Component with a mineralized polymer structure and a method for its production

Abstract

In a process for producing a mineralized polymer component, a support structure (1) made of a polymer-based material is formed from an image data set, wherein the support structure (1) has at least a first region (5) in which the polymer-based material is formed and at least a second region (2) which is formed as a hollow structure. Subsequently, at least one inorganic mineral phase is formed on the surface of the support structure (1) and / or within the first region (5) and / or on at least one internal surface of the first region (5).

Description

[0001] The present invention relates to a mineralized polymer component and a method for producing a mineralized polymer component.

[0002] The integration of manufactured components into existing structures plays a crucial role in fields such as construction and medical technology. For implants or bone substitutes, in particular, successful and rapid integration into the body's own tissue structures is essential. The better the structural properties of the tissue structure, such as bone, can be replicated, the better the "artificial" implant integrates. Vascular structures play a particularly important role in ensuring good ingrowth into bone tissue. These specialized, highly branched, vertically and horizontally oriented channels (Haversian and Volkmann canals) ensure that the bone tissue is supplied with blood and nutrients from all sides, thus enabling natural tissue formation and resorption processes.These structures are very small-scale, ranging in size from 20 µm - 40 µm or 70 µm - 200 µm.

[0003] Currently, no technical solution exists to artificially create the aforementioned complex and branched structures from bone-like materials (containing calcium phosphate) and thus produce implants that enable ingrowth and therefore bone modeling, bone remodeling, bone restoration, or bone regeneration. Studies have already been conducted that attempt to create similarly fine structures to vascularization structures using bone-like materials. These studies primarily draw on biological models. Among other things, they demonstrate how nanoscale hydroxyapatite (i.e., a calcium phosphate) can be produced in natural collagen fibril structures (micrometer-sized, uniformly arranged vertical channel structures) through chemical reactions. This is done, for example, by...This involves infiltrating such fibril structures in a calcium solution with hydrogen phosphate to form a material hybrid of collagen and hydroxyapatite. It is also possible to use natural plant and wood structures (e.g., rattan) as a starting material, converting the naturally fiber-formed structure into calcium phosphate (also hydroxyapatite) via very energy-intensive subsequent processes. For this, the rattan structure must first be pyrolyzed at 1000 °C to transform it into a carbon structure. This is then converted to CaC₂ via a calcium vapor process, subsequently oxidized to CaO (and released CO₂), then carbonated to CaCO₃, and finally transformed to hydroxyapatite by phosphatation with potassium phosphate. Here, too, only uniform, vertical channel structures are present. This means that, at best, only one-dimensional fluid transport can occur.Furthermore, the process is very energy-intensive and therefore costly.

[0004] To avoid these disadvantages, DE 10 055 465 A1 discloses a method for manufacturing a bone replacement implant consisting of a polymer matrix with embedded inorganic, non-metallic filler particles. In this process, the implant is built up layer by layer from a powdered mixture of the matrix polymer and the filler particles using laser sintering. A disadvantage of this method is that the filler concentration must be determined at the beginning of the process and cannot be changed subsequently. Therefore, the implant properties, which are largely determined by the filler concentration, cannot be flexibly adapted to the specific application. This limits the individual integration capabilities of the component.

[0005] Furthermore, US 8,710,144 B2 describes a powder for use in the production of three-dimensional structures, i.e., shaped bodies, using a layer-by-layer process, as well as a method for their efficient production. The powders are characterized by their good flow properties and their composition, such that the shaped body produced with the powder in rapid prototyping exhibits significantly improved mechanical and / or thermal properties. The powder comprises a first component in the form of spherical powder particles formed by a matrix material, and a second component in the form of stiffening and / or reinforcing fibers, preferably embedded in the matrix material. A disadvantage of this method is the limited individual integration capability of the component.

[0006] The present invention is therefore based on the objective of proposing a method for manufacturing a component and a component itself which has an improved integration capability into existing material structures.

[0007] This problem is solved according to the invention by a method for producing a mineralized polymer component according to claim 1 and by a mineralized polymer component according to claim 6. Advantageous embodiments and further developments are described in the dependent claims.

[0008] In a process for manufacturing a mineralized polymer component, a support structure made of a polymer-based material is formed from an image data set. The support structure has at least a first region in which the polymer-based material is formed and at least a second region that is designed as a hollow structure. Subsequently, at least one inorganic mineral phase is formed on the surface of the support structure and / or within the first region and / or on at least one internal surface of the first region.

[0009] The image dataset provides a high-resolution representation of the support structure to be manufactured, which is either acquired at the beginning of the process or already exists at the start of the process. Structures can be resolved at the nanometer scale, allowing even complex natural structures to be digitally recreated as image datasets, i.e., captured, or complex artificial structures to be generated. This high-resolution image dataset enables the fabrication of an equally high-resolution support structure. The geometries and dimensions found in reality, such as those of various physiological bones, can be reproduced. This means that the support structure can not only be manufactured with physiological precision in terms of its external appearance (geometry and shape), but also replicate the Haversian and Volkmann canals that run through the real bone.As a result, the support structure has almost identical geometric properties to a given bone for which an implant or bone replacement material is to be provided.

[0010] The deposition of at least one inorganic mineral phase can further improve the similarity to the existing structure being replicated or replaced. The inorganic mineral phase, among other things, enhances the integration potential into the existing structure. This is advantageous, for example, for implants, bone implants, or bone substitute materials, as the formation of a bone-like inorganic mineral phase can significantly improve biointegration into the surrounding tissue.

[0011] Furthermore, it is advantageous that the targeted formation of the mineral phase at different locations within the support structure can further improve the similarity to the structure being replicated or replaced. This means that by selectively forming the mineral phase, for example, on the inner surface of the first region, the ideal properties for the respective application can be achieved. Moreover, formation "within" the first region means that the mineral phase is completely enclosed by the polymer-based material. This can also mean that the mineral phase can completely fill the polymer-based material. Formation of the mineral phase "on the surface of the support structure" or "on the inner surface of the first region" means that the mineral phase at least partially covers the surface.Furthermore, a mineral phase covering part of the surface can also extend into the first region. This results in the mineral phase being partially located on the inner surface of the first region or on the surface of the supporting structure, and partially within the first region itself.

[0012] Furthermore, it can be provided that the inorganic mineral phase is formed by first surrounding the support structure with at least one first fluid containing at least one first element of the mineral phase and subsequently with at least one second fluid containing at least one second element of the mineral phase, and / or by flooding at least one second area.

[0013] Initially, within this application, "element" refers to chemical elements. "Surrounded" means that at least one surface is in contact with the fluids. The preferred state is that the support structure is completely surrounded by the fluids. This means that the fluid forms around the support structure on all sides. The "fluid flow" of the second region refers to both the first and the second fluid. This means that both the first fluid and subsequently the second fluid come into contact with the outer surface of the support structure as well as with the inner surfaces of the first region formed by the formation of the second region.This offers the advantage that first, at least one element of the respective mineral phase, and subsequently at least one other element of the respective mineral phase, accumulate at the described locations within the supporting structure. The inorganic mineral phase is then formed through the subsequent mineralization reaction, which involves, among other things, the accumulated elements. In particular, the mineral phase can thus form both within the first region and on its inner surface. Liquid fluids can be used particularly advantageously as the first and / or second fluid to introduce the elements into the second region, allowing the elements to be transported into the first region both across the surface of the supporting structure and across the inner surface of the first region.Furthermore, these fluids exhibit particularly good wettability for the polymer material used to form the support structure. Gaseous fluids can also be used as an alternative to liquid fluids.

[0014] A further advantage of this design is that the concentration of the inorganic mineral phase can be determined by the controllable and modifiable reaction conditions, i.e., for example, by the reaction time, the composition of the elements, and the concentration of the respective elements. Provided that sufficient reactants are present, a longer reaction time, for instance, means an increase in the concentration of the formed mineral phase. Furthermore, the ratio of the time periods during which the supporting structure is in contact with the first fluid versus the second fluid plays a crucial role with regard to the degree of mineralization. In principle, the formation of the inorganic mineral phase is determined or limited by the concentrations of the respective elements required to form the inorganic mineral phase.This means that the mineralization reaction can only take place as long as enough reactants, i.e., at least the first elements and the second elements, are present.

[0015] Alternatively, the inorganic mineral phase can be formed by doping the polymer-based material with at least one first element of the inorganic mineral phase before forming the support structure, and then surrounding the support structure, preferably the doped support structure, with a second fluid that has at least one second element of the mineral phase and / or flooding at least one second area.

[0016] An advantage of pre-doping the polymer-based material is that a defined dopant concentration can be determined in advance. This makes it possible to precisely control the concentration of the mineral phase via the concentration of a first element. The reaction of the first element with the second element to form the inorganic mineral phase is thus determined or limited by the dopant concentration of the first element.

[0017] Furthermore, the image data set can be acquired using imaging techniques, in particular digital volume tomography (DVT), and / or generated using computer-aided design methods.

[0018] In principle, the image dataset can include both two-dimensional and three-dimensional image data. Volumetric image datasets are particularly desirable. Using, for example, cone beam computed tomography (CBCT) can further improve the resolution, allowing for the quick and easy digital mapping of the structure to be replicated. Alternatively, structures can be generated or constructed using computer-aided design (CAD) methods. This refers specifically to CAD models (computer-aided design), which can include two-dimensional or three-dimensional representations. This allows for the design of support structures tailored to the specific application.

[0019] Furthermore, the support structure can be produced using an additive manufacturing process, in particular three-dimensional volumetric printing (3DVP), a gelation process, or a casting process.

[0020] The use of additive manufacturing processes offers the advantage of being able to produce flexible support structures adapted to the specific application in a very short time. This increases the flexibility of the process and expands its potential applications.

[0021] A component with a mineralized polymer structure has a support structure formed from a polymer-based material based on an image dataset, wherein the support structure has at least a first region in which the polymer-based material is formed and at least a second region which is formed as a hollow structure. Furthermore, at least one inorganic mineral phase is formed on the surface of the support structure and / or within the first region and / or on at least one internal surface of the first region.

[0022] These components, with their realistically mimicked structures into which they are to be integrated, make it possible to improve their integration into their environment, e.g., within an organism. Furthermore, the specific material combination chosen—that is, the combination of polymer material and mineral phase—allows for a wide range of applications.

[0023] Furthermore, the inorganic mineral phase may include minerals of the mineral class of oxides and hydroxides, in particular ZrO2 and Al2O3, and / or carbonates, in particular CaCO3, and / or phosphates, in particular Ca3(PO4)2, CaHPO4 and Ca5(OH)(PO4)3.

[0024] This wide variety of usable mineral phases further expands the application range of the components. For example, the formation of calcium phosphate (Ca3(PO4)2), calcium hydrogen phosphate (CaHPO4), and hydroxyapatite (Ca5(OH)(PO4)3) is particularly suitable for use in medical technology, such as bone regeneration or bone substitute materials. The use of zirconium oxide (ZrO2) and aluminum oxide (Al2O3), on the other hand, is particularly relevant for applications as technical ceramics in aerospace, automotive, and similar fields.

[0025] Furthermore, the supporting structure can be made of a hydrogel, in particular gelatin, agar, alginate or a structural protein, in particular collagen, or of biopolymers such as polycaprolactone (PCL) or polylactic acid (PLA) and / or the supporting structure can contain active substances, in particular antibiotics and / or bacteria, in particular cyanobacteria and / or plant cells and / or fungal cells and / or animal cells and / or human cells.

[0026] By forming the support structure from the materials listed above, the potential for integration into the environment, e.g., biointegration into organisms, is significantly increased, allowing the mineralized polymer component to be introduced into the body easily and with minimal rejection reactions. Rejection reactions can also be reduced by the described additives. These additives can be added before, during, or after the structuring process.

[0027] Furthermore, the second region can consist of branched channels with diameters ranging from 10 nm to 10 cm, preferably from 1 µm to 1 mm, and particularly preferably from 20 µm to 200 µm. The degree of mineralization can also range from 10 vol.% to 80 vol.%, preferably from 20 vol.% to 60 vol.%, and particularly preferably from 30 vol.% to 50 vol.%.

[0028] Initially, "branched" means that the channels extend in all spatial directions and can be interconnected in any way, thus forming a network of channels. Alternatively, the second area can also consist of a combination of different hollow structures. This allows for the reproduction of highly complex and detailed structures, further increasing the degree of similarity between the component and the structure into which it is to be integrated. Furthermore, the wide variability in the concentration ranges of the mineral phase expands the potential applications of the component.

[0029] The component can be manufactured using the described method, i.e., the method is suitable for manufacturing the described component.

[0030] Exemplary embodiments of the invention are shown in the drawings and are described below with reference to the Fig. Sections 1 to 4 are described. Recurring features are identified with identical reference symbols.

[0031] They show: Fig. 1 a schematic drawing of a support structure with branched channels; Fig. 2 a schematic interior view of a section of a support structure with branched channels; Fig. 3 a schematic representation of a first embodiment of the process for manufacturing a component with mineralized polymer structures and Fig. 4 a schematic drawing of a second embodiment of the process for manufacturing a component with mineralized polymer structures.

[0032] Fig. Figure 1 represents a support structure 1 of a mineralized polymer component, wherein the support structure 1 is formed from a polymer-based material. The support structure 1 has a first region 5, in which the polymer-based material is formed, and a second region 2. In this embodiment, the second region 2 is formed from branched channels with different diameters and geometries. Furthermore, the support structure 1 has four openings that represent the inlets and outlets of some of the branched channels, which thus form a hollow structure or cavity within the first region 5. This means that no polymer-based material is formed in the branched channels, i.e., the hollow structures, i.e., in the second region 2.Since the hollow structure is formed within the first region, the first region 5 defines the boundary of the hollow structure, such that an inner surface of the first region 5 is understood to be the surface that forms the transition between the first region 5 and the second region 2. Not shown in this embodiment is the fact that the openings of the channels can also be located on other surfaces of the support structure 1. This means that the channels can form a highly branched network within the support structure 1, allowing the channels to run in all spatial directions.

[0033] The branching canals are in Fig. 2 is shown again within the support structure 1. Here, a section A of the support structure 1 is shown. Fig. Figure 1 shows an interior view of the supporting structure 1, revealing numerous branches between the various channels. These connections or branches can extend in any spatial direction and may link one or more channels together. The connections between the channels are themselves considered channels, resulting in a channel network. In addition to this channel network, further areas 2 can also be formed as hollow structures, for example, extending horizontally from the supporting structure 1. These further areas 2 may be connected to the existing channel network, or they may not be connected to it. This allows for the formation of complex hollow structures within the first area 5.

[0034] In this embodiment, the support structure 1 is manufactured using three-dimensional volumetric printing (3DVP) based on a previously acquired image dataset for use as a bone substitute material. The formation of channels within the support structure 1 allows for the artificial regeneration of physiological bone. The network of channels within the support structure 1 replicates the canal structure of physiological bone (vascular structures) formed by the so-called Haversian and Volkmann canals, which are crucial for supplying the bone with nutrients. By artificially reproducing this network of channels in the support structure 1, the biointegration capacity of the support structure 1 is increased after its insertion into the respective bone. Furthermore, at least the structural mechanical properties of the support structure 1 are adapted to the respective bone tissue (e.g., the course of load trajectories).

[0035] As previously mentioned, the support structure 1 is formed based on an image dataset. This image dataset can be acquired, for example, using digital volume tomography (DVT). Particularly in the medical field, it is advantageous that this image dataset is acquired for each application, i.e., for each patient, thus being patient-specific and individualized. Since the properties and geometry of bone differ from person to person, an individualized reconstruction of the respective bone based on an individualized image dataset offers significant advantages with regard to the individualized biointegration of the respective support structure 1 within the respective bone.

[0036] Fig. Figure 3 schematically illustrates a possible process flow for manufacturing a component with mineralized polymer structures. As previously described, a volumetric 3D printing process (3DVP) is used, which allows the production of high-resolution vascular structures based on patient-specific data (e.g., CBCT) of a bone. Alternatively, the image data set can be generated using other imaging techniques or computer-aided design (CAD) methods, i.e., computer-generated two-dimensional or three-dimensional models of artificial or abstract geometries. The support structure 1 can also be manufactured using another additive manufacturing process, a gelation process, or a casting process. A gelatin-based (bio)polymer is used as the material for the support structure 1: this so-called...Gel-MA (gelatin methacrylate) can be a porcine gelatin functionalized with methacrylate, making it suitable for light-curing additive manufacturing. Alternatively, any other polymer suitable for light-curing additive manufacturing can be used.

[0037] Furthermore, the polymeric base material forming the support structure 1 can be combined with photoinitiators [such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO or Igracure 819), 2,2-dimethoxy-2-phenylacetophenone (DMPA or Igracure 651), lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate (LAP), and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO)] and / or monomers for light-curing and additive / generative / volumetric manufacturing processes. For example, methacrylic anhydride (MA) can be used as a monomer, which, together with gelatin, forms a methacryloyl-modified gelatin (GelMA), thus creating a popular (photo)chemically cross-linked, protein-based hydrogel-based biopolymer.

[0038] In the newly created three-dimensional (bio)polymer structure (support structure 1), nanometer-scale (bio)mineralization to calcium phosphate – e.g., hydroxyapatite – takes place in situ following three-dimensional volumetric fabrication. For this purpose, after printing, support structure 1 is immersed for 12 hours in a tank containing a first fluid 3, in this case a calcium chloride solution (CaCl₂). It is then removed and finally immersed for 12 hours in a tank containing a second fluid 4, in this case a disodium hydrogen phosphate solution (Na₂HPO₄). This means that the actual mineralization reaction starts as soon as support structure 1 is introduced into the second fluid 4 and ends as soon as one of the reactants has been completely consumed. Alternatively, support structure 1 can also be introduced first into the second fluid 4 and then into the first fluid 3. In this case, support structure 1 is surrounded by the fluids, ensuring that the channels are completely saturated.This leads to the formation of hydroxyapatite as an inorganic material phase within the channels. This can be described by the following two-step reaction equation. CaCl2 + Na2HPO4 → 2 NaCl + CaHPO4 1) 7 CaHPO4 + H2O → Ca5(PO4)3(OH) + 2 Ca(H2PO4)2 2)

[0039] This reaction proceeds particularly at a pH value in the range of 9–10, with the reaction time ranging from a few minutes to several days, depending on the desired degree of mineralization of the support structure 1. The degree of mineralization can generally be up to 80 vol%. Preferably, it is in the range of 20 vol% to 60 vol%, and particularly preferably in the range of 30 vol% to 50 vol%. Regarding the degree of mineralization, i.e., the desired mineral concentration within the support structure 1, the following reaction conditions are also crucial: first, the polymer concentration within the support structure 1, and subsequently, the amount of mineral to be formed. The higher the polymer concentration at the beginning of the material production process, the lower the degree of mineralization at the end.

[0040] Since the starting material can be a polymer solution, the base fluid used to dope the material with a mineral phase element is crucial in this case. Depending on the choice of fluid, this influences the degree of mineralization. The ion concentration within fluids 3 and 4 also has a decisive effect on mineral synthesis. Generally speaking, the higher the concentration, the greater the degree of mineralization. However, this only applies up to the point where saturation occurs and the excess ions can no longer form a mineral within the supporting structure 1. Therefore, the ratio of the ion concentrations within the fluids 3 and 4 used is also relevant.

[0041] The duration for which the support structure 1 is immersed in the respective solution also affects the degree of mineralization. However, this effect is limited, as ion saturation occurs within the support structure at a certain point. While mineral formation continues, no further ion exchange with the fluid 3, 4 takes place. Furthermore, the choice of hydrogel-based (bio)polymer material influences the degree of mineralization. The interactions with the aforementioned reaction conditions are particularly noteworthy in this context.

[0042] The formation of hydroxyapatite further increases the similarity between bone tissue and the component, as hydroxyapatite is a major constituent of physiological bone. This further improves the biointegration capacity of the component with mineralized polymer structures. The concentration of the mineral phase depends on the duration of the insertion process, the available elements, and the flow conditions. To achieve ideal biointegration, i.e., the most bone-like properties possible for the component, the ideal concentration is between 30% and 50% by volume.

[0043] Alternatively, the channel network can also be flooded with fluids without inserting the support structure. In this case, the fluids can be introduced into the channel network separately. It is also possible to flood only a portion of the channel network with the fluids, so that, for example, only one channel comes into contact with the fluids. Additionally, it is possible for the first fluid 3 and / or the second fluid 4 to surround the support structure 1 dynamically, rather than statically. This means that the fluids can flow around the support structure 1 and through the channels. Furthermore, it is possible to include additional fluids that surround the support structure 1 after the first fluid 3 and after the second fluid 4. An alternating, i.e., repeated, introduction of the support structure 1 into the first fluid and then into the second fluid is also possible.

[0044] This wide range of fluid introduction options allows for the selective formation of the mineral phase within the supporting structure in specific areas. For example, it is possible to achieve a higher concentration of the mineral phase in a particular section of the canal network. This enables the supporting structure 1 to be mineralized in such a way that the mineral concentration matches that of the tissue to be integrated (e.g., bone). This ensures that the supporting structure 1 is optimally adapted to the topology and composition of the existing tissue. This means that the mineral phase concentration does not need to be uniformly distributed throughout the volume of the supporting structure 1.

[0045] Fig. Figure 4, in contrast, shows another process variant, the difference being that the polymer-based material is additionally doped with an element of the subsequent mineral phase. Here, gel-MA is again used as the polymer material, which is dissolved in Na₂HPO₄, so that a doped complex structure 1a is produced by 3D printing. Subsequently, the complex structure 1a is immersed for 24 hours in a second fluid 4, in this case a solution containing calcium ions such as calcium chloride, analogous to the process in Figure 4. Fig. 3. Thus, the mineralization reaction begins; the calcium ions now migrate into the (bio)polymeric matrix material and form calcium phosphate in the form of hydroxyapatite.

[0046] The mineralization of support structure 1 or doped support structure 1a is therefore based in each case on ion and electron migration as well as diffusion processes. As a result, in both cases, a polymer-mineral composite with bone-like properties is present, similar to real bone in its formation, and possessing mimicked highly branched vascular structures. Such a component can accordingly be used as an inorganic-organic composite material without heat treatment or, alternatively, after sintering, as a novel bioceramic bone imitation.

[0047] Similarly, the channel network can also be flooded with the second fluid 4 without inserting the doped support structure 1a. In this case, the second fluid 4 can be introduced into the channel network separately. Furthermore, it is possible to flood only a portion of the channel network with the second fluid 4, so that, for example, only one channel comes into contact with the second fluid 4. Additionally, it is also possible for the second fluid 4 to surround the doped support structure 1a dynamically rather than statically. This means that the fluid 4 can flow around the doped support structure 1a and through the channels. It is also possible to provide for additional fluids that surround the doped support structure 1a after the second fluid 4. An alternating, i.e., repeated, introduction of the doped support structure 1a into different fluids is also possible.

[0048] Other gelatins, such as bovine or fish-based gelatins, can also be used as organic support structures. Biodegradable biopolymers like PCL (polycaprolactone) and PLA (polylactic acid), as well as collagen or other hydrogels, can also be used. The functionalization of the hydrogels can also be achieved in other ways. When used with the 3DVP shown here, only light-curing polymerization of the material is required. Furthermore, the (bio)polymeric material can be manufactured using a variety of other additive manufacturing methods, such as two-photon polymerization, fused filament fabrication, bioplotting, or stereolithographic methods.

[0049] Alternatively, the support structure 1 can also be produced via gelation and casting processes. The mineralization process can then take place within these processes as well. The in-situ production of the inorganic mineral phases themselves can include mineralization syntheses such as the one described for calcium phosphates (hydroxyapatite, tricalcium phosphate, etc.), calcium carbonates, but also other mineralization syntheses such as those for materials based on ZrO₂ or Al₂O₃. Other similar oxide and non-oxide inorganic materials can also be synthesized in this way, where molecular compounds are generated via appropriate electron / ion movement.

[0050] The most important advantage here is that mineral components can be enriched in technologically and industrially manufactured, structurally highly complex, small-scale and delicate support structures, thus allowing, for example, the aforementioned vascularization structures of natural bone to be imitated in an artificial bone structure. This, in turn, should lead to improved osseointegration of the construct and improved bone regeneration in the human body, and therefore to faster patient rehabilitation.

[0051] Furthermore, the mechanical properties of the support structure 1 can be achieved through a higher mineral content. This can be adjusted by the mineralization time or the ion concentration. This higher mineral content ensures, for example, that a sufficiently strong structure is present after sintering. In conjunction with topologically optimized geometric replicas of real bone, comparable mechanical properties could be achieved in the artificial bone. Alternatively, the mechanical properties can also be adjusted without sintering. In this case, the component, in its polymer-based and powder-filled state, can be remodeled by replicating the structural composition of real bone. The underlying stiffness can be influenced and controlled via the mineral content (either through mineralization time or chemical ratios).Alternatively, the mechanical properties can also be influenced by drying processes, but also by the choice of the material itself, which forms the polymer base.

[0052] Particularly through geometric design or CBCT scans, a bone-cartilage transition can be created within a composite structure. For this purpose, one section of a model can be designed to contain trabecular or spongy bone structures, while the other section remains as polymer. Only the spongy structure is then mineralized. This allows for the creation of an artificial bone-cartilage implant.

[0053] Additional active ingredients (e.g. antibiotics), bacteria (e.g. cyanobacteria), plant cells or fungal cells, or animal or human cells can also be added either via the aforementioned 3D printing (additive processes) or casting or gelation processes during these structuring methods and thus before mineralization, or also after structuring and during or after mineralization.

[0054] The main application lies in the development and manufacturing of bone replacement materials and implant structures. If calcium carbonates are produced in polymer constructs, applications in the construction sector are also possible. Furthermore, technical ceramics can be produced through mineralization in delicate complex polymer structures with other inorganic materials, e.g., based on ZrO2, Al2O3, and similar oxide and non-oxide materials.

Claims

[1] Method for producing a mineralized polymer component wherein starting from an image data set, a support structure (1) made of a polymer-based material is formed, wherein the support structure (1) has at least one first area (5) in which the polymer-based material is formed and at least one second area (2) which is formed as a hollow structure and then at least one inorganic mineral phase is formed on the surface of the support structure (1) and / or within the first area (5) and / or on at least one internal surface of the first area (5). [2] Method for producing a mineralized polymer component according to claim 1, characterized by, that the inorganic mineral phase is formed by first surrounding the support structure (1) with at least one first fluid (3) containing at least one first element of the mineral phase and subsequently with at least one second fluid (4) containing at least one second element of the mineral phase and / or by flooding at least one second region (2). [3] Method for producing a mineralized polymer component according to claim 1, characterized by , that the inorganic mineral phase is formed by doping the polymer-based material with a first element of the inorganic mineral phase prior to the formation of the support structure (1) and subsequently surrounding the support structure (1) with a second fluid (4) which has at least a second element of the mineral phase and / or by flooding at least a second region (2). [4] Method for producing a mineralized polymer component according to any one of the preceding claims, characterized by that the image data set is acquired using imaging techniques and / or generated using computer-aided design methods. [5] Method for producing a mineralized polymer component according to any one of the preceding claims, characterized by , that the support structure (1) is manufactured using an additive manufacturing process. [6] Containing mineralized polymer components: a support structure (1) formed from a polymer-based material based on an image data set, wherein the support structure (1) has at least one first area (5) in which the polymer-based material is formed and at least one second area (2) which is formed as a hollow structure and at least one inorganic mineral phase is formed on the surface of the support structure (1) and / or within the first area (5) and / or on an inner surface of the first area (5). [7] Mineralized polymer component according to claim 6, characterized by that the inorganic mineral phase comprises the minerals of the mineral class of oxides and hydroxides. [8] Mineralized polymer component according to one of claims 6 and 7, characterized by that the support structure (1) is formed from a hydrogel or a structural protein or from biopolymers and / or the support structure (1) contains active substances. [9] Mineralized polymer component according to any one of claims 6 to 8, characterized by , that the second region (2) is formed from branched channels with diameters in a range of 10 nm to 10 cm. [10] Mineralized polymer component according to claims 6 to 9, characterized bythat the degree of mineralization is in a range of 10 vol.% to 80 vol.%.

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