Calcium silicate-calcium phosphate crystal phase composite and use thereof

Abstract

This invention discloses a calcium silicate-calcium phosphate crystalline phase composite material and its applications. The calcium silicate-calcium phosphate crystalline phase composite material is prepared by preparation method A or preparation method B. Preparation method A includes: obtaining a mixed system containing tetraethyl silicate, ethanol, and water; adjusting the pH of the mixed system to 1-2 with acid; adding calcium salt to obtain a first component; obtaining a mixed system containing phosphate, calcium salt, and water to obtain a second component; mixing the first and second components evenly, stirring at 50-80°C, drying at 110-130°C for 11-13 hours, sintering, cooling, mixing with ethanol, grinding, and sieving to obtain the calcium silicate-calcium phosphate crystalline phase composite material. This calcium silicate-calcium phosphate crystalline phase composite material is a milder active composition that can be applied in the fields of oral care, cosmetics, and skin and mucous membrane repair.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a calcium silicate-calcium phosphate crystalline phase composite material and its applications. Background Technology

[0002] Calcium silicate-based inorganic active materials were first used as a major component in novel dental restorations in the 1990s, demonstrating their excellent antibacterial and biocompatibility. Subsequent studies have proven their good bioactivity, including the ability to induce hydroxyapatite (HA) formation. Numerous research results indicate that calcium silicate-based inorganic active materials can block dentinal tubules through a self-curing process and induce dentin remineralization under physiological conditions, showing great potential for future effective treatment of dentin hypersensitivity. They effectively avoid thermal damage to surrounding tissues; possess good mechanical strength to meet the support requirements of bone repair materials; and exhibit good biocompatibility and osteogenic properties, making them suitable as injectable self-curing bone repair materials for dental and orthopedic bone repair surgeries. Furthermore, the hydration process of calcium silicate-based inorganic active materials releases a large amount of Ca(OH)₂, whose strong alkalinity provides antibacterial and anti-inflammatory effects. In existing technologies, toothpastes containing calcium silicate-based inorganic active materials (bioactive glass) as effective active ingredients have emerged. Oral clinical studies have found that these active ingredients can react rapidly and continuously with water and saliva in the mouth during use, releasing calcium and silicate ions to maintain a slightly alkaline pH in the oral cavity, inhibiting bacterial growth, improving the oral environment, and preventing bacteria from continuously producing acid on the enamel surface and damaging the enamel. At the same time, they fill damaged enamel and promote its fusion and regeneration, achieving the purpose of repair.

[0003] However, further in vitro and in vivo studies have revealed that the persistently high alkalinity of calcium silicate-based inorganic active materials also has certain negative effects on tissue repair. For example, in oral restoration, its irritation to tissues causes discomfort and allergic reactions in patients, significantly affecting the progress and effectiveness of tissue repair. These negative effects greatly limit the clinical application of calcium silicate materials. This is essentially due to the ease with which calcium silicate materials hydrolyze in their molecular structure.

[0004] Therefore, it is necessary to provide a new material to solve the above-mentioned technical problems.

[0005] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to provide a calcium silicate-calcium phosphate crystalline phase composite material, which is a milder active composition that can be applied in the fields of oral care, cosmetics, and skin and mucous membrane repair.

[0007] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution: a calcium silicate-calcium phosphate crystalline phase composite material, prepared by preparation method A or preparation method B;

[0008] The preparation method A includes the following steps:

[0009] A1. Obtain a mixed system containing tetraethyl silicate, ethanol and water, adjust the pH of the mixed system to 1-2 with acid, and then add calcium salt to obtain the first component;

[0010] A2. Obtain a mixed system containing phosphate, calcium salt and water to obtain the second component;

[0011] A3. After mixing the first component and the second component evenly, stir at 50-80℃, dry at 110-130℃ for 11-13h, sinter, cool, mix with ethanol, grind, and sieve to obtain the calcium silicate-calcium phosphate crystalline phase composite material.

[0012] The preparation method B includes the following steps:

[0013] B1. Obtain a mixed system containing phosphate, tetraethyl silicate, ethanol, calcium salt and water, adjust the pH of the mixed system to 1-2 with acid, stir and dry at 110-130℃ for 36-48h.

[0014] B2. The dried product is sintered, cooled, mixed with ethanol, ground, and sieved to obtain the calcium silicate-calcium phosphate crystalline composite material.

[0015] In one or more embodiments of the present invention, the phosphate is at least one selected from hydrogen ammonium phosphate, sodium hydrogen phosphate, and potassium dihydrogen phosphate; and / or,

[0016] The calcium salt includes at least one of the water-soluble calcium oxalate, calcium nitrate, calcium citrate, calcium gluconate, calcium hypochlorite, and calcium acetate; and / or,

[0017] In step A1 and / or step B1, the acid used to adjust the pH of the mixed system is any one of nitric acid, hydrochloric acid, and acetic acid.

[0018] In one or more embodiments of the present invention, the sintering step in preparation method A and / or preparation method B specifically includes:

[0019] After drying, the product is heated to 1200-1400℃ at a heating rate of 5-10℃ / min and held at that temperature for 3-6 hours.

[0020] In one or more embodiments of the present invention, step A1 of preparation method A, the step of obtaining a mixed system containing tetraethyl silicate, ethanol and water, includes:

[0021] Tetraethyl silicate and ethanol were mixed evenly at a molar ratio of (0.1-0.4):1, and water was added.

[0022] In one or more embodiments of the present invention, in step A1 of the preparation method A, the molar ratio of calcium salt to tetraethyl silicate is (0.5-1):1.

[0023] In one or more embodiments of the present invention, step A2 of preparation method A, the step of obtaining a mixed system containing phosphate, calcium salt and water, includes:

[0024] The phosphate and calcium salts were mixed evenly in a molar ratio of 1:(1-1.5) and dissolved in water.

[0025] In one or more embodiments of the present invention, in preparation method A, the molar ratio of tetraethyl silicate in the first component to phosphate in the second component is (0.5-2):1.

[0026] In one or more embodiments of the present invention, in preparation method B,

[0027] The molar ratio of the phosphate to tetraethyl silicate is (0.5-2):1;

[0028] The molar ratio of tetraethyl silicate to ethanol is (0.1-0.4):1

[0029] The molar ratio of the phosphate to the calcium salt is 1:(1-1.5).

[0030] In one or more embodiments of the present invention, the stirring step in step B1 of the preparation method B specifically includes:

[0031] When the calcium salt is a weak electrolyte, the pH-adjusted mixture is magnetically stirred at room temperature for 50-70 minutes to form a white slurry; or,

[0032] When the calcium salt is a strong electrolyte, the mixed system after pH adjustment is magnetically stirred in a constant temperature water bath at 50-80℃ for 50-70 minutes to form a sol state, and then aged at 50-80℃ for 12-36 hours to form a wet gel.

[0033] A specific embodiment of the present invention also provides the application of the calcium silicate-calcium phosphate crystalline phase composite material as described above in the fields of oral cavity, cosmetics, and skin and mucous membrane repair.

[0034] Compared with the prior art, the calcium silicate-calcium phosphate crystal phase composite material of the present invention can be prepared by the above-mentioned preparation method A or preparation method B, which can slowly form a calcium silicate-calcium phosphate precursor by using strong and weak electrolytes of calcium salts, and then by sintering treatment, thereby obtaining a calcium phosphate / wollastonite material with a composite crystal phase structure, namely the calcium silicate-calcium phosphate crystal phase composite material of the present invention. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is a flowchart of method A for preparing calcium silicate-calcium phosphate crystalline phase composite material in one embodiment of the present invention;

[0037] Figure 2 This is a flowchart of method B for preparing calcium silicate-calcium phosphate crystalline phase composite material in one embodiment of the present invention;

[0038] Figure 3 The above are XRD patterns of the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4 of the present invention.

[0039] Figure 4 The following are the FTIR spectra of the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4 of the present invention;

[0040] Figure 5 SEM images of the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4 of the present invention;

[0041] Figure 6 The particle size distribution diagrams are shown for the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4 of the present invention.

[0042] Figure 7 These are XRD images of the bioglass in Comparative Example 1 of the present invention after reacting in SBF solution for different times;

[0043] Figure 8 These are SEM images of the bioglass in Comparative Example 1 of this invention after reacting in SBF solution for different times.

[0044] Figure 9 These are SEM images of the calcium silicate-calcium phosphate crystalline composite materials in Examples 1-4 of the present invention after reacting in SBF solution for different times.

[0045] Figure 10 The images show the XRD patterns of the calcium silicate-calcium phosphate crystalline composite materials in Examples 1-4 of the present invention after reacting in SBF solution for different times. Detailed Implementation

[0046] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0047] like Figure 1 and 2 As shown, a calcium silicate-calcium phosphate crystalline phase composite material in one embodiment of the present invention is prepared by preparation method A or preparation method B;

[0048] The preparation method A includes the following steps:

[0049] A1. Obtain a mixed system containing tetraethyl silicate, ethanol and water, adjust the pH of the mixed system to 1-2 with acid, and then add calcium salt to obtain the first component.

[0050] In step A1, the purpose of adding calcium salt is to form a weakly bonded calcium silicate cluster structure.

[0051] Specifically, the steps to obtain a mixed system containing tetraethyl silicate, ethanol and water can be as follows: mix tetraethyl silicate and ethanol evenly at a molar ratio of (0.1-0.4):1, and then add water.

[0052] It is understandable that water acts as a solvent, so an appropriate amount of water is sufficient. For example, the volume of water can be equal to the combined volume of tetraethyl silicate and ethanol, or it can be more or less than the combined volume.

[0053] The molar ratio of calcium salt to tetraethyl silicate is (0.5-1):1.

[0054] The acid used to adjust the pH of the mixture is any one of nitric acid, hydrochloric acid, and acetic acid. Preferably, nitric acid is used to adjust the pH of the mixture.

[0055] A2. Obtain a mixed system containing phosphate, calcium salt and water to obtain the second component;

[0056] Specifically, the steps to obtain a mixed system containing phosphate, calcium salt, and water are as follows: The phosphate and calcium salt are mixed evenly at a molar ratio of 1:(1-1.5) and dissolved in water. It is understood that this molar ratio mainly refers to the molar ratio of phosphorus to calcium in the second component. Water acts as a solvent; therefore, an appropriate amount of water is sufficient. For example, the volume of water in step A2 can be the same as the volume of water in step A1, or it can be more or less than the volume of water in step A1.

[0057] In step A2, the purpose of adding calcium salt is to form a weakly bound calcium phosphate cluster structure.

[0058] A3. After mixing the first component and the second component evenly, stir at 50-80℃, dry at 110-130℃ for 11-13 hours, sinter, cool, mix with ethanol, grind, and sieve to obtain the calcium silicate-calcium phosphate crystalline composite material.

[0059] Specifically, the molar ratio of tetraethyl silicate in the first component to phosphate in the second component is (0.5-2):1.

[0060] Specifically, the sintering step may include: heating the dried product to 1200-1400℃ at a heating rate of 5-10℃ / min, and holding it at that temperature for 3-6 hours. The sintering step can be carried out in a muffle furnace.

[0061] Specifically, the cooling process can be as follows: the sintered product is rapidly cooled in air. Rapid cooling in air can be understood as directly placing the product at 1200-1400℃ in room temperature and air for cooling until it reaches room temperature. Room temperature can be considered to be around 25℃, for example, 20-30℃.

[0062] It is understood that in preparation method A, the phosphate can be at least one of ammonium hydrogen phosphate, sodium hydrogen phosphate, and potassium dihydrogen phosphate; wherein, ammonium hydrogen phosphate can be considered as ammonium dihydrogen phosphate or diammonium hydrogen phosphate, and sodium hydrogen phosphate can be considered as sodium dihydrogen phosphate or disodium hydrogen phosphate; the calcium salt includes at least one of water-soluble calcium oxalate, calcium nitrate, calcium citrate, calcium gluconate, calcium hypochlorite, and calcium acetate.

[0063] The choice of calcium salt (i.e., whether the calcium salt is a strong electrolyte or a weak electrolyte) can lead to differences in the microstructure, bioactivity, and other properties of the final calcium silicate-calcium phosphate crystalline composite material.

[0064] The preparation method B includes the following steps:

[0065] B1. Obtain a mixed system containing phosphate, tetraethyl silicate, ethanol, calcium salt and water. Adjust the pH of the mixed system to 1-2 with acid, stir and dry at 110-130℃ for 36-48h.

[0066] Specifically, the molar ratio of the phosphate to tetraethyl silicate is (0.5-2):1; the molar ratio of the calcium salt to tetraethyl silicate is (0.5-1):1; and the molar ratio of the phosphate to the calcium salt is 1:(1-1.5).

[0067] It is understood that in preparation method B, the phosphate can be at least one of ammonium hydrogen phosphate, sodium hydrogen phosphate, and potassium dihydrogen phosphate. Ammonium hydrogen phosphate can be considered as ammonium dihydrogen phosphate or diammonium hydrogen phosphate, and sodium hydrogen phosphate can be considered as sodium dihydrogen phosphate or disodium hydrogen phosphate. The calcium salt includes at least one of water-soluble calcium oxalate, calcium nitrate, calcium citrate, calcium gluconate, calcium hypochlorite, and calcium acetate.

[0068] The acid used to adjust the pH of the mixture is any one of nitric acid, hydrochloric acid, and acetic acid. Preferably, nitric acid is used to adjust the pH of the mixture.

[0069] The choice of calcium salt (i.e., whether the calcium salt is a strong electrolyte or a weak electrolyte) can lead to differences in the microstructure, bioactivity, and other properties of the final calcium silicate-calcium phosphate crystalline composite material.

[0070] Specifically, the stirring process in step B1 is as follows:

[0071] When the calcium salt is a weak electrolyte, the mixture after pH adjustment is magnetically stirred at room temperature for 50-70 minutes to form a white slurry.

[0072] When the calcium salt is a strong electrolyte, the mixed system after pH adjustment is magnetically stirred in a constant temperature water bath at 50-80℃ for 50-70 minutes to form a sol state, and then aged at 50-80℃ for 12-36 hours to form a wet gel.

[0073] B2. The dried product is sintered, cooled, mixed with ethanol, ground, and sieved to obtain the calcium silicate-calcium phosphate crystalline composite material.

[0074] Specifically, the sintering step may include: heating the dried product to 1200-1400℃ at a heating rate of 5-10℃ / min and holding it at that temperature for 3-6 hours.

[0075] Specifically, the cooling process can be as follows: the sintered product is rapidly cooled in air. Rapid cooling in air can be understood as directly placing the product at 1200-1400℃ in room temperature and air for cooling until it reaches room temperature. Room temperature can be considered to be around 25℃, for example, 20-30℃.

[0076] It should be noted that the ethanol used in preparation method A or preparation method B can be anhydrous ethanol; and the water used can be deionized water.

[0077] A specific embodiment of the present invention also provides the application of the calcium silicate-calcium phosphate crystalline phase composite material as described above in the fields of oral cavity, cosmetics, and skin and mucous membrane repair.

[0078] The calcium silicate-calcium phosphate crystalline phase composite material of the present invention and its application will be described in detail below with reference to specific embodiments.

[0079] Example 1

[0080] First, tetraethyl silicate (5.0 g) and anhydrous ethanol (100 mL) were mixed thoroughly and added to 150 mL of deionized water. The pH of the solution was then adjusted to 1-2 with nitric acid. After stirring magnetically at room temperature for 30 min, 10.2 g of calcium oxalate was completely dissolved in the solution to form component A. Diammonium hydrogen phosphate (3.2 g) and calcium oxalate (5.3 g) were mixed thoroughly and dissolved in 150 mL of deionized water to form component B. Components A and B were mixed thoroughly and magnetically stirred in a 60°C constant temperature water bath for 30 min. The mixture was then dried in a forced-air drying oven at 120°C for 12 hours. The dried powder was then placed in a muffle furnace and heated to 1400°C at a heating rate of 5°C / min, held at that temperature for 4 hours, and then rapidly cooled in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200 rpm for 2 hours. The resulting powder was sieved to obtain the desired powder, which is the calcium silicate-calcium phosphate crystalline composite material.

[0081] Example 2

[0082] Diammonium hydrogen phosphate (3.2 g), tetraethyl silicate (5.1 g), calcium oxalate (16.2 g), and anhydrous ethanol (120 mL) were mixed thoroughly in a molar ratio of 1:1:4.5:5 and then added to 300 mL of deionized water. The pH of the solution was adjusted to 1-2 with nitric acid, and the mixture was magnetically stirred at room temperature for 60 min to form a white slurry. This slurry was then dried in a forced-air drying oven at 120 °C for 48 hours. The dried powder was then placed in a muffle furnace and heated to 1400 °C at a heating rate of 5 °C / min, held at that temperature for 4 hours, and then rapidly cooled in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200 rpm for 2 hours. The resulting powder was sieved to obtain the desired powder, which is the calcium silicate-calcium phosphate crystalline composite material.

[0083] Example 3

[0084] First, tetraethyl silicate (5.6g) and anhydrous ethanol (130ml) were mixed thoroughly and added to 150ml of deionized water. The pH of the solution was then adjusted to 1-2 with nitric acid to form a SiO2 sol. 17.8g of calcium nitrate was then completely dissolved in the solution to form component A. 3.4g of diammonium hydrogen phosphate and 8.9g of calcium nitrate were mixed thoroughly and dissolved in 150ml of deionized water to form component B. Components A and B were then mixed thoroughly and magnetically stirred in a 60℃ constant temperature water bath for 60min to form a sol state. The mixture was then aged at 60℃ for 24h to form a wet gel. The gel was dried in a forced-air drying oven at 120℃ for 48h. The dried gel was then placed in a muffle furnace and heated to 1400℃ at a rate of 5℃ / min, held at that temperature for 4h, and then rapidly cooled in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200 rpm for 2 hours. The powder required for the experiment was obtained by sieving, which is the calcium silicate-calcium phosphate crystalline phase composite material.

[0085] Example 4

[0086] 3.4 g of diammonium hydrogen phosphate, 5.3 g of tetraethyl silicate, 26.7 g of calcium nitrate, and 120 mL of anhydrous ethanol were mixed thoroughly and then added to 300 mL of deionized water. The pH of the solution was adjusted to 1-2 with nitric acid. The mixture was magnetically stirred in a 60°C water bath for 60 min to form a sol. The sol was then aged at 60°C for 24 h to form a wet gel. The gel was dried in a forced-air drying oven at 120°C for 48 h. The dried gel was then placed in a muffle furnace and heated to 1400°C at a rate of 5°C / min, held at that temperature for 4 h, and then rapidly cooled in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200 rpm for 2 h. The resulting powder, the calcium silicate-calcium phosphate crystalline composite material, was obtained by sieving.

[0087] Example 5

[0088] First, 4.2 g of tetraethyl orthosilicate and 90 mL of anhydrous ethanol were mixed thoroughly and added to 150 mL of deionized water. The pH of the solution was then adjusted to 1-2 with hydrochloric acid. After stirring magnetically for 30 min at room temperature, 13.5 g of calcium oxalate was completely dissolved in the solution to form component A. 6.3 g of diammonium hydrogen phosphate and 12.3 g of calcium oxalate were mixed thoroughly and dissolved in 150 mL of deionized water to form component B. Components A and B were mixed thoroughly and magnetically stirred in a 50°C constant temperature water bath for 30 min. The mixture was then dried in a forced-air drying oven at 110°C for 13 hours. The dried powder was then placed in a muffle furnace and heated to 1300°C at a rate of 6°C / min, held at that temperature for 3 hours, and then rapidly cooled to room temperature in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200 rpm for 2 hours. The resulting powder was sieved to obtain the desired powder, which is the calcium silicate-calcium phosphate crystalline composite material. The calcium silicate-calcium phosphate crystalline composite material obtained in this embodiment has roughly the same composition and microstructure as the calcium silicate-calcium phosphate crystalline composite material obtained in Example 1.

[0089] Example 6

[0090] First, 7.8g of tetraethyl silicate and 150ml of anhydrous ethanol were mixed thoroughly and added to 150ml of deionized water. The pH of the solution was then adjusted to 1-2 with nitric acid. After stirring magnetically at room temperature for 30 minutes, 16.8g of calcium citrate was completely dissolved in the solution to form component A. 3.5g of diammonium hydrogen phosphate and 6.8g of calcium citrate were mixed thoroughly and dissolved in 150ml of deionized water to form component B. Components A and B were mixed thoroughly and magnetically stirred in an 80℃ constant temperature water bath for 30 minutes. The mixture was then dried in a forced-air drying oven at 130℃ for 11 hours. The dried powder was then placed in a muffle furnace and heated to 1200℃ at a rate of 10℃ / min, held at that temperature for 6 hours, and then rapidly cooled to room temperature in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200rpm for 2 hours. The resulting powder was sieved to obtain the desired experimental powder, which is the calcium silicate-calcium phosphate crystalline composite material. The calcium silicate-calcium phosphate crystalline composite material obtained in this embodiment has roughly the same composition and microstructure as the calcium silicate-calcium phosphate crystalline composite material obtained in Example 1.

[0091] Example 7

[0092] 6.8 g of diammonium hydrogen phosphate, 3.2 g of tetraethyl silicate, 18.5 g of calcium oxalate, and 90 mL of anhydrous ethanol were mixed thoroughly and then added to 300 mL of deionized water. The pH of the solution was adjusted to 1-2 with nitric acid, and the mixture was magnetically stirred at room temperature for 50 min to form a white slurry. This slurry was then dried in a forced-air drying oven at 110 °C for 40 hours. The dried powder was then placed in a muffle furnace and heated to 1300 °C at a rate of 10 °C / min, held at that temperature for 3 hours, and then rapidly cooled in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200 rpm for 2 hours. The resulting powder was sieved to obtain the desired powder, which is the calcium silicate-calcium phosphate crystalline phase composite material. The calcium silicate-calcium phosphate crystalline phase composite material obtained in this example has approximately the same composition and microstructure as the calcium silicate-calcium phosphate crystalline phase composite material obtained in Example 2.

[0093] Example 8

[0094] 3.7g of diammonium hydrogen phosphate, 7.9g of tetraethyl silicate, 16.8g of calcium oxalate, and 150mL of anhydrous ethanol were mixed thoroughly and then added to 300mL of deionized water. The pH of the solution was adjusted to 1-2 with nitric acid, and the mixture was magnetically stirred at room temperature for 70min to form a white slurry. This slurry was then dried in a forced-air drying oven at 130℃ for 36 hours. The dried powder was then placed in a muffle furnace and heated to 1200℃ at a rate of 6℃ / min, held at that temperature for 6 hours, and then rapidly cooled in air. The cooled product was mixed with anhydrous ethanol and ground in a ball mill at 200rpm for 2 hours. The resulting powder was sieved to obtain the desired powder, which is the calcium silicate-calcium phosphate crystalline phase composite material. The calcium silicate-calcium phosphate crystalline phase composite material obtained in this example has approximately the same composition and microstructure as the calcium silicate-calcium phosphate crystalline phase composite material obtained in Example 2.

[0095] Comparative Example 1

[0096] 4510 bioactive glass (hereinafter referred to as bioglass) produced by Shanghai Nuosheng Medical Technology Co., Ltd.

[0097] The following tests were conducted on the calcium silicate-calcium phosphate crystalline composite materials in Examples 1-4.

[0098] (1) X-ray diffractometer (XRD)

[0099] The ground samples were characterized using an XRD instrument.

[0100] (2) FTIR infrared spectroscopy

[0101] Take about 2 mg of the ground sample, add KBr powder, grind, compress into tablets, and characterize using an infrared spectrometer.

[0102] (3) Nano particle size

[0103] Take a small amount of sample and place it in ultrapure water. Disperse it evenly by ultrasonication and test the particle size distribution of the sample. Take the average value after measuring a group of samples three times.

[0104] (4) Specific surface area and pore size analysis (BET)

[0105] Take about 200mg of dry powder sample, degas at 150℃ for 5 hours, and test it after degassing.

[0106] (5) Scanning electron microscope (SEM): Take a small amount of sample, spray it with gold, and use an SEM instrument to observe its morphology.

[0107] (6) Transmission electron microscopy:

[0108] Take a small amount of sample and add it to anhydrous ethanol. Sonicate for 2 hours to disperse it evenly. Drop the well dispersed suspension onto a carbon film copper grid and let it air dry naturally before testing the sample.

[0109] Some of the test data are shown in Table 1:

[0110] Table 1

[0111]

[0112]

[0113] For ease of description, R-01 represents Example 1, R-02 represents Example 2, R-03 represents Example 3, and R-04 represents Example 4.

[0114] Figure 3 The images show the XRD patterns of the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4. Figure 1 The XRD patterns show that R-01 is mainly composed of dicalcium silicate (C2S), while R-02 and R-04 consist of C2S and calcium oxide (CaO). R-03 may contain α-TCP and tricalcium silicate (C3S) phase components. Additionally, diffraction peaks for calcium oxide and C2S are present. This is a typical amorphous structure, a type of amorphous material, and its characteristic peaks in XRD are typically broad due to the disordered atomic arrangement in amorphous materials.

[0115] Figure 4 The images show the FTIR spectra of the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4, at approximately 1000-1300 cm⁻¹. -1 Within this range, a strong peak typically appears, representing the stretching vibration of the silicon-oxygen bond (Si-O). 1099 cm⁻¹ -1 The reflection peak at 993 cm⁻¹ is due to the Si-O stretching vibration; -1The reflection peak at approximately 450-600 cm⁻¹ is the PO stretching vibration peak; -1 Within this range, a weak peak typically appears, representing the bending vibration of the silicon-oxygen bond. This characteristic peak can be used to determine the presence and structure of silicon-oxygen bonds in a material.

[0116] Figure 5 These are SEM images of the calcium silicate-calcium phosphate crystalline phase composite materials in Examples 1-4. Figure 6 The SEM images show the particle size distribution of the calcium silicate-calcium phosphate crystalline composite materials in Examples 1-4. As can be seen from the SEM images, the microstructure of each powder group exhibits an irregular, flaky shape, with an average particle size of less than 5 μm. The particle size distribution of R-01 and R-02 is concentrated around 1100 nm, R-03 has an average particle size of around 500 nm, and R-04 has an average particle size of around 1000 nm.

[0117] The following tests were conducted on the bioactivity of the calcium silicate-calcium phosphate crystalline composite materials in Examples 1-4 and the bioglass in Comparative Example 1:

[0118] SBF solution was prepared according to T / CSBM 0027—2022 standard and used immediately after preparation. 15 ml of SBF solution was added to a polyethylene bottle. 0.05 g of each sample was accurately weighed and poured into the bottle, then fixed in a constant-temperature shaker at 37°C and 165 rpm. The samples were shaken for 8 h, 1 d, 3 d, and 5 d, respectively. After shaking for different times, the reacted SBF solution, along with the sample powder, was filtered through filter paper. The filtered sample powder was washed with acetone to inhibit the reaction. The powder was dried in a 95°C oven for 1 hour, sealed in a sample bag, and stored in a desiccator for FTIR, XRD, and SEM analysis. Samples of SBF solution corresponding to different reaction times were taken and frozen for ICP testing.

[0119] Figure 7 The images show the XRD patterns of the bioglass in Comparative Example 1 after reacting in SBF solution for different times. Figure 8 SEM images of the bioglass from Comparative Example 1 after reacting in SBF solution for different times. Figure 8 As seen in the SEM images, the surface morphology of the material changed significantly after immersion in SBF for 3 days and 5 days, respectively. The different surface morphologies may be due to the formation of hydroxyapatite morphology through mineralization, and the material surface provides favorable nucleation sites for the nucleation of calcium phosphate compounds. Figure 7 The XRD pattern shows that after the material reacts in SBF solution for 3 days, there is a diffuse apatite diffraction peak at about 2θ = 32°, which is due to the formation of low-crystallinity hydroxyapatite on the material surface during the biomineralization process.

[0120] Figure 9 These are SEM images of the calcium silicate-calcium phosphate crystalline phase composite materials from Examples 1-4 after reacting in SBF solution for different times. Figure 9 As shown in the SEM images, the surface morphology of all materials changed significantly after immersion in SBF for 3 days and 5 days, respectively. The different surface morphologies may be due to the formation of hydroxyapatite morphology through mineralization, which is likely caused by the presence of Ca in the solution. 2+ PO4 3- OH - and CO3 2- Plasma diffuses into the micro-electric layer on the material surface, promoting the nucleation of HCA. The material surface provides favorable nucleation sites for the nucleation of calcium phosphate compounds.

[0121] Figure 10 The images show the XRD patterns of the calcium silicate-calcium phosphate crystalline composite materials in Examples 1-4 after reacting in SBF solution for different times. Figure 10 It can be seen that the XRD patterns of each group of materials after reacting in SBF solution for 3 days show a sharp diffraction peak at around 2θ = 32°. This is due to the formation of low-crystallinity hydroxyapatite on the material surface during the biomineralization process. However, the XRD patterns of the original samples R-01, R-02, R-03 and R-04 do not show this diffraction peak, indicating that more hydroxyapatite was formed on the surface of samples R-01, R-02, R-03 and R-04.

[0122] comprehensive Figure 7-10 As shown, both the sample and the control sample in this embodiment produced different degrees of apatite mineralization. The calcium silicate-calcium phosphate crystal phase composite materials of Examples 1-4 of this invention have the same remineralization ability as bioglass.

[0123] Immersion test:

[0124] Equipment: Electronic balance with an accuracy of 0.01g; pH meter with a graduation value not exceeding 0.02 pH units, equipped with a glass electrode and a reference electrode; and a magnetic stirrer with a PTFE-coated rotor.

[0125] Weigh (2.50±0.01) g of the calcium silicate-calcium phosphate crystal phase composite materials from Examples 1-4 and the bioglass from Comparative Example 1, and place them in 47.5±0.01) g of distilled water. Soak for 12 h, and then test the pH value (measured with a pH meter at 20°C under magnetic stirring, and read the value after the pH meter reading stabilizes). The data are shown in the table below:

[0126] sample pH value / after soaking for 12 hours Comparative Example 1 12.8 Example 1 8.7 Example 2 8.6 Example 3 8.2 Example 4 8.5

[0127] As can be seen from the data in the table above, the calcium silicate-calcium phosphate crystal phase composite materials prepared in Examples 1-4 of the present invention have a milder alkaline environment after soaking for 12 hours compared to the bioglass in Comparative Example 1. That is, the alkalinity is less than that of the bioglass in Comparative Example 1. When the calcium silicate-calcium phosphate crystal phase composite material of the present invention is applied to the oral field and the field of skin and mucous membrane repair, the impact on the progress and effect of tissue repair is reduced.

[0128] In summary, through extensive experimentation and serendipitous discovery, the inventors successfully prepared a calcium silicate-calcium phosphate crystalline composite material using metal alkoxides as raw materials and under acidic conditions, stabilizing the gel state with an electrolyte salt of calcium salts. Simultaneously, phosphate groups were added to form a composite phase of silicic acid and phosphate groups. Further compounding of weakly crystalline calcium salt clusters slowly formed a calcium silicate-calcium phosphate precursor. By mixing and sintering the two materials, a calcium silicate-calcium phosphate crystalline composite material was successfully prepared. By adjusting the ratio of the two materials, its microstructure, bioactivity, and degradation properties can be regulated, thus enabling the preparation of biomaterials with suitable properties according to actual needs.

[0129] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0130] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A calcium silicate- calcium phosphate crystalline phase composite material, characterized in that, obtained by the preparation method A or the preparation method B; the preparation method A comprises the following steps: A1, obtaining a mixed system containing tetraethyl orthosilicate, ethanol and water, adjusting the pH value of the mixed system to 1-2 with an acid, and then adding a calcium salt to obtain a first component; A2, obtaining a mixed system containing a phosphate, a calcium salt and water to obtain a second component; A3, mixing the first component and the second component uniformly, stirring at a temperature of 50-80℃, drying at 110-130℃ for 11-13h, sintering, mixing with ethanol after cooling, grinding and sieving to obtain the calcium silicate-calcium phosphate crystal phase composite material; the preparation method B comprises the following steps: B1, obtaining a mixed system containing a phosphate, tetraethyl orthosilicate, ethanol, a calcium salt and water, adjusting the pH value of the mixed system to 1-2 with an acid, stirring, and drying at 110-130℃ for 36-48h; B2, sintering the dried product, mixing with ethanol after cooling, grinding and sieving to obtain the calcium silicate-calcium phosphate crystal phase composite material; In step A1 of the preparation method A, the step of obtaining a mixed system containing tetraethyl orthosilicate, ethanol and water comprises: mixing tetraethyl orthosilicate and ethanol uniformly at a molar ratio of (0.1-0.4):1, and adding water; In step A1 of the preparation method A, the molar ratio of the calcium salt to tetraethyl orthosilicate is (0.5-1):1; In step A2 of the preparation method A, the step of obtaining a mixed system containing a phosphate, a calcium salt and water comprises: mixing the phosphate and the calcium salt uniformly at a molar ratio of 1:(1-1.5), and dissolving in water; In the preparation method A, the molar ratio of tetraethyl orthosilicate in the first component to the phosphate in the second component is (0.5-2):1; In the preparation method B, the molar ratio of the phosphate to tetraethyl orthosilicate is (0.5-2):1; the molar ratio of tetraethyl orthosilicate to ethanol is (0.1-0.4):1; and the molar ratio of the phosphate to the calcium salt is 1:(1-1.5).

2. The calcium silicate- calcium phosphate crystalline phase composite material according to claim 1, characterized in that, The phosphate is at least one of ammonium hydrogen phosphate, sodium hydrogen phosphate and potassium dihydrogen phosphate; and / or, The calcium salt comprises at least one of water-soluble calcium oxalate, calcium nitrate, calcium citrate, calcium gluconate, calcium hypochlorite and calcium acetate; and / or, In step A1 and / or step B1, the acid for adjusting the pH value of the mixed system is any one of nitric acid, hydrochloric acid and acetic acid.

3. The calcium silicate- calcium phosphate crystalline phase composite material according to claim 1, characterized in that, The sintering step in the preparation method A and / or the preparation method B specifically comprises: After the dried product is heated to 1200-1400℃ at a heating rate of 5-10℃ / min, it is kept at this temperature for 3-6 hours.

4. The calcium silicate- calcium phosphate crystalline phase composite material according to claim 1, characterized in that, The stirring treatment step in step B1 of the preparation method B is specifically: When the calcium salt is a weak electrolyte, the mixed system with adjusted pH value is magnetically stirred at room temperature for 50-70min to form a white slurry; or, When the calcium salt is a strong electrolyte, the mixed system with adjusted pH value is magnetically stirred in a constant temperature water bath at 50-80℃ for 50-70min to form a sol state, and then aged at 50-80℃ for 12-36h to form a wet gel.

5. Use of the calcium silicate-calcium phosphate crystalline phase composite material according to any one of claims 1 to 4 in the field of oral cavity, in the field of cosmetics, and in the field of skin and mucous membrane repair.

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