CN116553907A - Porous ceramic material of cross-scale half-tube-like structure, preparation method thereof and metal mold - Google Patents
Porous ceramic material of cross-scale half-tube-like structure, preparation method thereof and metal mold Download PDFInfo
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- CN116553907A CN116553907A CN202310525624.4A CN202310525624A CN116553907A CN 116553907 A CN116553907 A CN 116553907A CN 202310525624 A CN202310525624 A CN 202310525624A CN 116553907 A CN116553907 A CN 116553907A
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- B28B7/18—Moulds for making shaped articles with cavities or holes open to the surface, e.g. with blind holes the holes passing completely through the article
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- 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
- C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
- C04B38/045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances the dissolved-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a prepreg obtained by bonding together dissolvable particles
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- A61F2/02—Prostheses implantable into the body
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- A61F2002/2835—Bone graft implants for filling a bony defect or an endoprosthesis cavity, e.g. by synthetic material or biological material
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/40—Porous or lightweight materials
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Abstract
The invention relates to the field of porous ceramic materials, and particularly provides a porous ceramic material with a cross-scale half-tube-like structure, a preparation method thereof and a metal mold. The material comprises a plurality of imitated haverse pipe structure units; the halfling-like tube structure unit consists of an organic carrier and ceramic loaded on the organic carrier; the organic carrier has a hierarchical pore structure; the multistage holes comprise through holes and micropores; the directions of the through holes and the micropores are different; the aperture of the through hole is larger than that of the micropore. Compared with the prior art, the porous ceramic material of the trans-scale simulated haverse tube structure has a multi-scale anisotropic hole structure, and the micropores and the through holes realize hole interconnection, so that the whole structure is similar to the haverse tube structure in dense bones; the porous ceramic material with the cross-scale half-tube imitation structure has the excellent characteristics of light weight, high strength and the like, and can be used in the fields of biomedicine, aerospace, military protection and the like.
Description
Technical Field
The invention relates to the field of porous ceramic materials, in particular to a porous ceramic material with a cross-scale half-tube imitating structure, a preparation method thereof and a metal mold.
Background
Although bone tissue has a natural regenerative capacity sufficient to repair small damaged sites, such as cracks and certain types of fractures, bone defects typically greater than the two cm critical dimension threshold are difficult to naturally heal, requiring clinical intervention. Currently, bone fixation or bioinert metal devices using autologous bone, allogeneic bone are currently the gold standard treatment for large bone defects. However, the use of autologous bone often results in additional morbidity associated with donor-site healing; the use of allogeneic bone is related to the risk of disease transmission from donor materials, the bioactivity of metal materials is poor, the price is high, secondary surgery is usually required for excision, and meanwhile, due to the fact that the mechanical properties of the allogeneic bone are not matched with those of natural bones, stress shielding is easy to cause, adjacent bone tissue absorption is caused, and finally loosening and failure of an implant body are caused; the field of bone tissue engineering has witnessed a substantial development towards materials that induce the bone regeneration process at the defect site without creating these risks.
With the rapid development of tissue engineering techniques, a series of biomaterials are designed as porous scaffolds for bone defect repair, because the porous scaffolds can provide three-dimensional space for the implantation of blood vessels and new bone tissue. An ideal bone repair scaffold should have superior structural characteristics to provide an osteogenic microenvironment while excluding fibrous tissue interference with normal bone regeneration. Previous studies have demonstrated that scaffolds with an oriented porous structure are more conducive to infiltration and migration of cells, exchange of nutrients and waste, and deposition of extracellular matrix than scaffolds with a random porous structure. It should be emphasized that the above bone scaffolding functions are achieved by pore structures of different pore sizes, respectively, large pore sizes being beneficial for mass transport, and micropores being beneficial for cell attachment and migration. Although a variety of bone scaffolds with oriented porosity have been designed effectively by 3D printing or oriented freeze casting techniques, their pore size is single and it is difficult to achieve multiple functions in combination. Therefore, how to construct a ceramic matrix material with a multilevel pore structure is a current serious difficulty, and the ceramic matrix material with the multilevel pore structure can be applied to the field of bone repair and is also expected to be applied to the fields of aerospace and military.
Disclosure of Invention
In view of the above, the invention aims to provide a porous ceramic material of a cross-scale half-life pipe structure, a preparation method thereof and a metal mold, wherein the porous ceramic material of the cross-scale half-life pipe structure has a multi-scale anisotropic pore structure, the pore structure of the porous ceramic material is adjustable and controllable, and the porous ceramic material has excellent mechanical properties; the preparation method of the porous ceramic material with the cross-scale half-tube-like structure has expansibility.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a porous ceramic material of a cross-scale half-tube imitation structure comprises a plurality of half-tube imitation structure units; the halfling-like tube structure unit consists of an organic carrier and ceramic loaded on the organic carrier;
the organic carrier has a hierarchical pore structure;
the multistage holes comprise through holes and micropores;
the directions of the through holes and the micropores are different;
the aperture of the through hole is larger than that of the micropore;
the mass ratio of the organic carrier to the ceramic is 1 (0.1-2).
In the present invention, the hierarchical pores include large-scale through-holes and small-scale lamellar micropores; the ceramic is preferably grown on the organic carrier in a deposition manner, and in the in-situ growth process, the ceramic is not simply deposited on the surface of the organic carrier due to strong interaction between the inorganic and organic carriers, but is mutually fused into an integrated structure through intermolecular forces.
In the present invention, the micropores are distributed around the through holes; the through holes are communicated with the micropores;
the pore diameter of the micropore on the side close to the through hole is small, and the pore diameter of the micropore on the side far from the through hole is large; with the increase of the distance between the micropore and the through hole, the pore diameter of the micropore is gradually increased;
the aperture of the through hole is more than or equal to 400 mu m, preferably 0.4-2 mm, and the length of the through hole is more than 100 mu m, preferably 1-15 mm;
the average pore diameter of the micropores is less than or equal to 100 mu m, preferably 1-20 mu m, and the length of the micropores is more than 10 mu m, preferably 0.5-5 mm.
In the invention, the number of the imitated haverse pipe structural units is 1-50.
In the invention, the mass ratio of the organic carrier to the ceramic is preferably 1 (0.25-1.5); in one embodiment of the invention, the mass ratio of the organic carrier to the ceramic is 1:1.
in one embodiment of the invention, the porous ceramic material of the cross-scale half-imitating tube structure comprises 25 half-imitating tube structure units, wherein through holes of the half-imitating tube structure units are distributed in parallel, the length of each through hole is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of micropores is 1-20 mu m, and the length of each micropore is 2mm. In the porous ceramic material with the cross-scale imitated Harvard pipe structure, micropores and through holes are interconnected, and the whole structure is similar to the Harvard pipe structure in dense bones.
When the biological ceramic material is used, the porous ceramic material with the trans-scale half-tube-like structure has good biocompatibility, can be used in the field of bone repair, wherein the through holes have the capacity of inducing vascularization and bone formation, and are beneficial to mineralization of extracellular matrix deposition and vascular infiltration, and the micropores are beneficial to cell adhesion and interconnectivity among the through holes, and are beneficial to cell migration and substance transmission.
In the invention, the organic carrier comprises one or more of fibroin frames, sodium alginate frames, polyvinyl alcohol frames, collagen frames, chitin frames, gelatin frames and polystyrene sodium sulfonate frames.
In the invention, the ceramic is one or more of calcium carbonate, barium carbonate, hydroxyapatite, silicon dioxide, ferric oxide, aluminum oxide, titanium oxide, zirconium oxide, silicon carbide and boron nitride;
the grain size of the ceramic is 10-200nm.
The invention also provides a metal mold, which comprises a containing cavity for bearing the coolant and a forming column group arranged at the outer bottom of the containing cavity; the number, diameter and mutual clearance of the molding columns can be adjusted according to specific requirements;
the molding column group comprises a plurality of molding columns.
In the invention, the molding column group comprises molding columns distributed in an array;
the gap between adjacent shaped pillars is >10 μm, preferably 2mm;
the length of the shaped pillars is >100 μm and the diameter is >400 μm.
In the present invention, the number of the molding columns is 2 to 50, preferably 25 to 50;
the gap between adjacent shaped pillars is >10 μm, preferably 2mm;
the length of the molding column is >100 μm, preferably 1 to 15mm, and the diameter of the molding column is >400 μm, preferably 0.4 to 2mm.
In the invention, the accommodating cavity and the forming column group form an integrated structure; the forming column is preferably a cylinder;
the material of the metal mold is preferably one or more of aluminum, copper and silver, and preferably copper.
In one embodiment of the invention, the metal mold consists of a containing cavity and a forming column, and the containing cavity and the forming column group form an integral structure; the molding column group is a 5*5 array and a metal copper column array with the diameter of 1mm and the gap between columns of 2mm.
The invention also provides a preparation method of the porous ceramic material with the cross-scale half-tube-like structure, which comprises the following steps:
a. contacting the organic matter solution with the metal mold, freezing the metal mold, and removing the metal mold to obtain an organic matter carrier;
b. mixing the organic matter carrier obtained in the step a with a ceramic precursor mother solution to obtain a porous ceramic material with a cross-scale half-tube imitation structure;
the organic matter solution comprises one or more of fibroin solution, sodium alginate solution, polyvinyl alcohol solution, collagen solution, chitin solution, gelatin solution and sodium polystyrene sulfonate solution.
In the present invention, the metal mold includes a receiving cavity for carrying a coolant and a molding column group provided at an outer bottom of the receiving cavity; the number, diameter and mutual clearance of the molding columns can be adjusted according to specific requirements;
the molding column group comprises a plurality of molding columns.
In the invention, the molding column group comprises molding columns distributed in an array;
the gap between adjacent shaped pillars is >10 μm, preferably 2mm;
the length of the shaped pillars is >100 μm and the diameter is >400 μm.
In the invention, the number of the molding columns is 2-50;
the gap between adjacent shaped pillars is >10 μm, preferably 2mm;
the length of the molding column is >100 μm, preferably 1 to 15mm, and the diameter of the molding column is >400 μm, preferably 0.4 to 2mm.
In the invention, the accommodating cavity and the forming column group form an integrated structure; the forming column is preferably a cylinder;
the material of the metal mold is preferably one or more of aluminum, copper and silver, and preferably copper.
In one embodiment of the invention, the metal mold consists of a containing cavity and a forming column, and the containing cavity and the forming column group form an integral structure; the molding column group is a 5*5 array and a metal copper column array with the diameter of 1mm and the gap between columns of 2mm.
In the present invention, 1 to 5 copper columns with a diameter of 0.3 to 0.5mm are preferably inserted between the arrays of the metal molds before the organic solution is brought into contact with the metal molds.
In the present invention, the concentration of the organic matter solution is 1-4w/v%, preferably 1-2w/v%;
the organic matter carrier obtained in the step a has a half-tube imitating hierarchical pore structure.
In the present invention, the preparation method of the organic matter solution includes:
mixing the organic matters with a solvent, and adjusting the pH value to obtain an organic matter solution; the solvent is preferably water; the mixing time is 12-16h;
the preparation method of the organic matter solution preferably comprises the following steps:
mixing water and organic matters, stirring, adding acetic acid, and stirring to finally obtain an organic matter solution; the ratio of the organic matter to the solvent is 1 (40-50) g/ml; the stirring speed is 300-500rpm; preferably, the pH is adjusted with acetic acid.
In the present invention, it is preferable to insert a metal mold into the organic solution;
the freezing metal mold is realized by injecting a refrigerant into the metal mold;
the freezing also comprises freezing at-80deg.C under 4-10mbar for 70-72 hr;
the refrigerant is one or more of liquid nitrogen, dry ice or precooled ethanol solution.
In the present invention, the method of the step a specifically includes:
the organic solution was placed in the vessel and a metal mold was inserted into the solution, randomly inserting metal columns between the arrays. And then introducing a refrigerant into the upper part of the metal mold to realize the freezing of the organic matter solution, placing the metal mold in a freeze dryer for 70-72 hours under the pressure of 4-10mbar, removing the metal mold at the cold trap temperature of-80 ℃, obtaining a primary organic matter carrier, immersing the organic matter carrier in a mixed solution of methanol and acetic anhydride with the volume ratio of 9:1 for acetylation reaction, and washing with water to obtain the organic matter carrier.
In the invention, the concentration of the ceramic precursor in the ceramic precursor mother liquor is 1-4wt%; in the embodiment of the invention, the concentration of the ceramic precursor is 10-15 mM;
the ceramic precursor is one or more of a calcium carbonate precursor, a barium carbonate precursor, a hydroxyapatite precursor, a silicon dioxide precursor, an iron oxide precursor, an aluminum oxide precursor, a titanium oxide precursor, a zirconium oxide precursor, a silicon carbide precursor, a boron nitride precursor, a tetrabutyl titanate and tetraethyl silicate, and is preferably one or more of a calcium carbonate precursor, a barium carbonate precursor, a hydroxyapatite precursor, tetrabutyl titanate and tetraethyl silicate;
the particle size of the ceramic precursor is 5-25nm; the ceramic precursors of the invention are deposited in the organic support by in situ growth. The advantages of in situ growth over simple mixing are as follows: the combination between the organic matters and the inorganic matters is firmer, and the interaction is stronger; in-situ growth can control the micro-nano structure of inorganic matters through polyelectrolyte, temperature, pH and other thermodynamic or kinetic factors, so as to control the mechanical properties of the inorganic matters.
The ceramic precursor mother liquor also comprises polyelectrolyte;
the concentration of the polyelectrolyte is 6-50mM;
the polyelectrolyte is an anionic polymer and/or a cationic polymer;
the anionic polymer is polyacrylic acid;
the cationic polymer is a polyacrylamide salt. The polyelectrolyte can regulate the growth of the ceramic.
In the invention, the preparation method of the ceramic precursor mother liquor comprises the following steps:
mixing a ceramic precursor with a solvent and polyelectrolyte to obtain a ceramic precursor mother solution;
the temperature of the mixing is 20-30 ℃ and the time is 1-2h;
the solvent is preferably water;
the volume ratio of the polyelectrolyte to the solvent is 1 (100-1000);
in one embodiment of the present invention, the method for preparing the ceramic precursor mother liquor includes:
mixing tetrabutyl titanate solution, ceramic growth regulator and water, regulating pH of the solution to 7-8, and adding polyacrylic acid (molecular weight 1800, final concentration 0.6 mM);
the ceramic growth regulator is preferably magnesium chloride.
In one embodiment of the present invention, the method for preparing the ceramic precursor mother liquor includes:
adding calcium carbonate powder into 1L of water, stirring in a constant-temperature water tank at 25 ℃ for 1 hour, and continuously introducing carbon dioxide during the stirring; filtering the solution after the reaction is finished, removing solid calcium carbonate, and collecting supernatant, wherein the final calcium ion concentration is 10mM; 400mL of the supernatant was taken, and 4.8mL of 2mM magnesium chloride hexahydrate and 1.2mL of 0.2mM polyacrylic acid having a molecular weight of 1800 were added thereto.
In the invention, the temperature of the mixture of the organic carrier and the ceramic precursor mother liquor is 40-50 ℃ and the time is more than 12 days.
In the present invention, the step b preferably includes:
and (3) pouring the ceramic precursor mother liquor into an organic carrier at the temperature of 40 ℃ for at least 12 days, respectively replacing the ceramic precursor mother liquor on the fourth day and the seventh day, wherein the optimal ceramic precursor mother liquor flow rates for 1-4 days, 4-7 days and 7-12 days are 25 mL/min, 50 mL/min and 15 mL/min respectively, taking out the ceramic frame after the frame is converted into the ceramic frame, washing the ceramic frame with ultrapure water, replacing water with an organic solvent, and performing supercritical drying to obtain the ceramic-based material with the half-tube-like structure.
The beneficial effects of the invention are as follows:
1. the invention combines the modeling freeze drying technology and the in-situ growth mode to prepare the porous ceramic material with the multi-scale anisotropic pore structure and the trans-scale half-tube imitating structure. The porous ceramic material of the cross-scale simulated haverse tube structure provided by the invention has multi-scale pores, comprises through holes which penetrate through the material and are larger than 400 mu m, and lamellar micropores which are smaller than 100 mu m and surround the through holes, wherein the micropores and the through holes realize hole interconnection, and the whole structure is similar to a haverse tube structure in dense bones. In addition, the porous ceramic material with the cross-scale half-tube-like structure has the excellent characteristics of light weight, high strength and the like.
2. The method provided by the invention is simple and reliable, has the advantages of readily available raw materials, low price and less time consumption, is suitable for large-scale industrialized popularization and application, provides a new means for preparing the lightweight and high-strength bionic structure ceramic material, and can be used in the fields of biomedicine, aerospace, military protection and the like. When the bioceramic is used, the porous ceramic material with the trans-scale half-tube-like structure has good biocompatibility and can be used in the field of bone repair, wherein the through holes have the capacity of inducing vascularization and bone formation, and are beneficial to the deposition of mineralized extracellular matrixes and vascular infiltration, and the micropores are beneficial to the attachment of cells and the interconnectivity among the through holes, so that the migration of cells and the transmission of substances are beneficial.
Drawings
FIG. 1 is a diagram showing the structure of a copper mold used in example 1 of the present invention;
FIG. 2 is a diagram of a copper mold used in example 1 of the present invention;
FIG. 3 is a diagram of the chitosan frame of example 1 of the present invention;
FIG. 4 is a scan of a chitosan frame of example 1 of the present invention;
FIG. 5 is a scanning pattern of a ceramic matrix material with a simulated haverse structure according to example 1 of the present invention;
FIG. 6 is a scan of a ceramic matrix material of hydroxyapatite-chitin-simulated haverse tube structure in accordance with example 2 of the present invention;
FIG. 7 is a graph showing the proliferation of CCK8 cells of the ceramic matrix material of the simulated haverse tube structure obtained in example 2 of the present invention;
FIG. 8 is the alkaline phosphatase (ALP) staining test data of the ceramic-based material of the simulated haverse tube structure obtained in example 2 of the present invention;
FIG. 9 is a photograph of a model of a rat bone defect made of ceramic matrix material of simulated haverse tube structure obtained in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
The embodiment provides a calcium carbonate-chitin-haverse tube-imitating ceramic matrix material, and the preparation method comprises the following steps:
1) Preparing a chitosan solution: 2 g of chitosan powder (Guozhen 69047438, molecular weight: about 4800 g/mol) was weighed into a 200mL beaker, 98mL of deionized water was added thereto, 2mL of acetic acid was slowly added dropwise to the mixed system under vigorous stirring (300 rpm), and stirring was carried out for 12 hours, thereby obtaining a uniform 2w/v% (20 mg/mL) chitosan solution.
2) 15mL of the upper chitosan solution was measured and placed in a square polydimethylsiloxane mold (12 mm long, 12mm wide and 15mm high), a 5*5 array copper mold (as shown in FIGS. 1 and 2, FIG. 1 is a block diagram of the copper mold used in the present example, and FIG. 2 is a physical diagram of the copper mold used), a 1mm diameter copper mold with a 2mm gap between the columns, and 5 copper columns with a 0.5mm diameter were inserted between the arrays. Then liquid nitrogen is introduced into the upper part of the copper mold to realize the freezing of chitosan solution, and the chitosan solution is placed in a freeze dryer for 72 hours, the pressure is 4-10mbar, and the temperature of a cold trap is-80 ℃, so that the chitosan frame can be obtained. The chitosan frame is soaked in a mixed solution of methanol (national medicine) and acetic anhydride (national medicine) in a volume ratio of 9:1 for acetylation reaction, the reaction is sealed and placed at 45 ℃ for 4 hours, and the chitin frame is obtained after the reaction, as shown in figure 3, and is washed 10 times by ultrapure water and placed in a clean beaker full of ultrapure water for standby.
3) Preparing a ceramic precursor mother solution: adding excessive calcium carbonate powder (Guozhi) into 1L of ultrapure water, stirring in a constant temperature water tank at 25 ℃ for 1 hour, and continuously introducing carbon dioxide during the stirring; after the reaction was completed, the solution was filtered to remove suspended calcium carbonate, and the supernatant was left to give a final calcium ion concentration of 10mM. 400mL of the supernatant was taken, and 1.2mL of 2mM magnesium chloride hexahydrate (Guozhu) 4.8mL and 0.2mM polyacrylic acid (Sigma Co.) having a molecular weight of 1800 were added thereto.
4) Preparation of a ceramic-based material with a calcium carbonate-chitosan-haverse tube-imitating structure: cutting the chitin frame obtained in the step 2) into blocks, putting the blocks into a silica gel square mold, opening holes (diameter is 12 mm) at two ends of the mold, sealing the mold by using a clamp, putting the mold into a baking oven at 40 ℃, repeatedly filling the ceramic precursor mother liquor into an organic frame by using a 100mL syringe (inner diameter is 30 mm), and respectively replacing the ceramic precursor mother liquor on the fourth day and the seventh day, wherein the optimal ceramic precursor mother liquor flow rates are 25 mL/min, 50 mL/min and 15 mL/min respectively in 1-4 days, 4-7 days and 7-12 days. After the frame is converted into a mineral ceramic frame, taking out, washing with ultrapure water for 3 times to remove free ions, replacing water with acetone, and performing supercritical drying to obtain the ceramic matrix material with the simulated haverse structure, wherein the mass ratio of the chitin frame to the calcium carbonate is 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
Fig. 4 is a scanned image of a chitosan frame, and as can be seen from fig. 4, through holes of the chitosan frame and micropores distributed around the through holes, fig. 5 is a scanned image of a ceramic-based material with a haverse tube-like structure, and as can be seen from fig. 5, the microporous surface of the chitosan frame still maintains a porous structure after ceramic is grown, and the pore size distribution of the micropores is 1-20 μm.
Example 2
The embodiment provides a hydroxyapatite-chitin-haverse tube-imitating ceramic matrix material, and the preparation method comprises the following steps:
1) The chitosan solution formulation was the same as in example 1.
Chitin frameworks were prepared as in example 1.
2) Preparing a ceramic precursor mother solution: according to the 5-time SBF scheme, 450mL of deionized water is measured and placed in a 1L plastic container, sodium chloride, sodium bicarbonate, disodium hydrogen phosphate dodecahydrate and magnesium chloride hexahydrate are sequentially added for dissolution, then polyacrylamide hydrochloride PAH (20 mM finally) is added, 1M hydrochloric acid 10mL is added, after uniform stirring, 1M calcium chloride solution 6.25mL is added dropwise, the pH is regulated to 6.2 by tris buffer solution with pH of 9.0, and finally the solution is fixed to 500mL, so that the final sodium ion concentration is 733mM, magnesium ion concentration is 30mM, calcium ion concentration is 12.5mM, chloride ion concentration is 720mM, phosphate ion concentration is 5.0mM, and carbonate ion concentration is 21mM.
3) The preparation of the hydroxyapatite-chitin-haverse tube-imitating ceramic matrix material is the same as that of example 1, and the mass ratio of the chitin frame to the hydroxyapatite is 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
Fig. 6 is a scanned view of a ceramic matrix material of hydroxyapatite-chitin-haverse tube structure, and as can be seen from fig. 6, ceramic particles are grown on micropores of the ceramic matrix material of hydroxyapatite-chitin-haverse tube structure.
Taking the material as an example, biocompatibility verification is carried out, and 3T3 cells are used for verifying cytotoxicity, cell proliferation, cell differentiation and in vivo induction of bone regeneration.
The CCK8 cell proliferation assay procedure was as follows:
1) Cells were packed at a density of 2X 10 4 The individual/wells were seeded on the sample surface in a 24-well plate.
2) The original medium was discarded and washed 3 times with PBS.
3) According to 1:10 preparing CCK-8 solution, and operating in dark place.
4) CCK-8 solution was added after days 1, 4 and 7 of incubation.
5) The reaction was carried out at 37℃for 2 hours.
6) 100 μl of the solution was taken into a 96-well plate, and the OD at 450nm wavelength was measured using an enzyme-labeled instrument.
7) Statistical data was plotted using Origin 2020.
The experimental results of CCK8 cell proliferation are shown in fig. 7, and it can be seen from fig. 7 that the ceramic-based material with the haverse tube-like structure of the embodiment has less cytotoxicity and certain biocompatibility.
Alkaline phosphatase (ALP) staining experiments were as follows:
1) Preparing a phenol standard solution with the concentration of 0.02 ng/mL;
2) Reagents were added to 96-well plates: buffer 50Ul; base fluid 50Ul;
3) The shaking table reacts for 15 minutes in dark at 37 ℃;
4) 150. Mu.L of color developer was added to each well
5) Photographing
The results of the staining experiments are shown in fig. 8, and it can be seen from fig. 8 that the results of staining the huff-tube-like structure material are better than those of the unordered group, indicating that the trans-scale pore structure contributes to cell proliferation.
Fig. 9 is a photograph of a model of a bone defect of a rat, and fig. 9 shows the whole experimental modeling process, in which the sample size used in this experiment was 3 μm in diameter and 6 μm in height (cylinder).
Example 3
The embodiment provides a hydroxyapatite-fibroin-haverse tube-imitating ceramic matrix material, and the preparation method comprises the following steps:
1) Fibroin extraction: in the first step, degumming, cutting the dried cocoons into small pieces, putting the small pieces into 2L of sodium carbonate hot solution with the concentration of 0.02moL/L, magnetically stirring the small pieces for 30 minutes until the cocoons are gradually dissolved and disappear into white filiform substances, washing the white filiform substances with deionized water for 3-5 times, and putting the white filiform substances into a 35 ℃ oven for drying for 2 days. And (3) dissolving again, namely rapidly putting the degummed silk into a fresh 9.3moL/L lithium bromide solution, controlling the concentration of the final fibroin to be 10w/v%, centrifuging at 8000rpm for 10 minutes, removing bubbles, sucking clear liquid into an MWCO3500 dialysis bag, dialyzing with ultrapure water for 2 days, and changing water for 6 times. The fibroin finally obtained was diluted to 1% with ultrapure water.
2) The fibroin frame preparation is the same as in example 1, the preparation of the ceramic precursor mother liquor is the same as in example 2, the preparation of the hydroxyapatite-fibroin-haverse tube structure ceramic base material is the same as in example 2, and the mass ratio of chitin frame to hydroxyapatite is about 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
Example 4
The embodiment provides a silicon dioxide-chitin-haverse tube-imitating ceramic matrix material, and the preparation method comprises the following steps:
1) Chitin frameworks were prepared as in example 1.
2) Preparing a ceramic precursor mother solution: 100mL of tetraethyl silicate precursor solution (concentration 2 wt%) was measured and the pH was adjusted to 8.5 with 1M sodium hydroxide solution; or the pH was adjusted to 5.5 with 1M hydrochloric acid.
The preparation of the silica-chitin-haverse tube-like ceramic matrix material was the same as in example 2, in which the mass ratio of chitin framework to silica was about 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
Example 5
The embodiment provides a barium carbonate-chitin-haverse tube-imitating ceramic matrix material, and the preparation method comprises the following steps:
1) Chitin frameworks were prepared as in example 1.
2) Preparing a ceramic precursor mother solution: 10 g of barium carbonate powder was weighed into 1L of ultrapure water, stirred in a constant temperature water tank at 25℃for 4 hours, and carbon dioxide (one bubble per second in flow rate) was continuously introduced. The solution was then filtered to remove suspended barium carbonate (final barium ion concentration 10 mM). 400mL of the supernatant was taken, to which magnesium chloride (final concentration 24 mM) and polyacrylic acid (final concentration 0.6 mM) were added.
3) The barium carbonate-chitin-haverse tube-imitating ceramic base material is the same as in example 1, and the mass ratio of the chitin frame to the barium carbonate is 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
Example 6
The embodiment provides a titanium dioxide-chitin-haverse tube-imitating ceramic matrix material, and the preparation method comprises the following steps:
1) Chitin frameworks were prepared as in example 1.
2) Preparing a ceramic precursor mother solution: mixing tetrabutyl titanate solution with deionized water according to a proportion, controlling the concentration of tetrabutyl titanate in a ceramic precursor mother solution to be 2wt%, then adjusting the pH value of the solution to 7-8, and adding polyacrylic acid (the molecular weight is 1800 and the final concentration is 0.6 mM).
3) The preparation of the titanium dioxide-chitin-haverse tube-imitating ceramic matrix material is the same as that of example 1, and the mass ratio of the chitin frame to the titanium dioxide is 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
Example 7
The embodiment provides a ceramic-based material with a calcium carbonate-gelatin-haverse tube structure, and the preparation method comprises the following steps:
1) Gelatin solution preparation: 2 g of gelatin powder (Sigma Co.) was weighed into a 200mL beaker, and 98mL of deionized water was added under vigorous stirring (300 rpm) and heated to 90℃to finally obtain a uniform 2w/v% (20 mg/mL) gelatin solution.
2) The preparation method of the gelatin frame is the same as that of the embodiment 1, the configuration of the ceramic precursor mother liquor is the same as that of the embodiment 1, the preparation of the calcium carbonate-gelatin-simulated hafr tube structure ceramic-based material is the same as that of the embodiment 1, and the mass ratio of the gelatin frame to the calcium carbonate is 1:1, the length of the through holes is 15mm, the aperture is 1mm, the interval between the through holes is 2mm, the average aperture of the micropores is 1-20 mu m, and the length of the micropores is 2mm.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The porous ceramic material of the cross-scale imitated Harvard pipe structure is characterized by comprising a plurality of imitated Harvard pipe structure units; the halfling-like tube structure unit consists of an organic carrier and ceramic loaded on the organic carrier;
the organic carrier has a hierarchical pore structure;
the multistage holes comprise through holes and micropores;
the directions of the through holes and the micropores are different;
the aperture of the through hole is larger than that of the micropore;
the mass ratio of the organic carrier to the ceramic is 1 (0.1-2).
2. The porous ceramic material of a trans-scale haverse tube structure according to claim 1, wherein the micropores are distributed around the through holes; the through holes are communicated with the micropores.
3. The porous ceramic material of a cross-scale haverse tube structure according to claim 2, wherein the pore diameter of the micropores is small on the side close to the through holes and the pore diameter is large on the side far from the through holes.
4. The porous ceramic material of a trans-scale haverse tube structure according to claim 1, wherein the pore diameter of the through holes is more than or equal to 400 μm and the length is more than 100 μm;
the average pore diameter of the micropores is less than or equal to 100 mu m, and the length is more than 10 mu m.
5. The porous ceramic material of a trans-scale haverse tube structure according to claim 1, wherein the number of haverse tube structure units is 1-50.
6. The porous ceramic material of the cross-scale haverse tube structure according to claim 1, wherein the organic carrier comprises one or more of a fibroin frame, a sodium alginate frame, a polyvinyl alcohol frame, a collagen frame, a chitin frame, a gelatin frame, a sodium polystyrene sulfonate frame;
the ceramic is one or more of calcium carbonate, barium carbonate, hydroxyapatite, silicon dioxide, ferric oxide, aluminum oxide, titanium oxide, zirconium oxide, silicon carbide and boron nitride;
the grain size of the ceramic is 10-200nm.
7. The metal mold is characterized by comprising a containing cavity for bearing a coolant and a forming column group arranged at the outer bottom of the containing cavity;
the molding column group comprises a plurality of molding columns.
8. The metal mold of claim 7, wherein the molding columns are in an array distribution;
the gap between adjacent molding columns is >10 μm;
the length of the shaped pillars is >100 μm and the diameter is >400 μm.
9. The preparation method of the porous ceramic material with the cross-scale simulated haverse tube structure is characterized by comprising the following steps of:
a. contacting the organic matter solution with the metal mold according to claim 7 or 8, freezing the metal mold, and removing the metal mold to obtain an organic matter carrier;
b. mixing the organic matter carrier obtained in the step a with a ceramic precursor mother solution to obtain a porous ceramic material with a cross-scale half-tube imitation structure;
the organic matter solution comprises one or more of fibroin solution, sodium alginate solution, polyvinyl alcohol solution, collagen solution, chitin solution, gelatin solution and sodium polystyrene sulfonate solution.
10. The method for preparing a porous ceramic material with a cross-scale half-pipe imitation structure according to claim 9, wherein the temperature at which the organic matter carrier is mixed with the ceramic precursor mother liquor is 40-50 ℃ for more than 12 days;
the ceramic precursor is one or more of a calcium carbonate precursor, a barium carbonate precursor, a hydroxyapatite precursor, a silicon dioxide precursor, an iron oxide precursor, an aluminum oxide precursor, a titanium oxide precursor, a zirconium oxide precursor, a silicon carbide precursor, a boron nitride precursor, tetrabutyl titanate and tetraethyl silicate;
the particle size of the ceramic precursor is 5-25nm;
the concentration of the organic matter solution is 1-4w/v%.
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