CN109925534B - Method for synchronously improving degradation rate and bioactivity of iron-based implant - Google Patents
Method for synchronously improving degradation rate and bioactivity of iron-based implant Download PDFInfo
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Abstract
The invention relates to a method for synchronously improving the degradation rate and the bioactivity of an iron-based implant, belonging to the technical field of biomedical implant design and manufacture. The scheme is as follows: taking iron powder and calcium sulfate as raw materials, and carrying out a selective laser melting process; obtaining an iron-based implant; the iron-based implant comprises the following components in percentage by mass: 0.5 to 12 percent of calcium sulfate; 88 to 99.5 percent of iron. The invention solves the problem that the conventional iron-based implant is degraded too slowly, and controls the degradation speed within a reasonable range; in addition, calcium sulfate can form a bone-like apatite layer through degradation, and forms good bone bonding with tissues, so that the bioactivity of the iron-based implant is improved. Meanwhile, the preparation process is optimized, so that the calcium sulfate can be uniformly dispersed in the iron matrix and the structural integrity is kept, and the improvement effect of the calcium sulfate on the degradation behavior and the biological activity of the iron-based implant is fully exerted.
Description
Technical Field
The invention relates to a method for synchronously improving the degradation rate and the bioactivity of an iron-based implant, belonging to the technical field of biomedical implant design and manufacture.
Background
Recently, researchers have proposed absorbable and degradable iron as a human bone repair material, which is easily corroded in a humid environment, which is medically regarded as biodegradable. The iron-based implant can be gradually degraded in vivo along with the gradual recovery of bone tissues, so that the necessity of surgical extraction of the traditional metal implant after the recovery of the bone tissues is avoided, and patients have small pain, quick recovery and less sequelae. In the aspect of biocompatibility, iron is an important trace element in a human body, can be combined with hemoglobin, and plays an important role in mechanisms such as oxygen transportation, enzyme reaction and the like; meanwhile, the enzyme activity, RNA and DNA structures and the physiological functions of participating in bone tissue metabolism and the like can be influenced. A large number of experimental studies show that the iron degradation process is slow, almost no toxic effect is caused on cells, and tissue inflammatory reaction and adverse effects on organs are not observed. In addition, iron has high strength and ductility, and can provide sufficient mechanical support, which is particularly suitable for the field of load bearing orthopedic implants.
Studies have shown that iron remains in the body for a long period of time with only slight corrosion of the surface after one year of implantation in the body, due to its too slow degradation rate. Meanwhile, iron is difficult to form osseous bond with surrounding tissues due to lack of biological activity, and cannot induce growth of cells and tissues. In order to increase the degradation rate of iron, a great deal of research work has been carried out, mainly by developing novel iron alloys such as Fe — Mn alloy, Fe — Zn alloy, Fe — C alloy, etc. by alloying methods. Compared with pure iron, the degradation rates of the iron alloys are improved to different degrees, but are limited by the biocompatibility of alloy elements, the addition amount of the elements is limited, the degradation rate has a larger distance from the requirement of clinical use, and the degradation rate of the iron-based alloy also has a great promotion space. More importantly, the accelerated degradation causes the release of a large amount of iron ions and alloying elements, further damages the original lacking bioactivity of the iron alloy, and even generates serious toxicity to inhibit the growth and reproduction of cells.
Therefore, the preparation of the iron-based implant with high degradation rate and good bioactivity is a key for promoting the application of the iron-based implant in the field of biomedical implants and is also a research focus and difficulty of scholars at home and abroad at present.
Disclosure of Invention
Aiming at the problems of slow degradation and poor bioactivity of the iron-based implant, the invention provides a method for synchronously improving the degradation rate and bioactivity of the iron-based implant.
The invention relates to a method for synchronously improving the degradation rate and the biological activity of an iron-based implant; the scheme is as follows: taking iron powder and calcium sulfate as raw materials, and carrying out a selective laser melting process; an iron-based implant was obtained.
The invention relates to a method for synchronously improving the degradation rate and the biological activity of an iron-based implant; the iron-based implant comprises the following components in percentage by mass:
0.5 to 12 percent of calcium sulfate;
88 to 99.5 percent of iron.
As a preferred scheme, the invention relates to a method for synchronously improving the degradation rate and the bioactivity of an iron-based implant; the iron-based implant comprises the following components in percentage by mass:
5-10% of calcium sulfate;
the iron content is 90-95%.
As a further preferred embodiment, the present invention provides a method for simultaneously increasing the degradation rate and bioactivity of an iron-based implant; the iron-based implant comprises the following components in percentage by mass:
7-8.5% of calcium sulfate;
the iron content is 91.5-93%.
As a further preferred embodiment, the present invention provides a method for simultaneously increasing the degradation rate and bioactivity of an iron-based implant; the iron-based implant comprises the following components in percentage by mass:
8 percent of calcium sulfate;
the iron content is 92%.
As a further preferred embodiment, the present invention provides a method for simultaneously increasing the degradation rate and bioactivity of an iron-based implant; in the iron-based implant, calcium sulfate is uniformly distributed in the iron-based implant in a particle form; the particle size of the calcium sulfate particles is 1-10 μm.
The invention relates to a method for synchronously improving the degradation rate and the biological activity of an iron-based implant; the method comprises the following steps:
step one
Under a protective atmosphere; uniformly mixing iron powder and calcium sulfate powder which are proportioned according to a certain proportion; obtaining mixed powder;
step two
And (3) taking the mixed powder obtained in the step one as a raw material, and preparing the iron-based implant through selective laser melting, wherein during selective laser melting, the laser power is controlled to be 80-120W, the laser spot diameter is controlled to be 0.1-0.3mm, and the scanning speed is controlled to be 40-80 mm/s.
As a preferred scheme, the invention relates to a method for synchronously improving the degradation rate and the bioactivity of an iron-based implant; in the first step, the iron powder and the calcium sulfate powder are mechanically stirred and mixed for 20-40 minutes according to a certain proportion, and then stirred, ball-milled and mixed for 90-120 minutes to obtain uniformly dispersed iron-calcium sulfate mixed powder.
As a preferred scheme, the invention relates to a method for synchronously improving the degradation rate and the bioactivity of an iron-based implant; the particle size of the iron powder is 30-50 mu m, and the particle size of the calcium sulfate powder is 1-10 mu m.
As a preferred scheme, the invention relates to a method for synchronously improving the degradation rate and the bioactivity of an iron-based implant; the selective laser melting is carried out under a protective atmosphere. The protective atmosphere is preferably selected from argon.
The invention relates to a method for synchronously improving the degradation rate and the biological activity of an iron-based implant; after optimization, the degradation rate of the iron-based implant in human body simulated body fluid is 0.14-0.3 mm/y. And the surface of the iron-based implant is corroded uniformly in the corrosion process.
Principles and advantages
The invention prepares the iron-calcium sulfate implant with quick degradation and excellent bioactivity by using a selective laser melting process for the first time. Under the environment of body fluid, calcium sulfate embedded in the iron matrix is preferentially degraded to generate calcium ions and sulfate ions, and the calcium ions are easily ionized with water to generate OH-The reaction forms calcium hydroxide precipitate, thus breaking the ionization balance of water, and H generated by water ionization+An acid environment is formed, and the acid environment can neutralize the alkaline environment (OH) generated by the degradation of the iron matrix-) And can directly corrode iron matrix; in addition, the non-metallurgical bonding between the ceramic and the metal and the gaps left by the degradation of the calcium sulfate can increase the exposed area of the iron matrix in the corrosive liquid, and the degradation of the iron-based implant is greatly accelerated by the combined action of multiple factors. Meanwhile, the laser processing has the characteristics of concentrated energy, small heat affected zone, rapid melting and rapid solidification, and can avoid calcium sulfate in an iron matrixThe decomposition in the melting process ensures the structure and chemical stability of the calcium sulfate, and the rapid solidification of the laser melting pool is also beneficial to the uniform dispersion of the calcium sulfate and avoids agglomeration, thereby achieving the purpose of eliminating local corrosion. Calcium sulfate as bioactive ceramic widely used in clinic can be completely degraded in vivo and absorbed by cell tissue or metabolized out of body, and has excellent biocompatibility and osteoinduction effect. The high calcium environment formed by degradation is beneficial to the rapid nucleation and growth of bone-like apatite on the one hand, so that the bone combination is formed with surrounding tissues, and on the other hand, the calcium channel receptor expression on the surface of a cell membrane is changed, so that the proliferation and differentiation of osteocytes are promoted, the repair of the osteocytes is induced efficiently, and the biological activity of the iron-based implant is further improved greatly. Meanwhile, after optimization, the invention can reasonably control the degradation speed of the iron-based implant in a living body; avoid the generation of toxicity caused by too fast degradation.
In the optimization scheme of the invention, the dosage and granularity of calcium sulfate must be strictly controlled, because calcium sulfate is a ceramic material, the surface tension of powder is large, the fluidity is poor, and a plurality of particles are accumulated together, so that the particles are easy to agglomerate in an iron matrix when the content is too high, the forming performance of the iron-based implant is reduced, even serious local corrosion is caused, and the implant fails in service; if the amount of the additive is too low, the effect of improving the degradation of the iron matrix is limited, and the use requirement cannot be met. Meanwhile, the excessive granularity of the calcium sulfate can cause the calcium sulfate to be distributed in an iron matrix concentratedly, and a uniform degradation mode is difficult to obtain; while too small a particle size increases the technical requirements and costs of dispersion and even agglomerates can result in localized corrosion.
In the optimization scheme of the invention, the ball milling and the control of laser process parameters are the key to solve the problem of calcium sulfate agglomeration. According to the invention, the ball milling process parameters can realize uniform distribution of calcium sulfate powder in iron powder, and when the ball milling parameters exceed the range of the invention, the calcium sulfate powder can be dispersed unevenly to cause agglomeration, or the shape and properties of the powder can be changed, so that the degradation behavior and the bioactivity of the iron-based implant are influenced. The main parameters in the laser melting process are the laser power: when the laser power is too high, a heat affected zone is enlarged, so that the melting amount of iron powder is increased, and calcium sulfate floats upwards in liquid-phase iron and is aggregated together due to low density and high density of calcium sulfate, so that the molding surface is rough and the molding quality is poor; the laser power is too low, and the iron powder can not be completely melted, so that particle inclusion is easily caused, and even the molding can not be realized.
In addition, other parameters of the laser process, such as the diameter of a laser spot and the scanning speed, must be strictly controlled, and the proper laser process parameters can avoid the chemical property change and the structural damage of the calcium sulfate.
Compared with the prior art, the invention has the following advantages:
(1) in the invention, the calcium sulfate is dispersed in the iron matrix and degraded to generate an acidic environment (H)+)，H+Can neutralize alkaline environment (OH) generated by iron matrix degradation-) And the degradation of the iron-based implant is accelerated.
(2) In the invention, the calcium sulfate is dispersed in the iron matrix and degraded to generate an acidic environment (H)+) Can directly corrode the iron matrix, thereby achieving the purpose of secondarily accelerating the degradation of the iron-based implant.
(3) In the invention, the calcium sulfate has good biocompatibility and bone induction performance, the biological activity of the iron-based implant can be obviously improved, and the calcium ions generated after degradation can accelerate bone healing.
(4) According to the invention, the iron-based implant can be naturally corroded and decomposed in vivo, disappears after reaching the treatment effect, and avoids the defect that the traditional implants such as stainless steel, titanium alloy and the like need to be taken out after the tissue is healed through a secondary operation.
(5) In the invention, the calcium sulfate is embedded in the iron matrix, so that the mechanical property of the iron matrix can be properly reduced, and the side effect generated by stress shielding is reduced.
Drawings
FIG. 1 surface topography after 20 days of immersion in example 1;
FIG. 2 surface topography after 20 days of immersion in example 2;
FIG. 3 surface profile after 20 days of immersion in comparative example 1;
figure 4 surface profile after 20 days of soaking in comparative example 4.
Detailed Description
Example 1
Calcium sulfate powder (the granularity is 3-10 mu m) and iron powder (the granularity is 30-40 mu m) are adopted as raw materials, and the weight ratio of the calcium sulfate powder to the iron powder is 8: 92 weight ratio of 8g of calcium sulfate powder and 92g of iron powder; under the protection of argon, mechanically stirring and mixing iron powder and calcium sulfate powder for 30 minutes, and then stirring, ball-milling and mixing for 100 minutes to obtain uniformly dispersed iron-calcium sulfate mixed powder; the uniformly dispersed iron-calcium sulfate mixed powder is used as a raw material, a selective laser melting process is adopted, the laser power is 100W, the diameter of a laser spot is 0.1mm, the scanning speed is 50mm/s, and the iron-based implant is obtained after melting and solidification under the protection of argon.
The implementation effect is as follows: the prepared iron-based implant is tested, calcium sulfate is uniformly dispersed in an iron matrix, after the iron-based implant is soaked in a human body simulation body liquid for 20 days, the degradation rate is calculated to be 0.29mm/y, the surface of the implant is uniformly corroded and is relatively flat, and meanwhile, a large amount of bone-like apatite is formed on the surface (figure 1); cell culture experiments found that MG-63 cells had better morphology and increased cell numbers on the iron-based implant compared to pure iron.
Example 2
Calcium sulfate powder (the granularity is 3-10 mu m) and iron powder (the granularity is 30-40 mu m) are adopted as raw materials, and the weight ratio of the raw materials is 3: 97 3g of calcium sulfate powder and 97g of iron powder are weighed according to the mass ratio; under the protection of argon, mechanically stirring and mixing iron powder and calcium sulfate powder for 30 minutes, and then stirring, ball-milling and mixing for 100 minutes to obtain uniformly dispersed iron-calcium sulfate mixed powder; the uniformly dispersed iron-calcium sulfate mixed powder is used as a raw material, a selective laser melting process is adopted, the laser power is 100W, the diameter of a laser spot is 0.1mm, the scanning speed is 50mm/s, and the iron-based implant is obtained after melting and solidification under the protection of argon.
The implementation effect is as follows: testing the prepared iron-based implant, and finding that calcium sulfate is uniformly dispersed in an iron matrix, the calculated degradation rate is 0.14mm/y after the iron-based implant is soaked in a human body simulation body liquid for 20 days, the surface of the implant is uniformly corroded and is relatively flat, and meanwhile, more bone-like apatite is formed on the surface (figure 2); cell culture experiments found that MG-63 cells had better morphology and significantly increased cell numbers on the iron-based implant compared to pure iron.
Example 3
Calcium sulfate powder (the granularity is 3-10 mu m) and iron powder (the granularity is 30-40 mu m) are adopted as raw materials, and the weight ratio of the calcium sulfate powder to the iron powder is 8: 92 weight ratio of 8g of calcium sulfate powder and 92g of iron powder; under the protection of argon, mechanically stirring and mixing iron powder and calcium sulfate powder for 30 minutes, and then stirring, ball-milling and mixing for 100 minutes to obtain uniformly dispersed iron-calcium sulfate mixed powder; the uniformly dispersed iron-calcium sulfate mixed powder is used as a raw material, a selective laser melting process is adopted, the laser power is 120W, the laser spot diameter is 0.1mm, the scanning speed is 50mm/s, and the iron-based implant is obtained after melting and solidification under the protection of argon.
The implementation effect is as follows: the prepared iron-based implant is tested, and calcium sulfate is found to be uniformly dispersed in an iron matrix, after the iron-based implant prepared by the method is soaked in human body simulation body liquid for 20 days, the calculated degradation rate is 0.21mm/y, the surface of the implant is uniformly corroded, and meanwhile, a large amount of bone-like apatite is formed on the surface; cell culture experiments found that MG-63 cells had better morphology and increased cell numbers on the iron-based implant compared to pure iron.
Example 4
Calcium sulfate powder (the granularity is 3-10 mu m) and iron powder (the granularity is 30-40 mu m) are adopted as raw materials, and the weight ratio of the calcium sulfate powder to the iron powder is 8: 92 weight ratio of 8g of calcium sulfate powder and 92g of iron powder; under the protection of argon, mechanically stirring and mixing iron powder and calcium sulfate powder for 20 minutes, and then stirring, ball-milling and mixing for 90 minutes to obtain uniformly dispersed iron-calcium sulfate mixed powder; the uniformly dispersed iron-calcium sulfate mixed powder is used as a raw material, a selective laser melting process is adopted, the laser power is 100W, the diameter of a laser spot is 0.1mm, the scanning speed is 50mm/s, and the iron-based implant is obtained after melting and solidification under the protection of argon.
The implementation effect is as follows: testing the prepared iron-based implant, finding that calcium sulfate is uniformly dispersed in an iron matrix, and after the iron matrix is soaked in a human body simulation body liquid for 20 days, calculating to obtain that the degradation rate is 0.26mm/y, the surface of the implant is uniformly corroded, and meanwhile, a large amount of bone-like apatite is formed on the surface; cell culture experiments found that MG-63 cells had better morphology and increased cell numbers on the iron-based implant compared to pure iron.
In the process of developing the technology of the invention, the following schemes (such as comparative example 1, comparative example 2 and comparative example 3) are also tried, but the performance of the obtained product is far worse than that of the examples.
Comparative example 1
The other conditions were the same as in example 1 except that: according to the following steps of 20: 80 weight ratio 20g calcium sulfate and 80g iron powder were weighed to obtain an iron-based implant. The detection shows that the calcium sulfate is seriously agglomerated, the calcium sulfate hinders the bonding of liquid-phase iron in the selective laser melting process, the obtained iron-based implant has poor forming performance, and after the iron-based implant is soaked in human body simulation body liquid for 20 days, the degradation rate is calculated to be 0.40mm/y, but the corroded surface is uneven and serious corrosion pits appear (figure 3). Although osteoid apatite is also formed, the distribution is uneven, and too fast degradation results in cell morphology and proliferation rate that are substantially equal to pure iron.
Comparative example 2
The other conditions were the same as in example 1 except that: according to the weight ratio of 0.2: 99.8 weight ratio 0.2g calcium sulfate and 99.8g iron powder were weighed to obtain an iron-based implant. After the artificial body is soaked in the human body simulated body liquid for 20 days, the degradation rate is calculated to be 0.08mm/y, and compared with the degradation rate of pure iron, the degradation rate has no significant difference. A small amount of bone-like apatite appears on the corroded surface, and compared with pure iron, the shape of cells is similar and the number of the cells is slightly increased.
Comparative example 3
The other conditions were the same as in example 1 except that: the laser power is 180W, and the iron-based implant is obtained. Tests have found that the iron powder is fully fused but the calcium sulphate is decomposed. After the artificial body is soaked in the human body simulated body liquid for 20 days, the corroded surface is smooth, the degradation rate is calculated to be 0.10mm/y, and the degradation rate is not significantly different compared with that of pure iron. Meanwhile, a small amount of bone-like apatite is formed on the surface, and compared with pure iron, the shape of cells is similar and the number of the cells is slightly increased.
Comparative example 4
The other conditions were the same as in example 1 except that: the particle size of the calcium sulfate powder was 40 μm, and an iron-based implant was obtained. Tests show that the calcium sulfate with too large particle size is distributed and concentrated in an iron matrix, obvious gaps appear at the interface, and after the iron matrix is soaked in human simulated body fluid for 20 days, the degradation rate is calculated to be 0.18mm/y, but the corrosion surface is not uniform and a small amount of corrosion pits appear (figure 4). Although the osteoid apatite is also formed, the distribution is uneven, and the cell morphology and the proliferation rate are not significantly different from those of pure iron.
As can be seen from example 1 and comparative examples 1, 2, 3 and 4, the components and preparation process of the present invention are an organic whole, and the effect is significantly reduced when any one or more of the key parameters is out of the scope of the present invention. The inherent comparison of examples 1, 2, 3 and 4 of the present invention shows that the preferred embodiment of the present invention has unexpected effects.
Claims (8)
1. A method for synchronously improving the degradation rate and the bioactivity of an iron-based implant is characterized in that: the iron-based implant comprises the following components in percentage by mass:
0.5 to 12 percent of calcium sulfate;
88 to 99.5 percent of iron;
the method comprises the following steps:
step one
Under a protective atmosphere; uniformly mixing iron powder and calcium sulfate powder which are proportioned according to a certain proportion; obtaining mixed powder;
step two
And (3) taking the mixed powder obtained in the step one as a raw material, and preparing the iron-based implant through selective laser melting, wherein during selective laser melting, the laser power is controlled to be 80-120W, the laser spot diameter is controlled to be 0.1-0.3mm, and the scanning speed is controlled to be 40-80 mm/s.
2. The method of claim 1, wherein the iron-based implant is one of an iron-based implant and a dental implant; the iron-based implant comprises the following components in percentage by mass:
5-10% of calcium sulfate;
the iron content is 90-95%.
3. The method of claim 2, wherein the iron-based implant is one of an iron-based implant and a dental implant; the iron-based implant comprises the following components in percentage by mass:
7-8.5% of calcium sulfate;
the iron content is 91.5-93%.
4. A method for simultaneously increasing the degradation rate and bioactivity of an iron-based implant according to claim 3, wherein; the iron-based implant comprises the following components in percentage by mass:
8 percent of calcium sulfate;
the iron content is 92%.
5. A method for simultaneously increasing the degradation rate and bioactivity of an iron-based implant according to any one of claims 1-4, wherein: in the iron-based implant, calcium sulfate is uniformly distributed in the iron-based implant in a particle form; the particle size of the calcium sulfate particles is 1-10 μm.
6. The method of claim 1, wherein the iron-based implant is one of: in the first step, the iron powder and the calcium sulfate powder are mechanically stirred and mixed for 20-40 minutes according to a certain proportion, and then are stirred, ball-milled and mixed for 90-120 minutes to obtain uniformly dispersed iron-calcium sulfate mixed powder.
7. The method of claim 1, wherein the iron-based implant is one of: the particle size of the iron powder is 30-50 mu m, and the particle size of the calcium sulfate powder is 1-10 mu m.
8. The method of claim 1, wherein the iron-based implant is one of: the selective laser melting is carried out under a protective atmosphere.
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| CN110699607B (en) * | 2019-10-22 | 2021-08-27 | 中南大学 | Bio-iron-based alloy with optimized tissue structure and accelerated degradation and preparation method thereof |
| CN112024895B (en) * | 2020-09-08 | 2023-01-24 | 江西理工大学南昌校区 | Preparation method of iron-calcium chloride biological composite material |
| CN116328024A (en) * | 2021-12-22 | 2023-06-27 | 湖南理工学院 | Method for compact forming of large-section bone defect implant with low melting point |
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