CN109224137B - Preparation method of iron-based bone implant capable of accelerating degradation - Google Patents
Preparation method of iron-based bone implant capable of accelerating degradation Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 91
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 61
- 239000007943 implant Substances 0.000 title claims abstract description 61
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 41
- 230000015556 catabolic process Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 74
- 238000000498 ball milling Methods 0.000 claims abstract description 59
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 230000007847 structural defect Effects 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 230000020477 pH reduction Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000000149 argon plasma sintering Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 abstract description 18
- 239000010839 body fluid Substances 0.000 abstract description 12
- 210000001124 body fluid Anatomy 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- -1 iron ions Chemical class 0.000 abstract description 8
- 239000007857 degradation product Substances 0.000 abstract description 6
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 5
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 abstract description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 11
- 229910001448 ferrous ion Inorganic materials 0.000 description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 10
- 229910001447 ferric ion Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000001727 in vivo Methods 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000399 orthopedic effect Effects 0.000 description 3
- 239000012890 simulated body fluid Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002900 effect on cell Effects 0.000 description 1
- 230000002828 effect on organs or tissue Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical class [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 210000001539 phagocyte Anatomy 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/042—Iron or iron alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention relates to a preparation method of an iron-based bone implant capable of accelerating degradation, which comprises the following steps: (1) ball milling to break the wall; (2) acidizing; (3) filtering and drying; (4) dispersing powder; (5) and (4) laser sintering. The invention has the advantages that the end of the carbon nano tube generates structural defects by utilizing a ball milling wall breaking process, carboxyl and hydroxyl functional groups are formed at the structural defects by acidification treatment, and divalent and trivalent iron ions generated by the degradation of an iron matrix are adsorbed by utilizing the coulomb adsorption effect between the structural defects and the iron ions, so that the iron matrix is prevented from being covered by degradation products such as ferric hydroxide, ferrous hydroxide and the like, the full contact between the iron matrix and human body fluid is promoted, and the degradation process of the iron-based bone implant is accelerated; meanwhile, the carboxyl and hydroxyl functional groups can further accelerate the degradation of the iron-based bone implant by improving the hydrophilicity of the iron-based bone implant.
Description
Technical Field
The invention belongs to the technical field of metal bone implants, and particularly relates to a preparation method of an iron-based bone implant capable of accelerating degradation.
Background
The existing orthopedic implants, such as inert metal materials like stainless steel, titanium-based alloy, nickel-based alloy and the like, need to be taken out after a bone repair task is completed in a human body by a secondary operation, and bring great physiological pain and economic burden to patients. Iron is a metal material which is easy to corrode in the atmosphere and seawater medium, so that the iron-based alloy needs to be subjected to corrosion protection treatment in engineering and structural applications, but the corrosion characteristic just meets the requirement of a biodegradable material. In addition to its excellent comprehensive properties and biocompatibility, iron-based alloys have gradually attracted extensive attention of researchers and clinicians in recent years.
However, as degradable bone implant materials, iron faces the problem of degrading too slowly in vivo, not matching the recovery rate of bone tissue. Studies have shown that iron, when implanted in vivo, is only slightly corroded on the surface and often remains in the body after the bone tissue has healed, which limits its application in orthopedics clinics. For this reason, development of a novel degradable iron-based alloy by alloying has been sought, which, although increasing the degradation rate of iron to some extent, still has difficulty in meeting the requirements of degradable bone implants.
The main reason that iron degrades slowly in vivo is the degradation products, which include ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide and ferric carbonate, and the like, and the degradation products have low solubility in human body fluid and can be tightly packed on the iron matrix to prevent the body fluid from further contacting with the iron matrix, thus causing the problems of fast degradation in the early stage of implantation and slow degradation in the middle and later stages. Therefore, how to solve the problem of accumulation of degradation products so as to accelerate the degradation of the iron-based bone implant is a key problem for realizing the wide application of the iron-based bone implant in the field of orthopedics.
Disclosure of Invention
In order to overcome the defects of slow degradation and the like of the iron-based bone implant in the prior art, the invention provides a preparation method of the iron-based bone implant capable of accelerating degradation from a degradation mechanism, and particularly provides a preparation method of the iron-based bone implant capable of acidifying carbon nano tubes to form carboxyl and hydroxyl, and preventing iron ions generated by degradation of an iron matrix from forming products such as ferric hydroxide and ferrous hydroxide to cover the iron matrix by adsorbing the iron ions, so that the iron matrix is promoted to be in full contact with body fluid, and the degradation process of the iron matrix is accelerated.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method of making an iron-based bone implant with accelerated degradation, comprising the steps of:
(1) ball milling and wall breaking: performing mechanical ball milling on the carbon nano tube to generate structural defects at the tube end;
(2) acidifying: preparing mixed acid by using nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95%, then putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, and performing acidification treatment to form carboxyl and hydroxyl at the structural defect part of the carbon nano tube so as to obtain acidified carbon nano tube solution;
(3) and (3) filtering and drying: repeatedly filtering and washing the acidified carbon nanotube solution to remove residual mixed acid, and drying to obtain an acidified carbon nanotube;
(4) powder dispersion: respectively measuring the acidified carbon nano tube and the iron powder according to the mass percentage, wherein the mass fraction of the acidified carbon nano tube is 0.5-5%, and the balance is the iron powder; placing the two kinds of powder in absolute ethyl alcohol for ultrasonic dispersion, and filtering and drying to obtain mixed powder of the acidified carbon nano tube and the iron powder;
(5) laser sintering: and sintering the mixed powder by using laser to obtain the iron-based bone implant.
Preferably, in the step (1), the rotation speed of the mechanical ball milling is 100-.
More preferably, the mechanical ball milling is performed at a speed of 150 rpm for a period of 2 hours.
Preferably, in the step (2), the volume ratio of the nitric acid to the sulfuric acid is 1:4-1:2, and the acidification treatment is carried out for 15-45 minutes.
More preferably, the acidification is for 45 minutes.
Preferably, in the step (4), the ultrasonic dispersion is carried out for 60 to 100 minutes.
Preferably, in the step (5), the laser power is 65-150W, the sintering speed is 20-50 mm/s, the scanning interval is 0.2-0.5 mm, and the laser diameter is 0.1-0.2 mm.
The invention utilizes a combined process of acidizing and laser sintering to prepare the iron-based bone implant and realize the rapid degradation of the iron-based bone implant. Specifically, the carbon nano tube is acidified to form hydroxyl and carboxyl, and iron ions generated by degradation are adsorbed to prevent the product from covering the surface of the matrix, so that the purpose of accelerating the degradation of the iron-based bone implant is realized.
In the ball milling wall breaking process, after the carbon nano tubes are continuously impacted by the grinding balls and continuously rubbed by the adjacent carbon nano tubes, the carbon-carbon covalent bonds at the tube ends are easily broken to form structural defects. The ball milling process parameters have important influence on the wall breaking degree of the pipe end structure, and if the ball milling time is too short, the wall breaking effect cannot be achieved; if the ball milling time is too long, the overall structure of the carbon nanotubes may be damaged. Meanwhile, the ball milling speed is controlled in the ball milling process, and if the ball milling speed is too low, the wall breaking effect cannot be achieved; the ball milling speed is too high, and the carbon nano tubes can be stuck on the inner wall of the ball milling tank under the action of centrifugal force, so that the wall breaking effect cannot be achieved.
In the acidification treatment process, because the carbon atom bonds at the end defects of the carbon nanotube are destroyed, the outer layer electrons are in an unsaturated state, the chemical properties become active and easy to oxidize, and hydroxyl and carboxyl functional groups with negative charges are formed under the action of mixed acid. On one hand, the negatively charged functional groups can adsorb divalent and trivalent iron ions generated by the degradation of the iron matrix, and prevent degradation products such as ferric hydroxide, ferrous hydroxide and the like from covering the iron matrix; on the other hand, the hydrophilicity of the iron-based bone implant is improved, the contact with body fluid is promoted, and the degradation of the iron-based bone implant is accelerated under the combined action of the iron-based bone implant and the body fluid. The acidification process parameters directly influence the acidification effect of the carbon nano tube, and if the acidification time is too short, fewer carboxyl and hydroxyl functional groups are generated; and the acidification time is too long, which can cause the damage of the whole structure of the carbon nano tube.
In the invention, the dosage of the acidified carbon nano tube must be strictly controlled, the content of the acidified carbon nano tube is too small, the adsorption to ferrous ions and ferric ions is limited, and the accelerated degradation effect on the iron-based bone implant is not obvious; the iron-based bone implant is easy to aggregate due to excessive content of the acidified carbon nanotubes, the forming performance of the iron-based bone implant is reduced, and even serious pitting corrosion and local corrosion are caused, so that the iron-based bone implant fails in service. In addition, the laser sintering process parameters are controlled, and if the energy density is too low, the powder is not sufficiently melted, and the molding quality is poor; if the energy density is too high, the structure of the carbon nanotube is easily damaged due to the excessively high forming temperature.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the acidified carbon nanotube is simple, the formed hydroxyl and carboxyl can not only improve the hydrophilicity of the iron-based bone implant, but also adsorb ferrous ions and ferric ions generated by degradation, so that the sediment is prevented from covering the surface of a matrix, and the degradation of the iron-based bone implant is accelerated;
(2) the iron-based bone implant can be naturally degraded in vivo, can be completely degraded in vivo after the treatment effect is achieved, and avoids the defect that the traditional implants such as stainless steel, titanium alloy and the like need to be taken out through a secondary operation after the bone tissue is healed.
(3) The iron-based bone implant can not generate adverse effects on cells, tissues and organs of a human body after being degraded, for example, ferrous ions can be combined with hemoglobin to participate in oxygen transportation, and the carbon nano tubes can be dissolved by phagocytes in the human body and discharged out of the body along with metabolism.
(4) The carbon nano tube can be inserted into an iron matrix to play a role of a threading needle, so that the mechanical property of the iron matrix is enhanced, and sufficient mechanical support can be provided for the iron-based bone implant.
(5) The iron powder adopted by the invention has the advantages of wide material source, low price and simple preparation process, reduces the production cost of the iron-based implant, and meets the requirement of actual production cost.
(6) In the invention, the iron-based bone implant is prepared by adopting a laser sintering process, and the formed shape can be customized according to the requirements of bone implants.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
(1) Ball milling and wall breaking: performing mechanical ball milling on the carbon nano tube to generate structural defects at the tube end, wherein the rotation speed of the mechanical ball milling is 150 r/min, the time is 2 hours, argon is filled into a ball milling tank to prevent oxidation reaction from generating impurities, and the machine is stopped for 2 minutes after each ball milling is performed for 20 minutes to prevent the temperature in the ball milling tank from being overhigh;
(2) acidifying: preparing mixed acid by using nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95% according to the volume ratio of 1:4, then putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, and carrying out acidification treatment for 45 minutes to form carboxyl and hydroxyl at the structural defect part of the carbon nano tube so as to obtain acidified carbon nano tube solution;
(3) and (3) filtering and drying: repeatedly filtering and washing the acidified carbon nanotube solution to remove residual mixed acid, and drying to obtain an acidified carbon nanotube;
(4) powder dispersion: according to the weight ratio of 1.2: weighing 0.6g of carbon nano tube and 49.4g of iron powder according to the mass ratio of 98.8; placing the two powders in absolute ethyl alcohol for ultrasonic dispersion for 60 minutes, and filtering and drying to obtain mixed powder of the acidified carbon nano tube and the iron powder;
(5) laser sintering: the iron-based bone implant was obtained by sintering the above mixed powder using a laser at a laser power of 75 watts, a sintering speed of 25 mm/sec, a scanning pitch of 0.2 mm, and a laser diameter of 0.1 mm.
The obtained iron-based bone implant is soaked in a human body simulation body fluid, and tests show that the concentrations of ferrous ions and ferric ions in the solution are lower, and the degradation rate of the iron-based bone implant is 0.24 mm/year.
Example 2
(1) Ball milling and wall breaking: performing mechanical ball milling on the carbon nano tube to generate structural defects at the tube end, wherein the rotation speed of the mechanical ball milling is 150 r/min, the time is 2 hours, argon is filled into a ball milling tank to prevent oxidation reaction from generating impurities, and the machine is stopped for 2 minutes after each ball milling is performed for 20 minutes to prevent the temperature in the ball milling tank from being overhigh;
(2) acidifying: preparing mixed acid by using nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95% according to the volume ratio of 1:4, then putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, and carrying out acidification treatment for 45 minutes to form carboxyl and hydroxyl at the structural defect part of the carbon nano tube so as to obtain acidified carbon nano tube solution;
(3) and (3) filtering and drying: repeatedly filtering and washing the acidified carbon nanotube solution to remove residual mixed acid, and drying to obtain an acidified carbon nanotube;
(4) powder dispersion: according to the weight ratio of 1.0: 99 weight ratio of 0.5g of carbon nanotubes and 49.5g of iron powder; placing the two powders in absolute ethyl alcohol for ultrasonic dispersion for 60 minutes, and filtering and drying to obtain mixed powder of the acidified carbon nano tube and the iron powder;
(5) laser sintering: the iron-based bone implant was obtained by sintering the above mixed powder using a laser at a laser power of 75 watts, a sintering speed of 25 mm/sec, a scanning pitch of 0.2 mm, and a laser diameter of 0.1 mm.
The obtained iron-based bone implant is soaked in a human body simulation body fluid, and tests show that the concentrations of ferrous ions and ferric ions in the solution are lower, and the degradation rate of the iron-based bone implant is 0.21 mm/year.
Example 3
(1) Ball milling and wall breaking: performing mechanical ball milling on the carbon nano tube to generate structural defects at the tube end, wherein the rotation speed of the mechanical ball milling is 150 r/min, the time is 2 hours, argon is filled into a ball milling tank to prevent oxidation reaction from generating impurities, and the machine is stopped for 2 minutes after each ball milling is performed for 20 minutes to prevent the temperature in the ball milling tank from being overhigh;
(2) acidifying: preparing mixed acid by using nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95% according to the volume ratio of 1:4, then putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, and performing acidification treatment for 20 minutes to form carboxyl and hydroxyl at the structural defect part of the carbon nano tube so as to obtain acidified carbon nano tube solution;
(3) and (3) filtering and drying: repeatedly filtering and washing the acidified carbon nanotube solution to remove residual mixed acid, and drying to obtain an acidified carbon nanotube;
(4) powder dispersion: according to the weight ratio of 1.2: weighing 0.6g of carbon nano tube and 49.4g of iron powder according to the mass ratio of 98.8; placing the two powders in absolute ethyl alcohol for ultrasonic dispersion for 60 minutes, and filtering and drying to obtain mixed powder of the acidified carbon nano tube and the iron powder;
(5) laser sintering: the iron-based bone implant was obtained by sintering the above mixed powder using a laser at a laser power of 75 watts, a sintering speed of 25 mm/sec, a scanning pitch of 0.2 mm, and a laser diameter of 0.1 mm.
The obtained iron-based bone implant is soaked in a human body simulation body fluid, and tests show that the concentrations of ferrous ions and ferric ions in the solution are lower, and the degradation rate of the iron-based bone implant is 0.18 mm/year.
Example 4
(1) Ball milling and wall breaking: performing mechanical ball milling on the carbon nano tube to generate structural defects at the tube end, wherein the rotation speed of the mechanical ball milling is 100 r/min, the time is 1 hour, argon is filled into a ball milling tank to prevent oxidation reaction from generating impurities, and the machine is stopped for 2 minutes after each ball milling is performed for 20 minutes to prevent the temperature in the ball milling tank from being overhigh;
(2) acidifying: preparing mixed acid by using nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95% according to the volume ratio of 1:4, then putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, and carrying out acidification treatment for 45 minutes to form carboxyl and hydroxyl at the structural defect part of the carbon nano tube so as to obtain acidified carbon nano tube solution;
(3) and (3) filtering and drying: repeatedly filtering and washing the acidified carbon nanotube solution to remove residual mixed acid, and drying to obtain an acidified carbon nanotube;
(4) powder dispersion: according to the weight ratio of 1.2: weighing 0.6g of carbon nano tube and 49.4g of iron powder according to the mass ratio of 98.8; placing the two powders in absolute ethyl alcohol for ultrasonic dispersion for 60 minutes, and filtering and drying to obtain mixed powder of the acidified carbon nano tube and the iron powder;
(5) laser sintering: the iron-based bone implant was obtained by sintering the above mixed powder using a laser at a laser power of 75 watts, a sintering speed of 25 mm/sec, a scanning pitch of 0.2 mm, and a laser diameter of 0.1 mm.
The obtained iron-based bone implant is soaked in a human body simulation body fluid, and tests show that the concentrations of ferrous ions and ferric ions in the solution are lower, and the degradation rate of the iron-based bone implant is 0.16 mm/year.
In the process of developing the technology of the invention, the following schemes (such as comparative example 1, comparative example 2, comparative example 3 and comparative example 4) 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 weight ratio of 0.2: the iron-based bone implant is obtained by weighing 0.1g of carbon nano tubes and 49.9g of iron powder according to the mass ratio of 99.8, the concentrations of ferrous ions and ferric ions in a solution are found to be close to pure iron after the simulation body fluid is soaked, the degradation rate of the iron-based bone implant is 0.08 mm/year, and the degradation rate of the iron-based bone implant is not obviously different from that of the pure iron.
Comparative example 2
The other conditions were the same as in example 1 except that: preparing mixed acid by nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95% according to the volume ratio of 1:8, putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, acidifying for 120 minutes, detecting to find that the overall structure of the acidified carbon nano tube is damaged, finding that the concentration of ferrous ions and ferric ions in the solution is close to that of pure iron after the simulated body fluid is soaked, covering a large amount of corrosion products on the surface of the implant, and calculating the degradation rate to be 0.09 mm/year.
Comparative example 3
The other conditions were the same as in example 1 except that: the rotating speed of the mechanical ball milling is 350 r/min, and the ball milling time is 5 hours; after the ball milling is finished, almost all the carbon nanotubes are adhered to the inner wall of a ball milling tank, the detection shows that the wall breaking phenomenon is not generated at the end part of the carbon nanotube basically, carboxyl and hydroxyl functional groups generated after acidification are few, the concentration of ferrous ions and ferric ions in the solution is basically consistent with that of pure iron after the solution is soaked in simulated body fluid, and the calculated degradation rate is 0.085 mm/year.
Comparative example 4
The other conditions were the same as in example 1 except that: the laser power is 150W, detection after sintering finds that the carbon nano tube not only has the damage to the whole structure, but also generates iron-carbon compounds, the concentration of ferrous ions and ferric ions in the solution is basically consistent with that of pure iron after the simulated body fluid is soaked, and the degradation rate is 0.079 mm/year.
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 provides unexpected benefits.
In conclusion, the invention utilizes the ball milling wall breaking process to enable the end part of the carbon nano tube to generate structural defects, forms carboxyl and hydroxyl functional groups at the structural defects through acidification treatment, and utilizes the coulomb adsorption effect between the carboxyl and hydroxyl functional groups and iron ions to adsorb bivalent and trivalent iron ions generated by the degradation of an iron matrix, thereby avoiding generating degradation products such as ferric hydroxide, ferrous hydroxide and the like to cover the iron matrix, promoting the full contact of the iron matrix and human body fluid and further accelerating the degradation process of the iron-based bone implant; meanwhile, the carboxyl and hydroxyl functional groups can further accelerate the degradation of the iron-based bone implant by improving the hydrophilicity of the iron-based bone implant.
Claims (5)
1. A method of making an iron-based bone implant that accelerates degradation, comprising the steps of:
(1) ball milling and wall breaking: performing mechanical ball milling on the carbon nano tube to generate structural defects at the tube end, wherein the rotation speed of the mechanical ball milling is 100-;
(2) acidifying: preparing mixed acid by using nitric acid with the concentration of 98% and sulfuric acid with the concentration of 95%, wherein the volume ratio of the nitric acid to the sulfuric acid is 1:4-1:2, then putting the carbon nano tube subjected to ball milling wall breaking into the mixed acid, and performing acidification treatment to form carboxyl and hydroxyl at the structural defect part of the carbon nano tube so as to obtain acidified carbon nano tube solution;
(3) and (3) filtering and drying: repeatedly filtering and washing the acidified carbon nanotube solution to remove residual mixed acid, and drying to obtain an acidified carbon nanotube;
(4) powder dispersion: respectively measuring the acidified carbon nano tube and the iron powder according to the mass percentage, wherein the mass fraction of the acidified carbon nano tube is 0.5-5%, and the balance is the iron powder; placing the two kinds of powder in absolute ethyl alcohol for ultrasonic dispersion, and filtering and drying to obtain mixed powder of the acidified carbon nano tube and the iron powder;
(5) laser sintering: and sintering the mixed powder by using laser to obtain the iron-based bone implant, wherein the laser power is 65-75 watts, the sintering speed is 20-50 mm/s, the scanning interval is 0.2-0.5 mm, and the laser diameter is 0.1-0.2 mm.
2. The method for preparing an iron-based bone implant capable of accelerating degradation according to claim 1, wherein in the step (1), argon is filled into a ball milling tank to prevent impurities generated by oxidation reaction, and the ball milling tank is stopped for 2 minutes after each ball milling for 20 minutes to prevent the temperature in the ball milling tank from being too high.
3. The method of claim 1, wherein in step (1), the mechanical ball milling is performed at a speed of 150 rpm for a period of 2 hours.
4. The method for preparing an iron-based bone implant with accelerated degradation according to claim 1, wherein in the step (2), the acidification treatment is performed for 15-45 minutes.
5. The method for preparing an iron-based bone implant with accelerated degradation according to claim 1, wherein in the step (4), the ultrasonic dispersion is performed for 60-100 minutes.
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| US20110112628A1 (en) * | 2009-11-10 | 2011-05-12 | Biotronik Vi Patent Ag | Implant and method for manufacturing same |
| CN102961787A (en) * | 2012-12-13 | 2013-03-13 | 北京大学 | Iron-based composite material used for full-degradation cardiovascular support and preparation method thereof |
| CN104587534A (en) * | 2013-10-31 | 2015-05-06 | 先健科技(深圳)有限公司 | An absorbable iron-base alloy support |
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| US20060271168A1 (en) * | 2002-10-30 | 2006-11-30 | Klaus Kleine | Degradable medical device |
| US20110112628A1 (en) * | 2009-11-10 | 2011-05-12 | Biotronik Vi Patent Ag | Implant and method for manufacturing same |
| CN102961787A (en) * | 2012-12-13 | 2013-03-13 | 北京大学 | Iron-based composite material used for full-degradation cardiovascular support and preparation method thereof |
| CN104587534A (en) * | 2013-10-31 | 2015-05-06 | 先健科技(深圳)有限公司 | An absorbable iron-base alloy support |
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