CN112811936B - CaP biological coating with fine crystal particles on surface of C/C composite material and preparation method thereof - Google Patents
CaP biological coating with fine crystal particles on surface of C/C composite material and preparation method thereof Download PDFInfo
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- CN112811936B CN112811936B CN202110036429.6A CN202110036429A CN112811936B CN 112811936 B CN112811936 B CN 112811936B CN 202110036429 A CN202110036429 A CN 202110036429A CN 112811936 B CN112811936 B CN 112811936B
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- C04B41/5007—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
- C04B41/5015—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing containing phosphorus in the anion, e.g. phosphates
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Abstract
The invention relates to a CaP biological coating with fine crystal grains on the surface of a C/C composite material and a preparation method thereof. The grain size of the Cap biological coating on the surface of the C/C composite material prepared by the invention is 0.1-3.5 μm, while the grain size of the Cap biological coating on the surface of the C/C composite material reported in the background art is 10-180 μm, and the grain size of the Cap biological coating prepared by the invention is obviously reduced. In addition, the bonding strength of the prepared Cap biological coating and the C/C composite material is 8.24-12.68MPa, while the bonding strength of the Cap biological coating and the C/C composite material reported in the background art is 1.55-5.76MPa, and the interface bonding strength of the Cap biological coating is obviously improved.
Description
Technical Field
The invention belongs to a preparation method of a biological material, and relates to a CaP biological coating with fine crystal grains on the surface of a C/C composite material and a preparation method thereof.
Background
The C/C composite material is a composite material formed of carbon fiber reinforced carbon, and both the reinforcing phase and the matrix phase thereof are composed of carbon elements. The material inherits the inherent biocompatibility of the carbon material and has higher strength and toughness, thereby having good application prospect in the field of human skeleton repair and replacement. However, the surface of the C/C composite material is biologically inert, cannot form chemical bond combination with bone tissues, and is easy to induce the loosening and failure of a bone implant, thereby limiting the wide application of the C/C composite material in the field of human bone repair and replacement. The application of CaP biological coating on the surface of the C/C composite material is an effective method for solving the problem, wherein the CaP biological coating mainly comprises hydroxyapatite, brushite, tricalcium phosphate and the like. The CaP biological coating has good biological activity and osteoconductivity, is nontoxic, harmless and non-carcinogenic after being implanted into a human body, and can form chemical bond combination with human skeletal tissues. Therefore, the biological inertia of the C/C composite material can be improved by applying the Cap biological coating, so that the problems of looseness and failure of the C/C composite material bone implant are effectively avoided. However, the grain size of the CaP biological coating prepared on the surface of the C/C composite material is large, so that the bonding strength between the CaP biological coating and the C/C composite material is generally low, and the CaP coating is easy to crack and fall off.
Document 1 "bear Xinbai, li Xinjun, li Kezhi, etc. Effect of current density on structure and morphology of sono-electro-deposited bioactive brushite coatings, rare metal materials and engineering, 2003,32 (11): 923-926' report the preparation of a CaP biological coating on the surface of a C/C composite material. As a result, the grain size distribution of the Cap bio-coating was found to be 10-180. Mu.m.
The above documents successfully prepare the Cap biological coating on the surface of the C/C composite material, but the grain size of the prepared Cap biological coating is distributed in the range of 10-180 μm, the grain size is larger, the large grain size causes the pores among the grains to be larger, so that the coating is loose, the bonding strength between the prepared Cap biological coating and the C/C composite material is insufficient, the bonding strength value between the Cap biological coating and the C/C composite material reported in the documents is distributed in the range of 1.55-5.76MPa, and the CaP biological coating is easy to crack and fall off due to the insufficient bonding strength.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a CaP biological coating with fine crystal grains on the surface of a C/C composite material and a preparation method thereof, and solves the problems of large crystal grain size and insufficient bonding strength of the CaP biological coating on the surface of the C/C composite material.
Technical scheme
A C/C composite material surface fine crystal particle CaP biological coating, caP biological coating includes but is not limited to hydroxyapatite, brushite or tricalcium phosphate; the feature is that the grain size of the said Cap biological coating is 0.1-3.5 μm, and the bonding strength with the C/C composite material is 8.24-12.68MPa.
A method for preparing a CaP biological coating with fine crystal grains on the surface of a C/C composite material is characterized by comprising the following steps:
step 1: placing the C/C composite material under a laser with the power of 400-800w and the beam spot diameter of 2-4mm for irradiation, wherein the distance between irradiation points of the beam spots is 1-5mm; then placing the mixture in a high-temperature furnace, treating the mixture at 400-700 ℃ under the static air condition, and preparing a honeycomb surface structure on the surface of the C/C composite material;
step 2: dissolving ammonium dihydrogen phosphate in water to prepare 0.5-3.5 mmol/L solution, preparing calcium nitrate solution according to the molar ratio of 0.3-0.8 of calcium nitrate and ammonium dihydrogen phosphate, and uniformly mixing the calcium nitrate and the ammonium dihydrogen phosphate according to the same volume to obtain solution B;
completely immersing the C/C composite material with the cellular surface structure on the surface in the solution B, and placing the C/C composite material and the solution B together in a closed high-pressure kettle, and treating the C/C composite material for 30 to 90 minutes at the temperature of between 80 and 110 ℃ so as to plant 'CaP nanometer seeds' in the cellular surface structure;
and 3, step 3: dissolving ammonium dihydrogen phosphate in water to prepare a solution with the concentration of 60-150 mmol/L, preparing a calcium nitrate solution according to the molar ratio of 1.6-1.8 of calcium nitrate to ammonium dihydrogen phosphate, and uniformly mixing the calcium nitrate and the ammonium dihydrogen phosphate according to the same volume to obtain a solution D;
placing the C/C composite material planted with the 'CaP nano seeds' in an electrodeposition device, taking a graphite sheet as an anode and the C/C composite material planted with the 'CaP nano seeds' as a cathode, wherein the distance between the cathode and the anode is 10-40 mm, taking the solution D as electrolyte, applying a voltage of 1-5V, depositing for 10-120 minutes at a deposition temperature of 70-90 ℃, and obtaining the CaP biological coating with the surface grain size of 0.1-3.5 mu m of the C/C composite material after the reaction is finished.
The laser irradiation time in the step 1 is 1 to 5 seconds.
The step 1 is carried out for 5 to 30 minutes at 400 to 700 ℃ under static air conditions.
Advantageous effects
The invention provides a CaP biological coating with tiny crystal grains on the surface of a C/C composite material and a preparation method thereof. The invention realizes the formation of the CaP biological coating with fine grains on the surface of the C/C composite material through the induction action of the nucleation sites and the nucleation spaces provided by the honeycomb surface structure and the CaP nano seeds. The grain size of the Cap biological coating on the surface of the C/C composite material prepared by the invention is 0.1-3.5 μm, while the grain size of the Cap biological coating on the surface of the C/C composite material reported in the background art is 10-180 μm, and the grain size of the Cap biological coating prepared by the invention is obviously reduced. In addition, the bonding strength of the prepared Cap biological coating and the C/C composite material is 8.24-12.68MPa, while the bonding strength of the Cap biological coating and the C/C composite material reported in the background art is 1.55-5.76MPa, and the interface bonding strength of the Cap biological coating is obviously improved.
The invention has the beneficial effects that: according to the invention, firstly, a honeycomb-shaped surface structure is prepared on the surface of the C/C composite material through the step (1) of the technical scheme, so that a nucleation site and a nucleation space are provided for the CaP biological coating, then, a CaP nano seed is prepared through the step (2) of the technical scheme, and an induction effect is provided for the growth of the CaP biological coating by means of the CaP nano seed. The formation of the CaP biological coating with fine grains on the surface of the C/C composite material is realized through the comprehensive action of the cellular surface structure and the CaP nano seeds. The grain size of the Cap biological coating on the surface of the C/C composite material prepared by the invention is 0.1-3.5 μm, while the grain size of the Cap biological coating on the surface of the C/C composite material reported in the background art is 10-180 μm, and the grain size of the Cap biological coating prepared by the invention is obviously reduced. In addition, the bonding strength of the CaP biological coating prepared by the invention and the C/C composite material is 8.24-12.68MPa, while the bonding strength of the CaP biological coating reported in the background art and the C/C composite material is 1.55-5.76MPa, and the interface bonding strength of the CaP biological coating prepared by the invention is obviously improved.
Drawings
FIG. 1 is a scanning electron micrograph of the fine-grained Cap bio-coating on the surface of the C/C composite material prepared in example 3, and it can be seen from the micrograph that the grain size distribution of the Cap bio-coating prepared in this example is 0.1-0.4 μm, and the interfacial bonding strength between the Cap bio-coating and the C/C composite material is 11.46MPa.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
(1) Placing the C/C composite material under a laser with the power of 400w and the beam spot diameter of 2mm for irradiating for 1 second, wherein the distance between the irradiation points of the beam spots is 1mm, then placing the C/C composite material in a high-temperature furnace, and treating for 5 minutes under the conditions of 400 ℃ and static air, thereby preparing a honeycomb surface structure on the surface of the C/C composite material, and marking the honeycomb surface structure as a sample A;
(2) Ammonium dihydrogen phosphate was dissolved in water to prepare a 0.5mmol/L solution, a calcium nitrate solution was prepared so that the molar ratio of calcium nitrate to ammonium dihydrogen phosphate was 0.3, and the calcium nitrate and ammonium dihydrogen phosphate were uniformly mixed and designated as solution B. Placing the sample A and the solution B in a closed high-pressure kettle, completely immersing the sample A in the solution B, and treating at the temperature of 80 ℃ for 30 minutes, so as to plant 'CaP nano seeds' in a 'honeycomb surface structure', and marking as a sample C;
(3) Dissolving ammonium dihydrogen phosphate in water to obtain a solution of 60mmol/L, preparing a calcium nitrate solution according to a molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.6, and uniformly mixing the calcium nitrate and the ammonium dihydrogen phosphate to obtain a solution D. And (3) placing the sample C in the solution D, taking the graphite flake as an anode and the sample C as a cathode, wherein the distance between the cathode and the anode is 10mm, applying a voltage of 1V, depositing for 10 minutes at a deposition temperature of 70 ℃, and obtaining the CaP biological coating with fine crystal grains on the surface of the C/C composite material after the reaction is finished.
The grain size of the CaP biological coating with fine grains on the surface of the C/C composite material obtained in the example 1 is 2.1-3.5 microns, and the interfacial bonding strength of the CaP biological coating and the C/C composite material is 9.22MPa.
Example 2
(1) Placing the C/C composite material under a laser with the power of 800w and the beam spot diameter of 4mm for irradiating for 5 seconds, wherein the distance between the irradiation points of the beam spots is 5mm, then placing the C/C composite material in a high-temperature furnace, and treating for 30 minutes under the conditions of 700 ℃ and static air, thereby preparing a honeycomb surface structure on the surface of the C/C composite material, and marking the honeycomb surface structure as a sample A;
(2) Dissolving ammonium dihydrogen phosphate in water to obtain 3.5mmol/L solution, preparing calcium nitrate solution according to the molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 0.8, and mixing calcium nitrate and ammonium dihydrogen phosphate uniformly to obtain solution B. Placing the sample A and the solution B in a closed high-pressure kettle, completely immersing the sample A in the solution B, and treating at 110 ℃ for 90 minutes, so as to plant 'CaP nano seeds' in a 'honeycomb surface structure', and marking as a sample C;
(3) Ammonium dihydrogen phosphate was dissolved in water to prepare a 150mmol/L solution, a calcium nitrate solution was prepared in a molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.8, and the calcium nitrate and ammonium dihydrogen phosphate were uniformly mixed and designated as solution D. And (3) putting the sample C into the solution D, taking the graphite sheet as an anode and the sample C as a cathode, wherein the distance between the cathode and the anode is 40mm, applying a voltage of 5V, the deposition time is 120 minutes, the deposition temperature is 90 ℃, and obtaining the CaP biological coating with fine crystal grains on the surface of the C/C composite material after the reaction is finished.
The grain size of the Cap biological coating with fine grains on the surface of the C/C composite material obtained in the embodiment 2 is 0.8-1.8 μm, and the interfacial bonding strength of the Cap biological coating and the C/C composite material is 10.02MPa.
Example 3
(1) Placing the C/C composite material under a laser with the power of 600w and the beam spot diameter of 3mm for irradiating for 3 seconds, wherein the distance between the irradiation points of the beam spots is 3mm, then placing the C/C composite material in a high-temperature furnace, and treating the C/C composite material for 20 minutes under the conditions of 600 ℃ and static air, thereby preparing a honeycomb surface structure on the surface of the C/C composite material, and marking the honeycomb surface structure as a sample A;
(2) Dissolving ammonium dihydrogen phosphate in water to obtain 2.5mmol/L solution, preparing calcium nitrate solution according to the molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 0.5, and mixing calcium nitrate and ammonium dihydrogen phosphate uniformly to obtain solution B. Placing the sample A and the solution B in a closed high-pressure kettle, completely immersing the sample A in the solution B, and treating at 90 ℃ for 60 minutes, so that a 'CaP nanometer seed' is planted in a 'honeycomb surface structure', and is marked as a sample C;
(3) Ammonium dihydrogen phosphate was dissolved in water to prepare a 100mmol/L solution, a calcium nitrate solution was prepared so that the molar ratio of calcium nitrate to ammonium dihydrogen phosphate was 1.67, and the calcium nitrate and ammonium dihydrogen phosphate were uniformly mixed and designated as solution D. And (3) placing the sample C in the solution D, taking the graphite flake as an anode and the sample C as a cathode, wherein the distance between the cathode and the anode is 30mm, applying a voltage of 3V, the deposition time is 90 minutes, the deposition temperature is 80 ℃, and obtaining the CaP biological coating with fine crystal grains on the surface of the C/C composite material after the reaction is finished.
The scanning electron microscope photo of the Cap biological coating with fine crystal grains on the surface of the C/C composite material obtained in the embodiment 3 is shown in the attached figure, the crystal grain size of the Cap biological coating is distributed in 0.1-0.4 μm, and the interface bonding strength of the Cap biological coating and the C/C composite material is 11.46MPa.
Example 4
(1) Placing the C/C composite material under a laser with the power of 600w and the beam spot diameter of 4mm for irradiating for 3 seconds, wherein the distance between the irradiation points of the beam spots is 2mm, then placing the C/C composite material in a high-temperature furnace, and treating the C/C composite material for 20 minutes under the conditions of 500 ℃ and static air, thereby preparing a honeycomb-shaped surface structure on the surface of the C/C composite material, and marking the honeycomb-shaped surface structure as a sample A;
(2) Dissolving ammonium dihydrogen phosphate in water to obtain 100mmol/L solution, preparing calcium nitrate solution according to the molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.65, and mixing calcium nitrate and ammonium dihydrogen phosphate uniformly to obtain solution B. Sample a was placed in solution B with graphite flake as anode and sample a as cathode at a distance of 30mm, a voltage of 3V was applied for 90 minutes and a deposition temperature of 80 ℃.
Example 4 step (2) of the present invention was not performed, and thus "CaP nanopaste" was not prepared. Although the CaP biological coating is prepared on the surface of the C/C composite material in this example 4, the grain size of the prepared CaP biological coating is distributed in the range of 20.1-35.4 μm, the grain size is large, and the interfacial bonding strength between the CaP biological coating and the C/C composite material is only 6.16MPa.
Example 5, step (1) of the present invention was not carried out, and thus a "honeycomb surface structure" was not prepared.
(1) Dissolving ammonium dihydrogen phosphate in water to obtain 1.5mmol/L solution, preparing calcium nitrate solution according to the molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 0.4, and mixing calcium nitrate and ammonium dihydrogen phosphate uniformly to obtain solution A. Placing the C/C composite material and the solution A in a closed high-pressure kettle, completely immersing the C/C composite material in the solution A, and treating at the temperature of 90 ℃ for 50 minutes, so that CaP nano seeds are planted on the surface of the C/C composite material and are marked as a sample B;
(2) Ammonium dihydrogen phosphate was dissolved in water to prepare a solution of 80mmol/L, a calcium nitrate solution was prepared in a molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.8, and the calcium nitrate and ammonium dihydrogen phosphate were uniformly mixed and designated as solution C. Sample B was placed in solution C with graphite flake as the anode and sample B as the cathode, the distance between the cathode and anode was 20mm, voltage was applied at 4V for 90 minutes and deposition temperature was 80 ℃.
Although the CaP biological coating is prepared on the surface of the C/C composite material in the embodiment 5, the grain size of the CaP biological coating is distributed between 40.4 μm and 65.8 μm, the grain size is large, and the interface bonding strength between the CaP biological coating and the C/C composite material is only 4.28MPa.
Claims (3)
1. A C/C composite material surface fine crystalline particle CaP biological coating, caP biological coating includes hydroxyapatite, brushite or tricalcium phosphate; the method is characterized in that the grain size of the Cap biological coating is 0.1-3.5 μm, the bonding strength with the C/C composite material is 8.24-12.68MPa, and the method for preparing the coating is as follows:
step 1: placing the C/C composite material under a laser with the power of 400-800w and the beam spot diameter of 2-4mm for irradiation, wherein the distance between the irradiation points of the beam spots is 1-5mm; then placing the mixture in a high-temperature furnace, treating the mixture at 400-700 ℃ under the static air condition, and preparing a honeycomb surface structure on the surface of the C/C composite material;
step 2: dissolving ammonium dihydrogen phosphate in water to prepare 0.5-3.5 mmol/L solution, preparing calcium nitrate solution according to the molar ratio of 0.3-0.8 of calcium nitrate and ammonium dihydrogen phosphate, uniformly mixing the calcium nitrate and the ammonium dihydrogen phosphate according to the same volume, and recording the mixture as solution B;
completely immersing the C/C composite material with the cellular surface structure on the surface in the solution B, and placing the C/C composite material and the solution B together in a closed high-pressure kettle, and treating the C/C composite material for 30 to 90 minutes at the temperature of between 80 and 110 ℃ so as to plant 'CaP nanometer seeds' in the cellular surface structure;
and step 3: dissolving ammonium dihydrogen phosphate in water to prepare a solution with the concentration of 60-150 mmol/L, preparing a calcium nitrate solution according to the molar ratio of 1.6-1.8 of calcium nitrate and ammonium dihydrogen phosphate, and uniformly mixing the calcium nitrate and the ammonium dihydrogen phosphate according to the same volume to obtain a solution D;
placing the C/C composite material planted with the 'CaP nano seeds' in an electrodeposition device, taking a graphite sheet as an anode and the C/C composite material planted with the 'CaP nano seeds' as a cathode, wherein the distance between the cathode and the anode is 10-40 mm, taking the solution D as electrolyte, applying a voltage of 1-5V, depositing for 10-120 minutes at a deposition temperature of 70-90 ℃, and obtaining the CaP biological coating with the surface grain size of 0.1-3.5 mu m of the C/C composite material after the reaction is finished.
2. The C/C composite material surface fine-grained Cap biological coating of claim 1, wherein: the laser irradiation time in the step 1 is 1 to 5 seconds.
3. The C/C composite material surface fine-grained Cap biological coating of claim 1, wherein: the step 1 is carried out for 5 to 30 minutes at 400 to 700 ℃ under static air conditions.
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| EP0975285B1 (en) * | 1997-04-01 | 2008-10-01 | CAP Biotechnology, Inc. | Calcium phosphate microcarriers and microspheres |
| US8491936B2 (en) * | 2005-03-16 | 2013-07-23 | North Carolina State University | Functionally graded biocompatible coating and coated implant |
| CN102560590B (en) * | 2012-02-14 | 2015-01-28 | 陕西科技大学 | Anode in-situ electrochemical method for preparing hydroxyapatite coating |
| CN102908669B (en) * | 2012-09-17 | 2014-04-02 | 西北工业大学 | Preparation method of carbon foam/hydroxyapatite composite coating |
| CN108546157B (en) * | 2018-05-31 | 2020-11-20 | 西北工业大学 | Surface modification method of carbon/carbon composite material |
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