CN-122005913-A - Additive manufactured antibacterial composite material, application and preparation method thereof

Abstract

The present disclosure relates to antibacterial composites made by Additive Manufacturing (AM), and methods of use and preparation thereof.

Inventors

• ZHANG RENXIAN
• TANG WEICHENG
• HUANG YANGSHENG
• LIU XISHENG

Assignees

• 新亚精密材料股份有限公司

Dates

Publication Date

20260512

Application Date

20251112

Priority Date

20241112

Claims (18)

1. 1. An additively manufactured antibacterial composite comprising: (a) A substrate made of a substrate 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; (b) An inorganic support comprising a material selected from the group consisting of phosphates of alkaline earth metals or group 4 (IVB) metals, carbonates of alkaline earth metals, sulfates of alkaline earth metals, zeolites, bentonite, diatomaceous earth, bioglass, and any mixtures thereof; (c) An antibacterial metal in elemental or ionic form and 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 mixtures thereof in non-alloyed form; Wherein the antibacterial metal is supported within the inorganic carrier, and the inorganic carrier is provided within or embedded within the substrate metal or alloy.
2. 2. The composite of claim 1, wherein the weight ratio of the antibacterial metal to the inorganic carrier is no greater than 0.03.
3. 3. The composite material of any one of the preceding claims, wherein the antibacterial metal is provided within the inorganic support.
4. 4. The composite material of any one of the preceding claims, wherein the substrate is porous.
5. 5. The composite material of any one of the preceding claims, wherein the antibacterial metal in ionic form is supported in the inorganic support without an ionic bond between the antibacterial metal and the inorganic support.
6. 6. The composite material of any one of the preceding claims, wherein the antibacterial metal in ionic form is formed in situ during an additive manufacturing process.
7. 7. The composite of any one of the preceding claims, wherein the antibacterial metal is provided in an amount of at least 0.005 wt% (50 ppm) by total weight of the composite.
8. 8. The composite of any one of the preceding claims, wherein the combination of the antibacterial metal and the inorganic carrier is provided in an amount of at least 0.1 wt% by total weight of the composite.
9. 9. The composite of any one of the preceding claims, wherein the relative density of the composite with respect to the components (a), (b), and (c) is at least 20%.
10. 10. The composite material of any one of the preceding claims, wherein the substrate is made of Ti, ti alloys (e.g. Ti-6Al-4V, ti6242, etc.), 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. 11. The composite material of any one of the preceding claims, wherein the inorganic carrier does not exhibit or provide an antibacterial effect.
12. 12. Use of a composite material according to any of the preceding claims in an implant component.
13. 13. Use according to claim 12, wherein the implant component is part or all of an artificial joint, an insert associated with an artificial joint, or a temporary anchorage device, a cosmetic implant such as a facial implant, a cranioplasty plate, a cardiovascular implant such as a cardiac pacemaker, a stent and an artificial heart valve, or a dental implant.
14. 14. A method of preparing an additively manufactured antibacterial composite material, the composite material comprising: (a) A substrate made of a substrate 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; (b) An inorganic support comprising a material selected from the group consisting of phosphates of alkaline earth metals or group 4 (IVB) metals, carbonates of alkaline earth metals, sulfates of alkaline earth metals, zeolites, bentonite, diatomaceous earth, bioglass, and any mixtures thereof; (c) An antibacterial metal in elemental or ionic form and 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 mixtures thereof in non-alloyed form; the method comprises the following steps: (i) Providing particles of the substrate metal or the substrate alloy, particles of the inorganic support, and particles of the antibacterial metal; (ii) Powder bed melting of the particles is performed by selectively melting designated regions of the particles and melting the particles into a solid layer, and (Iii) Repeating steps (i) and (ii) to build the additive-fabricated antibacterial composite layer-by-layer according to a digital design, Such that the antibacterial metal is supported within the inorganic carrier, and the inorganic carrier is provided within or embedded within the substrate metal or alloy.
15. 15. The method of claim 14, wherein the antibacterial metal in ionic form is formed in situ during an additive manufacturing process.
16. 16. A method according to claim 14 or 15, wherein the time period during which the materials (a), (b) and (c) are provided in molten form and the time period during which the materials (a), (b) and (c) are provided in solid form are controlled so as to reduce oxidation of these materials.
17. 17. The method of any one of claims 14 to 16, wherein the inorganic carrier does not exhibit or provide an antibacterial effect.
18. 18. The method of any one of claims 14 to 17, wherein the additive manufacturing is performed by powder bed melting.

Description

Additive manufactured antibacterial composite material, application and preparation method thereof Technical Field The present disclosure relates to an antibacterial composite material made by Additive Manufacturing (AM), and applications and methods of making the same. Background Medical implant assemblies are used in a variety of clinical and healthcare applications to provide benefits during or after medical treatment. Advances in materials science and medical science continue to benefit patients undergoing surgery or implants. For example, artificial joints can improve motor function in patients with age-related disorders or diseases, and can extend the active life of the patient. However, concerns remain regarding prognosis of surgical or medical implants, particularly bacterial infections or related effects, which may be the basis for additional surgery or even lead to implant failure and removal. Thus, there is a need for novel and cost-effective antibacterial composite materials, in particular medical implants, and methods for their preparation. Disclosure of Invention The present disclosure thus relates to an additively manufactured antibacterial composite comprising: (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); (b) An inorganic support comprising a material selected from the group consisting of phosphates of alkaline earth metals or group 4 (IVB) metals, carbonates of alkaline earth metals, sulphates of alkaline earth metals, zeolites, bentonite, diatomaceous earth, bioglass and any mixtures thereof, and (C) An antibacterial metal in elemental or ionic form and 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 mixtures thereof in non-alloyed form, wherein the antibacterial metal is supported within the inorganic carrier and the inorganic carrier is provided within or embedded within the substrate metal or alloy. The disclosure also relates to the use of the composite material for an implant component. The present disclosure also relates to a method of preparing an additively manufactured antibacterial composite material, the composite material comprising: (a) A substrate of a substrate 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); (b) An inorganic support comprising a material selected from the group consisting of phosphates of alkaline earth metals or group 4 (IVB) metals, carbonates of alkaline earth metals, sulphates of alkaline earth metals, zeolites, bentonite, diatomaceous earth, bioglass and any mixtures thereof, and (C) An antibacterial metal in elemental or ionic form and 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 mixtures thereof in non-alloyed form, the method comprising: (i) Providing particles of the substrate metal or the substrate alloy, particles of the inorganic support, and particles of the antibacterial metal; (ii) Powder bed melting of the particles is performed by selectively melting designated regions of the particles and melting the particles into a solid layer, and (Iii) Repeating steps (i) and (ii) to build an additive manufacturing antibacterial composite layer by layer according to a digital design. The additive manufactured antibacterial composite thus prepared is characterized in that the antibacterial metal is supported in an inorganic carrier, and the inorganic carrier is provided in or embedded in the substrate metal or alloy. In one embodiment, the combination of antibacterial metal and inorganic carrier is provided in an amount of at least 0.1 wt%, such as at least 0.2wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 0.75 wt%, at least 1 wt%, at least 2wt%, at least 3 wt%, at least 4 wt%, or at least 5wt%, based on the total weight of the composite. In any of the foregoing embodiments, the antibacterial metal is provided in an amount of at least 0.005 wt%, such as at least 0.01wt%, at least 0.02 wt%, at least 0.03 wt%, at least 0.04 wt%, at least 0.05wt%, at least 0.075 wt%, at least 0.1wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, or at least 0.5 wt% by total weight of the composite. In any of the foregoing embodiments, the antibacterial metal is provided within an inorganic carrier. In any of the foregoing embodiments, the inorganic carrier is provided within and embedded within the substrate metal or alloy. In any of the foregoing embodiments, examples of phosphate include, but are not limited to, apatite (e.g., hydroxyapatite/chloroapatite/fluoroapatite) or pure phosphate, preferably calcium phosphate, calcium hydroxyapatite or zi