TWI669135B - Iron-based biodegradable component applications thereof and method for fabricating the same - Google Patents

Abstract

An iron-based biodegradable component comprising: iron (Feron) in an amount of substantially between 60 and 99.5 parts by weight; and a modified material in a weight fraction substantially between 0.5 and 40; Wherein, the modified material comprises: at least one of zinc (Zinc, Zn) substantially in the range of 0.1 to 5 parts by weight and biodegradable ceramic material in the range of substantially 0.1 to 40 parts by weight. .

Description

Iron-based biodegradable composition and application and production method thereof

The present disclosure relates to a biodegradable composition and its application and method of manufacture. In particular, it relates to an iron-based biodegradable composition and its application and production method.

As the world moves into an aging society, the proportion of medical expenditure continues to increase, and the demand for implantable medical devices (medical implants) continues to grow. Typical medical implants, such as bone nails and bone plates used in orthopedics, are usually made of metal materials such as stainless steel, cobalt-chromium alloy, titanium and titanium alloy, and have high strength, high toughness and high. Anti-fatigue strength, corrosion resistance, plasticity, processability and high economics. However, metal medical implants do not decompose in the human body after being implanted into the human body, which may cause foreign body sensation and potential infection concerns. Therefore, when the wound is healed, it needs to be removed with a second surgery.

Since the second surgery to remove medical implants has clinical risks that are prone to complications and nerve damage, it has been used, including polylactic acid (PLA), polyglycolic acid (PGA), polycyanopropene ester ( Biodegradable polymer materials such as PACA) The technology for making implantable medical devices. By utilizing the characteristics that the polymer can be absorbed by the human body, it is no longer necessary to take out the implant by secondary surgery, and the danger and injury caused by the second operation to the patient can be avoided. However, medical implants prepared using biodegradable polymer materials still have problems such as insufficient strength, poor mechanical properties, and too high a rate of decomposition to withstand large stresses.

In order to solve the problem of insufficient mechanical strength, a technique for producing a medical implant using a biodegradable composition based on a metal material such as magnesium, iron, manganese or the above alloy has been proposed. However, medical implants made using a magnesium-based biodegradable composition have a too high rate of decomposition in the human body, resulting in difficulty in maintaining mechanical strength; medical implants made using an iron-based biodegradable composition are Because the decomposition rate is relatively slow, it is difficult to regulate the time of its existence in the body; and when the manganese content is too high, it is easy to produce biological toxicity.

Therefore, it is an urgent problem to provide an advanced iron-based biodegradable composition and its application and production method.

An embodiment of the present specification discloses an iron-based biodegradable component comprising: iron (Iron, Fe) having a weight of substantially between 60 and 99.5; and a weight substantially between 0.5 and 40. a modified material; wherein the modified material comprises: zinc (Zinc, Zn) substantially in the range of 0.1 to 5 parts by weight, and biodegradable ceramic material in the range of substantially 0.1 to 40 parts by weight. At least one of them.

Another embodiment of the present specification discloses a biodegradable medical implant comprising the above iron-based biodegradable component.

A method of making a biodegradable medical implant comprising the steps of: firstly providing a composition comprising the aforementioned iron-based biodegradable component. Next, a plurality of iron metal particles and a plurality of modified particles contained in the iron-based biodegradable component are thoroughly mixed.

According to the above embodiment, the present specification is to provide an iron-based biodegradable composition, and an application and a production method thereof. The iron-based biodegradable composition is mainly based on iron metal and contains other modified materials, such as a zinc-containing material, a biodegradable ceramic material, or a combination of a zinc-containing material and a biodegradable ceramic material. Wherein, the weight fraction of the iron element may be substantially between 60 and 99.5; the weight fraction of the zinc element may be substantially between 0.1 and 5; and the weight fraction of the biodegradable ceramic material may be substantially between 0.1 and 40. And by mixing, smelting, hot pressing or sintering the above materials to form a biodegradable medical implant having various structures such as a powder, a sheet, a block or a three-dimensional component, etc., which can be applied to, for example, dental implants. Implants, orthopedic implants, cardiac implants, or orthopedic implants solve the problem that conventional medical implants are not absorbed by the body, have insufficient stress intensity, or are difficult to regulate the rate of biodegradation.

10, 20, 30, 40, 50‧‧‧ biodegradable medical implants

11‧‧‧Iron-based biodegradable components

11a‧‧‧ iron metal particles

11b‧‧‧Modified particles

11b1‧‧‧Zinc-containing material particles

11b2‧‧‧ceramic material particles

11b3‧‧‧Magnesium-containing metal particles

41‧‧‧ hole

200‧‧‧ plates

201‧‧‧Hot pressing mould

202‧‧‧Tools

300, 300', 300'', 400, 400', 400'' ‧ ‧ layers

301‧‧‧Loading substrate

302‧‧‧Focus energy beam

303‧‧‧Preset scan path

500‧‧‧Metal 碇

501‧‧‧melting furnace

S11‧‧‧ provides iron-based biodegradable components containing modified particles of ferrous metal particles

S12‧‧‧ Mix the iron metal particles and the modified particles thoroughly

S21‧‧‧ provides iron-based biodegradable components containing modified particles of ferrous metal particles

S22‧‧‧ for hot pressing

S23‧‧‧ hardening and cooling

S31‧‧‧ provides iron-based biodegradable components containing modified particles of ferrous metal particles

S32‧‧‧Sintering/melting process for iron-based biodegradable components

S33‧‧‧Curing the sintered/melted iron-based biodegradable component

S51‧‧‧ provides iron-based biodegradable components containing modified particles of ferrous metal particles

S52‧‧‧ granulation and smashing process for iron-based biodegradable components Into several metal 碇

S53‧‧‧Smelting process for metal crucibles

S54‧‧‧Cooling, solidification

In order to better understand the above and other aspects of the present specification, the following specific embodiments are described in detail below with reference to the accompanying drawings: 1A is a flow chart of a method of fabricating a biodegradable medical implant according to an embodiment of the present specification; FIG. 1B is a view showing the method of fabricating a biodegradable medical implant according to the method described in FIG. 1A; 2A is a flow chart of a method for fabricating a biodegradable medical implant according to another embodiment of the present specification; FIGS. 2B to 2C are diagrams shown in FIG. 2A Method for making a partial process structure of a biodegradable medical implant; FIG. 3A is a flow chart of a method for manufacturing a biodegradable medical implant according to still another embodiment of the present specification; FIG. 3B to FIG. 3C A schematic diagram of a partial process structure for fabricating a biodegradable medical implant by the method described in FIG. 3A; and FIG. 4 is a structure of the biodegradable medical implant 40 according to still another embodiment of the present specification. Figure 5A is a flow chart showing a method of making a biodegradable medical implant according to still another embodiment of the present specification; and Figures 5B to 5C are diagrams shown in Figure 5A. Method for making biodegradable Treatment process partial schematic configuration of the implant.

The present specification provides an iron-based biodegradable composition, and an application and a manufacturing method thereof, so as to solve the problem that a conventional medical implant cannot be absorbed by a human body and is stressed. The problem of insufficient strength or difficulty in regulating the rate of biodegradation. The above-described embodiments, as well as other objects, features and advantages of the present invention, will be apparent from the accompanying drawings.

However, it must be noted that these specific embodiments and methods are not intended to limit the invention. The invention may be practiced with other features, elements, methods and parameters. The preferred embodiments are merely illustrative of the technical features of the present invention and are not intended to limit the scope of the invention. Equivalent modifications and variations will be made without departing from the spirit and scope of the invention. In the different embodiments and the drawings, the same elements will be denoted by the same reference numerals.

Referring to FIGS. 1A and 1B, FIG. 1A is a flow chart of a method of making a biodegradable medical implant 10 in accordance with an embodiment of the present specification. FIG. 1B is a schematic view showing a partial process structure of the biodegradable medical implant 10 produced by the method described in FIG. 1A. In the present embodiment, the method of making the biodegradable composition 10 may include the following steps:

First, an iron-based biodegradable composition component 11 is provided (as described in step S11). In some embodiments of the present specification, in some embodiments of the present specification, the iron-based biodegradable component 11 may include a plurality of iron metal particles 11a and a plurality of modified particles 11b. Wherein, the modified particles 11b may be composed of only one zinc-containing material particle 11b1, or may be composed of only one biodegradable ceramic material particle 11b2, or may include both zinc-containing material particles 11b1 and biodegradable ceramic material particles. 11b2. In the iron-based biodegradable composition, the weight fraction of iron can be substantially Between 60 and 99.5; the parts by weight of the zinc element may be substantially between 0.1 and 5; the parts by weight of the biodegradable ceramic material may be substantially between 0.1 and 40.

The zinc-containing material particles 11b1 may be zinc metal particles, zinc oxide particles or a combination of the two. The material constituting the biodegradable ceramic material particles 11b2 may be, for example, hydroxyapatite (HA), tricalcium phosphate (TCP), titanium oxide (titanium oxide), aluminum oxide (aluminum oxide), Any combination of the above materials of silicon oxide, zirconia oxide. Further, the modified particles 11b may further include at least one magnesium-containing metal particle 11b3 such as magnesium metal particles. In some embodiments of the present specification, the weight fraction of magnesium (Magnesium, Mg) may be substantially between 0.1 and 5.

In the present embodiment, the biodegradable component 11 may include a plurality of iron metal particles 11a having an average particle size substantially between 1 micrometer (μm) and 500 micrometers, and a plurality of average particle size sizes substantially Modified particles 11b between 0.1 micrometers (μm) and 500 micrometers. The modified particles 11b simultaneously include a plurality of zinc metal particles (containing zinc material particles 11b1), a plurality of particles of tricalcium phosphate (biodegradable ceramic material 11b2), and a plurality of magnesium metal particles (magnesium containing metal particles 11b3). The parts by weight of the iron metal particles are substantially 85; the parts by weight of the zinc metal particles are substantially 3; the parts by weight of the tricalcium phosphate particles are substantially 10; and the parts by weight of the magnesium metal particles are substantially 1.

However, the content of the biodegradable component 11 is not limited thereto. For example, in other embodiments of the present specification, the biodegradable component 11 may include only a plurality of iron metal particles 11a, and a plurality of average particle size sizes. Zinc-containing material particles 11b1 and a plurality of tricalcium phosphate (biodegradable ceramic materials) substantially between 0.1 micrometers (μm) and 500 micrometers Feed 11b2) particles. Wherein, the zinc-containing material particles 11b1 may account for substantially 1 to 5 by weight of the biodegradable component 11; the tricalcium phosphate (biodegradable ceramic material 11b2) particles may account for 11% by weight of the biodegradable component. Between 5 and 30.

In still other embodiments of the present specification, the biodegradable component 11 may include only a plurality of iron metal particles 11a, and a plurality of zinc-containing materials having an average particle size substantially between 0.1 micrometers (μm) and 500 micrometers. Particle 11b1. Wherein, the zinc-containing material particles 11b1 may be substantially between 0.5 and 5 by weight of the biodegradable component. In a specific embodiment, the weight fraction of the iron metal particles is substantially 95; and the weight fraction of the zinc-containing material particles 11b1 is substantially 5. In another specific embodiment, the parts by weight of the iron metal particles 11a are substantially 90; and the parts by weight of the zinc-containing material particles 11b1 are substantially 3.

In still other embodiments of the present specification, the biodegradable component 11 may include only a plurality of iron metal particles 11a, and a plurality of particles of tricalcium phosphate (biodegradable ceramic material 11b2). Among them, the tricalcium phosphate (biodegradable ceramic material 11b2) particles may be substantially between 1 and 40 in a biodegradable composition of 11% by weight. In a specific embodiment, the weight fraction of the iron metal particles is substantially 90; the weight fraction of the particles of the tricalcium phosphate material (biodegradable ceramic material 11b2) is substantially 10.

Next, the iron metal particles 11a and the modified particles 11b are thoroughly stirred and mixed (as shown in step S12) to complete the biodegradable medical implant 10 having a powder structure (as shown in FIG. 1B). Preparation. In some embodiments of the present specification, the biodegradable medical implant 10 can be applied, for example, in dental implants, orthopedics, or orthopedic surgery, for example, as periodontal tissue (alveolar bone), bone or connective tissue. (eg leather Filler, etc. In other embodiments of the present specification, the biodegradable medical implant 10 having a powdery structure can also be used as a starting material for other processing methods to further produce biodegradable medical implants having different structures. . The process steps and materials for making biodegradable medical implants of different structures are detailed below:

Please refer to FIG. 2A to FIG. 2B . FIG. 2A is a flow chart of a method for manufacturing the biodegradable medical implant 20 according to another embodiment of the present specification; FIG. 2B to FIG. 2C are diagrams according to FIG. A schematic diagram of a portion of a process structure for making a biodegradable medical implant 20 by the method of FIG. 2A. In the present embodiment, the method of making the biodegradable composition 20 may include the following steps:

First, an iron-based biodegradable composition 11 as described in Fig. 1B is provided (as described in step S21). Since the composition and formation steps of the biodegradable component 11 have been described in detail in FIGS. 1A to 1C, they will not be described here. A hot press is then performed (as described in step S22). The biodegradable component 11 after thorough mixing is injected into the hot press mold 201 (as shown in FIG. 2B); the heating temperature and time are controlled to make the biodegradable component 11 into a hot melt state, and then the tool 202 is used. Compression molding is performed on the biodegradable component 11 in a molten state by mechanical stress. After hardening and cooling (as described in step S23), a sheet material 200 having a sheet-like structure is formed (as shown in FIG. 2C). In some embodiments of the present specification, the operating temperature of the hot press is substantially between 500 ° C and 800 ° C.

Subsequent, it can be made by other post-processing processes, such as machining, cutting, stamping, drilling, welding, etc. (not shown), For example, dental implants, orthopedics, or orthopedics, biodegradable medical implants 20 used in surgery. In some embodiments of the present specification, the biodegradable medical implant 20 can be an artificial bone plate for use in orthopedic surgery.

Please refer to FIG. 3A to FIG. 3C . FIG. 3A is a flow chart of a method for manufacturing the biodegradable medical implant 30 according to still another embodiment of the present specification; FIGS. 3B to 3C are diagrams showing A schematic diagram of a partial process structure for making a biodegradable medical implant 30 by the method described in FIG. 3A. In the present embodiment, the method of making the biodegradable composition 30 may include the steps of first providing an iron-based biodegradable composition 11 on a carrier substrate 301 (as described in step S31). In the present embodiment, the iron-based biodegradable component 11 is provided in such a manner that the iron-based biodegradable component 11 after thorough mixing is laid flat on the surface of the carrier substrate 301. Since the composition and formation steps of the iron-based biodegradable component 11 have been described in detail in FIGS. 1A to 1C, they will not be described here.

Next, the iron-based biodegradable component 11 is subjected to a sintering/melting process (as described in step S32). In some embodiments of the present specification, the sintering/melting process can include providing a focused energy beam 302 for sintering/melting the iron-based biodegradable component 11 along a predetermined scan path 303 (eg, Figure 3B) Drawn). For example, in the present embodiment, the sintering/melting process may be a laser beam (focusing energy beam 302) having a power substantially between 200 watts (W) and 340 watts, substantially in the range of 1500 mm/sec (mm/ s) to a scanning speed of 4500 mm/sec, sintering/melting the iron-based biodegradable component 11 powder particles along the X-axis direction.

Then, the sintered/melted iron-based biodegradable composition component 11 (as described in step S33) is cured to form a lamination 300 at least on the surface 11a of the carrier substrate 11. In some embodiments of the present specification, the step of curing the sintered/melted iron-based biodegradable component 11 may include sintering/melting the iron-based biodegradable component in an air atmosphere. 11 is annealed.

Then, the above steps S1 to S3 are repeated to form a plurality of laminated layers, such as the base layers 300' and 300", stacked on each other on the stacked layer 300, thereby forming a columnar block having a three-dimensional structure (as shown in FIG. 3C). Subsequent, can be further processed by other post-processing processes, such as cutting, stamping, drilling, welding, etc. (not shown), such as dental implants, orthopedics, or orthopedics, used in surgery. The biodegradable medical implant 30. In some embodiments of the present specification, the biodegradable medical implant 30 can be an artificial bone nail for use in orthopedic surgery.

Please refer to Figure 4. 4 is a perspective view of the structure of the biodegradable medical implant 40 in accordance with yet another embodiment of the present specification. Among them, the materials and methods for producing the biodegradable medical implant 40 are substantially the same as those described in FIGS. 3A to 3C. The difference is that when the biodegradable medical implant 40 is fabricated, the cross-sectional appearance of each of the laminates can be changed by adjusting the predetermined scanning path for each sintering/melting process, and after stacking by stacking layers, The stacked three-dimensional structure has a preset shape. For example, in the present embodiment, by changing the shape appearance of the laminates 400, 400' and 400", the laminates 400, 400' and 400" can be constructed into a three-dimensional assembly having a three-dimensional thread and a tapered tubular structure. It can be used in orthopedic surgery as an artificial bone nail. In addition, it can further biodegrade The particular location of the medical implant 40 has at least one aperture 41 to promote the rate of biodegradation at that location.

5A to 5C, FIG. 5A is a flow chart of a method for manufacturing the biodegradable medical implant 50 according to still another embodiment of the present specification; FIGS. 5B to 5C are diagrams A schematic diagram of a portion of the process structure for making the biodegradable medical implant 50 in the manner described in FIG. 5A. In the present embodiment, the method of making the biodegradable composition 50 can include the following steps:

First, an iron-based biodegradable composition component 11 is provided (as described in step S51). In the present embodiment, the iron-based biodegradable component 11 is provided by first granulating and smashing the iron-based biodegradable component 11 after thorough mixing to form a plurality of metal ingots. 500 (as described in step S52). Thereafter, these metal crucibles 500 are placed (in the smelting furnace 501 (as shown in Fig. 5B). The composition and formation steps of the iron-based biodegradable composition component 11 have been described in detail in Figs. 1A to 1C. In the middle, it is not described here.

Next, the bulk metal crucible 500 is subjected to a melting process (as described in step S3). In some embodiments of the present specification, the operating temperature of the smelting process is substantially between 1000 ° C and 1500 ° C, and the iron-based biodegradable composition of the iron metal particles 11a, the zinc-containing material particles 11b1, and the bio- The decomposed ceramic material particles 11b2 and the magnesium-containing metal particles 11b3 form a molten state and are agglomerated in combination with each other. Thereafter, the smelting agglomerates having a powdery structure (as depicted in FIG. 5C) are formed by cooling solidification (as described in step S54) to complete the preparation of the biodegradable medical implant 50.

In some embodiments of the present specification, the biodegradable medical implant 50 can be applied, for example, to dental implants, orthopedics, or orthopedics, during surgery, as, for example, periodontal tissue (alveolar bone), bone, or a filler of connective tissue (eg, skin), etc. In other embodiments of the present specification, the biodegradable medical implant 50 having a powdery structure may also be used as another processing method (for example, the hot pressing process shown in FIG. 2B or the drawing in FIG. 3B). The starting material of the illustrated sintering/melting process) further produces biodegradable medical implants having different structures.

Subsequently, ISO 10993-5 "Standards for Biocompatibility Evaluation of Medical Devices", which is organized according to the International Standards Organization, targets iron metal particles 11a, zinc-containing material particles 11b1, biodegradable ceramic material particles 11b2, and magnesium-containing metal particles. 11b3 and the biodegradable medical implants 10, 20, 30 and 50 provided by the above examples were subjected to a biodegradability test and an acute biotoxicity test (for example, cell survival rate was tested by MTT assay). Tensile tests were performed on biodegradable medical implants 10, 20, 30 and 50 materials using the ASTM E8 test method developed by the American Society of Testing and Materials (ASTM).

As a result of the test, it was found that the iron metal particles 11a, the zinc-containing material particles 11b1, the biodegradable ceramic material particles 11b2, the magnesium-containing metal particles 11b3, and the biodegradable medical implants 10, 20, 30, and 50, for the cells to be tested The strain had no adverse effects and its cell viability was greater than 70%. The biodegradable medical implants 10, 20, 30, and 50 have a biodegradation rate greater than 0.2 mm/year, which can achieve clinical goals of gradual decomposition and eventually disappearance in the human body. Biodegradable medical implant The drop strength of the inlets 10, 20, 30 and 50 is greater than 200 MPa, indicating that the mechanical strength is suitable for the mechanical properties of the human bone.

In addition, in some embodiments of the present specification, the biodegradable medical implant can be produced by changing the ratio of the iron metal particles 11a, the zinc-containing material particles 11b1, the biodegradable ceramic material particles 11b2, the magnesium-containing metal particles 11b3, and the control. The hot pressing process of the 20, 30, 40 and 50, the air atmosphere in the sintering/melting process or the smelting process to control the oxidation degree of the metal element in the iron-based biodegradable component 11, thereby regulating the biodegradable medical treatment The iron, zinc and/or oxygen content of the implants 20, 30, 40 and 50 serves to modulate the rate of biodegradation of the biodegradable medical implants 20, 30, 40 and 50.

According to the above embodiment, the present specification is to provide an iron-based biodegradable composition, and an application and a production method thereof. The iron-based biodegradable composition is mainly based on iron metal and contains other modified materials, such as a zinc-containing material, a biodegradable ceramic material, or a combination of a zinc-containing material and a biodegradable ceramic material. Wherein, the weight fraction of the iron element may be substantially between 60 and 99.5; the weight fraction of the zinc element may be substantially between 0.1 and 5; and the weight fraction of the biodegradable ceramic material may be substantially between 0.1 and 40. And by mixing, smelting, hot pressing or sintering the above materials to form a biodegradable medical implant having various structures such as a powder, a sheet, a block or a three-dimensional component, etc., which can be applied to, for example, dental implants. Implants, orthopedic implants, cardiac implants, or orthopedic implants solve the problem that conventional medical implants are not absorbed by the body, have insufficient stress intensity, or are difficult to regulate the rate of biodegradation.

While the invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and it is to be understood by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

Claims (10)

An iron-based biodegradable composition comprising: iron (Feron), which is substantially between 60 and 99.5 parts by weight, and a modified material having a weight of substantially between 0.5 and 40; Wherein, the modified material comprises: at least one of a zinc element (Zinc, Zn) substantially between 0.1 and 5 parts by weight, and a biodegradable ceramic material in a weight part substantially between 0.1 and 10. The biodegradable ceramic material is composed of Tricalcium Phosphate (TCP). The iron-based biodegradable component as recited in claim 1 further comprises a magnesium element (Magnesium, Mg) in a weight fraction of substantially between 0.1 and 5. A biodegradable medical implant comprising one of the iron-based biodegradable components of claims 1 to 2. The biodegradable medical implant of claim 3, comprising a plurality of iron metal particles and a plurality of modified particles composed of the modified material. The biodegradable medical implant according to claim 3, comprising a plate, a piece of material or a three-dimensional component formed by the iron-based biodegradable component. A biodegradable medical implant according to claim 4, which is a dental implant, an orthopedic implant, a cardiological implant or an orthopedic implant. A method of making a biodegradable medical implant, comprising: providing an iron-based biodegradable component comprising a plurality of iron metal particles and a plurality of modified particles composed of a modified material; the iron-based organism The decomposable component is subjected to a granulation and smashing process to form a plurality of metal ingots; and a smelting process is performed, using an operating temperature substantially between 800 ° C and 1500 ° C for the metal bismuth Heating to melt the iron-based biodegradable component; and solidifying the molten iron-based biodegradable component. The method for fabricating a biodegradable medical implant according to claim 7, further comprising replacing the smelting process with a sintering/melting process to melt the iron-based biodegradable component. The method for producing a biodegradable medical implant according to claim 7, wherein the molten iron-based biodegradable component is cured. The step of forming includes a thermoforming process comprising an operating temperature substantially between 600 ° C and 800 ° C. The method for producing a biodegradable medical implant according to claim 7, wherein the step of melting the iron-based biodegradable component into a solidification forming step is an annealing.