阅读说明：本技术 一种C/C复合材料表面晶粒细小CaP生物涂层及制备方法 (CaP biological coating with fine crystal particles on surface of C/C composite material and preparation method thereof ) 是由 张磊磊 张悦 李贺军 于 2021-01-12 设计创作，主要内容包括：本发明涉及一种C/C复合材料表面晶粒细小CaP生物涂层及制备方法,对C/C复合材料进行激光处理和高温氧化,使得C/C复合材料表面呈现出“蜂窝状表面结构”,在“蜂窝状表面结构”中种植“CaP纳米种子”,采用电化学沉积工艺制备CaP生物涂层。本发明制备的C/C复合材料表面CaP生物涂层的晶粒尺寸为0.1-3.5μm,而背景技术报道的C/C复合材料表面CaP生物涂层的晶粒尺寸为10-180μm,本发明制备的CaP生物涂层的晶粒尺寸显著减小。此外,本发明制备的CaP生物涂层与C/C复合材料的结合强度为8.24-12.68MPa,而背景技术报道的CaP生物涂层与C/C复合材料的结合强度为1.55-5.76MPa,本发明制备的CaP生物涂层的界面结合强度显著提高。(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.)

1. 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 8.24-12.68 MPa.

2. A method for preparing the C/C composite material surface grain fine CaP biological coating, which 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 the irradiation points of the beam spots is 1-5 mm; then placing the composite material in a high-temperature furnace, treating the composite material at the temperature of 400-700 ℃ and 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 a solution of 0.5-3.5 mmol/L, preparing a calcium nitrate solution according to the molar ratio of 0.3-0.8 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 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 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, taking the C/C composite material planted with the CaP nano seeds as a cathode, setting the distance between the cathode and the anode to be 10-40 mm, taking the solution D as electrolyte, applying a voltage of 1-5V, setting the deposition time to be 10-120 minutes and the deposition temperature to be 70-90 ℃, and obtaining the CaP biological coating with the grain size of 0.1-3.5 mu m on the surface of the C/C composite material after the reaction is finished.

3. The C/C composite material surface fine-grained Cap biological coating of claim 1, wherein: and the laser irradiation time of the step 1 is 1-5 seconds.

4. The C/C composite material surface fine-grained Cap biological coating of claim 1, wherein: the step 1 is treated under the conditions of 400-700 ℃ and static air for 5-30 minutes.

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 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 C/C composite material is an effective method to solve the problem, wherein 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-. 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 8.24-12.68 MPa.

A method for preparing the CaP biological coating with fine crystal grains on the surface of the 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 the irradiation points of the beam spots is 1-5 mm; then placing the composite material in a high-temperature furnace, treating the composite material at the temperature of 400-700 ℃ and 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 a solution of 0.5-3.5 mmol/L, preparing a calcium nitrate solution according to the molar ratio of 0.3-0.8 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 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 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, taking the C/C composite material planted with the CaP nano seeds as a cathode, setting the distance between the cathode and the anode to be 10-40 mm, taking the solution D as electrolyte, applying a voltage of 1-5V, setting the deposition time to be 10-120 minutes and the deposition temperature to be 70-90 ℃, and obtaining the CaP biological coating with the grain size of 0.1-3.5 mu m on the surface of the C/C composite material after the reaction is finished.

And the laser irradiation time of the step 1 is 1-5 seconds.

The step 1 is treated under the conditions of 400-700 ℃ and static air for 5-30 minutes.

Advantageous effects

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. 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 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 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.

Drawings

FIG. 1 is a scanning electron micrograph of the fine-grained Cap biological 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 biological coating prepared in this example is 0.1-0.4 μm, and the interfacial bonding strength of the Cap biological coating and the C/C composite material is 11.46 MPa.

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) ammonium dihydrogen phosphate was dissolved in water to prepare a solution of 60mmol/L, a calcium nitrate solution was prepared in a molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.6, 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 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 9.22 MPa.

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) ammonium dihydrogen phosphate was dissolved in water to prepare a 3.5mmol/L solution, a calcium nitrate solution was prepared so that the molar ratio of calcium nitrate to ammonium dihydrogen phosphate was 0.8, 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 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 solution of 150mmol/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 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 40mm, applying a voltage of 5V, depositing for 120 minutes at a deposition temperature of 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 10.02 MPa.

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) ammonium dihydrogen phosphate was dissolved in water to prepare a solution of 2.5mmol/L, a calcium nitrate solution was prepared so that the molar ratio of calcium nitrate to ammonium dihydrogen phosphate was 0.5, and 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 90 ℃ for 60 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 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 11.46 MPa.

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) ammonium dihydrogen phosphate was dissolved in water to prepare a 100mmol/L solution, a calcium nitrate solution was prepared in a molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.65, and the calcium nitrate and ammonium dihydrogen phosphate were uniformly mixed and designated as solution B. Sample a was placed in solution B with graphite flake as anode and sample a as cathode at a distance of 30mm, voltage 3V was applied for 90 minutes at 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 6.16 MPa.

Example 5, step (1) of the present invention was not carried out, and thus a "honeycomb surface structure" was not prepared.

(1) Ammonium dihydrogen phosphate was dissolved in water to prepare a 1.5mmol/L solution, a calcium nitrate solution was prepared so that the molar ratio of calcium nitrate to ammonium dihydrogen phosphate was 0.4, and the calcium nitrate and ammonium dihydrogen phosphate were uniformly mixed and designated as 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 prepared 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 4.28 MPa.