CN114949341A - Preparation of biodegradable composite powder and dry spheroidizing process thereof - Google Patents
Preparation of biodegradable composite powder and dry spheroidizing process thereof Download PDFInfo
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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- A61L27/10—Ceramics or glasses
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/10—Ceramics or glasses
- A61L27/105—Ceramics or glasses containing Al2O3
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- General Health & Medical Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Crushing And Pulverization Processes (AREA)
Abstract
The invention discloses a preparation method of biodegradable composite powder and a dry-process spheroidizing process thereof, which comprises the following steps: mixing biological ceramic and a biodegradable high polymer material to obtain composite powder; freezing and crushing the composite powder by using a freezing crusher, drying in vacuum, and filtering to obtain uniformly mixed secondary composite powder with proper particle size and irregular shape; feeding the secondary composite powder into a polymer powder nodulizer at a constant speed for nodulizing until the nodulizing rate reaches over 95 percent, and then cooling to obtain the multi-component composite spherical powder. The invention combines the advantages of powder multicomponent components and powder dry-process balling process, on one hand, the biological ceramics and degradable macromolecules are utilized for compounding, thereby realizing the advantage complementation between materials and overcoming the defect that a single material can not meet the requirement of regenerated tissues and organs on performance; on the other hand, by utilizing a dry-method spheroidizing process and taking air as a medium, powder particles are fused and shrunk into spheres by regulating and controlling the spheroidizing process, the key problem that the powder particles are easy to degrade when meeting water in the traditional wet-method process is overcome, and the multi-component powder with high sphericity, controllable particle size and smooth surface is obtained.
Description
Technical Field
The invention relates to a preparation method of biodegradable composite powder and a dry-process spheroidizing process thereof, which are oriented to the field of 3D printing.
Background
The Selective Laser Sintering (SLS) technology is a 3D printing technology based on powder forming, single-layer powder is melted by utilizing laser beams, and layer-by-layer sintering forming of a product is realized through a discrete/stacking principle. Therefore, the SLS technique has drawn much attention in preparing regenerated tissues and organs that are complicated in structure and require customization.
The biodegradable powder material is used as a basic raw material for preparing regenerative tissues and organs by an SLS processing technology, and not only needs high sphericity to ensure good fluidity and spreadability, but also has reasonable granularity and granularity distribution to ensure good forming quality. However, no biodegradable powder material suitable for SLS exists in the market at present, which is mainly because the traditional powder sphericizing process is mainly a wet process, and the biodegradable material is sensitive to humidity and is easy to degrade after meeting water, so that the performance of the biodegradable powder material is sharply reduced. In addition, the conventional wet process may have impurities mixed therein, consumes organic solvents, and is not easy to separate products, which may have adverse effects on normal tissues and organs. Therefore, the development of a preparation process method of the biodegradable powder material, which is environment-friendly, efficient, economical, reliable and simple to operate, is urgent.
Disclosure of Invention
The invention aims to provide a preparation method of biodegradable composite powder suitable for preparing regenerated tissues and organs by SLS technology and a dry spheroidizing process thereof aiming at the defects of the prior art. The invention utilizes the technological processes of freezing, crushing, vacuum drying and the like to obtain composite powder with uniform mixing, proper particle size and irregular shape, then spheroidization is carried out based on the principle of lowest surface energy, and the key technical problems of low sphericity ratio, poor fluidity and the like are overcome by regulating and controlling spheroidization technological parameters and component distribution ratio, so that the multicomponent spherical powder suitable for preparing tissue organ regeneration by the SLS technology is obtained, the sphericity ratio of the obtained powder reaches more than 95 percent, and the fluidity collapse angle is less than 33 degrees.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a process for preparing biodegradable composite powder and dry-spheroidizing thereof, comprising the steps of:
step A, mixing biological ceramic and a biodegradable high polymer material to obtain composite powder;
step B, freezing and crushing the composite powder by using a freezing and crushing machine, drying in vacuum, and filtering to obtain uniformly mixed secondary composite powder with proper particle size and irregular shape;
and step C, feeding the secondary composite powder into a polymer powder spheroidizing machine at a constant speed for spheroidizing until the spheroidizing rate reaches over 95 percent, and then cooling to obtain the multi-component composite spherical powder.
Preferably, in the step a, the bioceramic is at least one of hydroxyapatite, calcium phosphate, silicon dioxide, calcium oxide, phosphorus pentoxide, aluminum oxide, silicon nitride, zirconium dioxide, semiconductor ceramic, or silicate, and the particle size of the bioceramic is 1-300 μm.
Preferably, the biodegradable polymer material is at least one of levorotatory polylactic acid, polyethylene glycol, polyurethane, aliphatic polyester, polyester ether, polyphosphazene, polyorthoester, polycarbonate, polyanhydride, polyamino acid, carbon dioxide polymer, polybutylene succinate, aliphatic aromatic polyester, polyethylene, acrylic resin, polycaprolactone, polytrimethylene terephthalate and polydioxanone.
Preferably, in the step A, by weight, 10 to 1000 parts of the bioceramic and 5 to 599 parts of the biodegradable polymer material are used.
Preferably, in the step C, the spheroidizing temperature of spheroidization includes an induced air port temperature and a discharge port temperature; wherein the temperature of the air induction port is 150-450 ℃, and is 10-50 ℃ above the deformation temperature of the composite powder; the temperature of the discharge port is 50-600 ℃, and the spheroidization time is 2-30 min; the temperature rise rate of the air induction port temperature is 40-90 ℃/min; the cooling rate is 40-90 ℃/min.
Preferably, in the step C, the spheroidizing air flow velocity is 5-30 m/s, the particle retention time is 5-60 min, and the preheating time is 0.5-3 h.
Preferably, in the step C, the secondary composite powder is fed into the polymer powder spheroidizing machine at a constant speed, the feeding speed is 1-20 kg/h, and the cooling time is 0.5-3 h.
Preferably, in the step B, the mesh number of the filtering screen is 100-300 meshes, and the particle size is 50 nm-200 um; and in the step C, the drying temperature is 40-90 ℃, and the drying time is 12-48 h.
Preferably, the freezing and crushing machine includes:
the feeding unit is used for storing and freezing materials and performing grading treatment;
a crushing unit for crushing the frozen material;
an output unit for separating the crushed material particles from the crushing unit;
a controller which is matched with the feeding unit, the crushing unit and the output unit to control the working state of the crushing unit;
wherein, a first feeding pipe, a second feeding pipe and a third feeding pipe which are communicated with liquid nitrogen supply equipment are respectively arranged on the pretreatment bin of the feeding unit, the crushing bin of the crushing unit and the discharge bin of the output unit;
a first temperature sensor in communication connection with the controller is arranged below the first feeding pipe;
a second temperature sensor is arranged on a first connecting pipeline between the crushing bin and the discharging bin, and a flow control valve is arranged at the position, matched with the third feeding pipe, of the discharging bin.
The invention provides a preparation of biodegradable composite powder and its dry-process spheroidizing process, based on the principle of lowest surface energy, utilizing high-speed jet technology to send irregular high-molecular powder into high-temperature cavity, the surface of powder particles flowing through high-temperature thermal field is instantaneously heated and melted, and under the combined action of surface tension, cohesion, gravity and the like, the surface of the particles is driven to change from thermodynamic non-equilibrium state with high free energy to equilibrium state, when the particles are contracted into spherical shape, all parts of the surface of the particles are stressed and balanced to reach thermodynamic stable state with lowest energy, and then the particles are condensed into spherical particles in the falling process. The preparation of the composite material meeting the requirements of regenerated tissues and organs is realized by regulating and controlling the mass ratio, the molecular weight, the particle size distribution and the like of the multiple components. The preparation of the biodegradable powder material with high sphericity, high fluidity and smooth surface is realized by regulating and controlling the air flow speed, the temperature field distribution, the particle residence time, the preheating time, the cooling time and other process parameters.
The invention at least comprises the following beneficial effects:
firstly, aiming at the problem that a single material is difficult to meet the performance requirement of a regenerated tissue organ, the invention provides a multi-component material obtained by compounding biological ceramics and degradable macromolecules, and realizes the advantage complementation between materials.
Secondly, compared with the traditional wet-process balling process, the method adopts a dry-process balling process technology, namely irregular powder particles are introduced into a high-temperature balling cavity under the action of high-speed airflow, the particles are fused and shrunk into balls under the high-temperature heating condition, air is used as a medium in the whole process, and the problem of the key performance of the traditional wet-process balling powder, which is easy to degrade when meeting water, is solved.
Thirdly, the invention realizes the preparation of multi-component powder with high sphericity, controllable particle size and smooth surface by regulating and controlling the spheroidization temperature, feeding frequency, air flow velocity, retention time and the like and changing the component proportion, the molecular weight, the particle size distribution and the like of the powder material, and breaks through the technical bottleneck that the ceramic-degradable polymer cannot be printed due to difficult flowing.
Fourthly, the dry-process pelletizing process method provided by the invention is simple to operate, high in production efficiency, free of toxic substances, clean and environment-friendly, and provides technical support for batch production of SLS processing biodegradable powder materials.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a schematic diagram of a dry-process balling according to the present invention;
FIG. 2 is an SEM image of the raw powder and spheroidized powder of example 2 of the present invention;
FIG. 3 is a schematic view of the angle of repose of the raw powder of example 2 of the present invention;
FIG. 4 is a schematic view of the angle of repose of the spheroidized powder of example 2 of the present invention;
FIG. 5 is a schematic view of the structural layout of the freezing pulverizer of the present invention;
FIG. 6 is a schematic view of the construction of the size reduction assembly of the present invention;
FIG. 7 is a schematic cross-sectional view of a size reduction assembly of the present invention
FIG. 8 is a schematic view of a retaining ring according to the present invention;
FIG. 9 is a schematic top view of the inner panel of the present invention;
fig. 10 is a longitudinal sectional structural view of the inner panel of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
A preparation method of biodegradable composite powder and a dry spheroidizing process thereof comprise the following steps:
in order to meet the individual requirements of SLS processing and adapt to the performance requirements of tissue organ regeneration, the process parameters of induced draft port and discharge port temperature, air flow velocity, temperature field distribution, particle residence time, feeding frequency, preheating time and the like are regulated and controlled by changing the factors of component distribution ratio, molecular weight, particle size and the like of the biological ceramic material and the degradable macromolecules, the multi-component spheroidized powder with high sphericity, good fluidity and excellent suitable particle size performance is obtained, the performance complementation among materials is realized, and the performance requirements of SLS technology for preparing tissue organ regeneration are met.
A reaction principle of the preparation of biodegradable composite powder and a dry spheroidizing process thereof comprises the following steps:
based on the principle of lowest surface energy, high-speed jet technology is utilized to send irregular high-molecular powder into a high-temperature cavity, the surface of powder particles flowing through a high-temperature thermal field is instantaneously heated and melted, the surfaces of the particles are driven to be converted from a thermodynamic non-equilibrium state with high free energy to an equilibrium state under the combined action of surface tension, cohesion, gravity and the like, all parts of the surfaces of the particles are stressed and balanced when the particles are contracted into spheres to reach a thermodynamic stable state with the lowest energy, and then the particles are condensed into spherical particles in the falling process, so that the multielement composite spherical powder with the sphericity as high as more than 95%, the flowability collapse angle less than 33 degrees, stable mechanical properties and excellent surface smoothness is obtained.
Example 1:
a preparation and dry spheroidizing process of biodegradable composite powder comprises the following steps:
spheroidizing single hydroxyapatite material (molecular weight 1004.62, purity 99%, particle size 20nm), adding into a freezing pulverizer, pulverizing, and vacuum drying at 50 deg.C for 36 hr; then putting the dried multi-component powder into a 100-mesh screen to filter to obtain the powder particle size of less than 150 um; starting a blower and an induced draft fan of the polymer powder spheroidizing machine in sequence, then starting a heating switch, setting the induced draft port temperature to be 282 ℃, the discharge port temperature to be 82 ℃, the spheroidizing time to be 15min, the air flow speed to be 10m/s, the particle retention time to be 30min and the feeding speed to be 6kg/h, and then starting heating, wherein the heating rate is 50 ℃/min; when the temperatures of the air inlet and the discharge port reach set temperature values, the spheroidizing chamber of the powder spheroidizing machine is continuously preheated for 1h, and when the preheating of the spheroidizing chamber is finished, feeding is started to the feed hopper; after the equipment normally operates, regularly receiving materials, regularly checking the operation condition of each system, and recording each process parameter; after the experiment is finished, firstly turning off the heating and feeding, then cooling at a cooling rate of 50 ℃/min, turning off the air feeder and the induced draft fan when the inlet temperature is lower than 100 ℃, and finally turning off the total power supply; after the power supply is turned off for a certain time, the temperature of the material outlet, the spheroidizing chamber, the pipeline and other parts is further reduced to 60 ℃, the spheroidized powder product can be taken out, and the spheroidizing is difficult to form due to the fact that hydroxyapatite lacks the characteristics of structural integrity and mechanical stability, and the obtained spheroidizing powder has the performances of spheroidizing rate of only 60%, poor flow behavior (collapse angle of 45 degrees), poor mechanical property, rough surface and the like through analysis.
Example 2:
adding a binary component powder consisting of 55% of hydroxyapatite (molecular weight of 1004.62, purity of 99%, particle size of 20nm) and 45% of levorotatory polylactic acid into a freezing pulverizer for pulverizing, and then placing in a vacuum drier at 50 ℃ for vacuum drying for 36 h; then putting the dried multi-component powder into a 200-mesh screen to filter to obtain the powder particle size smaller than 75 um; sequentially starting a blower and an induced draft fan of the polymer powder spheroidizing machine, then starting a heating switch, then setting the temperature of an induced draft port to be 270 ℃, the temperature of a discharge port to be 75 ℃, the spheroidizing time to be 20min, the air flow speed to be 12m/s, the particle retention time to be 30min and the feeding speed to be 8kg/h, then starting heating, wherein the heating rate is 65 ℃/min, when the temperatures of the induced draft port and the discharge port reach set temperature values, continuously preheating a spheroidizing chamber of the powder spheroidizing machine for 1.5h, and when the preheating of the spheroidizing chamber is finished, starting feeding the feed hopper; after the equipment normally operates, regularly receiving materials, regularly checking the operation condition of each system, and recording each process parameter; and after the experiment is finished, firstly turning off the heating and feeding, then cooling at a cooling rate of 60 ℃/min, turning off the air feeder and the induced draft fan when the inlet temperature is lower than 100 ℃, and finally turning off the total power supply. After the power supply is turned off for a certain time, the temperature of the discharge port, the spheroidizing chamber, the pipeline and other parts is further reduced to 60 ℃, the spheroidized multi-component powder product can be taken out, and the obtained multi-component spheroidized powder has the excellent performances of the spheroidizing rate of 95 percent, good fluidity (collapse angle of 30 degrees), good mechanical property, stable degradation, smooth surface and the like through analysis.
Example 3:
adding a binary component powder consisting of 80% of hydroxyapatite (molecular weight of 1004.62, purity of 99%, particle size of 20nm) and 20% of levorotatory polylactic acid into a freezing pulverizer to pulverize, placing in a vacuum drier at 55 ℃, and carrying out vacuum drying for 24 h; then putting the dried multi-component powder into a 100-mesh screen to filter to obtain the powder particle size of less than 150 um; starting a blower and an induced draft fan of the polymer powder spheroidizing machine in sequence, then starting a heating switch, setting the temperature of an induced draft port to be 275 ℃, the temperature of a discharge port to be 70 ℃, the spheroidizing time to be 10min, the air flow speed to be 7m/s, the particle retention time to be 15min and the feeding speed to be 20kg/h, and then starting heating, wherein the heating rate is 52 ℃/min; when the temperatures of the air inlet and the discharge port reach set temperature values, the spheroidizing chamber of the powder spheroidizing machine is continuously preheated for 0.5h, and when the preheating of the spheroidizing chamber is finished, feeding is started to the feed hopper; after the equipment normally operates, regularly receiving materials, regularly checking the operation condition of each system, and recording each process parameter; and after the experiment is finished, firstly turning off the heating and feeding, then cooling at the cooling rate of 85 ℃/min, turning off the air feeder and the induced draft fan when the inlet temperature is lower than 100 ℃, and finally turning off the total power supply. After the power is turned off for a certain time, the temperature of the discharge port, the spheroidizing chamber, the pipeline and other parts is further reduced to 60 ℃, the spheroidized multi-component powder product can be taken out, and the obtained multi-component spheroidized powder has good fluidity (collapse angle of 31 degrees), stable degradation and smooth surface through analysis, is difficult to spheroidize and form due to excessive hydroxyapatite and has low mechanical stability, so the spheroidization rate of the powder is only 60 percent and the mechanical property is general.
Example 4:
adding 60% hydroxyapatite (molecular weight is 1004.62), 30% L-polylactic acid and 10% polyethylene glycol into the ternary component powder, pulverizing, placing in a vacuum drier at 60 deg.C, and vacuum drying for 24 hr; then putting the dried multi-component powder into a 200-mesh screen to filter to obtain the powder particle size smaller than 75 um; sequentially starting a blower and an induced draft fan of a high polymer powder spheroidizing machine, then starting a heating switch, setting the temperature of an induced air inlet to be 280 ℃, the temperature of a discharge port to be 79 ℃, the spheroidizing time to be 30min, the air velocity to be 14m/s, the particle retention time to be 35min and the feeding speed to be 10kg/h, then starting to heat up, wherein the heating rate is 62 ℃/min, when the temperature of the induced air inlet and the temperature of the discharge port reach set temperature values, continuing to preheat a spheroidizing chamber of the powder spheroidizing machine for 1.5h, and when the preheating of the spheroidizing chamber is finished, starting to feed a feed hopper; after the equipment normally operates, regularly receiving materials, regularly checking the operation condition of each system, and recording each process parameter; and after the experiment is finished, firstly turning off the heating and feeding, then cooling at the cooling rate of 64 ℃/min, turning off the air feeder and the induced draft fan when the inlet temperature is lower than 100 ℃, and finally turning off the total power supply. After the power supply is turned off for a certain time, the temperature of the discharge port, the spheroidizing chamber, the pipeline and other parts is further reduced to 60 ℃, the spheroidized multi-component powder product can be taken out, and the obtained multi-component spheroidized powder has the excellent performances of the spheroidizing rate of 95.5 percent, good fluidity (collapse angle of 29 degrees), good mechanical property, stable degradation, smooth surface and the like through analysis.
Example 5:
adding 80% hydroxyapatite (molecular weight is 1004.62), 10% L-polylactic acid and 10% polyethylene glycol into the ternary component powder, pulverizing, placing in a vacuum drier at 60 deg.C, and vacuum drying for 24 hr; then putting the dried multi-component powder into a 100-mesh screen to filter to obtain powder with the particle size of less than 75 um; sequentially starting a blower and an induced draft fan of the polymer powder spheroidizing machine, then starting a heating switch, setting the induced draft port temperature to be 280 ℃, the discharge port temperature to be 79 ℃, the spheroidizing time to be 10min, the air flow speed to be 5m/s, the particle retention time to be 17min and the feeding speed to be 18kg/h, and then starting heating, wherein the heating rate is 50 ℃/min; when the temperatures of the air inlet and the discharge port reach set temperature values, the spheroidizing chamber of the powder spheroidizing machine is continuously preheated for 0.5h, and when the preheating of the spheroidizing chamber is finished, feeding is started to the feed hopper; after the equipment normally operates, regularly receiving materials, regularly checking the operation condition of each system, and recording each process parameter; and after the experiment is finished, firstly turning off the heating and feeding, then cooling at the cooling rate of 50 ℃/min, turning off the air feeder and the induced draft fan when the inlet temperature is lower than 100 ℃, and finally turning off the total power supply. After the power is turned off for a certain time, the temperature of the discharge port, the spheroidizing chamber, the pipeline and other parts is further reduced to 60 ℃, and then the spheroidized multi-component powder product can be taken out, and after analysis, the obtained multi-component spheroidized powder has good fluidity (collapse angle of 30 degrees), stable degradation and smooth surface, is difficult to spheroidize and form due to excessive hydroxyapatite and has reduced mechanical stability, so the spheroidization rate of the powder is only 70 percent and the mechanical property is general.
Example 6:
adding multi-component powder composed of 50% hydroxyapatite (molecular weight of 1004.62), 20% L-polylactic acid, 20% polyethylene glycol and 10% alumina into a freezing pulverizer, pulverizing, placing in a vacuum drier at 50 deg.C, and vacuum drying for 24 hr; then putting the dried multi-component powder into a 100-mesh screen to filter to obtain powder with the particle size of less than 75 um; starting a blower and an induced draft fan of the polymer powder spheroidizing machine in sequence, then starting a heating switch, setting the induced draft port temperature of 290 ℃, the discharge port temperature of 90 ℃, the spheroidizing time of 13min, the air flow speed of 9m/s, the particle retention time of 19min and the feeding speed of 19kg/h, and then starting heating, wherein the heating rate is 51 ℃/min; when the temperatures of the air inlet and the discharge port reach set temperature values, the spheroidizing chamber of the powder spheroidizing machine is continuously preheated for 1.5 hours, and when the preheating of the spheroidizing chamber is finished, feeding is started to the feed hopper; after the equipment normally runs, the equipment is required to receive materials at regular time and check the running condition of each system at regular time, and each process parameter is recorded; and after the experiment is finished, firstly turning off the heating and feeding, then cooling at a cooling rate of 60 ℃/min, turning off the air feeder and the induced draft fan when the inlet temperature is lower than 100 ℃, and finally turning off the total power supply. After the power is turned off for a certain time, the temperature of the discharge port, the spheroidizing chamber, the pipeline and other parts is further reduced to 60 ℃, the spheroidized multi-component powder product can be taken out, and the obtained multi-component spheroidized powder has the sphericity as high as 95 percent, good fluidity (collapse angle of 28 degrees), stable degradation, smooth surface and excellent mechanical property after analysis.
The freezing pulverizer adopted in embodiments 1 to 6 of the present invention includes:
the feeding unit is used for storing and freezing materials and performing grading treatment;
a crushing unit for crushing the frozen material;
an output unit for separating the crushed material particles from the crushing unit;
a controller which is matched with the feeding unit, the crushing unit and the output unit to control the working state of the crushing unit and the output unit;
in practical application, the pretreatment bin is connected with the liquid nitrogen supply equipment through the first feeding pipe, so that pre-cooling operation of the high polymer material in the pretreatment bin is realized, the second feeding pipe can feed liquid nitrogen into the crushing bin in real time, the crushing effect of the crushing bin meets the use requirement, and further, the output unit is provided with a matched third feeding pipe, so that cooling compensation can be performed on long-distance output, and the processing quality of the material is ensured;
a first temperature sensor 7 in communication connection with the controller is arranged below the first feeding pipe, is arranged below the first feeding pipe and is used for acquiring the temperature inside the pretreatment bin in real time so as to control the working state of the first feeding pipe according to the real-time detection of the temperature, and further a third temperature sensor matched with the first temperature sensor can be arranged below the feeding screw rod according to the requirement and can be used for acquiring the temperature of the material in the transmission process in real time so as to determine whether the temperature compensation is required in real time according to the temperature and ensure the processing stability of the material;
the first connecting pipeline 8 between the crushing bin and the discharging bin is provided with a second temperature sensor 9, the discharging bin is provided with a flow control valve at the position matched with the third feeding pipe, in the structure, a matched temperature sensor (temperature sensor) is arranged between a processing bin provided with a fan and the crushing bin for monitoring the real-time change of the temperature, and a switch (flow control valve) matched with temperature regulation is arranged at the terminal of the third feeding pipe of the liquid nitrogen, so that the supply state of the liquid nitrogen can be regulated according to the environmental temperature, the flow is supplied, the environmental temperature is kept stable, the water absorption degradation caused by insufficient cold energy in the long-distance pipeline output process of the highly-distributed degradable medical sub-materials is avoided, and in the structure, each feeding pipe is matched with the temperature sensor and the switch, so that the invention can perform the real-time compensation along the process of the crushing processing of the materials, the liquid nitrogen supply is adjusted according to the temperature change, so that the problem that the degradable medical high polymer material absorbs water and degrades due to insufficient cold energy in the long-distance pipeline output process is solved.
As in fig. 5-7, the feed unit is configured to include:
in practical application, a hopper 10 communicated with the preprocessor can be provided with a matched stirring mechanism as required to stir the materials in the hopper in real time so as to ensure the stability of material transmission;
in actual installation, each device of the scheme is packaged through a box body 21, a hopper is arranged above the box body, the pretreatment bin is arranged in the box body and is communicated with the feed hopper, the front and back directions of the feeding screws are arranged (the feeding screws are not shown in the figure 5 due to position reasons), the front ends of the feeding screws are connected with the pretreatment bin, and the back ends of the feeding screws are connected with the crushing bin;
the first electric control valve (not shown) and the second electric control valve (not shown) are arranged between the hopper and the pretreatment bin and between the feeding screw and the pretreatment bin, and when the first electric control valve and the second electric control valve are actually applied, through the switching of the working states of the electric control valves, the hopper does not convey materials to the pretreatment bin any more and the pretreatment bin does not convey materials to the crushing bin during pretreatment work until pretreatment is completed;
the first electric control valve and the second electric control valve are configured to be in communication connection with the controller, in the structure, the control over feeding of the hopper is completed through the cooperation of the controller and the first electric control valve, the control over feeding of the pretreatment bin to the crushing bin is completed through the cooperation of the controller and the second electric control valve, the automation of control of all links is guaranteed, and the intellectualization and controllability of equipment operation are guaranteed.
The shell of the pretreatment bin is configured to be of a double-layer structure, so that a cavity for containing heat insulation materials is defined between layers of the shell, and compared with the existing single-layer bin, the double-layer structure has the advantages that the cold insulation effect is better, the structural stability of equipment in work is better, and the influence on the external structures of other parts in the equipment due to cold energy exchange is avoided;
the inside wall of shell is configured to be the arc structure, through the design of arc structure for when it receives pressure, the dispersion degree of consistency of pressure is better, and equipment structure stability is better, and when actual application, the interference between material and the equipment is littleer.
The stirring mechanism for mixing materials is arranged in the pretreatment bin, and in practical application, the stirring mechanism matched with the pretreatment bin can be arranged in the pretreatment bin as required to stir the materials in the pretreatment bin in real time, so that the contact uniformity and consistency of the materials and the refrigerant are better when the refrigerant is input.
The pulverization unit is configured to include:
the crushing assembly is arranged inside the crushing bin and is used for crushing the materials input into the crushing bin;
in the structure, a hollow shaft liquid nitrogen direct injection device is arranged at the joint of the second feeding pipe introduced with liquid nitrogen and the crushing bin, so that the liquid nitrogen can directly pass through the crushing bin, the transmission path of the liquid nitrogen is shortened, and the rapid cooling of the material is realized;
wherein the shredding assembly is configured to include:
a power mechanism (not shown) disposed below the pulverizing bin for providing power during operation, typically using a motor as a power source;
a rotating shaft (not shown) disposed inside the crushing bin and connected to a power output shaft of the power mechanism, for transmitting rotation generated by the motor to the blades connected to the fixing mechanism to generate crushing force when rotating;
a fixing mechanism 12 connected with the rotating shaft;
a plurality of blades 13 detachably connected with the fixed member, for generating cutting force in the rotating process to crush and cut the material;
the setting is on smashing the storehouse inside wall to cooperate with the blade and carry out at least one tooth shape dish 14 of crushing operation, it is used for taking the material person striking crushing operation on the lateral wall to the centrifugation, carries out crushing operation to the material through cutting, striking broken synergism, makes after the preliminary treatment, and the material becomes dry and brittle material can be in effectual time, and broken quality to needs guarantees the efficiency of material processing.
The securing mechanism is configured to include:
a fixing member 15 having a barrel-shaped structure;
the fixing parts and the fixing parts are arranged integrally, the limiting grooves are arranged in the fixing plates, the arrangement mode and the number of the fixing plates are matched with the distribution requirement of the blades, and the rotating shaft drives the fixing mechanism to rotate during operation so as to rotate the blades connected with the fixing plates;
one end of the fixing plate is configured to be connected with the rotating shaft, and the other end of the fixing plate is configured to be connected with the annular side wall of the fixing piece;
the fixing piece is provided with a limiting groove 17 extending into the fixing plate at the position matched with each fixing plate, namely the limiting groove penetrates through the annular side wall of the fixing piece in space and extends into the fixing plate, so that the fixing of the blade is completed, and the fixing rigidity of the blade is ensured;
the blade is provided with a plurality of positioning holes 18, the fixing plate is provided with fixing holes (not shown), the blade is adjustably arranged in the limiting groove through screws, in the structure, the blade can be positioned in the limiting groove through bolts, the extension length of the blade space can be adjusted through matching of different positioning holes, then the gap between the blade and the toothed disc can be freely adjusted according to the requirement of the grinding particle size, the precise regulation and control of the particle size of powder are realized, and the actual application requirements of different processing scenes are met.
As shown in fig. 5, the output unit is configured to include:
a fan (not shown) disposed inside the discharging bin and cooperating with the first connecting pipeline, for sucking out the material from the crushing bin by a suction force generated in operation;
a discharge hopper 19 communicated with the discharge end of the discharge bin through a second connecting pipeline;
wherein, the discharge gate passes through matched with third connecting line 20 and preliminary treatment storehouse, smashes the storehouse intercommunication, goes out the hopper position and is linked together with preliminary treatment storehouse and crushing storehouse respectively through matched with third connecting line, constitutes multistage cold source closed circulation system, improves the utilization efficiency of liquid nitrogen, avoids causing the waste of liquid nitrogen, can adjust the inside working air pressure in each storehouse simultaneously for it can be invariable be under comparatively stable operational environment.
The outer sides of the first feeding pipe, the second feeding pipe and the third feeding pipe are respectively provided with a first heat preservation layer which is matched with the first feeding pipe;
in the structure, through the design of the heat-insulating layers, the cold energy generated in the operation of the equipment can be reduced to the greatest extent, and the working temperature of other parts of the equipment is not influenced;
wherein each insulating layer is configured to include:
the inner layer is matched with the outside of each pipeline and is used for being matched with the surface of the pipeline and protecting the pipeline through the rigidity of the inner layer;
the polystyrene foam layer is arranged above the inner layer through the bonding layer and is used for playing a role in isolation and reducing cold loss;
the metal coating is arranged above the polystyrene foam layer and used for prolonging the service life of the foam layer and preventing the problem that the service life is shortened due to the influence on the material performance of equipment after the foam layer is cooled and exposed for a long time;
the inner layer is prepared from polyurethane plastics, is used for ensuring the service life of equipment, has certain hardness, and can reduce the acting force of the foam layer directly acting on the pipeline to protect the pipeline when the foam layer deforms;
the polystyrene foam layer is configured into an annular structure with the inner diameter larger than the outer diameter of each pipeline, and the polystyrene foam layer is provided with notches matched with the length direction of each pipeline, so that the polystyrene foam layer can be directly clamped under the pipelines as required through the design of the notches, the polystyrene foam layer is suitable for protection operation after the pipelines are installed, and the polystyrene foam layer is simple to assemble and easy to realize;
polystyrene foam layer is through a plurality of ribbons or clamps that interval predetermined distance set up and then fixed, and it is used for fixing the foam layer after establishing the cover, guarantees its and pipeline complex stability.
As in fig. 8-10, the inner layer is configured to include:
a plurality of fixing rings 22 fitted around the outside of each pipeline;
the structure is characterized in that the structure is arranged between two adjacent fixing rings so as to form a plurality of arc inner plates 23 which are in an enclosing shape to each pipeline in space, the inner layer is in a split structure through the matching of the fixing rings and the arc inner plates, the pipeline after being installed can be protected and installed, and meanwhile, the structure is designed so that the later maintenance is easier, namely, the pipeline does not need to be disassembled and assembled during maintenance, the operation is simpler, the loss can be obviously reduced, the maintenance time can be shortened by a large radian, and the arc structure is designed so that the arc structure can be better matched with the external structure of the pipeline;
the inner diameter of the fixing ring is configured to be larger than the outer diameter of each pipeline, a plurality of trapezoid fixing grooves 24 are formed in the inner side wall of the fixing ring, and the stability of the inner plate after being inserted is guaranteed through the setting of the trapezoid fixing grooves;
two ends of each arc-shaped inner plate are respectively provided with a clamping head 25 matched with the fixed groove;
the arc inner panel height is configured to the height that is greater than the dop, and keeps flushing in space with solid fixed ring's external diameter, be provided with a plurality of arc protruding portions 26 with the contact of pipeline outer wall on the inside wall of inner panel, it is injectd through the structure, make solid fixed ring support fixed ring through arc structure's protruding portion in space, and then make inner panel and pipeline surface can not have the contact, can not produce the interference, and then make equipment pipeline surface when meetting the impact, at first cushion through the foam, and when impact pressure is too big, because solid fixed ring does not produce the contact with the pipeline surface, its impact force can release and partly absorb through arc protruding portion, reduce its impaired degree, guarantee the job stabilization nature and the life of equipment.
The use method of the liquid nitrogen freezing pulverizer comprises the following steps: adjusting the distance between the blade and the toothed disc according to the requirement, setting the pre-cooling temperature for performing the predetermined treatment on the composite powder in the pre-treatment bin to be 165 ℃, and setting the crushing temperature for crushing the composite powder in the crushing bin to be-150 ℃;
step two, closing the second electric control valve, opening the first electric control valve, enabling the composite powder to enter a pretreatment bin through a hopper for storage, closing the first electric control valve, enabling liquid nitrogen for precooling to enter the pretreatment bin through a first feeding pipe, and carrying out precooling operation on the composite powder;
step three, when the pre-treatment bin reaches the set pre-cooling temperature and the crushing bin reaches the preset crushing temperature, opening a second electric control valve, starting a feeding screw to feed the composite powder into the crushing bin according to the preset feeding speed, feeding the liquid nitrogen for cooling into the crushing bin through a second feeding pipe, and crushing the composite powder into powder under the action of the blades and the toothed disc;
outputting the powder from the crushing bin to a discharge hopper under the action of a fan in the discharge hopper so as to finish the collection operation of the powder at the discharge hopper, detecting the temperature of the output material in real time through a second thermometer in the process, switching the working state of a third feeding pipe into an open state through the limitation of a switch when the temperature of the output material is overhigh, inputting a refrigerant into the output bin again according to the setting, and ensuring the stability of material performance indexes in the long-distance transmission process;
and step five, drying the collected powder in a drying box, wherein the drying temperature is controlled at 60 ℃, and the drying time is 24 hours.
Compared with the traditional pulverizer, the freezing pulverizer adopted by the invention solves the problem that the biodegradable composite powder absorbs water and degrades due to insufficient cold energy caused by long-distance pipeline output in the pulverizing process;
in addition, the telescopic fine-tuning blade device is adopted, the gap between the blade and the toothed disc can be freely adjusted, and the precise regulation and control of the powder particle size are realized; according to the invention, the hollow shaft is adopted in the crushing cavity to enable liquid nitrogen to directly pass through the crushing cavity, so that the liquid nitrogen transmission path is shortened, and the rapid cooling of materials is realized; the invention adopts a multi-stage cold source closed circulation system, thereby realizing the high-efficiency cyclic utilization of cold energy; the connection pipeline is subjected to cold insulation protection, so that the influence on the service life of other parts of equipment and the working stability is prevented in the use process, the cold loss is reduced, and the use effect is ensured to meet the use requirement.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. It is therefore intended that the invention not be limited to the exact details and illustrations described and illustrated herein, but fall within the scope of the appended claims and equivalents thereof.
Claims (10)
1. A preparation and dry spheroidizing process of biodegradable composite powder is characterized by comprising the following steps:
step A, mixing biological ceramic and a biodegradable high polymer material to obtain composite powder;
step B, freezing and crushing the composite powder by using a freezing and crushing machine, drying in vacuum, and filtering to obtain uniformly mixed secondary composite powder with proper particle size and irregular shape;
and step C, feeding the secondary composite powder into a polymer powder spheroidizing machine at a constant speed for spheroidizing until the spheroidizing rate reaches over 95 percent, and then cooling to obtain the multi-component composite spherical powder.
2. The preparation and dry spheroidizing process of the biodegradable composite powder according to claim 1, wherein in the step A, the bioceramic is at least one of hydroxyapatite, calcium phosphate, silicon dioxide, calcium oxide, phosphorus pentoxide, aluminum oxide, silicon nitride, zirconium dioxide, semiconductor ceramic, or silicate, and the particle size of the bioceramic is 1-300 μm.
3. The preparation and dry spheroidizing process of biodegradable composite powder according to claim 1, wherein the biodegradable polymer material is at least one of poly-L-lactic acid, polylactic acid, polyethylene glycol, polyurethane, aliphatic polyester, polyester ether, polyphosphazene, polyorthoester, polycarbonate, polyanhydride, polyamino acid, carbon dioxide polymer, polybutylene succinate, aliphatic aromatic polyester, polyethylene, acrylic resin, polycaprolactone, polytrimethylene terephthalate, and polydioxanone.
4. The preparation and dry spheroidizing process of biodegradable composite powder according to claim 1, wherein in the step A, by weight, 10-1000 parts of bioceramic and 5-599 parts of biodegradable high polymer material are used.
5. The preparation and dry spheroidization process of the biodegradable composite powder of claim 1, wherein in the step C, the spheroidization temperature comprises an induced air port temperature and a discharge port temperature; wherein the temperature of the air induction port is 150-450 ℃, and is 10-50 ℃ above the deformation temperature of the composite powder; the temperature of the discharge port is 50-600 ℃, and the spheroidization time is 2-30 min; the temperature rise rate of the air induction port temperature is 40-90 ℃/min; the cooling rate of the cooling is 40-90 ℃/min.
6. The preparation and dry spheroidization process of the biodegradable composite powder of claim 1, wherein in the step C, the spheroidization air flow velocity is 5-30 m/s, the particle retention time is 5-60 min, and the preheating time is 0.5-3 h.
7. The preparation and dry spheroidizing process of biodegradable composite powder according to claim 1, wherein in the step C, the feeding speed of the secondary composite powder into the polymer powder spheroidizing machine at constant speed is 1-20 kg/h, and the cooling time is 0.5-3 h.
8. The preparation and dry spheroidizing process of the biodegradable composite powder according to claim 1, wherein in the step B, the mesh number of the filtering screen is 100-300 meshes, and the particle size is 50 nm-200 um; and in the step C, the drying temperature is 40-90 ℃, and the drying time is 12-48 h.
9. The preparation and dry spheroidizing process of biodegradable composite powder according to claim 1, wherein the freezing pulverizer comprises:
the feeding unit is used for storing and freezing materials and performing grading treatment;
a crushing unit for crushing the frozen material;
an output unit for separating the crushed material particles from the crushing unit;
a controller which is matched with the feeding unit, the crushing unit and the output unit to control the working state of the crushing unit;
wherein, a first feeding pipe, a second feeding pipe and a third feeding pipe which are communicated with liquid nitrogen supply equipment are respectively arranged on the pretreatment bin of the feeding unit, the crushing bin of the crushing unit and the discharge bin of the output unit;
a first temperature sensor in communication connection with the controller is arranged below the first feeding pipe;
a second temperature sensor is arranged on a first connecting pipeline between the crushing bin and the discharging bin, and a flow control valve is arranged at the position, matched with the third feeding pipe, of the discharging bin.
10. Use of the biodegradable composite powder according to any one of claims 1 to 9 as a printing material in a selective laser sintering technique.
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