Additive-type antimicrobial composite material, its applications, and preparation method

Abstract

This invention provides novel and cost-effective antimicrobial composite materials, particularly for medical implants, and methods for preparing them. [Solution] A compound antimicrobial material is provided in which an antimicrobial metal is adsorbed within an inorganic carrier, and the inorganic carrier is present in or embedded within a base metal or base alloy.

Description

Technical Field

[0001] The present disclosure relates to an antibacterial composite material manufactured by additive manufacturing (AM), as well as its uses and preparation methods.

Background Art

[0002] Medical implant components are used in various clinical and healthcare applications to provide benefits during or after medical procedures. The development of materials science and medicine has continued to benefit patients undergoing surgery or receiving implants. As an example, artificial joints can improve the motor function of people suffering from age-related conditions or diseases and may extend the patient's active lifespan.

[0003] However, concerns remain regarding the prognosis of surgery or medical implants, particularly with associated bacterial infections or effects, which can require additional surgery or even lead to implant failure and retrieval.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, there is a need for novel and cost-effective antibacterial composite materials, particularly for medical implants, and methods for their preparation.

Means for Solving the Problems

[0005] Therefore, the present disclosure is an additive manufacturing antibacterial composite material, comprising:

[0006] (a) a substrate of a metal or alloy comprising at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu) and magnesium (Mg);

[0007] (b) an inorganic carrier comprising a material selected from the group consisting of alkaline earth metals (or more) or phosphates of Group IV (IVB) metals, alkaline earth metals (or more) carbonates, alkaline earth metals (or more) sulfates, zeolites, bentonite, diatomaceous earth, bioglass and any mixture thereof,

[0008] (c) Antimicrobial metals in elemental or ionic form, selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), tantalum (Ta), and any mixture thereof in non-alloy form. This invention relates to an additively manufactured antimicrobial composite material, wherein the antimicrobial metal is adsorbed within an inorganic carrier, and the inorganic carrier is present within or embedded within a base metal or base alloy.

[0009] This disclosure also relates to the use of composite materials in implant components.

[0010] This disclosure also relates to a method for preparing an additively manufactured antimicrobial composite material, wherein the composite material is

[0011] (a) A base metal or base alloy containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu), and magnesium (Mg),

[0012] (b) an inorganic carrier comprising a material selected from the group consisting of alkaline earth metals (or more) or phosphates of Group IV (IVB) metals, alkaline earth metals (or more) carbonates, alkaline earth metals (or more) sulfates, zeolites, bentonite, diatomaceous earth, bioglass and any mixture thereof,

[0013] (c) Antimicrobial metals in elemental or ionic form, selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), tantalum (Ta), and any mixture thereof in non-alloy form. The method includes,

[0014] (i) A step of providing particles of a base metal or base alloy, particles of an inorganic carrier, and particles of an antimicrobial metal, (ii) A step of performing powder bed fusion on the particles by selectively melting a specified region of the particles and fusing the particles with a solid layer, (iii) A process of repeating steps (i) and (ii) to construct an additively manufactured antimicrobial composite material layer by layer according to the digital design. The present invention relates to a method including the above. The additively fabricated antimicrobial composite material prepared in this manner is characterized in that the antimicrobial metal is adsorbed within an inorganic carrier, and the inorganic carrier is present within or embedded within the base metal or base alloy.

[0015] In one embodiment, the antimicrobial metal combined with the inorganic carrier is present in an amount of at least 0.1% by weight, for example, at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight, at least 0.5% by weight, at least 0.75% by weight, at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 4% by weight, or at least 5% by weight, relative to the total weight of the composite material.

[0016] In any of the aforementioned embodiments, the antimicrobial metal is present in an amount of at least 0.005% by weight relative to the total weight of the composite material, for example, at least 0.01% by weight, at least 0.02% by weight, at least 0.03% by weight, at least 0.04% by weight, at least 0.05% by weight, at least 0.075% by weight, at least 0.1% by weight, at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight, or at least 0.5% by weight.

[0017] In any of the aforementioned embodiments, the antimicrobial metal is present within an inorganic carrier. In any of the aforementioned embodiments, the inorganic carrier is present within a base metal or base alloy and is embedded within the base metal or base alloy.

[0018] In any of the aforementioned embodiments, examples of phosphates include, but are not limited to, apatite (e.g., hydroxy- / chloro- / fluoro-apatite) or pure phosphates, preferably calcium phosphate, calcium hydroxyapatite, or zirconium phosphate. In any of the aforementioned embodiments, the Group IV (IVB) metal is zirconium (Zr).

[0019] In any of the aforementioned embodiments, the substrate is porous. In any of the aforementioned embodiments, the inorganic carrier is porous. In any of the aforementioned embodiments, the composite material is porous. In any of the aforementioned embodiments, the porosity of the substrate, inorganic carrier or composite material is about 0.1%, for example, at least 0.2%, at least 0.3%, at least 0.4%, at least 0.5%, at least 0.75%, at least 1%, at least 1.5%, at least 2%, or at least 2.5%.

[0020] In any of the aforementioned embodiments, the antimicrobial metal in ionic form is adsorbed onto the inorganic carrier in the absence of ionic bonding between the antimicrobial metal and the inorganic carrier. In any of the aforementioned embodiments, the antimicrobial metal in ionic form is adsorbed onto the inorganic carrier via electrostatic force.

[0021] In any of the aforementioned embodiments, the antimicrobial metal in ionic form is formed in situ during the additive manufacturing process.

[0022] In any of the aforementioned embodiments, the antimicrobial metal combined with the inorganic carrier is present in an amount of at least 0.1% by weight, for example, at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight, at least 0.5% by weight, at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 3.5% by weight, at least 4% by weight, at least 5% by weight, or at least 7.5% by weight, relative to the total weight of the composite material.

[0023] In any of the foregoing embodiments, the relative density of the composite material of the antibacterial composite material components (a), (b), and (c) is at least 20%, and the relative density can be obtained, for example, by calculating the ratio of the pore area to the total area based on imaging.

[0024] In any of the foregoing embodiments, the substrate is Ti, a Ti-Ni alloy, a Zr alloy, stainless steel, a cobalt-chromium (Co-Cr) alloy, or a Ti-6Al-4V alloy.

[0025] In any of the foregoing embodiments, the inorganic carrier does not exhibit or provide an antibacterial effect.

[0026] In any of the foregoing embodiments of use, the implant component is part or all of an artificial joint, an insert related to an artificial joint, or a temporary fixation device, a facial implant, a cosmetic implant such as a cranial forming plate, a pacemaker, a stent, and a cardiovascular implant such as an artificial heart valve, or a dental implant.

[0027] In any of the foregoing embodiments of the method, the composite materials (a), (b), and (c) are present in a molten form, and the period during which (a), (b), and (c) are present in a solid form is controlled to reduce the oxidation of the material. In one embodiment, the period is controlled by adjusting the holding time of the laser to a maximum of 40 μs, such as a maximum of 37 μs, a maximum of 35 μs, a maximum of 30 μs. The energy density should be sufficient to melt the material.

[0028] In any of the foregoing embodiments of the method, the inorganic carrier does not exhibit or provide an antibacterial effect.

[0029] In any of the foregoing embodiments of the method, the additive manufacturing is performed using powder bed fusion, and the heat source may include, but is not limited to, a laser.

Mode for Carrying Out the Invention

[0030] To facilitate understanding of the disclosures herein, the terms used herein are defined herein as follows:

[0031] In the context of this specification and the claims, the singular forms “a,” “an,” and “the” refer to multiple subjects unless otherwise specified. Unless otherwise specified, any examples or illustrative language provided herein (e.g., “such as”) are used solely to better illustrate this disclosure and not to limit its scope.

[0032] It should be understood that any numerical range listed herein is intended to include all subranges contained therein. For example, the range "50 to 70°C" includes all subranges between the stated minimum value of 50°C and the stated maximum value of 70°C, as well as specific values ​​(including the minimum and maximum values), such as 58°C to 67°C, and 53°C to 62°C, 60°C, or 68°C. Since the disclosed numerical ranges are continuous, they include each value between the minimum and maximum values. Unless otherwise specified, the various numerical ranges shown herein are approximations.

[0033] In this disclosure, the term “about” means an acceptable deviation of a given value measured by a person skilled in the art, depending in part on the method of measuring or determining the value.

[0034] In this disclosure, the term "alkaline earth metals" refers to the elements of Group 2 in the periodic table.

[0035] In this disclosure, the term "zeolite" refers to the general formula "M n+ 1 / n (AlO2)-(SiO2) x This refers to a microporous crystalline aluminosilicate material that can be represented as "·yH2O", M n+ 1 / n is a metal ion or H + It is one of the following, and preferably M is H, Na, or K.

[0036] In this disclosure, the term "bentonite" refers to clay primarily derived from montmorillonite (sheet silicate).

[0037] In this disclosure, the term "diatomaceous earth" refers to naturally occurring soft siliceous sedimentary rocks mainly composed of fossilized residues of diatoms, with a chemical composition mainly consisting of approximately 80-90% silica, approximately 2-4% alumina, and approximately 0.5-2% iron oxide.

[0038] In this disclosure, the terms “bioglass” and “bioactive glass” refer to surface-reactive glass-ceramic biomaterials that are considered biocompatible with humans, and whose chemical composition mainly comprises silicates, calcium oxide, sodium oxide and / or phosphorus pentoxide, and optionally other metal oxides, such as potassium oxide and magnesium oxide.

[0039] In this disclosure, the terms "biocompatible" or "biocompatible" mean having the ability to come into contact with living systems without causing adverse effects, such as (severe) allergic reactions or damage to cells, tissues or organs in a living body.

[0040] In this disclosure, the term "antimicrobial metal" refers to a metal or metal ion that exhibits antimicrobial effects.

[0041] In this disclosure, the term "porosity" refers to the level of pore space in a material.

[0042] In this disclosure, “relative density” has a specific meaning in the context of 3D printing and powder metallurgy, referring to the ratio of the actual density of a material to the theoretical maximum density of the material. To determine the relative density of a metal sample, the following steps are typically included: (a) polishing the sample with abrasive paper (80-4,000 grit) and polishing with 0.05 μm of Al2O3; (b) acquiring high-resolution micrographs of the sample using a Hitachi TM4000Plus; (c) analyzing the acquired images using ImageJ software. By carefully selecting an appropriate threshold, pores in the microstructure can be accurately identified; (d) using the built-in functions of ImageJ to determine the total black area in the micrograph corresponding to the porosity of the sample. The relative density is calculated using the following formula. Relative density = 1 - porosity.

[0043] A common cause of infection in implant surgery is the vigorous proliferation of bacteria on the surface of the implant. Severe complications resulting from this can necessitate further surgery or implant removal, potentially leading to surgical failure and increased patient distress. Therefore, conferring antibacterial properties to implants to reduce bacterial growth has become a critical medical issue.

[0044] Antimicrobial materials can be organic or inorganic. Because the former are prone to microbial growth and have low heat resistance, inorganic antimicrobial materials are receiving more attention and are being applied more frequently. Generally, metal ions adsorb to the surface of bacterial cell walls and react with their functional groups, affecting the structure or function of microbial cells and achieving a bacteriostatic effect.

[0045] Currently, antimicrobial metal ions can be attached to surfaces by electroplating, ion implantation, chemical vapor deposition, or coating to form an antimicrobial layer. However, drawbacks still need to be overcome. For example, a porous support or structure may be immersed in a hydrogel containing an organic bioactive agent such as an antibiotic, and the hydrogel can be fixed onto the support or structure. However, when placed in a biological environment, the hydrogel is affected by various environmental factors such as temperature, pH, and enzymes, making it susceptible to degradation or denaturation, which affects the effectiveness of antibiotic release. Another method involves anodizing a bioactive substrate, such as a titanium alloy, to form a layer of TiO2, for example, in the form of nanotubes, and then immersing the treated substrate in an antimicrobial metal-containing solution (e.g., silver ions) to allow the metal ions to adhere and form an antimicrobial surface. However, since the surface treatment gives an oxide layer, the antimicrobial layer may peel or break due to the limited bonding strength between the oxide layer and the metal body under the influence of adsorption and friction, or due to the brittleness of the material, potentially leading to a premature loss of the antimicrobial effect. Antimicrobial alloy substrates having a porous structure on their surface can be obtained by directly adding / mixing an antimicrobial metal (e.g., copper) with a metal substrate and subjecting them to anodizing and high-temperature nitriding treatments, thereby releasing antimicrobial metal ions and exhibiting an antimicrobial effect. Nevertheless, the antimicrobial metal in the alloy does not have ionic bonds or polarity, and its ability to release ions in aqueous solutions (e.g., under biological conditions) is weakened, which may reduce the antimicrobial effect.

[0046] Therefore, this disclosure provides additively manufactured antimicrobial composite materials, their applications, and methods for manufacturing the same to overcome these problems.

[0047] Additive-type antimicrobial composite materials

[0048] The additively manufactured antimicrobial composite material comprises (a) a metal or alloy substrate, (b) an inorganic carrier, and (c) an antimicrobial metal, the antimicrobial metal being present within the substrate metal or substrate alloy, or adsorbed within the embedded inorganic carrier. Details of the components and structure are as follows.

[0049] (a) base metal or base alloy

[0050] The antimicrobial composite materials in this disclosure are prepared by additive manufacturing (AM). Various metallic and nonmetallic materials can be used in the AM method, and biocompatible materials, particularly metals or alloys thereof such as titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu), and magnesium (Mg), are used herein. Preferably, Ti, Ti alloys (e.g., Ti-6Al-4V, Ti6242, etc.), Zr alloys (e.g., Zr-Cu-Al-Nb, Zr-Cu-Ni-Al-Ti, Zr-Cu-Ni-Al-Nb), stainless steel, and Co alloys (e.g., Co-Cr-Mo, Co-Cr-W, etc.) are used.

[0051] While not bound by theory, the base metal or base alloy is either not alloyed with the antimicrobial metal used herein, or is alloyed with it in minimal or trace amounts, in order to avoid interfering with the release of the antimicrobial metal.

[0052] (b) Inorganic support

[0053] In this disclosure, inorganic carriers are used to support (adsorb) antimicrobial materials and are present within and / or embedded within a base metal or base alloy. Inorganic carriers can also prevent or interfere with oxidation / reduction reactions or alloying between the antimicrobial metal and the base metal / alloy. Furthermore, inorganic carriers are advantageous in the release of antimicrobial metals compared to existing antimicrobial composite materials in implants. For example, in one embodiment, the antimicrobial metal in ionic form is adsorbed within the inorganic carrier in the absence of ionic bonding between the antimicrobial metal and the inorganic carrier. In any of the aforementioned embodiments, the antimicrobial metal in ionic form is adsorbed within the inorganic carrier via electrostatic force. In another embodiment, the inorganic carrier is present within a base metal or base alloy. In yet another embodiment, the inorganic carrier is present within a base metal or base alloy and embedded within the base metal or base alloy.

[0054] In particular, alkaline earth metals or Group IV (IVB) metals phosphates, alkaline earth metals carbonates, alkaline earth metals(plural) or alkali metals(plural) sulfates, zeolites, bentonite, diatomaceous earth, bioglass, and any mixture thereof can be used as inorganic carriers according to this specification.

[0055] Examples of phosphates include, but are not limited to, apatite (e.g., hydroxy- / chloro- / fluoro-apatite) or pure phosphates (e.g., those that do not contain hydroxy / chloro / fluoro in the crystal). Examples of alkaline earth metals include, but are not limited to, magnesium (Mg) and calcium (Ca), preferably Ca. The metal of Group IVB is preferably zirconium (Zr). Examples of phosphates of alkaline earth metals or metals of Group IVB include, but are not limited to, calcium phosphate, calcium hydroxyapatite, or zirconium phosphate.

[0056] Examples of alkaline earth metal carbonates include, but are not limited to, calcium carbonate.

[0057] Examples of sulfates of alkaline earth metals (or alkali metals) (or alkali metals) include, but are not limited to, sodium sulfate, potassium sulfate, magnesium sulfate, and calcium sulfate, preferably calcium sulfate.

[0058] Examples of zeolites include, but are not limited to, LTA (Linde A type), MOR type, HEU type, and ANA type.

[0059] Examples of bentonite include, but are not limited to, Na-montmorillonite and Ca-montmorillonite.

[0060] Examples of bioglass include, but are not limited to, bioglass 45S5 or derivative forms of bioglass 45S5, such as those having different CaO / P2O5 ratios.

[0061] In one embodiment, the inorganic support is present in an amount of 1.0% by weight or less relative to the total weight of the composite material, for example, 0.8% by weight or less, 0.6% by weight or less, 0.5% by weight or less, 0.4% by weight or less, or 0.3% by weight or less.

[0062] (c) Antibacterial metal

[0063] Antimicrobial metals exhibit potent inhibition of bacterial adhesion, growth, and / or proliferation. In this disclosure, the antimicrobial metals are in the form of elements or ions, rather than alloys.

[0064] Examples of antimicrobial metals include, but are not limited to, silver (Ag), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), tantalum (Ta), and their ionic forms(s), preferably Ag, Cu, Zn, Co and their ionic forms(s), and any mixture thereof in non-alloy forms.

[0065] In one embodiment, the antimicrobial metal is present in an amount that exhibits an antimicrobial effect, for example, at least 0.005% by weight (50 ppm), for example, at least 0.01% by weight (100 ppm), at least 0.1% by weight, at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight, at least 0.5% by weight, at least 0.75% by weight, at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 4% by weight, or at least 5% by weight, relative to the total weight of the composite material.

[0066] In one embodiment, the antimicrobial metal in ionic form is formed in situ during the additive manufacturing process. In another embodiment, the antimicrobial metal in ionic form is released under specific conditions, such as biological conditions.

[0067] In one embodiment, the antimicrobial metal combined with the inorganic carrier is present in an amount of at least 0.1% by weight, for example, at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight, at least 0.5% by weight, at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 3.5% by weight, at least 4% by weight, at least 5% by weight, or at least 7.5% by weight, relative to the total weight of the composite material.

[0068] In one embodiment, the weight ratio of the antimicrobial metal to the inorganic carrier is 0.03 or less, for example, 0.025 or less, 0.02 or less, 0.019 or less, 0.018 or less, or 0.015 or less. While not theoretically bound, this weight ratio may reflect the effectiveness or limitation of protection provided by the inorganic carrier.

[0069] In one embodiment, the antimicrobial metal includes less than 0.05 mol%, preferably less than 0.025 mol%, of its oxide form. While not bound by theory, the release of the oxide form of the antimicrobial metal may be slower than the release of the elemental or ionic form of the antimicrobial metal, particularly under certain conditions.

[0070] In one embodiment, the relative density of the composite material to components (a), (b), and (c) is at least 20%.

[0071] The antimicrobial composite material is prepared by additive manufacturing, and details are described herein.

[0072] In one embodiment, component (b) is present in an amount of 0.05% to 0.3% by weight relative to the total weight of the composite material, and component (c) is present in an amount of 0.005% (50 ppm) to 0.015% (150 ppm) relative to the total weight of the composite material. In any of the aforementioned embodiments, component (c) is silver. In any of the aforementioned embodiments, component (b) is bioglass. In any of the aforementioned embodiments, component (a) is titanium or a titanium alloy.

[0073] Additive manufacturing method for producing antimicrobial composite materials

[0074] Conventional powder metallurgy, metal injection molding (MIM), binder smelting, and material extrusion modeling (MEX) can all be used to manufacture metallic and nonmetallic composites. A common feature of these methods is the use of a binder (usually organic) to pre-form the powder, followed by a debindering process at high temperatures to remove the binder, and then sintering the metallic particles together while retaining the nonmetallic particles within the metallic substrate. Nevertheless, sintering methods are typically more complex, and the finished product usually has a lower relative density (e.g., 85-93%) than additively manufactured products, resulting in reduced mechanical strength.

[0075] Therefore, this disclosure relates to a method for preparing an additively manufactured antimicrobial composite material, wherein the composite material is

[0076] (a) A base metal or base alloy containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu), and magnesium (Mg),

[0077] (b) an inorganic carrier comprising a material selected from the group consisting of alkaline earth metals (or multiple) or phosphates of Group IV (IVB) metals, alkaline earth metals (or multiple) carbonates, alkaline earth metals (or multiple) sulfates, zeolites, bentonite, diatomaceous earth, bioglass and any mixture thereof, or

[0078] (c) Antimicrobial metals in elemental or ionic form, selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), tantalum (Ta), and any mixture thereof in non-alloy form. Includes,

[0079] The method is The antimicrobial metal is filled into an inorganic carrier, and the inorganic carrier is present in or embedded within the base metal or alloy.

[0080] (i) A step of providing particles of a base metal or base alloy, particles of an inorganic carrier, and particles of an antimicrobial metal,

[0081] (ii) A step of performing powder bed fusion on the particles by selectively melting a specified region of the particles and fusing the particles with a solid layer,

[0082] (iii) A process of repeating steps (i) and (ii) to construct an additively manufactured antimicrobial composite material layer by layer according to the digital design. This provides a method that includes [something].

[0083] In one embodiment, step (i) includes ball milling of particles. In a particular embodiment, the ball milling method includes (1) sequentially feeding inorganic carrier, base metal or base alloy powder and grinding medium into a ball mill chamber; (2) rotating the chamber at a controlled speed for a specified period of time to achieve close contact between materials by impact and shear; and (3) discharging the homogenized mixture when a predetermined level of uniformity is reached. In one embodiment, step (i) includes spreading a thin layer of (fresh) particles on a platform.

[0084] In one embodiment, materials (a), (b), and (c) exist in a molten state, and the period during which (a), (b), and (c) exist in a solid state is controlled to reduce their oxidation. While not bound by theory, controlling the melting / solidification period in the method prevents or reduces oxidation-reduction between the inorganic support, antimicrobial metal, and metal substrate. This allows the inorganic support and antimicrobial metal to be retained and uniformly dispersed within the metal substrate, and the antimicrobial properties can still be maintained even if the composite material is subjected to abrasion during use.

[0085] Furthermore, additive manufacturing methods can provide metal substrates with a high specific surface area and porous structure, which leads to increased release of metal ions, and the method can be adjusted to modify or improve the mechanical strength of the product. Lastly and importantly, additive manufacturing methods can reduce cumbersome post-processing and minimize the risk of bacterial contamination during transport.

[0086] In one embodiment, the antimicrobial metal in ionic form is formed in situ during the additive manufacturing process, particularly during melting.

[0087] In one embodiment, the inorganic carrier does not exhibit or provide an antibacterial effect.

[0088] In one embodiment, additive manufacturing is performed using laser powder bed fusion.

[0089] In additive manufacturing methods, one or more of the following process parameters can be adopted or adjusted.

[0090] (1) Laser output of 1W to 300W, for example 5W to 15W, 10W to 250W, 15W to 35W, 50W to 75W, approximately 100W, 40W to 180W, 25W to 275W, approximately 150W, 60W to 90W, 80W to 200W, 120W to 130W, 20W to 30W, 175W to 225W, or any single point, or a reasonable numerical range composed of the values ​​of the above points, for example 275W to 300W, 30W to 80W, etc.

[0091] (2) Scanning speed of 3 m / s or less, for example, 2.5 m / s or less, 2 m / s or less, 1 m / s or less,

[0092] (3) A scanning strategy selected from the group consisting of checkerboard, stripe, contour and meander,

[0093] (4) Preheating temperature of the platform in additive manufacturing: 50°C to 200°C, for example, approximately 175°C, 65°C to 70°C, 60°C to 120°C, 55°C to 100°C, approximately 150°C, 80°C to 130°C, or any single point, or a reasonable numerical range composed of the values ​​of the above points, for example, 120°C to 130°C, approximately 80°C, etc.

[0094] (5) Thickness of each layer: 20 μm to 100 μm, for example, approximately 25 μm, approximately 50 μm, approximately 75 μm, 30 μm to 40 μm, 80 μm to 90 μm, 35 μm to 60 μm, or any single point, or a reasonable numerical range composed of the values ​​of the above points, for example, 40 μm to 50 μm, approximately 80 μm, etc.

[0095] (6) Oxygen content (v / v): 0.05% to 3% (v / v) of the total volume in the construction chamber, for example, about 0.5%, about 1.5%, about 0.15%, 0.075% to 0.1%, less than 2.5%, 0.25% to 0.75%, less than 2%, or any single point, or a reasonable numerical range consisting of the values ​​of the points mentioned above, and

[0096] (7) Inert gas flow velocity: 0.1 m / s to 3 m / s, for example, approximately 1.75 m / s, 0.3 m / s to 0.5 m / s, 1.5 to 2.5 m / s, 1 m / s to 2 m / s, or any single point, or a reasonable numerical range consisting of the values ​​of the points mentioned above.

[0097] Applications of additive manufacturing antimicrobial composite materials

[0098] The additively manufactured antimicrobial composite material may be applied to part or all of implant components, such as artificial joints, inserts or temporary fixation devices associated with artificial joints, cosmetic implants such as facial implants and cranial implantation plates, pacemakers, stents, and cardiovascular implants such as artificial heart valves, or dental implants.

[0099] While not bound by theory, as described herein, implant components containing composite materials can maintain their antimicrobial properties even when subjected to wear during use, thereby extending the lifespan and durability of the implant components. [Examples]

[0100] The following examples are provided to illustrate the present invention to those skilled in the art without limiting its scope.

[0101] Materials, methods, and test models Ti64 powder with a particle size of 15-53 μm (available from Shandong Lianhong New Material Technology Co., Ltd.) was used. Silver-containing glass powder is available from Ishizuka Glass Co., Ltd.

[0102] The porosity can be measured with the Hitachi TM4000Plus.

[0103] Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) were employed for imaging and elemental analysis to position the materials.

[0104] The antibacterial effect was evaluated according to JIS Z 2801, using Staphylococcus aureus (BCRC 10451 strain). Mechanical properties, including tensile strength and elongation, were evaluated based on ASTM E8. Surface properties were evaluated using ULVAC-PHI PHI 5000 Versaprobe II.

[0105] Additive manufacturing is performed using a Trumpf laser (e.g., Truprint 2000).

[0106] Examples Ti64 powder was used as the base metal / alloy. Silver-containing glass powder adsorbed within the inorganic support was used as an antimicrobial metal in combination with the inorganic support. The powders were mixed and used in additive manufacturing or processed by arc melting under vacuum. Different proportions or levels of material were used. The parameters are listed in Table 1 below. [Table 1]

[0107] The powder composition (weight %) is P (20-30), Al (2-10), Mg (1-5), Na (1-5), Si (0.1-1.0), Ag (1-5), with the remainder being O.

[0108] The properties of the product are summarized in Table 2 below. [Table 2]

[0109] To determine the dispersion of antimicrobial metal / inorganic carriers within the substrate, samples were polished, pulverized, and examined by SEM. Samples were selected from specific locations, and images were obtained. The contrast between light and dark zones allowed for preliminary observation and confirmation of the inorganic carrier distribution.

[0110] Further analysis of elemental distribution was performed using EDS. The elemental distribution map allows for confirmation of the location of the inorganic support and whether or not the antimicrobial metal is retained within the inorganic support. The homogeneity of the material can also be evaluated.

[0111] The present invention exhibits superior effects that exceed existing objectives, for example, providing sufficient antimicrobial effects while maintaining equivalent mechanical properties. Although not bound by theory, in conventional metal forming methods, high-temperature metals are highly reactive, and reduction or alloying may reduce the release of antimicrobial metals in inorganic oxides. However, according to this disclosure, by optimizing the process parameters of the powder bed laser, the reaction time between the antimicrobial metal and the metal substrate at high temperatures can be shortened, thereby reducing the reaction at high temperatures. The retained non-alloyed antimicrobial metal can be more easily released from the surface, achieving a better antimicrobial effect.

[0112] Those skilled in the art should understand that modifications and alterations may be made to the teachings and disclosures of the present invention without departing from the spirit and scope of this application. Based on the foregoing, this application is intended to encompass such modifications and alterations, or equivalents thereof, provided that such modifications or alterations fall within the scope defined in the appended claims.

Claims

1. A laminated antimicrobial composite material, (a) A base metal or base alloy made of a base metal containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu), and magnesium (Mg), (b) an inorganic carrier comprising a material selected from the group consisting of alkaline earth metals (or more) or phosphates of Group IV (IVB) metals, alkaline earth metals (or more) carbonates, alkaline earth metals (or more) sulfates, zeolites, bentonite, diatomaceous earth, bioglass and any mixture thereof, (c) Antimicrobial metals in elemental or ionic form, selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), tantalum (Ta), and any mixture thereof in non-alloy form. Includes, The antibacterial metal is adsorbed within the inorganic carrier, and the inorganic carrier is present in or embedded within the base metal or base alloy. Additive-type antimicrobial composite material.

2. The composite material according to claim 1, wherein the weight ratio of the antibacterial metal to the inorganic carrier is 0.03 or less.

3. The composite material according to any one of claims 1 to 2, wherein the antibacterial metal is present within the inorganic carrier.

4. The composite material according to any one of claims 1 to 3, wherein the substrate is porous.

5. The composite material according to any one of claims 1 to 4, wherein the antibacterial metal in ionic form is adsorbed within the inorganic carrier in the absence of ionic bonding between the antibacterial metal and the inorganic carrier.

6. The composite material according to any one of claims 1 to 5, wherein the antibacterial metal in ionic form is formed in situ during the additive manufacturing method.

7. The composite material according to any one of claims 1 to 6, wherein the antibacterial metal is present in an amount of at least 0.005% by weight (50 ppm) relative to the total weight of the composite material.

8. The composite material according to any one of claims 1 to 7, wherein the antibacterial metal combined with the inorganic carrier is present in an amount of at least 0.1% by weight relative to the total weight of the composite material.

9. The composite material according to any one of claims 1 to 8, wherein the relative density of the composite material with respect to the constituent elements (a), (b), and (c) is at least 20%.

10. The composite material according to any one of claims 1 to 9, wherein the substrate is made of Ti, Ti alloys (e.g., Ti-6Al-4V, Ti6242, etc.), Zr, Zr alloys (Zr-Cu-Al-Nb, Zr-Cu-Ni-Al-Ti, Zr-Cu-Ni-Al-Nb), stainless steel, Co alloys (e.g., Co-Cr-Mo, Co-Cr-W, etc.).

11. The composite material according to any one of claims 1 to 10, wherein the inorganic carrier does not exhibit or provide an antibacterial effect.

12. Use of the composite material according to any one of claims 1 to 11 in an implant component.

13. The use according to claim 12, wherein the implant component is an artificial joint, an insert or temporary fixation device related to an artificial joint, a cosmetic implant such as a facial implant or cranial plate, a pacemaker, a stent, and a cardiovascular implant such as an artificial heart valve, or part or all of a dental implant.

14. A method for preparing an additively manufactured antimicrobial composite material, wherein the composite material is (a) A base metal or base alloy made of a base metal containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu), and magnesium, (b) an inorganic carrier comprising a material selected from the group consisting of alkaline earth metals (or more) or phosphates of Group IV (IVB) metals, alkaline earth metals (or more) carbonates, alkaline earth metals (or more) sulfates, zeolites, bentonite, diatomaceous earth, bioglass and any mixture thereof, (c) Antimicrobial metals in elemental or ionic form, selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), tantalum (Ta), and any mixture thereof in non-alloy form. Includes, The method described above is The antibacterial metal is adsorbed within the inorganic carrier, and the inorganic carrier is present in or embedded within the base metal or base alloy. (i) A step of providing particles of the base metal or the base alloy, particles of the inorganic carrier and particles of the antibacterial metal, (ii) A step of performing powder bed fusion on the particles by selectively melting a specified region of the particles and fusing the particles with a solid layer, (iii) A process of repeating steps (i) and (ii) to construct the additively manufactured antimicrobial composite material layer by layer according to the digital design. Methods that include...

15. The method according to claim 14, wherein the antimicrobial metal in ionic form is formed in situ during the additive manufacturing method.

16. The method according to claim 14 or 15, wherein the period during which materials (a), (b), and (c) exist in a molten state, and the period during which materials (a), (b), and (c) exist in a solid state, are controlled to reduce oxidation of these materials.

17. The method according to any one of claims 14 to 16, wherein the inorganic carrier does not exhibit or provide an antibacterial effect.

18. The method according to any one of claims 14 to 17, wherein the additive manufacturing is performed using powder bed fusion.

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