Method for enhancing biological performance of silicate material coating and coating thereof
阅读说明：本技术 一种增强硅酸盐材料涂层生物性能的方法及其涂层 (Method for enhancing biological performance of silicate material coating and coating thereof ) 是由 赵晓兵 马振 于 2021-07-20 设计创作，主要内容包括：本发明属于材料表面处理技术领域,具体涉及一种增强硅酸盐材料涂层生物性能的方法及其涂层。通过等离子喷涂设备对制备在钛合金或者其它基体上的硅酸盐材料涂层进行原位热处理。该方法可以有效重塑涂层的微观形貌和结晶结构,增强涂层的成骨性能,提高硅酸盐材料涂层植入体的骨修复能力。(The invention belongs to the technical field of material surface treatment, and particularly relates to a method for enhancing the biological performance of a silicate material coating and a coating thereof. The silicate material coating prepared on the titanium alloy or other base bodies is subjected to in-situ heat treatment by plasma spraying equipment. The method can effectively remold the microscopic appearance and the crystalline structure of the coating, enhance the osteogenic property of the coating and improve the bone repair capability of the silicate material coating implant.)
1. The method for enhancing the biological performance of the silicate material coating is characterized in that the method is to carry out in-situ heat treatment on the prepared strontium-containing silicate material coating by adopting plasma spraying equipment to remold the microscopic morphology and the crystalline structure of the coating, wherein the strontium-containing silicate material is (Sr)XCa(2-X))ZnSi2O7Or SrZrSi2O7And the value range of X is 0-2.
2. The method for enhancing the biological performance of the silicate material coating according to claim 1, wherein the strontium silicate containing material coating is prepared by the following steps:
(1) preparation of silicate powder
Preparing strontium-containing silicate powder by using a high-temperature solid-phase method;
(2) preparation of strontium-containing silicate material coating
A coating of strontium containing silicate material was prepared on a titanium alloy substrate by a-2000 atmospheric plasma spray apparatus model Sulzer Metco AG.
3. The method for enhancing the biological performance of the silicate material coating according to claim 2, wherein the strontium-containing silicate powder is prepared by the following steps: weighing the raw materials according to the molar ratio of the target powder, uniformly mixing, and then placing in a muffle furnace for high-temperature sintering to obtain the strontium-containing silicate powder.
4. The method for enhancing the biological performance of a silicate material coating according to claim 3, wherein the high temperature sintering temperature in the muffle furnace is: 1200-1350 ℃, and the temperature rising speed is 5 ℃/min.
5. The method for enhancing the biological performance of a silicate material coating according to claim 2, wherein the plasma spraying parameters are: the spraying distance is 60-120 mm, the spraying power is 30-50 kw, the powder feeding rate is 10-40 g/min, the linear speed is 377-2262 mm/s, the gun walking speed is 10mm/s, the spraying frequency is 10-30 times, the gun mouth is 1 time from top to bottom, and the current is fixed to be 600A.
6. The method for enhancing the biological performance of a silicate material coating according to claim 1, wherein the parameters of the in-situ heat treatment plasma spraying are as follows: the spraying distance is 60-120 mm, the spraying power is 30-50 kw, the linear speed is 377-2262 mm/s, the gun moving speed is 10mm/s, the in-situ heat treatment frequency is 10-50 times, the gun mouth is 1 time from top to bottom, and the current is fixed at 600A.
7. The method of claim 1, wherein the silicate material coating has a formula of (Sr)0.4Ca1.6)ZnSi2O7Strontium calcium zinc silicate.
8. A coating of a silicate material prepared according to the method of claim 1.
Technical Field
The invention belongs to the technical field of material surface treatment, and relates to a method for enhancing the biological performance of a silicate material coating and a coating thereof.
Background
The silicate material coating has good bone repair capability and is widely applied to implant coatings. However, the existing implant coating cannot better meet the requirement of bone repair, and the lower crystallization degree causes explosive release of silicate material coating ions to generate cytotoxicity; or the strontium silicate-containing material coating has high stability, slow release of bioactive ions and poor biological performance.
In order to achieve a better bone repair effect and inhibit the explosive release of ions in the coating, more materials are added, but the cost of the implant coating is improved, the mechanical property of the implant coating is damaged, the wear resistance and corrosion resistance of the implant coating are reduced, and the long-term use of the implant coating is not facilitated. Or the bonding strength of the coating and the matrix is sacrificed, and the stability of the coating is reduced, so that the biological performance is enhanced, the coating is easy to fall off, and the stable use of the implant in a human body is not facilitated.
The surface treatment technology is a method for preparing a surface with a special structure by performing surface treatment on the surface of a material, and is widely applied to the surface of an inorganic material. By remolding the microscopic morphology and the crystalline structure of the implant coating, the aims of regulating and controlling the crystallinity of the coating and releasing bioactive ions to enhance the osteogenesis performance of the coating and improve the bone repair capability of the implant coating are achieved on the premise of not damaging the mechanical property of the implant coating.
The existing surface treatment technology has complex operation steps and long period, and simultaneously needs to add additional chemical reagents. For example, in the conventional alkali heat treatment, a solution of NaOH (a common reagent) with a certain concentration is prepared, and the temperature is fixed and constant for a certain period of time in a reaction kettle with a teflon lining. Or constant-temperature mineralization in a carbon dioxide atmosphere, it is difficult to ensure uniformity (or quantification) of the carbon dioxide gas concentration, and if the uniformity (or quantification) of the carbon dioxide gas concentration is ensured, the carbon dioxide gas is introduced into a gas device, thereby increasing additional cost.
Disclosure of Invention
Aiming at the problem that the crystallization degree of the existing silicate material coating implant is low, so that the explosive release of silicate material coating ions is caused, and cytotoxicity is generated; or the strontium silicate-containing material has the technical problems of high coating stability, slow release of bioactive ions and poor biological performance. The invention provides a method for enhancing the biological performance of a silicate material coating and the coating thereof. To achieve the purpose, the invention provides a method for reshaping the surface morphology and the crystalline structure of a silicate coating through plasma in-situ heat treatment.
And carrying out in-situ heat treatment on the prepared silicate material coating by adopting plasma spraying equipment, and remolding the microscopic morphology and the crystalline structure of the coating. Not only retains excellent mechanical properties, but also regulates and controls the crystallinity of the silicate material coating and the release of bioactive ions in the material, enhances the biological properties of the silicate material coating, and improves the bone repair capability of the silicate coating implant.
Parameters of in-situ heat treatment spraying: the distance is 60-120 mm, the power is 30-50 kw, the linear speed is 377-2262 mm/s, the gun moving speed is 10mm/s, the in-situ heat treatment frequency is 10-50 times, the gun mouth is 1 time from top to bottom, and the current is fixed at 600A.
The preparation method of the silicate material coating comprises the following steps:
(1) preparation of silicate powder
Preparing strontium-containing silicate powder by using a high-temperature solid-phase method;
the preparation method of the strontium-containing silicate powder comprises the following steps: weighing the raw materials according to the molar ratio of the target powder, uniformly mixing, and then placing in a muffle furnace for high-temperature sintering to obtain the strontium-containing silicate powder.
The high-temperature sintering temperature is as follows: the temperature is 1200-1350 ℃, the constant temperature time is 3-4h, and the temperature rising speed is 5 ℃/min.
(2) Preparation of strontium-containing silicate biomaterial coating
Strontium containing silicate biomaterials were prepared on titanium alloy substrates by a-2000 atmospheric plasma spray equipment model Sulzer Metco AG.
Wherein, plasma spraying parameters are as follows: the spraying distance is 60-120 mm, the spraying power is 30-50 kw, the powder feeding rate is 10-40 g/min, the linear speed is 377-2262 mm/s, the gun walking speed is 10mm/s, the spraying frequency is 10-30 times, the gun mouth is 1 time from top to bottom, and the current is fixed to be 600A.
The chemical composition general formula of the silicate material coating is (Sr)XCa(2-X))ZnSi2O7Or SrZrSi2O7Wherein, the value range of X is 0-2.
The silicate material coating preferably has the molecular formula of (Sr)0.4Ca1.6)ZnSi2O7(20% Sr-HT).
The strontium-containing silicate material prepared by the high-temperature solid phase method has a single crystal phase structure, has excellent mechanical property, biocompatibility and osteoinduction capacity, can be used as an artificial joint coating, improves the osteoinduction capacity of the existing metal implant, and ensures the long-term stability of the implant.
The invention has the beneficial effects that:
(1) the method has simple process, and the in-situ heat treatment process does not need to replace equipment and can directly use a plasma spraying machine for preparing the coating to carry out in-situ heat treatment.
(2) The cost is greatly reduced. The machines and materials required for the surface treatment process are all required for the preparation of strontium containing silicate coated implants.
(3) On the premise of not reducing the mechanical property of the silicate material coating implant, the bone repair capability of the silicate material coating implant is obviously improved.
Description of the drawings:
FIG. 1 shows X-ray diffraction patterns of a silicate material coating before and after in-situ heat treatment; wherein A is the X-ray diffraction pattern of comparative example 1 and example 1, B is the X-ray diffraction pattern of comparative example 2 and example 4, and C is the X-ray diffraction pattern of comparative example 3 and example 5;
FIG. 2 is an SEM image of a silicate material coating before and after in-situ heat treatment; wherein, A is SEM pictures of comparative example 1 and example 1, B is SEM pictures of comparative example 2 and example 4, and C is SEM pictures of comparative example 3 and example 5;
FIG. 3 is a line graph showing ion concentrations before and after in-situ heat treatment of a silicate material coating; wherein A is a line graph of the ion concentration of comparative example 1 and example 1, B is a line graph of the ion concentration of comparative example 2 and example 4, and C is a line graph of the ion concentration of comparative example 3 and example 5;
FIG. 4 is a bar graph showing cell proliferation of example 1 and comparative example 1;
FIG. 5 shows the morphology of cells after 7 days of culture on the silicate material coating of example 1.
FIG. 6 is a bar graph showing the ALP activity of cells of example 1 and comparative example 1.
FIG. 7 is a bar graph showing cell growth in examples 1, 2 and 3.
FIG. 8 is a bar graph showing the bond strength of the silicate materials of examples 1-5 to a substrate.
FIG. 9 is a bar graph showing the frictional wear of the silicate material coatings of examples 1-5.
Detailed Description
For further understanding of the present invention, the method of coating the implant with strontium-containing biomaterial provided by the present invention is described in detail below with reference to the examples.
Example 1
(1) Preparation of silicate powder
Preparation of SrZrSi by high-temperature solid phase method2O7A material. Weighing strontium carbonate (Shanghai type, AR), silicon dioxide (Shanghai type, AR) and zirconium dioxide (Shanghai type, AR) according to the molar ratio of the target powder, uniformly mixing the weighed reagents, and then placing the reagents in a muffle furnace for 3h high-temperature sintering at the constant temperature of 1350 ℃. The temperature rising speed is 5 ℃/min, and the furnace is cooled after the constant temperature is finished.
(2)SrZrSi2O7Preparation of the coating
Strontium containing silicate biomaterial coatings were prepared on titanium alloy substrates by a-2000 atmospheric plasma spray equipment manufactured by Sulzer Metco AG (switzerland).
The atmospheric plasma spraying equipment consisted of an F4-MB torch and an S3 robot from ABB. The powder feeder was a 10-C type double powder feeding system (Sulzer Metco).
The size of a Ti-6Al-4V titanium alloy base material sample (metal implant) is phi 15 multiplied by 1mm, and before spraying, absolute ethyl alcohol and alcohol are used for ultrasonic cleaning to remove surface oil stains. In order to increase the surface roughness of the base material and improve the bonding strength of the coating and the matrix, the titanium alloy base material sample is subjected to sand blasting. In order to increase the stability of the powder feeding, the powder is granulated: mixing the powder with 5% PVA solution until the powder can be bonded into granules, drying in a forced air drying oven, and grinding through an 80-mesh sieve. After spraying, the prepared silicate material coating implant is ultrasonically cleaned by absolute ethyl alcohol and deionized water.
Plasma spraying parameters: the plasma gas is Ar and H2The flow rates are respectively 40slpm and 12slpm, the powder feeding rate is 40g/min, the power used for spraying is 45kw, and the spraying distance is 100mmThe spraying times are 20 times, the linear speed is 754mm/s, and the gun moving speed is 10 mm/s.
(3) In-situ heat treatment process
The prepared strontium-containing silicate coating is continuously placed on a rotary table, and silicate spraying raw materials in a powder feeder are taken out. The plasma gas is Ar and H2(the flow rates are respectively 40slpm and 12slpm) are kept unchanged, and the spraying distance is adjusted to 80mm, the spraying power is adjusted to 45kw, the linear velocity is adjusted to 754mm/s, the gun moving velocity is adjusted to 10mm/s, and the in-situ heat treatment times are adjusted to 20 times.
And carrying out subsequent in-situ heat treatment on the prepared strontium-containing silicate coating by using a high-temperature plasma fire source under the condition of no strontium-containing silicate raw material.
Example 2
SrZrSi2O7The coating was prepared as in example 1.
(3) In-situ heat treatment process
The spraying distance was adjusted to 100mm, and the other parameter processes were consistent with those of example 1 (3).
Example 3
SrZrSi2O7The coating was prepared as in example 1.
(3) In-situ heat treatment process
The spraying distance was adjusted to 120mm, and the other parameters and processes were consistent with those of example 1 (3).
Example 4
(1) Preparation of silicate powder
Preparation of (Sr) by high-temperature solid-phase method0.4Ca1.6)ZnSi2O7A material. Weighing calcium carbonate (Shanghai type, AR), strontium carbonate (Shanghai type, AR), silicon dioxide (Shanghai type, AR) and zinc oxide (Shanghai type, AR) reagents according to the molar ratio of the target powder, uniformly mixing the weighed reagents, and then placing the reagents in a muffle furnace for sintering at the constant temperature of 1200 ℃ for 3 h. The temperature rising speed is 5 ℃/min, and the furnace is cooled after the constant temperature is finished.
(2)(SrXCa(2-X))ZnSi2O7Preparation of the coating
The preparation procedure and the plasma spraying apparatus were the same as in example 1. Plasma spraying parameters: plasma processThe sub-gases are Ar and H2The flow rates are 40slpm and 12slpm respectively, the powder feeding rate is 20g/min, the power used for spraying is 42kw, the spraying distance is 100mm, the spraying times are 20 times, the linear speed is 754mm/s, and the gun moving speed is 10 mm/s.
(3) In-situ heat treatment process
The prepared strontium-containing silicate coating is continuously placed on a rotary table, and the strontium-containing silicate raw material in the powder feeder is taken out. The plasma gas is Ar and H2(the flow rates are respectively 40slpm and 12slpm) are kept unchanged, and the spraying distance is adjusted to 80mm, the spraying power is adjusted to 35kw, the linear velocity is adjusted to 754mm/s, the gun moving velocity is adjusted to 10mm/s, and the in-situ heat treatment times are adjusted to 20 times.
And carrying out subsequent in-situ heat treatment on the prepared strontium-containing silicate coating by using a high-temperature plasma fire source under the condition of no strontium-containing silicate raw material.
Example 5
(1) Preparation of silicate powder
Preparation of Sr by high-temperature solid-phase method2ZnSi2O7A material. Weighing strontium carbonate (Shanghai type, AR), silicon dioxide (Shanghai type, AR) and zinc oxide (Shanghai type, AR) reagents according to the molar ratio of the target powder, uniformly mixing the weighed reagents, and then placing the reagents in a muffle furnace for sintering at the constant temperature of 1200 ℃ for 3 h. The temperature rising speed is 5 ℃/min, and the furnace is cooled after the constant temperature is finished.
(2)Sr2ZnSi2O7Preparation of the coating
The preparation procedure and the plasma spraying apparatus were the same as in example 1. Plasma spraying parameters: the plasma gas is Ar and H2The flow rates are 40slpm and 12slpm respectively, the powder feeding rate is 20g/min, the power used for spraying is 45kw, the spraying distance is 100mm, the spraying times are 20 times, the linear speed is 754mm/s, and the gun moving speed is 10 mm/s.
(3) In-situ heat treatment process
The prepared strontium-containing silicate coating is continuously placed on a rotary table, and the strontium-containing silicate raw material in the powder feeder is taken out. The plasma gas is Ar and H2(the flow rates are respectively 40slpm and 12slpm) are kept unchanged, the spraying distance is adjusted to be 100mm, the spraying power is adjusted to be 40kw, the linear speed is 1508mm/s, and the walking is carried outThe gun speed was 10mm/s and the number of in situ heat treatments was 30.
And carrying out subsequent in-situ heat treatment on the prepared strontium-containing silicate coating by using a high-temperature plasma fire source under the condition of no strontium-containing silicate raw material.
Comparative example 1
(1) The silicate powder was prepared as in example 1.
(2)SrZrSi2O7Preparation of the coating
The preparation procedure, plasma spraying apparatus and plasma spraying parameters were the same as in example 1.
Comparative example 2
(1) The silicate powder was prepared as in example 4.
(2)(Sr0.4Ca1.6)ZnSi2O7Preparation of the coating
The preparation procedure, plasma spraying apparatus and plasma spraying parameters were the same as in example 4.
Comparative example 3
(1) The silicate powder was prepared as in example 5.
(2)Sr2ZnSi2O7Preparation of the coating
The preparation procedure, plasma spraying apparatus and plasma spraying parameters were the same as in example 5.
Example 6
(1) X-ray diffraction pattern
The composition of the phase of the coating was mainly analyzed by X-ray diffractometer (XRD) model D/max 2500PC manufactured by Rigaku corporation, Japan. The specific test parameters were set as follows: cu target Ka radiation, characteristic wavelengthThe diffraction angle (2 theta) scan range was 10 DEG to 80 DEG, the scan speed was 0.02 DEG/s, the current was 100mA, and the voltage was 40 kV.
According to the analysis of XRD result, 20 percent of Sr-HT and Sr are obtained after the plasma in-situ heat treatment2ZnSi2O7The degree of crystallization of the main peak in the coating is higher, and the degree of crystallization is also increased; at the same time SrZrSi2O7The crystallinity of (2) is decreased.
(2)SEM
After the gold spraying, the surface morphology of the coating was observed by using a SUPRA55 model field emission scanning electron microscope (FE-SEM) manufactured by ZEISS, Germany. Signal a Signal source: SE II, the spraying distance is 8.4-10mm, and the voltage is 8 KV.
As can be seen from fig. 2, the surface topography of the coating is changed after the plasma in-situ heat treatment.
(3) Ion Release test
A 1M Tris-HCL solution was prepared at pH 7.4. The washed coating was placed in 10ml of Tris-HCl solution and then in a 37 ℃ incubator, the solution was changed every three days and the concentration of ions in the solution was measured for a total of 5 times for a period of 15 days. The ions measured were ions in the silicate coating. The results are shown in FIG. 3.
As can be seen from the results in FIG. 3, the in-situ heat treatment process can effectively change the ion release rate of the coating, SrZrSi2O7Increased release rate of the material coating, Sr2ZnSi2O7And (Sr)0.4Ca1.6)ZnSi2O7The ion release rate of the material coating decreases.
(4) Cell proliferation assay of coatings
The material was autoclaved and placed in 24-well plates, washed 3 times with PBS and hBMSCs cells were plated at 5X 104cells/well density were seeded onto the material and cultured in an incubator for 1, 3, and 7 days, respectively. At each time point, the stock culture was removed and 500. mu.L of DMEM medium (DMEM: CCK-8 ═ 9:1) was added to each well and incubated for 2h in the incubator with the material at the remaining time points being changed. After 2h incubation, the pools were transferred to 96-well plates, 200. mu.L of each well was added, and the absorbance was measured at 450nm using a microplate reader. The above experimental procedure was repeated until all time points were over, and all experiments were repeated three times.
As can be seen from the results in fig. 4, the cell proliferation results of example 2 are better compared to comparative example 1, indicating that the in situ heat treatment process can better enhance the cell proliferation ability of the strontium silicate-containing coating.
From the results in fig. 7, it can be seen that changing the spray parameters (adjusting the spray distance) can effectively change the cell proliferation ability of the coating.
(5) Morphology observation of coated cells
The morphology and adhesion of cells on the surface of the scaffold material were observed by SEM. Cells cultured for 7 days were fixed with 10% glutaraldehyde for 15min, then dehydrated with an alcohol gradient and dried with isoamyl acetate for 30 min. The fixed cells were observed under a scanning electron microscope, and the results are shown in FIG. 5.
(6) ALP Activity assay
This example examined ALP activity in rBMSCs cells cultured with different material extracts for cell 7 d. Preparing leaching liquor of materials of comparative example 1, example 2, comparative example 2 and example 8, and mixing the leaching liquor according to a mass-to-volume ratio of 1: 10 adding serum-free culture medium alpha-MEM, and soaking in a constant temperature and humidity environment at 37 deg.C for 24 h. And taking the supernatant, adding 10% of serum and 1% of double antibody, and storing in a refrigerator at 4 ℃ for later use.
Taking logarithmic growth phase rBMSCs at 8X 103cells/wells were seeded in 48-well plates individually, and 1d later the solution was exchanged with different material extracts. Culturing for 7 days, removing the culture solution, and washing with PBS for three times; add 200. mu.L of western and IP cell lysates. Fully blowing and cracking by using a gun head, shaking for 30min at 37 ℃, centrifuging at 12000rpm for 5 min. 50 μ L of each supernatant was transferred to a 96-well plate (triplicate). mu.L of pNPP was added to each well and incubated for 2h, and absorbance at 405nm was measured. ALP activity was the ratio of absorbance at 405nm to the corresponding total protein, and the total protein content of the lysate was determined by BCA kit, and the results are shown in FIG. 6.
From the results of fig. 6, it can be seen that the strontium-containing silicate coating after the post-treatment, i.e., the coating treated by the in situ heat treatment process, has high ALP activity, and thus increases the expression of cell ALP, and the coating after the post-treatment can promote osteogenic differentiation of cells.
(7) Bond strength test
The bonding strength of the coating was tested using a Chinese KASON group universal tester (30 KN/WDT-30). The bond strength test was performed according to GB/T8642-2002, and tensile bars of specified dimensions were customized according to the standard. Preparing a coating on the surface of the tensile sample by using plasma spraying equipment, carrying out sand blasting treatment before preparing the coating, carrying out ultrasonic cleaning after spraying, and drying for later use. The treated pair of tensile bars, one of which was not sprayed but sandblasted, was cured for 3 hours at 100 ℃ under a pressure of at least 40N by gluing with E7 (Kawayawa resin Co., Ltd.). The results are shown in FIG. 8.
From the results of fig. 8, it can be easily found that the bonding strength of the coating and the substrate is not changed by different heat treatment methods of the same material. The bonding strength difference between different materials is large, wherein SrZrSi2O7The material has the highest bonding strength.
(8) Frictional wear test
In the experiment, a friction and wear testing machine (MMW-1A) produced by the Jinan Yihua company is adopted to test the wear resistance of the surface of the coating, wherein the size of a sample is 20mm multiplied by 2mm, a friction pair is Si3N4 beads, the set load is 20N, the rotating speed is 300r/min, the friction radius is 3mm, and the time is 30 min. Before the frictional wear test, the surface of the sample was first polished to a roughness of about 4 μm with 1000# and 2000# sandpaper. Then ultrasonic cleaning is carried out, the dried product is placed into a drying dish for cooling, weighing is started after the temperature is reduced to the room temperature, the original mass is recorded, the weighing process is as fast as possible, and errors are reduced. And after the friction and wear experiment is finished, carrying out ultrasonic cleaning, drying, putting into a drying dish for cooling, weighing after cooling to room temperature, recording the mass of the sample, and calculating the difference between the beginning and the end, namely the wear loss. Each set of coatings was subjected to three repeated frictional wear tests to ensure the reliability of the results. The results are shown in FIG. 9.
From the results of FIG. 9, we found that different heat treatment methods of the same material changed the wear resistance of the coating; the wear resistance of different materials is different, SrZrSi2O7The material histogram is the lowest, and the wear resistance is the best.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
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