CN116283344A - Method for producing porous composite material - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 31
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000004698 Polyethylene Substances 0.000 claims abstract description 26
- 229920000573 polyethylene Polymers 0.000 claims abstract description 26
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 25
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 239000008202 granule composition Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
Abstract
A method for manufacturing HAP/beta-TCP porous composite material at least comprises providing a dry powder mixture, providing a pelletization mixture and performing an annealing step. The dry powder mixture comprises 40 to 55wt% of hydroxyapatite, 25 to 40wt% of beta-tricalcium phosphate, and 10 to 20wt% of Polyethylene (PE) particles having a particle size of 250 to 600 μm. The dry powder mixture is mixed with an aqueous sugar solution to form a particulate mixture and the annealing step is performed. The temperature control program of the annealing step comprises increasing the temperature from 80 ℃ to 100 ℃ to 400 ℃ to 600 ℃ at a heating rate of 20 ℃ to 30 ℃ per hour, followed by maintaining the temperature.
Description
Technical Field
The invention relates to a method for manufacturing a porous composite material, which can be applied as a filler of bone tissue.
Background
A common application of porous ceramic materials in medicine is to use them in the form of porous ceramic particle matrices for reconstructing bone tissue in surgery, trauma and dentistry. Ceramic materials based on Hydroxyapatite (HAP) and beta-tricalcium phosphate (beta-TCP) have their biological behaviour affected by a number of factors, such as chemical composition and phase composition, microstructure, pore size and distribution.
Bioactive materials with HAP and beta-TCP are similar in chemical composition to the structure of bone tissue. Due to the biological resistance of HAP and the biological reabsorption of beta-T C P, the HAP/beta-T C P composite material has advantages, and the biodegradation of beta-T C P can promote the bone tissue to grow. The composite material must have both macropores of 100-1000 μm and micropores of 1-20 μm as a filler of bone voids.
Studies have been conducted (Upgrading Calcium Phosphate Scaffolds for Tissue Engineering Application, key Engineering Materials, vol.377, pp.19-42, 2008) to indicate that the structure of such implant filler is similar to bone structure, providing the fastest bone recovery after surgery. In order to grow bone tissue in the implant filling, the minimum pore size required should be 100-135 μm, and furthermore, the more pores the more efficient the bone tissue growth and fixation process will be (Hydroxyapatite and Hydroxyapatite-Based Ceramics, inorganic Materials, vol.38, no.10, pp.973-984,2002). The presence of micropores in the material commensurate with the size of the plasma protein will increase the adsorption of the protein to proliferate the osteoblasts and promote the bio-integration process. Therefore, in practical applications, ceramics having a bimodal pore size distribution are desired.
The calcium phosphate material having a porous structure of macropores can be manufactured through a combustion additive, a polymer sponge replication method (impregnation through an organic sponge followed by annealing), and a slurry foaming method, but the existing granulation method does not allow the production of particles having macropores and micropores at the same time.
High microporosity can be achieved using a liquid porogen (liquid porogen), which can be a liquid hydrocarbon (liquid hydrocarbons) or water. The microporosity of the particles may be determined by the amount and composition of liquid in the interstices between the calcium phosphate crystallites, and the subsequent pattern of heat treatment (temperature and duration) of the particles determines the rate at which vapor and gas leave the particles upon heating.
U.S. patent publication No. US 20030193106 discloses a method for obtaining a porous material by adding a magnesium-containing material to a HAP/β -TCP mixture, forming the above powder material on the surface of a polyurethane sponge frame, and then annealing and burning at a high temperature of 1000-1200 ℃ to remove the sponge frame. The resulting ceramic material has macropores ranging in size from 200 to 600 μm through replication of the pore structure of the polymer matrix.
U.S. patent publication No. US 5171720A discloses a method for producing a porous ceramic sintered body having macropores of 20 to 2000 μm and three-dimensionally connected micropores formed by the voids between the secondary particles. The method comprises mixing hydroxyapatite spherical particles with an average particle diameter of 10 μm and an average particle diameter of 1 μm, mixing the above materials with methylcellulose solution to form gel, drying the gel, and annealing at 1200deg.C for 4 hr.
Russian patent publication No. RU2395476C1 discloses a method for producing porous hydroxyapatite particles, which comprises calcining hydroxyapatite powder obtained from natural biological bone material at 950-1000deg.C, and pulverizing the calcined material to obtain powder particles of no more than 35 μm. Then, a plastic block of 1 part by weight of paraffin wax and 3 parts by weight of hydroxyapatite powder was prepared, the block was extruded, and then heat-treated at 750 to 800 ℃ to remove paraffin wax, and granulated. The final product is 0.8mm to 2mm particles containing interconnected pores of 100 to 350 μm at a level of 50 to 70 vol%.
Russian patent publication No. RU2303580C2 discloses a method for preparing porous hydroxyapatite ceramics, which contains micropores smaller than 10 μm and interconnecting pores larger than 100 μm at a content of 41 to 70 vol%. The manufacturing method comprises forming a composition of hydroxyapatite powder and gelatin into spherical particles with a diameter of 400-600 mu m, pressing the spherical particles into a blank (raw blanks) with an internal opening ratio (open intergranular porosity) of 30-54 vol.%, and performing heat treatment on the blank at a temperature of 900-1250 ℃ while burning the gelatin and sintering the hydroxyapatite powder particles.
Russian patent publication No. RU2555348C discloses a method for producing ceramic particles through a calcium carbonate-hydroxyapatite system, which is to dry particles obtained by dispersing powder of calcium carbonate and hydroxyapatite through a suspension technology based on an immiscible principle and a suspension of a polyacrylamide solution in a vegetable oil medium, and then sintering the particles at 620-700 ℃. The obtained porous ceramic particles have a size of 100 to 2000 μm, an open porosity of 40 to 80%, and a pore size of 20 to 400 μm.
Disclosure of Invention
The invention provides a method for manufacturing a porous composite material, which at least comprises the steps of providing a dry powder mixture, providing a granulating mixture and performing an annealing step on the granulating mixture.
The dry powder mixture comprises 40 to 55wt% of Hydroxyapatite (HAP), 25 to 40wt% of beta-tricalcium phosphate (beta-TCP) and 10 to 20wt% of Polyethylene (PE) particles having a particle size of 250 to 600 μm.
The granulation mixture is prepared by mixing the dry powder mixture with an aqueous sugar solution having a concentration of 30g to 60g of mono-or disaccharides per 100ml of water, adding 8ml to 20ml of the aqueous sugar solution based on the total weight (100 wt%) of the dry powder mixture, and wet granulating to form a granule mixture.
The annealing step of the particle mixture is followed by the following control procedure:
procedure one, raising the temperature to 80-100 ℃, and then maintaining the temperature;
step two, raising the temperature to 400-600 ℃ at a temperature raising rate of 20-30 ℃ per hour, and then maintaining the temperature;
step three, raising the temperature to 900-1500 ℃ in 8-20 hours, and then maintaining the temperature;
and fourth, cooling from the temperature of the third step to obtain an annealing product.
In addition, disaccharides include sucrose, lactose or maltose.
In addition, in procedure one, the temperature was increased to 80℃to 100℃in 10 minutes to 30 minutes, followed by holding for 1 hour to 5 hours.
The production method as claimed in claim 1, wherein after the temperature is raised to 400 ℃ to 600 ℃ in procedure two, the temperature is held for 1 hour to 5 hours.
Wherein after the temperature is raised to 900 to 1500 ℃ in procedure three, the temperature is then maintained for 3 to 10 hours.
In the fourth procedure, the temperature of the third procedure was lowered to 300 to 500 ℃ within 20 hours, followed by cooling to room temperature.
Wherein the dry powder mixture is prepared by mixing hydroxyapatite and beta-tricalcium phosphate to form a premix, and mixing the premix with polyethylene.
The foregoing summary is merely an overview of the present application, and is provided to enable one of ordinary skill in the art to make and use the present application and to enable one of ordinary skill in the art to make and use the present application.
Detailed Description
In order to describe the possible application scenarios, technical principles, practical embodiments, and the like of the present application in detail, the following description is made with reference to the specific embodiments listed below. The embodiments described herein are only used to more clearly illustrate the technical solutions of the present application, and are therefore only used as examples and are not intended to limit the scope of protection of the present application.
In the present embodiment, a method for producing a porous composite material is provided, wherein the porous composite material is a particle containing Hydroxyapatite (HAP) and beta-tricalcium phosphate (beta-TCP) and can be used as a bone material, and the porous composite material is a particle containing 50 to 70vol.% of particles having a particle size of 100 to 500 μm.
The manufacturing method comprises the following steps:
providing a dry powder mixture comprising 45 to 55wt% HAP, 25 to 40wt% beta-TCP and 10 to 20wt% Polyethylene (PE) particles having a particle size of 250 to 600 μm;
providing a granulation mixture, mixing the dry powder mixture with an aqueous sugar solution having a concentration of 30g to 60g of mono-or disaccharides per 100g of water, adding 8ml to 20ml based on the total weight of the dry powder mixture (100 wt%) and granulating to form a granulation mixture; and
an annealing step is carried out on the particle mixture, and the annealing step is sequentially carried out by the following control procedures:
procedure one, raising the temperature to 80-100 ℃, and then maintaining the temperature;
step two, raising the temperature to 400-600 ℃ at a temperature raising rate of 20-30 ℃ per hour, and then maintaining the temperature;
step three, raising the temperature to 900-1500 ℃ in 8-20 hours, and then maintaining the temperature;
and step four, cooling from the temperature of the step three to 300-500 ℃ to obtain an annealing product.
The resulting pellet of annealed product may then be separated and classified to obtain pellets of a predetermined size.
In the above-mentioned manufacturing method, the disaccharide and the particulate PE in the aqueous sugar solution are used as a combination of pore-forming agents, the aqueous sugar solution is used as an adhesive and ensures high microporosity, PE can produce macropores up to 350 μm, and the size and the quantity of macropores can be adjusted by the size and the content of PE, so that the composite particles with macropores and micropores can be obtained.
In addition, the dry powder mixture is prepared by mixing HAP and beta-TCP to form a pre-mixture, and then mixing the pre-mixture with PE particles. The HAP content in the dry powder mixture was about 45wt%, 47wt%, 49wt%, 51wt%, 53wt% or 55wt%, the beta-TCP content was about 25wt%, 27wt%, 29wt%, 32wt%, 35wt%, 38wt% or 40wt%, and the PE particle content was 10wt%, 12wt%, 14wt%, 16wt%, 18wt% or 20wt%. The particle diameter of the PE particles may be about 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm or 600 μm, or may be a mixture of at least two of the above particle diameters.
The aqueous sugar solution may contain 30g, 35g, 40g, 45g, 50g, 55g, or 60g of a monosaccharide or disaccharide, such as glucose, fructose, and galactose, or a disaccharide such as sucrose, lactose, or maltose, per 100ml of water. In preparing the granulation mixture, the sugar water is added in an amount that is generally based on the total weight of the dry powder mixture (100 wt%) and 8ml, 9ml, 10ml, 13ml, 15ml, 18ml or 20ml of sugar water solution is added.
In one particular embodiment, the granulation mixture contains only HAP, β -T-c P, PE particles, and an aqueous sugar solution.
In one particular embodiment, the dry powder mixture has 51wt% HAP, 34wt% beta-T C P, and 15wt% PE of 400-600 mn, and the granulation mixture is about 10ml of sugar water added at a concentration of 45g/100g water, based on the total weight of the dry powder mixture (100%).
The annealing step serves to sinter the HAP and beta-TCP within the particle mixture and decompose the PE particles to provide a pore size of a predetermined size in the annealed product. For example, interconnect pores having an average size of 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm or 500 μm are formed.
In the first step of the annealing step, the temperature may be raised to 80 to 100 ℃ in 10 to 30 minutes, followed by holding for 1 to 5 hours. The time interval set to raise the temperature may be 12 minutes, 14 minutes, 16 minutes, 18 minutes or 20 minutes, and the raised temperature may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃. The time interval for holding the temperature may be 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.
In the second annealing step, the temperature set in the first annealing step is raised to 400-600 deg.c and maintained for 1-5 hr. The temperature increased in procedure two may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, or 600 ℃, and the time interval for holding the temperature may be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.
In the third step of the annealing, the temperature maintained in the second step is increased to 900 to 1500 ℃ and then maintained for 3 to 10 hours. The temperature to be increased in the third step may be 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, or 1500 ℃, the time period set to increase the temperature may be 8 hours, 12 hours, 14 hours, 16 hours, or 20 hours, and the time period for holding the temperature may be 3 hours, 4 hours, 5 hours, 7 hours, 9 hours, or 10 hours.
In the fourth annealing step, the maintained temperature of the third annealing step is lowered to 300 to 500 ℃ in 8 to 20 hours, and then the annealed product is naturally cooled to room temperature. The first cooling step of procedure four may be to 300 c, 350 c, 400 c, 450 c or 500 c for 8 hours, 12 hours, 14 hours, 16 hours or 20 hours, followed by allowing the product to cool naturally to room temperature.
In the foregoing embodiment, the reason why the PE particles are selected as the pore-forming agent is that PE has a non-water-absorbing property, which can reduce the factor in the reaction process, and the decomposition temperature of the PE particles is 380 degrees, which can make the pores more stable during annealing, so that larger perforations can be formed in the annealed product.
The following provides detailed examples to better understand the spirit of the present invention.
Experimental example 1 preparation of HAP/beta-T C P Complex
120g of HAP and 80g of beta-T-C P are weighed and poured into a pot, premixed for 10-15 seconds, poured into a laboratory knife mill (laboratory knife mill) and milled for 3 seconds. The ground powder was poured into a 2 liter jar, 35 grams of 400 μm to 600 μm PE particles were placed as porogen and mixed with a laboratory stirrer for 5 minutes. The resulting dry powder mixture was poured into a stainless steel bowl and stirring was continued.
Subsequently, 50ml of sugar water (45 g/100g distilled water) was added in two equal portions to the dry powder mixture, and the powder mass was judged to have reached the desired consistency by returning to the stainless steel bowl where the round agglomerates appeared, and the wet mass obtained was granulated on a wet granulator.
Uniformly distributing the granules obtained by the granulator on an Al2O3 ceramic plate of a high-temperature furnace, and carrying out high-temperature annealing at 1100 ℃ for 5 hours according to the following temperature control program:
(1) Raising to 85 ℃ within 15 minutes;
(2) Exposing at 85 ℃ for 3 hours;
(3) Raising the temperature to 500 ℃ at a heating rate of 26 ℃/hour;
(4) Exposing at 500 ℃ for 2 hours;
(5) Raising the temperature to 1100 ℃ within 12 hours;
(6) Exposure was carried out at 1100 ℃ for 5 hours;
(7) Falling from 1100 ℃ to 400 ℃ within 14 hours;
(8) And cutting off the power supply of the furnace to naturally cool to room temperature.
After annealing, the annealed product was poured into 1-2 plastic cans, which were fixed on a rotary shaker table, and treated at 100rpm for 2 minutes to separate the pellet into individual pellets.
Then, the particles were screened according to size using sieves and laboratory screening equipment with mesh sizes of 0.5mm, 1.0mm and 2.0mm in 2-3 minutes. The porosity of the product was 70%, at 50vol.% of the resulting particles, with interconnected pores having an average size of 300 μm.
Comparative example 1
Similar to experimental example 1, but step (3) of the temperature control program was changed to a rate of 50 ℃/hour heating rate, and finally the obtained granules disintegrated.
Comparative example 2
Similar to experimental example 1, but using granular PE with a size of less than 200 μm as porogen, there were almost no macropores (> 100 μm) in the resulting particles.
Finally, it should be noted that, although the foregoing embodiments have been described in the text of the present application, the scope of the patent protection of the present application is not limited thereby. All technical schemes generated by replacing or modifying equivalent structures or equivalent processes based on the essential idea of the application and by directly or indirectly implementing the technical schemes of the embodiments in other related technical fields and the like are included in the patent protection scope of the application.
Claims (9)
1. A method of making a porous composite comprising:
providing a dry powder mixture comprising 40 to 55wt% of Hydroxyapatite (HAP), 25 to 40wt% of beta-tricalcium phosphate (beta-TCP), and 10 to 20wt% of Polyethylene (PE) particles having a particle size of 250 to 600 μm;
providing a granulation mixture, mixing the dry powder mixture with an aqueous sugar solution having a concentration of 30g to 60g of mono-or disaccharides per 100ml of water, adding 8ml to 20ml of the aqueous sugar solution based on the total weight of the dry powder mixture, and granulating to form a granulation mixture; and
an annealing step is carried out on the particle mixture, and the annealing step is sequentially carried out by the following control procedures:
step one, raising the temperature to 80-100 ℃ and maintaining the temperature;
step two, raising the temperature to 400-600 ℃ at a temperature raising rate of 20-30 ℃ per hour, and then maintaining the temperature;
step three, raising the temperature to 900-1500 ℃ in 8-20 hours, and then maintaining the temperature;
and fourth, cooling from the temperature of the third procedure to obtain an annealing product.
2. The method of claim 1, wherein the disaccharide comprises sucrose, lactose, or maltose.
3. The manufacturing method according to claim 1, wherein in the first step, the temperature is raised to 80 ℃ to 100 ℃ within 10 minutes to 30 minutes, followed by holding for 1 hour to 5 hours.
4. The manufacturing method according to claim 1, wherein after the second process, the temperature is raised to 400 ℃ to 600 ℃, the temperature is maintained for 1 hour to 5 hours.
5. The manufacturing method according to claim 1, wherein after the temperature is raised to 900 ℃ to 1500 ℃ in the third process, the temperature is maintained for 3 hours to 10 hours.
6. The manufacturing method of claim 1, wherein the temperature of the third process is lowered to 300 ℃ to 500 ℃ and then cooled to room temperature in 8 to 20 hours in the fourth process.
7. The method of manufacture of claim 1, wherein the dry powder mixture comprises 49wt% to 53wt% of Hydroxyapatite (HAP), 30wt% to 35wt% of beta-tricalcium phosphate (beta-TCP), and 13wt% to 16wt% of Polyethylene (PE) particles having a particle size of 300 μm to 600 μm.
8. The process of claim 1 wherein the granulation mixture is added to 9ml to 12ml of the aqueous sugar solution based on the total weight of the dry powder mixture.
9. The method of claim 1, wherein the dry powder mixture is prepared by mixing the hydroxyapatite and the beta-tricalcium phosphate to form a pre-mixture, and mixing the pre-mixture with the polyethylene.
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