CN108543118B - Magnesium alloy fixing screw capable of being degraded controllably in vivo - Google Patents
Magnesium alloy fixing screw capable of being degraded controllably in vivo Download PDFInfo
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Abstract
The invention relates to a magnesium alloy fixing screw capable of being degraded controllably in vivo, belonging to the technical field of medical instruments. The magnesium alloy fixing screw with controllable degradation in vivo comprises a magnesium alloy screw body, wherein an oxide film layer with the thickness of 50-200 mu m is formed on the magnesium alloy screw body, and a degradable high polymer coating with the thickness of 1-50 mu m is coated on the oxide film layer. The magnesium alloy fixing screw can be controllably degraded in a body, the strength retention period of the fixing screw is about 3 months, the degradation period can be controlled to be about 6-8 months, and the magnesium alloy fixing screw is suitable for fixing tissues or fixing tissues and repairing materials, and is particularly suitable for repairing hernia and other soft tissue defects.
Description
Technical Field
The invention relates to the technical field of medical instruments, in particular to a magnesium alloy fixing screw capable of being degraded controllably in vivo.
Background
A setscrew used in the body is a typical medical implant material, and as a medical implant material, it is required to have good chemical stability, non-toxicity, and good adaptability to biological tissues. The medical implant materials which are widely used for clinical treatment at first are precious metals such as gold, silver, platinum and the like, but the application is limited due to the high price. The metal implant materials widely used in clinical applications at present include titanium alloy, stainless steel and cobalt-chromium alloy, which have good corrosion resistance and can maintain stable structure in vivo for a long time, but the above alloys can generate toxic metal ions due to abrasion in vivo, and may cause allergic reaction or inflammation, thereby reducing biocompatibility. And the material is a non-degradable material, and only needs to be implanted for a short time, and needs to be taken out through a secondary operation after the function of human tissue is recovered, so that the pain of a patient, the risk of the secondary operation and the medical cost are increased. In recent years, scholars at home and abroad have conducted a great deal of research on biomedical degradable metal implant materials, and magnesium alloys are called as research heat in the field of biomedical degradable metal implant materials due to good absorbability, biocompatibility, complete degradability and low priceAnd (4) point. However, the standard electrode potential of magnesium is very low, especially Cl in body fluids-The corrosion of the magnesium alloy can be accelerated, the implanted material is seriously corroded before the organism is not cured due to the higher degradation rate, the mechanical property and the stability of the material are reduced, the rapid corrosion of the magnesium alloy is accompanied with the release of a large amount of hydrogen, and the local pH value of body fluid near an implant is increased due to the excessively high degradation rate, so that the human skeleton and the growth of the group are damaged, and the clinical application of the magnesium alloy is seriously restricted.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a magnesium alloy fixing screw with controllable degradation in vivo.
In order to solve the technical problems and achieve the purpose of the invention, the invention adopts the following technical scheme:
the magnesium alloy fixing screw comprises a magnesium alloy screw body, wherein an oxide film layer with the thickness of 50-200 mu m is formed on the magnesium alloy screw body, and a degradable high polymer coating with the thickness of 1-50 mu m is coated on the oxide film layer.
Wherein the magnesium alloy comprises 3.70-4.30 wt% of yttrium, 2.4-4.4 wt% of neodymium and/or gadolinium, 0.3-1.0 wt% of Nb, and the balance of Mg and inevitable impurities; the inevitable impurities include zinc not higher than 0.20wt%, lithium not higher than 0.20wt%, manganese not higher than 0.15wt%, copper not higher than 0.03wt%, iron not higher than 0.01wt%, silicon not higher than 0.01wt%, and nickel not higher than 0.005 wt%.
The screw body comprises a spiral body, the number of spiral turns on the spiral body is 1-5 turns, and preferably 2-3 turns; the front end of the spiral body is a nail tip, and the tail end of the spiral body is a nail tail.
The length of the screw body is 2-10 mm, and preferably 4-7 mm.
Wherein the oxidation film layer is obtained by alternating current oxidation treatment, and the adopted oxidation treatment liquid comprises the following components: 15-50 g/L of organic acid, 1.5-5.0 g/L of calcium nitrate, 1.2-2.5 g/L of potassium fluoride, 1.0-5.0 g/L of magnesium silicate and the balance of water.
Wherein the organic acid is selected from one or more of oxalic acid, succinic acid, citric acid, malic acid or acetic acid.
Wherein the temperature of the oxidation treatment liquid is 5-25 ℃, and the current density is 0.05-0.5A/dm2The time of the oxidation treatment is 0.5-5 h.
Wherein the degradable polymer coating is selected from one or more of poly D, L-lactide (PDLLA), poly L-lactide (PLLA), Polycaprolactone (PCL), polylactic acid (PLA), polylactic-co-glycolic acid (PLGA) or poly 3-hydroxy fatty acid esters (PHAs).
Wherein, the degradable polymer coating can be loaded with therapeutic drugs, and the therapeutic drugs include but are not limited to anticoagulant drugs, anti-inflammatory drugs or antibiotics.
Compared with the closest prior art, the magnesium alloy fixing screw with controllable degradation in vivo has the following beneficial effects:
the magnesium alloy fixing screw can be controllably degraded in a body, the strength retention period of the fixing screw is about 3 months, the degradation period can be controlled to be about 6-8 months, and the magnesium alloy fixing screw is suitable for fixing tissues or fixing tissues and repairing materials, and is particularly suitable for repairing hernia and other soft tissue defects.
Drawings
Fig. 1 is a front view of a magnesium alloy set screw according to embodiment 1.
Fig. 2 is a rear view of the magnesium alloy set screw of embodiment 1.
Detailed Description
The magnesium alloy set screw with controlled degradation in vivo according to the present invention will be further described with reference to the following embodiments, in order to make a more complete and clear description of the technical solution of the present invention.
The fixing screw body adopted by the invention is obtained by processing WE43A magnesium alloy, for example, the screw body can be formed by laser cutting WE43A magnesium alloy or melting the magnesium alloyAnd (4) pouring the solution to obtain the product. As shown in fig. 1-2, the magnesium alloy screw body adopted by the invention comprises a hollow spiral body 2, the thickness of the hollow spiral body is 0.3-0.6 mm, the number of spiral turns on the spiral body is 1-5, and preferably 2-3; the front end of the spiral body 2 is a nail tip 1, and the tail end of the spiral body 2 is a nail tail 3. The length of the screw body is 2-10 mm. The WE43A magnesium alloy comprises 3.70-4.30 wt% of yttrium, 2.4-4.4 wt% of neodymium and/or gadolinium, 0.3-1.0 wt% of Nb and the balance of Mg and inevitable impurities; the inevitable impurities include zinc not higher than 0.20wt%, lithium not higher than 0.20wt%, manganese not higher than 0.15wt%, copper not higher than 0.03wt%, iron not higher than 0.01wt%, silicon not higher than 0.01wt%, and nickel not higher than 0.005 wt%. Illustratively, the magnesium alloy employed in the examples and comparative examples of the present invention had a composition of Mg-4 wt% Y-3.3 wt% Nd-0.5 wt% Nb (containing 4.0 wt% Y, 3.3 wt% Nd, 0.5 wt% Nb, and the balance Mg and inevitable impurities), and a helical body having a length of 5mm was employed. In the invention, an oxide film layer with the thickness of 50-200 mu m is formed on the magnesium alloy screw body, and the degradable high polymer coating with the thickness of 1-50 mu m is coated on the oxide film layer. The oxidation film layer is obtained by alternating current oxidation treatment, and the adopted oxidation treatment liquid comprises the following components: 15-50 g/L of organic acid, 1.5-5.0 g/L of calcium nitrate, 1.2-2.5 g/L of potassium fluoride, 1.0-5.0 g/L of magnesium silicate and the balance of water. The temperature of the oxidation treatment liquid is 5-25 ℃, and the current density adopted by the alternating current oxidation treatment is 0.05-0.5A/dm2The time of the oxidation treatment is 0.5 to 5 hours, preferably 1.0 to 3.0 hours. The oxidation treatment liquid is used and the alternating current oxidation treatment is carried out to obtain a porous oxide film layer, and EDX (electron-ray diffraction) spectrum analysis shows that the formed oxide film layer contains Mg, Ca, Si, F, O and other elements. And furthermore, the strength of the fixing screw in the body for a certain time can be ensured by dip-coating or spraying a degradable polymer coating, and the magnesium alloy fixing screw has a stable degradation period on the whole. In the invention, the degradable high molecular coating is selected from poly D, L-lactideOne or more of ester (PDLLA), poly L-lactide (PLLA), Polycaprolactone (PCL), polylactic acid (PLA), polylactic-co-glycolic acid (PLGA) or poly 3-hydroxy fatty acid ester (PHAs). The degradable polymer coating can be loaded with therapeutic drugs, and the therapeutic drugs include but are not limited to anticoagulant drugs, anti-inflammatory drugs or antibiotics.
Example 1
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 20g/L oxalic acid, 2.2g/L calcium nitrate, 1.8g/L potassium fluoride, 2.5g/L magnesium silicate and the balance of water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L poly L-lactide (PLLA) solution for 20 minutes, taken out and dried to obtain a poly L-lactide coating having a thickness of about 10 μm.
Example 2
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 32g/L citric acid, 1.8g/L calcium nitrate, 1.2g/L potassium fluoride, 3.0g/L magnesium silicate and the balance water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L poly L-lactide (PLLA) solution for 20 minutes, taken out and dried to obtain a poly L-lactide coating having a thickness of about 10 μm.
Example 3
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then is atAn alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 20g/L oxalic acid, 2.2g/L calcium nitrate, 1.8g/L potassium fluoride, 2.5g/L magnesium silicate and the balance of water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L polylactic acid (PLA) solution for 20 minutes, and then dried after being taken out to obtain a polylactic acid coating having a thickness of about 10 μm.
Example 4
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 32g/L citric acid, 1.8g/L calcium nitrate, 1.2g/L potassium fluoride, 3.0g/L magnesium silicate and the balance water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then dipping in 1.0mg/L Polycaprolactone (PCL) solution for 20 minutes, taking out and drying to obtain a polycaprolactone coating with the thickness of about 10 mu m.
Example 5
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 32g/L citric acid, 1.8g/L calcium nitrate, 1.2g/L potassium fluoride, 3.0g/L magnesium silicate and the balance water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L solution of poly-3-hydroxy fatty acid esters (PHAs) for 20 minutes, and then taken out and dried to obtain a poly-3-hydroxy fatty acid ester coating having a thickness of about 10 μm.
Comparative example 1
Selecting 5mm WE43A magnesium alloy screw body, and adoptingSanding with sand paper and ultrasonically cleaning to remove oxides and impurities on the surface, then soaking in 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 20g/L of oxalic acid, 2.2g/L of calcium nitrate, 1.8g/L of potassium fluoride and the balance of water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L polylactic acid (PLA) solution for 20 minutes, and then dried after being taken out to obtain a polylactic acid coating having a thickness of about 10 μm.
Comparative example 2
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 20g/L of oxalic acid, 2.2g/L of calcium nitrate, 1.8g/L of potassium fluoride, 2.5g/L of sodium silicate and the balance of water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L polylactic acid (PLA) solution for 20 minutes, and then dried after being taken out to obtain a polylactic acid coating having a thickness of about 10 μm.
Comparative example 3
Selecting a WE43A magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, an anodic oxidation treatment is performed in an oxidation treatment liquid to form an oxide film layer (using direct current). The oxidation treatment liquid comprises: 20g/L oxalic acid, 2.2g/L calcium nitrate, 1.8g/L potassium fluoride, 2.5g/L magnesium silicate and the balance of water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L polylactic acid (PLA) solution for 20 minutes, and then dried after being taken out to obtain a polylactic acid coating having a thickness of about 10 μm.
Comparative example 4
Selecting an AZ31B magnesium alloy screw body with the length of 5mm, removing oxides and impurities on the surface by sanding and ultrasonic cleaning, then soaking in a 50g/L NaOH solution for 10 minutes, taking out, washing with water and drying. Then, alternating current oxidation treatment was performed in the oxidation treatment liquid to form an oxide film layer having a thickness of about 50 μm. The oxidation treatment liquid comprises: 20g/L oxalic acid, 2.2g/L calcium nitrate, 1.8g/L potassium fluoride, 2.5g/L magnesium silicate and the balance of water. The temperature of the oxidation treatment liquid was 10 ℃ and the current density was 0.10A/dm2The oxidation treatment time was 2 hours. Then, the coating was dipped in a 1.0mg/L polylactic acid (PLA) solution for 20 minutes, and then dried after being taken out to obtain a polylactic acid coating having a thickness of about 10 μm.
The fracture toughness of each example and each comparative magnesium alloy fixing screw sample is measured, and then the soaking test is carried out in artificial blood at 37 ℃ by adopting a soaking test method to measure each example and each comparative magnesium alloy fixing screw, wherein the artificial blood contains 3.8g/L of sodium chloride, 2.2g/L of sodium bicarbonate, 0.2g/L of calcium chloride, 0.4g/L of potassium chloride, 0.1g/L of magnesium sulfate, 0.126g/L of disodium hydrogen phosphate and 0.026g/L of sodium dihydrogen phosphate, the ratio of the volume of the artificial blood to the area of the magnesium alloy fixing screw sample is 30 mL: 1cm2. The artificial blood was replaced once in 24 hours, and after 3 months of soaking, the fracture toughness of the test specimen was measured, and the results are shown in table 1:
TABLE 1 (fracture toughness MPa. m)1/2)
Of these, the sample of comparative example 4 had decomposed entirely after soaking for two months.
As can be seen from Table 1, the magnesium alloy set screws of examples 1-5 maintained about 50% of breaking strength after being soaked in artificial blood for 3 months. In addition, the ratio of the volume of the artificial blood to the area of the magnesium alloy fixing screw sample is 200 mL: 1cm2The soaking test in (1) shows that the magnesium alloy fixing screw of the embodiment of the invention has stable degradation period (degraded to 10% of the initial weight)The period is about 6-8 months. The magnesium alloy fixing screw is suitable for fixing tissues or tissues and repairing materials, and is particularly suitable for repairing hernia and other soft tissue defects.
It is obvious to those skilled in the art that the present invention is not limited to the above embodiments, and it is within the scope of the present invention to adopt various insubstantial modifications of the method concept and technical scheme of the present invention, or to directly apply the concept and technical scheme of the present invention to other occasions without modification.
Claims (7)
1. An in-vivo controllable degradable magnesium alloy fixing screw comprises a magnesium alloy screw body, wherein an oxide film layer with the thickness of 50-200 mu m is formed on the magnesium alloy screw body, and a degradable high polymer coating with the thickness of 1-50 mu m is coated on the oxide film layer; wherein the oxidation film layer is obtained by alternating current oxidation treatment, the temperature of oxidation treatment liquid is 5-25 ℃, and the current density is 0.05-0.5A/dm2The time of the oxidation treatment is 0.5-5 h; the adopted oxidation treatment liquid comprises the following components: 15-50 g/L of organic acid, 1.5-5.0 g/L of calcium nitrate, 1.2-2.5 g/L of potassium fluoride, 1.0-5.0 g/L of magnesium silicate and the balance of water; the organic acid is selected from one or more of oxalic acid, succinic acid, citric acid, malic acid or acetic acid.
2. The in vivo controllably degradable magnesium alloy set screw of claim 1, wherein: the magnesium alloy comprises 3.70-4.30 wt% of yttrium, 2.4-4.4 wt% of neodymium and/or gadolinium, 0.3-1.0 wt% of Nb, and the balance of Mg and inevitable impurities; the inevitable impurities include zinc not higher than 0.20wt%, lithium not higher than 0.20wt%, manganese not higher than 0.15wt%, copper not higher than 0.03wt%, iron not higher than 0.01wt%, silicon not higher than 0.01wt%, and nickel not higher than 0.005 wt%.
3. The in vivo controllably degradable magnesium alloy set screw of claim 1, wherein: the screw body comprises a spiral body, and the number of spiral turns on the spiral body is 1-5; the front end of the spiral body is a nail tip, and the tail end of the spiral body is a nail tail.
4. The in vivo controllably degradable magnesium alloy set screw of claim 3, wherein: the length of the screw body is 2-10 mm.
5. The in vivo controllably degradable magnesium alloy set screw of claim 4, wherein: the length of the screw body is 3-7 mm.
6. The in vivo controllably degradable magnesium alloy set screw of claim 1, wherein: the degradable high polymer coating is selected from one or more of poly D, L-lactide (PDLLA), poly L-lactide (PLLA), Polycaprolactone (PCL), polylactic acid (PLA), polylactic-co-glycolic acid (PLGA) or poly 3-hydroxy fatty acid esters (PHAs).
7. The in vivo controllably degradable magnesium alloy set screw of claim 6, wherein: the degradable polymer coating can be loaded with therapeutic drugs, and the therapeutic drugs include but are not limited to anticoagulant drugs, anti-inflammatory drugs or antibiotics.
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| CN111214711A (en) * | 2018-11-26 | 2020-06-02 | 洛阳市中心医院（郑州大学附属洛阳中心医院） | Spiral magnesium alloy nail with anti-inflammatory drug coating for soft tissue fixation |
| CN110538999A (en) * | 2019-08-23 | 2019-12-06 | 长沙师范学院 | energy-saving environment-friendly biological material and preparation method thereof |
| CN112451137B (en) * | 2020-12-07 | 2021-10-26 | 中日友好医院(中日友好临床医学研究所) | Just abnormal anchorage nail of medicine carrying convenient to remove |
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