.

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