CN112139489A - Preparation method of iron-tantalum pentoxide biological composite material - Google Patents
Preparation method of iron-tantalum pentoxide biological composite material Download PDFInfo
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- CN112139489A CN112139489A CN202011033138.3A CN202011033138A CN112139489A CN 112139489 A CN112139489 A CN 112139489A CN 202011033138 A CN202011033138 A CN 202011033138A CN 112139489 A CN112139489 A CN 112139489A
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- tantalum pentoxide
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- SUZZQRICJWPHQC-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].O.[Fe+2].[Ta+5] Chemical compound [O-2].[O-2].[O-2].[OH-].O.[Fe+2].[Ta+5] SUZZQRICJWPHQC-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 163
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 47
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011812 mixed powder Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000000875 high-speed ball milling Methods 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 238000010309 melting process Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011173 biocomposite Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002114 nanocomposite Substances 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 65
- 230000007797 corrosion Effects 0.000 abstract description 41
- 238000005260 corrosion Methods 0.000 abstract description 41
- 239000011159 matrix material Substances 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 26
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- 238000004088 simulation Methods 0.000 description 12
- 238000002791 soaking Methods 0.000 description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 11
- 239000012620 biological material Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 210000001124 body fluid Anatomy 0.000 description 6
- 239000010839 body fluid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000009818 osteogenic differentiation Effects 0.000 description 3
- 229910001460 tantalum ion Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000003462 bioceramic Substances 0.000 description 2
- 238000010349 cathodic reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000004821 effect on bone Effects 0.000 description 1
- 235000020774 essential nutrients Nutrition 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of an iron-tantalum pentoxide biological composite material, which comprises the following steps: carrying out high-speed ball milling on iron powder and tantalum pentoxide powder in a protective atmosphere (Ar) to obtain uniform mixed powder; the mixed powder was dried under vacuum (120 ℃); the iron-tantalum pentoxide biological composite material is obtained by taking mixed powder after vacuum drying as a raw material and adopting a selective laser melting process in a protective atmosphere (Ar). The invention makes the iron-tantalum pentoxide biological composite material quickly solidify through the selective laser melting process with specific parameters and extremely high cooling rate, is beneficial to further uniformizing the dispersion of the tantalum pentoxide in the iron matrix, and can uniformize the surface corrosion of the iron matrix in the corrosion process so as to ensure the good mechanical property of the iron matrix. On the other hand, the SLM technology has high processing flexibility, and can obtain iron-based composite materials with complex structures for clinical applications.
Description
Technical Field
The invention belongs to the technical field of biological material preparation, and particularly relates to an iron-tantalum pentoxide biological material accelerated in degradation by microscopic galvanic corrosion and microscale oxidation acceleration and a preparation method thereof.
Background
The degradable metal not only has excellent comprehensive mechanical property, but also can be absorbed by human body and has promotion effect on bone regeneration. The degradable metal changes the traditional idea that people usually use the metal implant as a biological inert material, and skillfully utilizes the corrosion characteristic of the degradable metal to realize the purpose that the metal implant gradually degrades in vivo until finally disappears. Iron, a representative degradable metal, is an essential nutrient element in the human body, not only participates in various metabolic processes, but also maintains the structure and function of bone cells, has good biocompatibility, and thus has received great attention in the field of artificial bones. However, iron has good mechanical properties, but the degradation rate is too slow, and the iron can hinder the growth of new bones when used as an implant, which seriously hinders the application of iron metal in artificial bones.
Alloying (e.g., Mn, Pd, Ag, etc.) is currently considered a common method of regulating the rate of iron degradation. However, the above alloying elements often present cytotoxicity problems. The other strategy is to prepare the iron-based composite material by utilizing the bioceramic with good degradation performance, and the principle is to utilize the bioceramic to preferentially degrade in an iron matrix to leave a large number of pores, so that the contact area of the iron matrix and body fluid is increased, and the degradation is accelerated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the iron-tantalum pentoxide biological material which is accelerated in micro galvanic corrosion and micro-scale oxidation so as to accelerate degradation and the preparation method thereof. The iron-tantalum pentoxide biological composite material prepared by the method can react with iron oxidation products in a body fluid environment to generate Ta/Fe oxide, the oxide can form a micro battery with an iron matrix, the specific surface of the oxide is relatively rough, the corrosion speed is increased on a micro scale, and the degradation of the iron matrix is accelerated in such a way.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing an iron-tantalum pentoxide biocomposite material, comprising the steps of:
firstly, carrying out high-speed ball milling on iron powder and tantalum pentoxide powder under a protective atmosphere to obtain uniform mixed powder;
step two, drying the mixed powder in vacuum;
and step three, taking the mixed powder after vacuum drying as a raw material, and obtaining the iron-tantalum pentoxide biological composite material by adopting a selective laser melting process in a protective atmosphere.
Preferably, the iron powder is in a trapezoid shape, the particle size is 15-50 mu m, and the particle size of the tantalum pentoxide powder is 10-30 mu m; the inventor finds that the particle size of tantalum pentoxide powder has a great influence on the performance of a final material, and if the particle size is too large, the formed iron-tantalum pentoxide biological composite material is unevenly doped, so that the forming quality is influenced, uneven corrosion is caused during corrosion, and the mechanical property of an iron matrix is reduced;
preferably, in the step one, the rotation speed of the high-speed ball milling is 280-300 rad/min, and the ball milling time is 2-5 h.
Preferably, in the second step, the temperature of vacuum drying is 120-130 ℃, and the drying time is 12-15 h.
Preferably, in the third step, the process parameters of the selective laser melting process are as follows: the laser power is controlled to be 120-140W, the scanning speed is 10-200 mm/s, the diameter of a light spot is controlled to be 60-80 mu m, the temperature of a molten pool is controlled to be 1560-1700 ℃, the scanning interval is 0.05-0.08 mm, and the powder spreading thickness is 0.1-0.2 mm.
Preferably, the specific process of the first step is as follows: introducing inert gas Ar into the ball milling tank until the pressure in the ball milling tank is 1.5MPa, releasing mixed gas in the ball milling tank through the gas valve, and repeating for three times to control H2O and O2For concentration purposes, ball milling is then performed.
Preferably, in the first step, the mass ratio of the tantalum pentoxide powder to the iron powder is 0.05-0.08: 0.92-0.95.
Preferably, the protective atmosphere in the first step and the third step is high-purity argon with the purity of 99.999 percent.
In the invention, iron powder (purity > 99.9%) and tantalum pentoxide powder are mixed by high-speed ball milling, and uniform dispersion of the tantalum pentoxide powder can be promoted by optimized selection of ball milling process and parameters. When the ball milling process and parameters are not in the selected range, a more serious powder agglomeration phenomenon occurs, so that the uniform dispersion of the doped phase is hindered, and the molding quality is further influenced; or impurities are introduced, so that the biocompatibility of the iron-tantalum pentoxide biological composite material is damaged, and the mechanical property and the degradation property of the alloy are also damaged.
The invention obtains a micro galvanic corrosion and micro-scale oxidation acceleration and thus accelerated degradation iron-tantalum pentoxide biomaterial by a Selective Laser Melting (SLM) technology; the subphase relation of tantalum pentoxide is 1200 ℃, and when the temperature is lower than the solidus temperature, the tantalum pentoxide can easily react with ferric oxide and ferrous oxide generated by the corrosion of an iron substrate to generate Ta/Fe oxide, and the oxides comprise: fe4TaO9/ FeTaO4/ Fe3Ta2O8/ FeTaO6Having a rough specific surface area, capable of promoting contact of body fluids with the iron matrix, resulting in a micro-scale oxidation rateIncreasing; on the other hand, Ta/Fe oxide generated by the reaction of tantalum pentoxide with ferric oxide and ferrous oxide can form galvanic corrosion with an iron substrate, the iron substrate serves as an anode, and the Ta/Fe oxide serves as a cathode, so that the corrosion of iron is further accelerated, meanwhile, the Ta/Fe oxide is poorer in corrosion resistance than ferric oxide and ferric oxide, and in conclusion, the addition of the tantalum pentoxide can accelerate the degradation of the iron substrate; in addition, the release of tantalum ions can improve the biocompatibility of the iron matrix as a biomaterial and promote osteogenic differentiation. On the other hand, the iron metal is rapidly solidified by utilizing the extremely high cooling rate of the SLM technology, and the tantalum pentoxide is uniformly dispersed in the iron matrix, so that a uniform corrosion mode is realized.
In the invention, the energy of ball milling is controlled to fully mix the iron-tantalum pentoxide biological composite material through a high-speed ball milling process, which is one of the keys of the iron-tantalum pentoxide biological material that the micro galvanic corrosion and the micro-scale oxidation are accelerated to accelerate the degradation, so that the control of the high-speed ball milling speed and the ball-to-material ratio is crucial in the forming process, the melting point of the tantalum pentoxide is very close to the melting point of the iron, the selection of the laser energy density is relatively easy, but the excessive ball milling energy can cause the powder welding, the powder flowability is reduced, the too small centrifugal rotating force is insufficient, the powder cannot be uniformly mixed and dispersed, the forming quality of the iron-tantalum pentoxide biological composite material can be influenced, the optimal ball-to-material ratio and the rotating speed are regulated, and the tantalum pentoxide can be fully mixed in an iron matrix, thereby finally accelerating the corrosion speed of the iron-tantalum pentoxide biological composite material.
The invention at least comprises the following beneficial effects:
(1) the invention adopts the technology of mixing iron and tantalum pentoxide powder by high-speed ball milling and compounding the tantalum pentoxide into an iron matrix by a Selective Laser Melting (SLM) technology for the first time to obtain the iron-tantalum pentoxide biological material which is accelerated in micro galvanic corrosion and micro-scale oxidation and thus accelerated in degradation. The subphase relation of the tantalum pentoxide is 1200 ℃, and when the temperature is lower than the solidus temperature, the tantalum pentoxide can easily react with ferric oxide and ferrous oxide generated by the corrosion of an iron substrate to generateTa/Fe oxides, these oxides being: fe4TaO9/ FeTaO4/ Fe3Ta2O8/ FeTaO6The material has rough specific surface area, can promote the contact of body fluid and an iron matrix, and leads to the increase of the micro-scale oxidation rate; on the other hand, Ta/Fe oxide generated by the reaction of tantalum pentoxide with ferric oxide and ferrous oxide can form galvanic corrosion with an iron substrate, the iron substrate serves as an anode, and the Ta/Fe oxide serves as a cathode, so that the corrosion of iron is further accelerated, meanwhile, the Ta/Fe oxide is poorer in corrosion resistance than ferric oxide and ferric oxide, and in conclusion, the addition of the tantalum pentoxide can accelerate the degradation of the iron substrate; in addition, the release of tantalum ions can improve the biocompatibility of the iron matrix as a biomaterial and promote osteogenic differentiation.
(2) The invention controls the energy of ball milling to fully mix the iron-tantalum pentoxide biological composite material through a high-speed ball milling process, is beneficial to further uniformizing the dispersion of the tantalum pentoxide in an iron matrix, and can uniformize the surface corrosion of the iron matrix in the corrosion process so as to ensure the good mechanical property and uniform corrosion of the iron matrix. On the other hand, the SLM technology has high processing flexibility, and can obtain iron-based composite materials with complex structures for clinical applications.
(3) The iron-tantalum pentoxide biological composite material provided by the invention has good biocompatibility and excellent mechanical property, the degradation behavior is improved, the corrosion rate of the environment in body fluid is higher, and in addition, the existence of tantalum can improve the biocompatibility of an iron matrix and promote bone differentiation to a certain extent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an SEM image of pure iron and iron-tantalum pentoxide biocomposites prepared in example 3 of the present invention;
FIG. 2 is a microscope image of an iron-tantalum pentoxide biocomposite prepared in example 3 of the present invention;
FIG. 3 is a graph of electrochemical testing (taf curve) of pure iron of the present invention and iron-tantalum pentoxide biocomposites prepared in example 3;
the specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of an iron-tantalum pentoxide biological composite material comprises the following steps:
step one, 0.6g of tantalum pentoxide powder (purity)>99.9%, average particle diameter 20 μm) and 9.4 g of iron powder (purity)>99.9 percent and the average grain diameter is 35 mu m), placing the mixture in a ball mill, introducing inert gas Ar into a ball milling tank until the pressure in the tank is 1.5MPa, then releasing mixed gas in the tank through a gas valve, and repeating the steps for three times to control H2O and O2And (3) performing ball milling for concentration, wherein the set rotating speed is 280 rad/min, and the ball-to-material ratio is 30: 1, ball milling for 2 hours to obtain uniformly dispersed mixed powder;
step two, drying the mixed powder in vacuum at the temperature of 120 ℃ for 13 h;
and step three, under the protection of high-purity argon with the purity of 99.999 percent, preparing the iron-tantalum pentoxide biological composite material by utilizing an SLM process under the parameters of 120W of laser power, 50mm/s of scanning speed, 1560 ℃ of controlled molten pool temperature, 70 mu m of light spot diameter, 0.07mm of scanning interval and 0.1 mm of powder laying thickness.
The observation of the powder appearance shows that the powder is uniformly mixed without welding phenomenon, and the particles of the powder are slightly deformed;
microstructure tests show that the tantalum pentoxide is uniformly dispersed on an iron matrix, the aggregation of the tantalum pentoxide is not detected, but the forming compactness is insufficient, and weak spheroidization is caused; and in an electrochemical workstation, a human body simulation solution is used as an electrolyte, electrochemical tests are carried out on the pure iron and the prepared iron-tantalum pentoxide biological composite material, and the corrosion potential of the iron-tantalum pentoxide biological composite material is-0.81V.
Carrying out a human body simulation liquid soaking experiment on pure iron and the prepared iron-tantalum pentoxide biological composite material, wherein the volume ratio of a soaked material (the pure iron or the prepared iron-tantalum pentoxide biological composite material) to the human body simulation liquid is 1: 6; the soaking temperature is 37 ℃, and after soaking for 28 ℃, the corrosion rate is calculated to be 0.18 mm/year;
the prepared iron-tantalum pentoxide biological composite material is subjected to mechanical property test, and the tensile strength is 882MPa and the compressive strength is 2002 MPa.
Example 2:
a preparation method of an iron-tantalum pentoxide biological composite material comprises the following steps:
step one, 0.6g of tantalum pentoxide powder (purity)>99.9%, average particle diameter 20 μm) and 9.4 g of iron powder (purity)>99.9 percent and the average grain diameter is 35 mu m), placing the mixture in a ball mill, introducing inert gas Ar into a ball milling tank until the pressure in the tank is 1.5MPa, then releasing mixed gas in the tank through a gas valve, and repeating the steps for three times to control H2O and O2And (3) performing ball milling for concentration, wherein the rotating speed is set to be 300 rad/min, and the ball-to-material ratio is 20: 1, ball milling for 3 hours to obtain uniformly dispersed mixed powder;
step two, drying the mixed powder in vacuum at the temperature of 120 ℃ for 13 h;
and step three, under the protection of high-purity argon with the purity of 99.999 percent, preparing the iron-tantalum pentoxide biological composite material by utilizing an SLM (selective laser melting) process under the parameters of 130W of laser power, 50mm/s of scanning speed, 1640 ℃ of controlled molten pool temperature, 70 mu m of light spot diameter, 0.07mm of scanning interval and 0.1 mm of powder paving thickness.
The appearance of the powder is observed, the powder is uniformly mixed, the welding phenomenon is avoided, and the particles of the powder are refined;
microstructure tests found that tantalum pentoxide was uniformly dispersed on the iron substrate, and no aggregation of tantalum pentoxide was detected; in an electrochemical workstation, a human body simulation solution is used as an electrolyte, electrochemical tests are carried out on pure iron and the prepared iron-tantalum pentoxide biological composite material, and the corrosion potential of the iron-tantalum pentoxide biological composite material is-0.90V.
Carrying out a human body simulation liquid soaking experiment on pure iron and the prepared iron-tantalum pentoxide biological composite material, wherein the volume ratio of a soaked material (the pure iron or the prepared iron-tantalum pentoxide biological composite material) to the human body simulation liquid is 1: 6; the soaking temperature is 37 ℃, and after soaking for 28 ℃, the corrosion rate is calculated to be 0.20 mm/year;
the prepared iron-tantalum pentoxide biological composite material is subjected to mechanical property test, wherein the tensile strength is 879MPa, and the compressive strength is 1997 MPa.
Example 3:
a preparation method of an iron-tantalum pentoxide biological composite material comprises the following steps:
step one, 0.6g of tantalum pentoxide powder (purity)>99.9%, average particle diameter 20 μm) and 9.4 g of iron powder (purity)>99.9 percent and the average grain diameter is 35 mu m), placing the mixture in a ball mill, introducing inert gas Ar into a ball milling tank until the pressure in the tank is 1.5MPa, then releasing mixed gas in the tank through a gas valve, and repeating the steps for three times to control H2O and O2And (3) performing ball milling for concentration, wherein the set rotating speed is 300 rad/min, and the ball-to-material ratio is 30: 1, ball milling for 3 hours to obtain uniformly dispersed mixed powder;
step two, drying the mixed powder in vacuum at the temperature of 120 ℃ for 13 h;
and step three, under the protection of high-purity argon with the purity of 99.999 percent, preparing the iron-tantalum pentoxide biological composite material by utilizing an SLM (selective laser melting) process under the parameters of 130W of laser power, 50mm/s of scanning speed, 1640 ℃ of controlled molten pool temperature, 70 mu m of light spot diameter, 0.07mm of scanning interval and 0.1 mm of powder paving thickness.
The iron-tantalum pentoxide nanocomposite and pure iron powder prepared in this example were pretreated: preparing a plurality of deionized water and 65% nitric acid solution, and preparing a nitric acid solution with four percent concentration as a corrosive solution; then polishing an experimental sample (an iron-tantalum pentoxide biological composite material and pure iron), wiping a polished surface of the experimental sample with corrosive liquid, washing away residual nitric acid solution with alcohol, observing the distribution of the mixed phase tantalum pentoxide under a metallographic microscope (as shown in figure 2), and finally searching a corroded part of a light microscope under SEM (scanning electron microscope) to observe whether the distribution of the tantalum pentoxide is uniform or not and whether agglomeration occurs or not (as shown in figure 1) by BSEM (scanning electron microscope); microstructure tests show that the tantalum pentoxide is uniformly dispersed on the iron matrix, and no aggregation of the tantalum pentoxide is detected;
at an electrochemical workstation, a human body simulation solution is used as an electrolyte, an electrochemical test is carried out on pure iron and the prepared iron-tantalum pentoxide biological composite material (as shown in figure 3), and the corrosion potential is reduced to-0.93V by adding the tantalum pentoxide. From the polarized cathodic reaction curve (taf polarized curve), it was found that the cathodic reaction rate of the iron-tantalum pentoxide biocomposite was significantly increased after addition of tantalum pentoxide; according to the taf polarization curve, the corrosion potentials of the pure iron and the biological composite material added with the tantalum pentoxide are-0.81 v and-0.93 v respectively, curve fitting is carried out on the cathode area on the left side and the anode passivation area on the right side respectively, the corrosion current densities of the two curves are obtained, and the corrosion current density of the pure iron is 7.5 muA/cm as shown in figure 32The corrosion current density of the biological composite material added with the tantalum pentoxide is 20.3 muA/cm2。
Carrying out a human body simulation liquid soaking experiment on pure iron and the prepared iron-tantalum pentoxide biological composite material, wherein the volume ratio of a soaked material (the pure iron or the prepared iron-tantalum pentoxide biological composite material) to the human body simulation liquid is 1: 6; the soaking temperature is 37 ℃, and after soaking for 28 ℃, the corrosion rate is calculated to be 0.24 mm/year;
in the present invention, the subphase relationship of tantalum pentoxide is 1200 ℃, and at a temperature lower than the solidus temperature, tantalum pentoxide can easily react with iron oxide and ferrous oxide generated by the corrosion of an iron substrate to generate Ta/Fe oxides, which are: fe4TaO9/ FeTaO4/ Fe3Ta2O8/ FeTaO6Has rough specific surface area, and can promoteContact of body fluids with the iron matrix, resulting in an increase in the rate of micro-scale oxidation; on the other hand, Ta/Fe oxide generated by the reaction of tantalum pentoxide with ferric oxide and ferrous oxide can form galvanic corrosion with an iron substrate, the iron substrate serves as an anode, and the Ta/Fe oxide serves as a cathode, so that the corrosion of iron is further accelerated, meanwhile, the Ta/Fe oxide is poorer in corrosion resistance than ferric oxide and ferric oxide, and in conclusion, the addition of the tantalum pentoxide can accelerate the degradation of the iron substrate; in addition, the release of tantalum ions can improve the biocompatibility of the iron matrix as a biomaterial and promote osteogenic differentiation.
The prepared iron-tantalum pentoxide biological composite material is subjected to mechanical property test, and the tensile strength is 880MPa and the compressive strength is 2000 MPa.
Example 4:
a preparation method of an iron-tantalum pentoxide biological composite material comprises the following steps:
step one, 0.6g of tantalum pentoxide powder (purity)>99.9%, average particle diameter 2 μm) and 9.4 g of iron powder (purity)>99.9 percent and the average grain diameter is 35 mu m), placing the mixture in a ball mill, introducing inert gas Ar into a ball milling tank until the pressure in the tank is 1.5MPa, then releasing mixed gas in the tank through a gas valve, and repeating the steps for three times to control H2O and O2And (3) performing ball milling for concentration, wherein the set rotating speed is 300 rad/min, and the ball-to-material ratio is 30: 1, ball milling for 5 hours to obtain uniformly dispersed mixed powder;
step two, drying the mixed powder in vacuum at the temperature of 120 ℃ for 13 h;
and step three, under the protection of high-purity argon with the purity of 99.999 percent, preparing the iron-tantalum pentoxide biological composite material by utilizing an SLM (selective laser melting) process under the parameters of 130W of laser power, 50mm/s of scanning speed, 1640 ℃ of controlled molten pool temperature, 70 mu m of light spot diameter, 0.07mm of scanning interval and 0.1 mm of powder paving thickness.
The observation of the powder morphology shows that the powder is uniformly mixed, but due to the problem of the ball milling time, the powder is partially flaky, the flowability is poor, and the size of the powder particles is increased because the powder particles are flaky;
microstructure analysis finds that the doped tantalum pentoxide is not uniformly dispersed, and a plurality of tantalum pentoxide agglomerate, so that the molding quality is poor and a plurality of air holes exist; and in an electrochemical workstation, a human body simulation solution is used as an electrolyte, electrochemical tests are carried out on the pure iron and the prepared iron-tantalum pentoxide biological composite material, and the corrosion potential of the iron-tantalum pentoxide biological composite material is-0.93V.
Carrying out a human body simulation liquid soaking experiment on pure iron and the prepared iron-tantalum pentoxide biological composite material, wherein the volume ratio of a soaked material (the pure iron or the prepared iron-tantalum pentoxide biological composite material) to the human body simulation liquid is 1: 6; the soaking temperature is 37 ℃, and after soaking for 28 ℃, the corrosion rate is calculated to be 0.24 mm/year;
the prepared iron-tantalum pentoxide biological composite material is subjected to mechanical property test, and the tensile strength is 653MPa, and the compressive strength is 1500 MPa.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (8)
1. A preparation method of an iron-tantalum pentoxide biological composite material comprises the following steps:
firstly, carrying out high-speed ball milling on iron powder and tantalum pentoxide powder in a protective atmosphere (Ar) to obtain uniform mixed powder;
step two, drying the mixed powder in vacuum (120 ℃);
and step three, taking the mixed powder after vacuum drying as a raw material, and obtaining the iron-tantalum pentoxide biological composite material by adopting a selective laser melting process in a protective atmosphere (Ar).
2. The method for preparing the iron-tantalum pentoxide biocomposite material according to claim 1, wherein the iron powder is trapezoid, the particle size is 15-50 μm, and the particle size of the tantalum pentoxide powder is 10-30 μm.
3. The preparation method of the iron-tantalum pentoxide nanocomposite material according to claim 1, wherein in the first step, the rotation speed of the high-speed ball milling is 260-300 rad/min, and the ball milling time is 2-4 h.
4. The preparation method of the iron-tantalum pentoxide biological composite material as claimed in claim 1, wherein in the second step, the temperature of vacuum drying is 120 ℃, and the drying time is 10-15 h.
5. The method for preparing the iron-tantalum pentoxide biological composite material according to claim 1, wherein in the third step, the technological parameters of the selective laser melting process are as follows: the laser power is controlled to be 100-140W, the scanning speed is 10-200 mm/s, the diameter of a light spot is controlled to be 60-80 mu m, the temperature of a molten pool is controlled to be 1500-1700 ℃, the scanning interval is 0.05-0.08 mm, and the powder spreading thickness is 0.1-0.2 mm.
6. The method for preparing the iron-tantalum pentoxide biological composite material according to claim 1, wherein the specific process of the first step is as follows: introducing inert gas Ar into the ball milling tank until the pressure in the ball milling tank is 1.5MPa, releasing mixed gas in the ball milling tank through the gas valve, and repeating for three times to control H2O and O2For concentration purposes, ball milling is then performed.
7. The method for preparing the iron-tantalum pentoxide nanocomposite material according to claim 1, wherein in the first step, the mass ratio of the tantalum pentoxide powder to the iron powder is 0.03-0.06: 0.94-0.97.
8. The method of claim 1, wherein the protective atmosphere in step one and step three is high purity argon gas with a purity of 99.999%.
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| CN110669979A (en) * | 2019-09-20 | 2020-01-10 | 江西理工大学 | Mesoporous carbon reinforced iron-based composite material and preparation method and application thereof |
| CN110699607A (en) * | 2019-10-22 | 2020-01-17 | 中南大学 | Bio-iron-based alloy with optimized tissue structure and accelerated degradation and preparation method thereof |
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| US20190228892A1 (en) * | 2016-08-25 | 2019-07-25 | Whirlpool S.A. | Coating Layers of Ferromagnetic Particles Surfaces for Obtaining Soft Magnetic Composites (SMCS) |
| CN110669979A (en) * | 2019-09-20 | 2020-01-10 | 江西理工大学 | Mesoporous carbon reinforced iron-based composite material and preparation method and application thereof |
| CN110699607A (en) * | 2019-10-22 | 2020-01-17 | 中南大学 | Bio-iron-based alloy with optimized tissue structure and accelerated degradation and preparation method thereof |
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