A selfcomposite

Abstract

The present invention fundamentally relates to a composite (selfcomposite) obtained by combining two physical forms of the same substance having different physical structures but the same chemical structure, and more particularly to a nano- micro hydroxyapatite selfcomposite substantially obtained by combining the properties of the microstructure of hydroxyapatite with the properties of its nanostructure.

Description

[0001] DESCRIPTION

[0002] A SELFCOMPOSITE

[0003] Technical Field

[0004] The present invention fundamentally relates to a composite (selfcomposite) obtained by combining two physical forms of the same substance having different physical structures but the same chemical structure, and more particularly to a nanomicro hydroxyapatite selfcomposite substantially obtained by combining the properties of the microstructure of hydroxyapatite with the properties of its nanostructure.

[0005] Background of the Invention

[0006] The fact that hydroxyapatite is a material that stands out with its properties of being biocompatible, having no cytotoxic effects, having various morphological structures and its ion-exchange and composite-combine capabilities makes its application areas rather wide. Hydroxyapatite has the most stable structure compared to calcium-phosphate (Ca / P) compounds; due to its Ca / P ratio being close to the Ca / P ratio in hard (tooth and bone) and soft (skin and muscle) tissues, and being a bioactive material by forming a structure completely integrated with the existing tissue by establishing chemical bonds in the body, it has become an indispensable biomaterial for bone-tissue engineering from the 1900s to the present day for the healing and repair of diseased and damaged structures in the body. Due to the porous structure of hydroxyapatite, the presence of both anionic and cationic sites in its structure and its capability to ionic exchanges, its crystallinity, its stability in temperature increases, and its being environmentally friendly as it does not contain cytotoxic effects and does not have toxic effects together with these properties, it is frequently used in the catalytic field. Hydroxyapatite is frequentlyused as an adsorbent due to its large surface area, its structural capability to ion exchange and composite formation, low water solubility and high thermal stability.

[0007] As can be understood from this brief information, the use of hydroxyapatite in industrial fields is very high. Hydroxyapatite has been used in these areas as microhydroxyapatite, nano-hydroxyapatite or composites of these two types with other materials different from hydroxyapatite. When used solely on their own, their own physical and chemical properties determine the efficiency of their use. Apart from the separate use of the two forms of hydroxyapatite, nano and micro, they are also used as composites with many different materials. The use of such composites combines the properties of two different materials; usually, in order to emphasize the properties of one of the components forming the composite, the support of the other material is provided by the composite. As a result, composite materials are used because the properties of the materials we have are insufficient in the relevant field; so far, solutions have always been sought for composites by using different materials together, which has caused time and economic losses.

[0008] However, a composite that will reveal high physical and chemical properties by combining two different forms of a material has not been found in the current technique. For this reason, there is a need for a structure that, through the use of the selfcomposite of an effective substance or material, will enable great breakthroughs in the field of science and materials in a very short time, make it possible to synthesize and produce many new materials, and reduce the production costs of many materials.

[0009] In the Chinese patent document no. CN115054733, an application included in the state of the art, discloses a preparation method of silk fibroin / hydroxyapatite composite micro-nano particle material. In the method, the auxiliary mineralization reaction is carried out by sequentially soaking the silk fibroin nanoparticle powder in a solution containing calcium ions and phosphate ions, and nucleation sites are generated on the surfaces of silk fibroin nanoparticles in the auxiliarymineralization reaction process; the growth of hydroxyapatite on silk fibroin nanoparticles can be promoted and meanwhile, the subsequent mineralization process is also facilitated; then, the mineralization reaction is carried out by soaking the silk fibroin nanoparticle powder subjected to auxiliary mineralization in simulated body fluid; so that hydroxyapatite crystals can be formed on the silk fibroin nanoparticle powder through self-assembly, and finally, after freeze-drying, the silk fibroin / hydroxyapatite composite micro-nano particle material is prepared. The silk fibroin / hydroxyapatite composite micro-nano particle material prepared according to the invention can be directly applied to the human body and has the properties of good biocompatibility, good stability and the capability to induce bone repair.

[0010] Summary of the Invention

[0011] An object of the present invention is to realize a composite (selfcomposite) obtained by combining two physical forms of the same substance having different physical structures but the same chemical structure.

[0012] Another object of the present invention is to realize a nano-micro hydroxyapatite selfcomposite obtained by combining the properties of the microstructure of hydroxyapatite with the properties of its nanostructure.

[0013] Detailed Description of the Invention

[0014] “A Selfcomposite” realized to fulfil the objectives of the present invention is shown in the figures attached, in which:

[0015] Figure 1 shows the XRD pattern of Nano-HA.

[0016] Figure 2 shows the XRD pattern of micro-HA.

[0017] Figure 3 shows the XRD pattern of Nano / Micro-HA (2:1).

[0018] Figure 4 is the SEM images of Nano-HA.Figure 5 is the TEM images of Nano-HA.

[0019] Figure 6 is the SEM images of Micro-HA.

[0020] Figure 7 is the TEM images of Micro-HA.

[0021] Figure 8 is the SEM images of Nano / Micro-HA (2:1).

[0022] Figure 9 is the TEM images of Nano / Micro-HA (2: 1).

[0023] Figure 10 is the PXRD patterns of a) nano-Fe-HA, b) micro-Fe-HA and c) nano / micro-Fe-HA materials.

[0024] Figure 11 is the EDS mapping images of Nano-Fe-HA.

[0025] Figure 12 is the EDS mapping images of Micro-Fe-HA.

[0026] Figure 13 is the EDS mapping images of Nano / Micro-Fe-HA (1:1).

[0027] Figure 14 is the TEM images of the synthesized materials magnified to 0.1 pm-50 nm (images of a; Nano-HA, b; Micro-HA, c; Nano / Micro-HA (2:1), d; Nano-Fe-HA, e; Micro-Fe-HA, f; Nano / Micro-Fe-HA (1:1)).

[0028] Figure 15 shows the photocatalytic effect of different catalyst types on methylene blue.

[0029] The inventive composite, in other words, the selfcomposite, is obtained by combining two physical forms of the same substance having different physical structures but the same chemical structures and reveals much more effective and superior properties than before they are combined or when combined with another substance.

[0030] The inventive nano- / micro-hydroxyapatite selfcomposite is obtained by combining nano-hydroxyapatite and micro-hydroxyapatite structures and reveals a much better performance than the catalytic effects of nano-hydroxyapatite and microhydroxyapatite structures.

[0031] In order to synthesize the inventive nano- / micro-hydroxyapatite selfcomposite, nano-hydroxyapatite (HA) and micro-hydroxyapatite (HA) are synthesized, and then nano-micro-HA is synthesized by using the synthesized nano-HA and micro-HA.For nano-HA synthesis; a 0.2M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water) by using 7-12 g of Ca(NO3)2’4H2O (CNTH, Calcium Nitrate Tetrahydrate). A 0.2M solution is prepared such that the Ca / P ratio is 1.67 at ambient temperature (25±2 °C) with DDW by using 2-4 g of (NH^HPCU (DAHP, Diammonium Hydrogen Phosphate). After these two solutions are added to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns, the pH is adjusted to 11 with 25% NH3(aq). After the process, it is left for aging for 72 hours by fixing the stirring speed. At the end of the aging period, the desired amount is taken from the resulting solution and left for drying process for 24-48 hours in 80°C vacuum as a result of washing (DDW) and filtering processes and Nano-HA is obtained.

[0032] For micro-HA synthesis; a 0.1M solution is prepared at ambient temperature (25±2°C) with DDW by using 2-2.5 g of Ca(NO3)2-4H2O (CNTH, Calcium Nitrate Tetrahydrate). A 0.06M solution is prepared such that the Ca / P ratio is 1.67 at ambient temperature (25±2°C) with DDW by using 0.5-1 g of (NH^HPC (DAHP, Diammonium Hydrogen Phosphate). A solution is prepared at ambient temperature (25±2°C) with 40 mL DDW by using 2, 1-2,5 g of CO(NH2)2 (Urea). After these solutions are added to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns, the pH is adjusted to 4 with 10% HNO3(aq) and then left for stirring process between 2-4 hours. At the end of the process, 70 mL is taken from the solution upon being autoclaved, and hydrothermally synthesized at 180°C for 5 hours. After washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Micro-HA is obtained.

[0033] For Nano / Micro-HA selfcomposite synthesis; 70 mL is taken from the prepared Nano-HA and Micro-HA solutions in the ratio of 2:1 and 6:1 (v / v) and autoclaved and then hydrothermally synthesized at 180°C for 5 hours. After washing (DDW)and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Nano / Micro-HA (2:1) and Nano / Micro-HA (6:1) selfcomposites are obtained.

[0034] In another embodiment of the invention, nano / micro-Fe-HA selfcomposite is synthesized and for this, nano-Fe-HA and micro-Fe-HA are synthesized and nano / micro-Fe-HA selfcomposite is obtained by using these synthesized substances.

[0035] For Nano-Fe-HA synthesis; a 0.2M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water) by using 7-10 g of Ca(NO3)2’4H2O (CNTH, Calcium Nitrate Tetrahydrate). A 0.2M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water), with a Ca / Fe ratio of 9:1, by using 1.4-2 g of Fe(NO3)3’9H2O (INNH, Iron(III) Nitrate Nonahydrate). A 0.2M solution is prepared such that the (Ca+Fe) / P ratio is 1.67 at ambient temperature (25±2°C) with DDW by using 2-4 g of (NH4)2HPO4 (DAHP, Diammonium Hydrogen Phosphate). After these solutions are added to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns, the pH is adjusted to 11 with 25% NH3(aq), after the process, it is left for aging for 72 hours by fixing the stirring speed. At the end of the aging period, the desired amount is taken from the resulting solution and left for drying process for 24-48 hours in 80°C vacuum as a result of washing (DDW) and filtering processes and Nano-Fe-HA is obtained.

[0036] For Micro-Fe-HA synthesis; a 0.09M solution is prepared at ambient temperature (25±2°C) with DDW by using 2-2.5 g of Ca(NO3)2-4H2O (CNTH, Calcium Nitrate Tetrahydrate). A 0.01M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water), with a Ca / Fe ratio of 9: 1, by using 0.4-0.8 g of Fe(NO3)3-9H2O (INNH, Iron(III) Nitrate Nonahydrate). A 0.06M solution is prepared such that the (Ca+Fe) / P ratio is 1.67 at ambient temperature (25±2°C) with DDW by using 0.5-1 g of (NF ^HPC (DAHP, Diammonium HydrogenPhosphate). A 40 mL solution is prepared at ambient temperature (25±2°C) with DDW by using 2, 1-2,5 g of CO(NH2)2 (Urea). The pH is adjusted to 4 with 10% HNCh aq) by adding these solutions to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns and then left for stirring process between 2-4 hours. At the end of the process, 70 mL is taken from the solution upon being autoclaved, and hydrothermally synthesized at 180°C for 5 hours. After washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Micro-Fe-HA is obtained.

[0037] For Nano / Micro-Fe-HA (1:1) selfcomposite synthesis; 70 mL is taken from the prepared Nano-Fe-HA and Micro-Fe-HA solutions in the ratio of 1:1 (v / v) and autoclaved and hydrothermally synthesized at 180°C for 5 hours. After washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Nano / Micro-Fe-HA (1 : 1) selfcomposite is obtained.

[0038] After the performed syntheses, photocatalytic experiments were carried out in order to examine the catalytic effect of the material. Iron doped Nano-, Micro- and Nano / micro-Fe-HA materials were synthesized to be used in photocatalytic experiments. 10 ppm, 100 mL solutions of methylene blue (MB) were prepared, and photocatalytic experiments were carried out under UV light in a reflux system. The characterizations of the obtained products were carried out by TGA (Thermal Gravimetric Analysis), FTIR (Fourier Transform Infrared Spectroscopy), PXRD (Powder X-Ray Diffraction Spectroscopy), SEM (Scanning Electron Microscopy), TEM (Transmission Electron Microscopy), and BET surface analysis techniques, and the analysis of the photocatalytic experiments were carried out by using UV-Vis Spectroscopy techniques. The most important analyses in the characterization of the synthesized materials are PXRD, SEM and TEM analyses. When the PXRD analyses of the obtained Nano-, Micro-, Nano / Micro-Hydroxyapatite samples are examined, it can be seen that Nano / Micro-Hydroxyapatite selfcomposite was synthesized.The XRD pattern of the synthesized micro hydroxyapatite is shown in Figure 2. The peaks with diffraction intensities above 10%, from left to right with respect to reference card JCPDS 9-432, are respectively 8.17 (1 0 0), 3.44 (0 0 2), 3.17 (1 0 2), 3.08 (2 1 0), 2.814 (2 1 1), 2. 778 (1 1 2), 2.720 (3 00), 2.631 (202), 2.262 (3 1 0), 1.943 (222), 1.890 (3 1 2), 1.841 (2 1 3), 1.780 (4 1 0), 1.754 (402, 3 03), 1.722 (0 0 4, 4 1 1). While the peak of 100 for nano hydroxyapatite is the (2 1 1) reflection peak, the peak of 100 for micro hydroxyapatite is the (3 0 0) reflection peak. However, it is seen that the intensity of the (0 0 2) reflection peak of 40 in nano hydroxyapatite is lower and the intensity of the (3 1 0) reflection peak is higher in micro hydroxyapatite.

[0039] The XRD pattern of the synthesized Nano / Micro-Hydroxyapatite (2: 1) is shown in Figure 3. The peaks with diffraction intensities above 10% of hydroxyapatite, from left to right with respect to reference card JCPDS 9-432, are respectively 8.17 (1 0 0 0), 3.44 (002), 3.17 (1 02), 3.08 (2 1 0), 2. 814 (2 1 1), 2.778 (1 1 2), 2.720 (3 0 0), 2.631 (202), 2.262 (3 1 0), 1.943 (222), 1.890 (3 1 2), 1.841 (2 1 3), 1.780 (4 1 0), 1.754 (4 02, 3 0 3), 1.722 (0 04, 4 1 1). The XRD patterns of Nano / Micro-HA (2:1) in Figure 3 exhibits consistency with the characteristic peaks numbered JCPDS 9-432. When the PXRD patterns of Nano / Micro-selfcomposite with nano-HA and micro-HA are compared, it is seen that the selfcomposite contains nano and micro hydroxyapatite structures.

[0040] From the SEM images of Nano-HA shown in Figure 4 and TEM images shown in Figure 5, it is understood that Nano-HA has a nanoscale rod-type morphology. SEM and TEM images of Micro-HA are shown in Figures 6 and 7. Figure 6 shows the SEM images of Micro-HA. When its morphological structure is examined, it is understood that it has a plate / sheet-like structure. It is seen in TEM images of Micro-HA in Figure 7 that microstructure is formed in hydroxyapatite. SEM and TEM images of nano / micro hydroxyapatite selfcomposite are shown in Figures 8 and 9. In Figure 8, when SEM images of Nano / Micro-HA (2:1) are examined, it is seen that the morphological structure contains nano and micro scale hydroxyapatiteparticles and has a rod-type structure. Figure 9 shows TEM images of Nano / Micro-HA (2:1). When the images are examined, it is understood that the micro structure interacts with the nano structure by shrinking and the composite structure is formed.

[0041] In order to compare the catalytic effects of nano / micro-HA selfcomposite, nano-HA and micro-hydroxyapatite structures, the removal of methylene blue (MB) from wastewater containing methylene blue by photocatalytic degradation was studied. With the aim of degrading methylene blue, increasing photocatalytic performance and improving mechanical properties, catalyst synthesis was carried out by synthesizing nano / micro-Fe-HA, a new material, by anchoring iron to nano hydroxyapatite and micro hydroxyapatite. The PXRD patterns of the synthesized nano-Fe-HA, micro-Fe-HA and nano / micro-Fe-HA materials are shown in Figure 10. The peaks with diffraction intensities above 10%, from left to right with respect to reference card JCPDS 9-432, are respectively 8.17 (1 0 0), 3.44 (002), 3.17 (1 0 2), 3.08 (2 1 0), 2.814 (2 1 1), 2. 778 (1 1 2), 2.720 (3 0 0), 2.631 (2 02), 2.262 (3 1 0), 1.943 (222), 1.890 (3 1 2), 1.841 (2 1 3), 1.780 (4 1 0), 1.754 (4 02, 3 0 3), 1.722 (0 0 4, 4 1 1). The PXRD patterns of the materials shown in Figure 10 exhibits consistency with the characteristic peaks of hydroxyapatite with card number JCPDS 9-432.

[0042] The Fe added to the structure entered into the structure without disrupting the hydroxyapatite structure. From the SEM-EDS mapping images of the synthesized products, it is seen that the elements forming the materials exhibit a homogeneous distribution in the material (Figures 11, 12 and 13). The TEM images of the synthesized Nano-Fe-HA, micro-Fe-HA and Nano / micro-Fe-HA selfcomposite structures are shown in Figure 14. It is also seen from the TEM images that there is no degradation in the structure with the introduction of iron into the structure.

[0043] When the BET analysis of the samples in Table 1 is examined, it is seen that the surface areas of the selfcomposites have areas at intermediate values compared to micro and nano, and accordingly, the pore diameters change.Table 1. BET surface area results of the materials.

[0044]

[0045] When SEM-TEM images were examined, it was seen that the selfcomposite hydroxyapatites contained nanorods of different sizes, and according to the Debye- Scherrer method, the average crystal sizes exhibited differences in the selfcomposite structures, and the sizes of the selfcomposite were between nano and microstructures. The average crystal sizes of the materials are given in Table 2.

[0046] Table 2. Average crystal sizes of the materials.

[0047]

[0048] After the synthesis of nano-micro selfcomposite, its catalytic effect was studied on the removal of methylene blue, one of the most common pollutants in wastewater, from water by photocatalytic degradation. In the photocatalytic experimental studies, it was observed that the basic environment increased the catalytic active site of the catalyst and had a positive effect on degradation. At pH 11, direct degradation occurred regardless of the catalyst. It was observed that the contribution of the best working pH point to the active site of hydroxyapatite was at pH 9. Accordingly, in the experiments carried out at the determined parameters, it was seen that the best working material was Nano / Micro-Fe-HA (1:1) and completed the degradation with 86%. The reusability of the catalyst was measured and averaged in 4 different sets and as a result, it yielded successful results in 3 cycles.

[0049] Effect of Catalyst Type on Degradation:

[0050] In order to determine the photocatalytic catalysis effects, optimum conditions were determined to examine the degradation effects of different catalyst types on methylene blue. Figure 15 shows the photocatalytic effect of different catalyst types applied with the selected parameters on methylene blue. The degradation of Nano / Micro-Fe-HA (1:1) reached 54.4% in the first 30 minutes. At the 2nd hour, the rate approached 72% for Nano / Micro-Fe-HA (1 : 1), while for the other catalysts it was 40% at the highest (Nano-Fe-HA). At the end of the 4th hour, Nano / Micro-Fe-HA (1:1) catalyst gave the highest degradation amount with 86.03% and it is seen that it is the catalyst type that works with the highest efficiency.

[0051] Within the scope of this invention, new selfcomposite materials of hydroxyapatite and iron anchored Nano / Micro-Micro-Fe-HA selfcomposite that can be used in photocatalytic treatment have been synthesized for the first time.

[0052] Industrial Application of the InventionThe importance of this invention is that for the first time a composite of a substance has been synthesized by using its nano and microstructures. This resulting structure is referred to by us as the “selfcomposite” of the substance. With this study, it has been proven that the composite, i.e. selfcomposite, prepared from different crystal structures of a substance can achieve superior properties compared to the single crystal form / structure of the substance. In fact, by paving the way for the synthesis of composites of selfcomposites of different materials, it has been shown to the scientific world that materials with new superior properties can be synthesized.

[0053] Within these basic concepts; it is possible to develop various embodiments of the inventive “A Selfcomposite”; the invention cannot be limited to examples disclosed herein and it is essentially according to claims.

Claims

CLAIMS1. A composite, in other words, a selfcomposite, characterized in that it is obtained by combining two physical forms of the same substance having different physical structures but the same chemical structures and reveals much more effective and superior properties than before they are combined or when combined with another substance.

2. Nano- / micro-hydroxyapatite selfcomposite obtained by combining nanohydroxyapatite and micro-hydroxyapatite structures, characterized in that it reveals a much better performance than the catalytic effects of nano-hydroxyapatite and micro-hydroxyapatite structures.

3. A nano- / micro-hydroxy apatite selfcomposite according to Claim 2; characterized in that nano-hydroxyapatite (HA) and micro-hydroxyapatite (HA) are synthesized, and then nano-micro-HA is synthesized by using the synthesized nano-HA and micro-HA.

4. A nano- / micro-hydroxyapatite selfcomposite according to Claim 2 or 3; characterized in that a 0.2M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water) by using 7-12 g of Ca(NO3)2’4H2O (CNTH, Calcium Nitrate Tetrahydrate); a 0.2M solution is prepared such that the Ca / P ratio is 1.67 at ambient temperature (25±2 °C) with DDW by using 2-4 g of (NH4)2HPO4(DAHP, Diammonium Hydrogen Phosphate); after these two solutions are added to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns, the pH is adjusted to 11 with 25% NH3(aq); after the process, it is left for aging for 72 hours by fixing the stirring speed; at the end of the aging period, the desired amount is taken from the resulting solution and left for drying process for 24-48 hours in 80°C vacuum as a result of washing (DDW) and filtering processes and Nano-HA is obtained.

5. A nano- / micro-hydroxyapatite selfcomposite according to Claim 2 or 3; characterized in that, for micro-HA synthesis; a 0.1M solution is prepared at ambient temperature (25±2°C) with DDW by using 2-2.5 g of Ca(NO3)2’4H2O (CNTH, Calcium Nitrate Tetrahydrate); a 0.06M solution is prepared such that the Ca / P ratio is 1.67 at ambient temperature (25±2°C) with DDW by using 0.5-1 g of (NH4)2HPO4(DAHP, Diammonium Hydrogen Phosphate); a solution is prepared at ambient temperature (25±2°C) with 40 mL DDW by using 2, 1-2,5 g of CO(NH2)2 (Urea); after these solutions are added to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns, the pH is adjusted to 4 with 10% HNOs(aq) and then left for stirring process between 2-4 hours; at the end of the process, 70 mL is taken from the solution upon being autoclaved, and hydrothermally synthesized at 180°C for 5 hours; after washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Micro-HA is obtained.

6. A nano- / micro-hydroxyapatite selfcomposite according to any one of Claims 2 to 5; characterized in that 70 mL is taken from the prepared Nano-HA and Micro-HA solutions in the ratio of 2:1 and 6:1 (v / v) and autoclaved and then hydrothermally synthesized at 180°C for 5 hours; after washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Nano / Micro-HA (2:1) and Nano / Micro-HA (6:1) selfcomposites are obtained.

7. A nano / micro-Fe-HA selfcomposite characterized in that it is obtained by synthesizing nano-Fe-HA and micro-Fe-HA and using these synthesized materials.

8. A nano / micro-Fe-HA selfcomposite according to Claim 7; characterized in that a 0.2M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water) by using 7-10 g of Ca(NO3)2’4H2O (CNTH, Calcium Nitrate Tetrahydrate); a 0.2M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water), with a Ca / Fe ratio of 9:1,by using 1.4-2 g of Fe(NO3)3’9H2O (INNH, Iron(III) Nitrate Nonahydrate); a 0.2M solution is prepared such that the (Ca+Fe) / P ratio is 1.67 at ambient temperature (25±2°C) with DDW by using 2-4 g of (NH4)2HPO4 (DAHP, Diammonium Hydrogen Phosphate); after these solutions are added to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns, the pH is adjusted to 11 with 25% NH3(aq), after the process, it is left for aging for 72 hours by fixing the stirring speed; at the end of the aging period, the desired amount is taken from the resulting solution and left for drying process for 24-48 hours in 80°C vacuum as a result of washing (DDW) and filtering processes and Nano-Fe-HA is obtained.

9. A nano / micro-Fe-HA selfcomposite according to Claim 7; characterized in that a 0.09M solution is prepared at ambient temperature (25±2°C) with DDW by using 2-2.5 g of Ca(NO3)2’4H2O (CNTH, Calcium Nitrate Tetrahydrate); a 0.01M solution is prepared at ambient temperature (25±2°C) with DDW (Deionized Decarbonized Water), with a Ca / Fe ratio of 9:1, by using 0.4-0.8 g of Fe(NO3)3’9H2O (INNH, Iron(III) Nitrate Nonahydrate); a 0.06M solution is prepared such that the (Ca+Fe) / P ratio is 1.67 at ambient temperature (25±2°C) with DDW by using 0.5-1 g of (NH4)2HPO4 (DAHP, Diammonium Hydrogen Phosphate); a 40 mL solution is prepared at ambient temperature (25±2°C) with DDW by using 2, 1-2,5 g of CO(NH2)2 (Urea); the pH is adjusted to 4 with 10% HNO3(aq) by adding these solutions to the flask in Ni(g) medium at room temperature (25±2°C) by dropping method with additional columns and then left for stirring process between 2-4 hours; at the end of the process, 70 mL is taken from the solution upon being autoclaved, and hydrothermally synthesized at 180°C for 5 hours; after washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Micro-Fe-HA is obtained.

10. A nano / micro-Fe-HA selfcomposite according to any one of Claims 7-9; characterized in that 70 mL is taken from the prepared Nano-Fe-HA and Micro-Fe-HA solutions in the ratio of 1:1 (v / v) and autoclaved and hydrothermallysynthesized at 180°C for 5 hours; after washing (DDW) and filtering processes at the end of synthesis, it is left to dry for 24-48 hours in 40°C vacuum and Nano / Micro-Fe-HA (1:1) selfcomposite is obtained.

Images