A 3D printing antibacterial orthotic material and its preparation method

Abstract

The present invention belongs to the technical field of 3D printing, and particularly relates to a 3D printing antibacterial orthotic material and a preparation method thereof. A functional nanocomposite MXene-ZnO is prepared based on a hydrothermal synthesis method, and a filament is prepared by extrusion molding. Further, a personalized orthotic material is constructed based on 3D printing technology. The orthotic material of the present invention has antibacterial properties, comfort and intelligence, and can improve the compliance and treatment effect of patients.

Description

Technical Field

[0001] The present invention belongs to the technical field of 3D printing, and in particular relates to a 3D printing antibacterial correction material and a preparation method thereof. Background Art

[0002] In the fields of medical treatment and rehabilitation, corrective materials are widely used to correct and support human tissues, such as spinal braces, orthopedic correction, soft tissue correction, etc. At present, common corrective materials on the market include metal alloys, bioceramic materials and polymer materials. Metal alloys are widely used in corrective devices due to their high strength and durability, but they are rigid and lack flexibility, are not easy to be processed into complex shapes, and are prone to discomfort or even allergic reactions during long-term wear. Although ceramic materials have good aesthetics and biocompatibility, they are brittle and easy to break, which limits their application in corrective devices. Polymer materials are widely used because of their good flexibility and biocompatibility. However, traditional polymer corrective materials have antibacterial properties, lack of intelligence, comfort, and difficulty in achieving personalized customization, which limits their wide application.

[0003] Current antibacterial orthodontic materials are usually achieved by coating antibacterial agents on the surface of the material, but this method has the problem that the antibacterial agent is easy to fall off and has poor durability. Therefore, introducing antibacterial materials into the correction material itself to maintain a stable antibacterial effect throughout its entire use cycle is a difficult problem that needs to be solved urgently. In addition, with the rapid development of intelligence, the intelligence of correction materials should also receive attention to realize intelligent monitoring (patient's wearing status, correction progress), etc., so as to make timely adjustments and interventions to formulate personalized treatment plans, improve treatment effects and patient compliance. In recent years, the development of 3D printing technology has also brought new opportunities for the preparation of correction materials. The application of 3D printing technology can achieve highly sophisticated and complex structural design, meet the personalized needs of different patients, and realize personalized customization.

[0004] Although some materials on the market have made breakthroughs in single performance, orthotic materials that can excel in all three aspects of antibacterial and intelligent monitoring are still scarce. Most orthotic materials cannot meet the requirements of antibacterial and intelligent monitoring at the same time, the antibacterial performance is difficult to sustain, and the intelligent monitoring function is single or ineffective. Therefore, exploring a corrective material with excellent antibacterial properties and intelligent monitoring and its preparation method will provide a new solution for the field of medical correction, significantly improving the treatment effect and patient experience. Summary of the invention

[0005] To solve the technical problems of the deficiencies in comfort, antibacterial property, and intelligence in the application of existing correction materials in the prior art, the present invention mainly provides a 3D printing antibacterial correction material additive, a correction material containing the additive, and a preparation method of the correction material. The specific solutions are as follows:

[0006] A 3D printing antibacterial correction additive, comprising MXene and zinc oxide in-situ synthesized on the surface of MXene.

[0007] A correction material using the above 3D printing antibacterial correction additive, by mass, comprising 0.1 - 5 parts of the additive described in claim 1, 70 - 100 parts of ABS plastic, and 0.1 - 30 parts of polyurethane.

[0008] A preparation method of the above correction material, comprising the following steps:

[0009] a, ABS plastic and polyurethane are respectively crushed to form fine powders;

[0010] b, the crushed ABS plastic, polyurethane, and additive are uniformly mixed using a ball mill to form a uniform composite powder;

[0011] c, the composite powder is put into a screw extruder, and through heating and the rotation of the screw, the composite powder is melted and extruded into filaments;

[0012] d, the extruded filaments are stretched, and the stretched filaments are rapidly cooled, shaped, and their dimensions are stabilized to obtain correction material filaments; the correction material filaments are printed according to a model by a 3D printer to obtain the correction material.

[0013] An application of the above correction additive in a device for correcting and / or supporting biological tissues, when the stress on the article changes, the resistance of the article changes accordingly.

[0014] Adopting the above solution, the method of the present invention has the following advantages:

[0015] 1. In the present invention, ZnO nanoparticles are synthesized on the surface of MXene, and the ZnO nanoparticles are uniformly distributed on the surface of MXene. The synthesized MXene-ZnO nanoparticles have antibacterial property, conductivity, and sensitivity at the same time, and their performance is more stable when compounded with other components.

[0016] 2. The present invention enhances the antibacterial property of the material, can effectively inhibit the growth of bacteria, enables the correction material to have a lasting antibacterial effect, effectively prevents the breeding and infection of bacteria, and reduces the infection risk of patients.

[0017] 3. The corrective material of the present invention has excellent sensing performance and can cooperate with detection devices to monitor parameters such as stress changes, so as to timely understand the wearing status and corrective progress of patients, and adjust and intervene in a timely manner to formulate appropriate treatment plans, such as replacing the corrective material, realizing intelligent correction, improving the accuracy and effectiveness of correction, and enhancing the compliance of patients.

[0018] 4. By utilizing the flexibility of 3D printing technology, the present invention can provide personalized solutions according to the specific conditions and needs of patients, realize the integrated design and manufacturing of corrective materials, simplify the preparation process, reduce production costs, and improve production efficiency.

[0019] 5. The present invention uses the composite of ABS and polyurethane to solve the problem of poor wearing comfort of traditional corrective materials. The high strength of ABS and the flexibility of polyurethane ensure the stability and durability of the corrective material during use. The flexibility of polyurethane improves the comfort of the corrective material during wearing and enhances the compliance of patients.

[0020] 6. The present invention can improve the comfort of the corrective material, ensure that an appropriate corrective force can be provided during the correction process, so as to improve the comfort of patients and reduce discomfort and pain caused by excessive rigidity of the material.

[0021] 7. The additives of the present invention and the corrective materials have a wide range of applications and can be applied to corrective insoles, spinal correction equipment, etc., with a low usage threshold. Description of the Drawings

[0022] Figure 1 It is the XRD pattern (a), SEM photograph (b), and TEM photograph (c) of the additive in Example 1.

[0023] Figure 2 It is the comparison chart of tensile strength (a), tensile modulus (b), and elongation at break (c) of the corrective materials of ABS and Examples 1-3 and Comparative Example 1.

[0024] Figure 3 It is the comparison chart of OD values (a) and inhibition zone (b) of the antibacterial properties of the corrective materials of Examples 2, 4, 5, 6 and Comparative Example 2.

[0025] Figure 4 It is the comparison chart of the sensing performance of different MXene-ZnO contents (10N) (a) in Examples 2, 4, 5, 6 and under different stresses (b) in Example 2.

[0026] Figure 5 It is the corrective insole (a) and spinal corrector (b) obtained by 3D printing the corrective material of Example 2. Detailed Embodiments

[0027] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0028] Example 1:

[0029] (1) Preparation of MXene-ZnO additive: Weigh a certain amount of MXene powder and ultrasonically disperse it in an appropriate amount of deionized water. Add 0.05 mol / L zinc acetate dihydrate and mechanically stir for 30 min. Prepare a 2 mol / L sodium hydroxide solution and slowly add it dropwise to the above solution while stirring to adjust the pH to 11. Then pour the mixed solution into the polytetrafluoroethylene liner of the reaction kettle, place the reaction kettle in the oven for hydrothermal reaction to in-situ synthesize ZnO powder on the surface of MXene. After the reaction, wait for the reaction kettle to cool, filter to obtain MXene-ZnO nanocomposite powder, wash it with deionized water until neutral first, then wash it with absolute ethanol 3 times, and freeze-dry for 24 h to obtain the additive.

[0030] The XRD pattern of the obtained sample is as Figure 1 (a) shown. The characteristic diffraction peaks of ZnO at 31.8°, 34.4°, 36.2°, 47.6°, 56.6°, 62.9°, 66.4° and 67.9° exist in the figure, indicating that high-purity ZnO is generated in the sample. Figure 1 (b) The SEM and Figure 1 (c) The TEM images in show that nano-ZnO is uniformly distributed on the surface of MXene, indicating that nano-ZnO particles are uniformly distributed on the surface of MXene, and MXene-ZnO nanoparticles are successfully synthesized.

[0031] (2) Preparation of ABS / PU / MXene-ZnO composite filaments: Use cryogenic grinding or shear milling to crush ABS plastic and polyurethane particles respectively to form fine powders. Weigh 90 parts by mass of the crushed ABS powder, 8 parts of polyurethane powder, and 2 parts of MXene-ZnO additive, and use a ball mill to mix them evenly. Set the rotation speed to 1000 r / min and the time to 2 h to form a uniform composite powder. Put the uniformly mixed composite powder into a screw extruder, set the temperature of the screw extruder (the temperature of the first heating zone is 200 °C, the temperature of the second heating zone is 220 °C, the temperature of the third heating zone is 240 °C, and the nozzle temperature is 230 °C). Through heating and the rotation of the screw, melt the composite powder and extrude filaments. Stretch the extruded filaments, and quickly cool the stretched filaments through a water bath or air cooling system to shape and stabilize their dimensions to obtain the final straightened filaments.

[0032] (3) Preparation of 3D printing correction materials: Load the wire into the feed inlet of the 3D printer, set the working parameters of the 3D printer, and perform printing through the imported STL model. The printing parameters are: nozzle temperature is 250 °C, nozzle diameter is 0.4 mm, printing speed is 40 mm / min, and thickness is 0.25 mm.

[0033] Example 2:

[0034] The difference from Example 1 is:

[0035] (2) Preparation of ABS / PU / MXene-ZnO composite wire: Crush ABS plastic and polyurethane particles separately into fine powders by using cryogenic grinding or shear milling method; Weigh 80 parts by mass of the crushed ABS powder, 18 parts of polyurethane powder, and 2 parts of MXene-ZnO additive, and use a ball mill to mix evenly. Set the rotation speed to 1000 r / min and the time to 2 h to form a uniform composite powder.

[0036] Example 3:

[0037] The difference from Example 1 is:

[0038] (2) Preparation of ABS / PU / MXene-ZnO composite wire: Crush ABS plastic and polyurethane particles separately into fine powders by using cryogenic grinding or shear milling method; Weigh 70 parts by mass of the crushed ABS powder, 28 parts of polyurethane powder, and 2 parts of MXene-ZnO additive, and use a ball mill to mix evenly. Set the rotation speed to 1000 r / min and the time to 2 h to form a uniform composite powder.

[0039] Example 4:

[0040] The difference from Example 1 is:

[0041] (2) Preparation of ABS / PU / MXene-ZnO composite wire: Crush ABS plastic and polyurethane particles separately into fine powders by using cryogenic grinding or shear milling method; Weigh 80 parts by mass of the crushed ABS powder, 19 parts of polyurethane powder, and 1 part of MXene-ZnO additive, and use a ball mill to mix evenly. Set the rotation speed to 1000 r / min and the time to 2 h to form a uniform composite powder.

[0042] Example 5:

[0043] The difference from Example 1 is:

[0044] (2) Preparation of ABS / PU / MXene-ZnO composite filaments: The ABS plastic and polyurethane particles were respectively pulverized by cryogenic grinding or shear milling to form fine powders; 80 parts by mass of the pulverized ABS powder, 17 parts of polyurethane powder, and 3 parts of MXene-ZnO additive were weighed, and uniformly mixed using a ball mill, with the rotation speed set at 1000 r / min and the time set at 2 h to form a uniform composite powder.

[0045] Example 6:

[0046] The difference from Example 1 is:

[0047] (2) Preparation of ABS / PU / MXene-ZnO composite filaments: The ABS plastic and polyurethane particles were respectively pulverized by cryogenic grinding or shear milling to form fine powders; 80 parts by mass of the pulverized ABS powder, 15 parts of polyurethane powder, and 5 parts of MXene-ZnO additive were weighed, and uniformly mixed using a ball mill, with the rotation speed set at 1000 r / min and the time set at 2 h to form a uniform composite powder.

[0048] Comparative Example 1:

[0049] (1) Preparation of ABS filaments: The ABS plastic was pulverized by cryogenic grinding or shear milling; 100 parts by mass of the pulverized ABS powder was weighed, and uniformly mixed using a ball mill, with the rotation speed set at 1000 r / min and the time set at 2 h to form a uniform composite powder; the ABS powder was put into a screw extruder, and the temperature of the screw extruder was set (the temperature of the first heating zone was 200 °C, the temperature of the second heating zone was 220 °C, the temperature of the third heating zone was 240 °C, and the nozzle temperature was 230 °C). Through heating and the rotation of the screw, the composite powder was melted and extruded into filaments; the extruded filaments were stretched, and the stretched filaments were rapidly cooled through a water bath or air cooling system, shaped, and stabilized in size to obtain the final corrected filaments.

[0050] (3) Preparation of 3D printing correction materials: The filaments were loaded into the feed port of a 3D printer, and the working parameters of the 3D printer were set, and printing was carried out through the imported STL model. The printing parameters were: nozzle temperature 250 °C, nozzle diameter 0.4 mm, printing speed 40 mm / min, and thickness 0.25 mm.

[0051] Comparative Example 2:

[0052] (1) Preparation of ABS / PU composite filaments: ABS plastics and polyurethane particles are respectively pulverized by cryogenic grinding or shear milling to form fine powders; 80 parts by mass of the pulverized ABS powder and 20 parts by mass of the polyurethane powder are weighed and evenly mixed using a ball mill, with the rotation speed set at 1000 r / min and the time set at 2 h to form a uniform composite powder; the uniformly mixed composite powder is put into a screw extruder, and the temperature of the screw extruder is set (the temperature of the first heating zone is 200 °C, the temperature of the second heating zone is 220 °C, the temperature of the third heating zone is 240 °C, and the temperature of the nozzle is 230 °C). Through heating and the rotation of the screw, the composite powder is melted and extruded into filaments; the extruded filaments are stretched, and the stretched filaments are rapidly cooled through a water bath or an air cooling system, shaped and stabilized in size to obtain the final corrected filaments.

[0053] (2) Preparation of 3D printing correction materials: The filaments are loaded into the feed inlet of a 3D printer, and the working parameters of the 3D printer are set, and printing is carried out through the imported STL model. The printing parameters are: the nozzle temperature is 250 °C, the nozzle diameter is 0.4 mm, the printing speed is 40 mm / min, and the thickness is 0.25 mm.

[0054] Example sample testing:

[0055] An electronic universal tensile testing machine is used to measure the mechanical properties of the correction materials. The mechanical strength and elongation at break of the corrected filaments prepared in Comparative Test Examples 1, 2, 3 and Comparative Example 1 are compared, and the results are as Figure 2 (a)(b)(c) shown. As can be seen from the figure, with the addition of PU, the mechanical strength of the filaments decreases, while the elongation at break increases significantly, indicating that the addition of PU improves the flexibility of the correction materials.

[0056] The antibacterial properties of the samples are characterized by the OD value (600 nm) and the diameter of the antibacterial zone. The correction materials of Example 2, 4, 5, 6 and Comparative Example 2 are 3D printed into samples of the same size, and Escherichia coli and Staphylococcus aureus are selected for testing. The results are as Figure 3 shown. The incorporation of the MXene-ZnO additive significantly improves the antibacterial properties of the correction materials, and the antibacterial rate gradually increases with the addition of the MXene-ZnO additive.

[0057] A digital multimeter is used to measure the sensing performance of the correction materials and evaluate their intelligent monitoring ability. The correction materials of Example 2, 4, 5, 6 and Comparative Example 2 are 3D printed into samples of the same size, placed in a stress-free state, the initial resistance value is recorded, stress is gradually applied, the corresponding resistance change is recorded, and the sensing sensitivity is calculated. The results are as Figure 4As shown in a, by comparison, the incorporation of the MXene-ZnO additive endows the sensing performance of the orthotic material, and the sensing performance increases with the increase in the content of the MXene-ZnO additive. It can be seen from this that the orthotic material of the present invention has high sensitivity and can accurately monitor subtle stress changes to judge the patient's movements and identify the orthotic state of the patient.

[0058] For those skilled in the art, various corresponding changes and deformations can be made according to the technical solutions and concepts described above, and all such changes and deformations should fall within the protection scope of the claims of the present invention.

Claims

1. A 3D printed antibacterial corrective additive, characterized in that: Including MXene and zinc oxide synthesized in situ on the surface of MXene; Its preparation comprises the following steps: S1, taking MXene powder and dispersing it in water by ultrasonication, adding zinc acetate to make the concentration of zinc acetate 0.01-0.1 mol / L, and mixing evenly; the molar ratio of the MXene powder to zinc acetate is (2-3):1; S2, prepare a sodium hydroxide solution with a concentration of 1-2 mol / L, slowly add it dropwise into the reaction system while stirring, adjust the pH of the system to 10.5-11.5, and perform a hydrothermal reaction at 100-120°C for 20-28 hours; S3, after the reaction is completed, cool to room temperature, separate the precipitate, wash the precipitate with water until it is neutral, then wash it thoroughly with ethanol, and freeze-dry it to obtain the product.

2. A correction material using the 3D printed antibacterial correction additive according to claim 1, characterized in that: Calculated by mass, it comprises 0.1 to 5 parts of the additive according to claim 1, 70 to 100 parts of ABS plastic and 0.1 to 30 parts of polyurethane.

3. A method for preparing the correction material according to claim 2, characterized in that: The following steps are involved: a. ABS plastic and polyurethane are crushed separately to form fine powder; b. Use a ball mill to evenly mix the crushed ABS plastic, polyurethane and additives to form a uniform composite powder; c. Put the composite powder into the screw extruder, melt the composite powder and extrude the wire through heating and screw rotation; d. stretching the extruded filament, rapidly cooling the stretched filament, shaping and stabilizing its size, and obtaining a correction material filament; and printing the correction material filament according to the model by a 3D printer, thereby obtaining a correction material.

4. The method for preparing the correction material according to claim 3, characterized in that: The ball milling speed in step b is 800-1500 r / min, and the time is 2-4 h.

5. The method for preparing a correction material according to claim 3, characterized in that: In step c, the temperature of the screw extruder is set as follows: the temperature of the first heating zone is 180-200°C, the temperature of the second heating zone is 200-220°C, the temperature of the third heating zone is 220-240°C, and the nozzle temperature is 210-230°C.

6. The method for preparing a correction material according to claim 3, characterized in that: In step d, the 3D printing temperature is 250° C., the nozzle diameter is 0.2-0.5 mm, the printing speed is 30-60 mm / min, and the layer thickness is 0.1-0.4 mm.

7. Use of the corrective additive according to claim 1 in preparing an article for correcting and / or supporting biological tissue, characterized in that: When the stress on the object changes, the resistance of the object changes accordingly.

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