CN113813452B

CN113813452B - Construction method of 3D printing titanium alloy support with photo-thermal and temperature control warning functions

Info

Publication number: CN113813452B
Application number: CN202111105653.2A
Authority: CN
Inventors: 蔡变云; 郭志君; 李光大
Original assignee: Henan University of Science and Technology
Current assignee: Henan University of Science and Technology
Priority date: 2021-09-22
Filing date: 2021-09-22
Publication date: 2022-06-14
Anticipated expiration: 2041-09-22
Also published as: CN113813452A

Abstract

The invention discloses a construction method of a 3D printing titanium alloy bracket with photo-thermal and temperature control warning functions, and relates to the technical field of surface functional modification of biomedical metal materials. The 3D printing titanium alloy bracket with photothermal and temperature control warning functions is developed by taking a 3D printing Ti64 titanium alloy bracket as a substrate, constructing a structural/component double-bionic Ca and P-containing nanofiber network structure coating (HR-Ti64) on the surface of the coating in situ by adopting a two-step hydrothermal method, and doping a lanthanide rare earth element neodymium Nd with temperature sensitivity on the surface of the coating by adopting a mechanical blending method.

Description

Construction method of 3D printing titanium alloy support with photo-thermal and temperature control warning functions

Technical Field

The invention relates to the technical field of surface functionalization modification of biomedical metal materials, in particular to a construction method of a 3D printing titanium alloy support with photo-thermal and temperature control warning functions.

Background

Bone tumor is a tumor which occurs in bones or accessory tissues thereof, is one of common diseases in orthopedics, and has high disability rate and lethality rate. At present, the most common treatment mode of bone tumor is surgical resection with radiotherapy and chemotherapy. Although the tumor can be removed by the operation treatment, many malignant bone tumors have unclear boundaries, and particularly, the tumor with multiple focuses is difficult to remove, and the recurrence and the metastasis of the tumor after the operation are easily caused. Bone tumors are different in parts, large-scale irregular bone defects are caused after resection, and due to large individual differences, repair of the bone tumors is also a great problem in clinic. In addition, although radiotherapy and chemotherapy are commonly used for adjuvant therapy of bone tumors, both of them can cause serious side effects, and a special bone microenvironment of bone tissues can provide a protective cavity for tumor cells, thereby greatly reducing the effects of radiotherapy and chemotherapy.

The photothermal ablation therapy has the characteristics of minimal invasion, small side effect, quick curative effect, strong tissue penetration capacity and the like, and has obvious advantages in bone tumor therapy. However, a hard tissue repair material which integrates photothermal effect, personalized conformal matching and osseointegration functions and can synchronously realize anti-tumor and bone repair is not available at present.

In the conventional photothermal therapy (PTT) process, the situation that the treatment efficacy cannot be controlled is easily caused because the accurate temperature of a tumor part cannot be monitored in real time: the PTT temperature is too low to effectively kill tumor cells, and the risk of burning surrounding normal tissues exists when the temperature is too high. Therefore, how to accurately measure the temperature of the focus part and realize the photothermal therapy without thermal injury side effect is one of the key problems to be solved in the development of the PTT.

Disclosure of Invention

The invention aims to provide a construction method of a 3D printing titanium alloy support with photo-thermal and temperature control warning functions, and aims to solve the problems that in the traditional bone tumor treatment process, anti-tumor/bone repair is difficult to achieve synchronously, and the traditional photo-thermal treatment cannot monitor the temperature of a focus in real time, so that the treatment efficacy is poor.

In order to achieve the purpose, the invention provides the following scheme:

a construction method of a 3D printing titanium alloy support with photo-thermal and temperature control warning functions comprises the following steps:

(1) the construction of the titanium alloy stent surface structure/component double bionic coating:

carrying out acid etching treatment, cleaning and drying on the 3D printed porous titanium alloy Ti64 bracket, and then placing the bracket in H₂O₂And H₃PO₄The mixed aqueous solution is subjected to hydrothermal reaction for 20 to 30 hours at the temperature of 200 ℃ and 250 ℃ and the pressure of 100kPa, washed and dried, and then placed in CaCl₂In the solution, the second hydrothermal reaction is carried out at the temperature of 100-150 ℃ and under the condition of 70-120kPa, and after the reaction is carried out for 4-14h, the solution is cleaned and driedObtaining the HR-Ti64 bracket after the coating treatment;

(2) doping of rare earth element neodymium Nd:

and (3) placing the coated HR-Ti64 stent in a neodymium nitrate hexahydrate aqueous solution, carrying out constant-temperature oscillation reaction for 3-48h at the temperature of 25-50 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy stent with the photo-thermal and temperature control warning functions.

Further, in the step (1), the H₂O₂And H₃PO₄In the mixed aqueous solution of (1), H₂O₂Has a mass concentration of 3-27%, H₃PO₄The mass concentration of (A) is 3-27%.

Further, in the step (1), the H₂O₂And H₃PO₄H in the mixed aqueous solution of₂O₂And H₃PO₄The mass ratio of (1-9) to (1-3).

Further, in the step (1), the treatment solution used for the acid etching treatment is a mixed solution of hydrofluoric acid, nitric acid and water according to a volume ratio of (1-2): (3-4):5, and the time of the acid etching treatment is 1-6 min.

Further, in the step (1), after the acid etching treatment, respectively performing ultrasonic cleaning by using acetone, absolute ethyl alcohol and ultrapure water in sequence, wherein the cleaning time is 10-60min each time.

Further, in the step (1), the CaCl₂The concentration of the solution is 0.2-1.2 g/mL.

Further, in the step (2), the concentration of the neodymium nitrate hexahydrate aqueous solution is 0.025-0.8 g/mL.

The invention also provides the 3D printing titanium alloy support with photo-thermal and temperature control warning functions, which is obtained by the construction method.

According to the invention, a Ca and P-containing nanofiber network structure coating with a structure/component dual bionic natural bone tissue is constructed on the surface of the 3D printing titanium alloy support by adopting a two-step hydrothermal method, and Ca and P active ingredients in the coating can improve bioactivity and accelerate osseointegration, so that the bionic osteogenesis performance of the 3D printing titanium alloy support is improved.

According to the invention, a lanthanide rare earth element neodymium Nd with fluorescence performance and temperature sensitivity is introduced into the surface coating of the 3D printing titanium alloy support, the focus temperature is monitored in real time by measuring fluorescence intensity, the fluorescence temperature control function can be realized, and tumor recurrence and metastasis are controlled in a high-safety and effective photothermal therapy mode (healthy tissues around can be prevented from being burned while bone tumors are ablated by photothermal therapy).

The invention discloses the following technical effects:

the method takes a 3D printed Ti64 titanium alloy bracket as a substrate, adopts a two-step hydrothermal method to construct a structural/component bionical Ca and P-containing nanofiber network structure coating (HR-Ti64) on the surface of the substrate in situ, and adopts a mechanical blending method to dope a lanthanide rare earth element Nd with temperature sensitivity on the surface of the coating. The 3D printing titanium alloy bracket (Nd-HR-Ti64) with photothermal and temperature control warning functions, which is prepared by the invention, can repair large irregular bone defects caused by resection of bone tumor with excellent osteogenic performance, can accurately monitor the temperature of the tumor part in real time through fluorescence, controls tumor recurrence and metastasis in a high-safety and effective photothermal therapy mode, and is expected to solve the bottleneck problem in clinical repair and treatment of tumorous bone defects.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is an SEM image of the surface of a Ti64 scaffold prior to hydrothermal treatment of example 1;

FIG. 2 is an SEM image of the surface of a Ti64 stent after phosphorylation treatment in example 1;

FIG. 3 is an SEM image of the surface of the HR-Ti64 scaffold after two hydrothermal calcification treatments of example 1;

FIG. 4 is the EDS composition, surface element distribution map of the HR-Ti64 alloy stent after two hydrothermal calcification treatments of example 1;

FIG. 5 is a schematic view ofExample 1 before and after the two hydrothermal calcification treatments, the Ti64 alloy stent was 0.5W/cm²Infrared thermal imaging graph and photo-thermal curve under the irradiation of power density near infrared light, wherein the upper graph is the infrared thermal imaging graph, and the lower graph is the photo-thermal curve;

FIG. 6 is an SEM photograph of a 0.025g/mL Nd-HR-Ti64 alloy stent in example 1;

FIG. 7 is the EDS composition, surface element distribution of the 0.025g/mL Nd-HR-Ti64 alloy stent in example 1;

FIG. 8 is an infrared thermography, a photothermal curve and a fluorescence emission spectrum of a 0.025g/mL Nd-HR-Ti64 alloy scaffold under 808nm near-infrared light irradiation in example 1, wherein (a) is the infrared thermography, (b) is the photothermal curve, and (c) is the fluorescence emission spectrum;

FIG. 9 is an SEM photograph of a 0.05g/mL Nd-HR-Ti64 alloy holder of example 2;

FIG. 10 is the EDS composition, surface element distribution of the 0.05g/mL Nd-HR-Ti64 alloy stent in example 2;

FIG. 11 is an infrared thermography, a photothermal curve and a fluorescence emission spectrum of a 0.05g/mL Nd-HR-Ti64 alloy scaffold under 808nm near-infrared light irradiation in example 2, wherein (a) is the infrared thermography, (b) is the photothermal curve, and (c) is the fluorescence emission spectrum;

FIG. 12 is an SEM photograph of a 0.1g/mL Nd-HR-Ti64 alloy holder of example 3;

FIG. 13 is a graph showing the EDS composition and surface element distribution of a 0.1g/mL Nd-HR-Ti64 alloy holder in example 3;

FIG. 14 is an infrared thermography, a photothermal curve and a fluorescence emission spectrum of a 0.1g/mL Nd-HR-Ti64 alloy scaffold under 808nm near-infrared light irradiation in example 3, wherein (a) is the infrared thermography, (b) is the photothermal curve, and (c) is the fluorescence emission spectrum;

FIG. 15 is an SEM photograph of a 0.2g/mL Nd-HR-Ti64 alloy holder of example 4;

FIG. 16 is a graph showing the distribution of the EDS composition and surface elements of a 0.2g/mL Nd-HR-Ti64 alloy holder in example 4;

FIG. 17 is an infrared thermography, a photothermal curve and a fluorescence emission spectrum of a 0.2g/mL Nd-HR-Ti64 alloy scaffold under 808nm near-infrared irradiation in example 4, wherein (a) is the infrared thermography, (b) is the photothermal curve, and (c) is the fluorescence emission spectrum;

FIG. 18 is an SEM photograph of a 0.4g/mL Nd-HR-Ti64 alloy holder of example 5;

FIG. 19 is an EDS composition, surface element distribution map of a 0.4g/mL Nd-HR-Ti64 alloy holder of example 5;

FIG. 20 is an infrared thermography, a photothermal curve and a fluorescence emission spectrum of a 0.4g/mL Nd-HR-Ti64 alloy scaffold under 808nm near-infrared irradiation in example 5, wherein (a) is the infrared thermography, (b) is the photothermal curve, and (c) is the fluorescence emission spectrum;

FIG. 21 is an SEM photograph of a 0.8g/mL Nd-HR-Ti64 alloy holder of example 6;

FIG. 22 is an EDS composition, surface element distribution diagram of a 0.8g/mL Nd-HR-Ti64 alloy holder of example 6;

FIG. 23 is an infrared thermography, a photothermal curve and a fluorescence emission spectrum of a 0.8g/mL Nd-HR-Ti64 alloy scaffold under 808nm near-infrared irradiation in example 6, wherein (a) is the infrared thermography, (b) is the photothermal curve, and (c) is the fluorescence emission spectrum;

FIG. 24 is a schematic construction flow chart of a titanium alloy support Nd-HR-Ti 64.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

Example 1

The steps of this example are as follows:

hydrofluoric acid, nitric acid and water are prepared according to the volume ratio of 1:3:5 to prepare an acid etching treatment solution.

Carrying out acid etching treatment on the 3D printed porous titanium alloy Ti64 stent in an acid etching treatment solution for 1min, respectively carrying out ultrasonic cleaning on the stent by using acetone, absolute ethyl alcohol and ultrapure water in sequence for 10min, drying the stent, and placing the stent in 50mL of H₂O₂And H₃PO₄In a mixed aqueous solution of (wherein H)₂O₂Mass concentration of 27%, H₃PO₄3 percent of mass concentration), performing hydrothermal reaction for 20 hours at 200 ℃ under the condition of 100kPa, cleaning, drying, and then placing in 50mL of CaCl with the concentration of 0.2g/mL₂Carrying out secondary hydrothermal reaction for 4h at 100 ℃ under 70kPa in the solution, cleaning and drying to obtain the HR-Ti64 stent after coating treatment.

(2) Doping of rare earth element neodymium Nd:

the coated HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) with a concentration of 0.025g/mL₃)₃·6H₂O) in water solution, carrying out constant-temperature oscillation reaction for 3h at 25 ℃, cleaning and drying to obtain the 3D printing titanium alloy bracket with the photo-thermal and temperature control warning functions, namely the 0.025Nd-HR-Ti64 alloy bracket.

Observing the microscopic morphology of the surface of the support in the embodiment by adopting a Scanning Electron Microscope (SEM), and analyzing the element composition and the distribution condition by combining an energy dispersive X-ray spectrometer (EDS) and element surface scanning; irradiating the surface of the support in the embodiment for 5min by using near-infrared laser with wavelength of 808nm, monitoring the temperature of each support in real time by using an infrared thermal imager, recording data, and drawing a temperature-time change graph by Origin software; the fluorescence emission spectrum of the stent in the present example under 808nm excitation light was measured by using a steady transient fluorescence spectrometer.

The experimental results are as follows: as shown in FIGS. 1-3, the Ti64 alloy scaffold before and after the hydrothermal treatment has a porous structure, and the statistical pore size is about 500 μm. The surface of the Ti64 stent before the hydrothermal treatment is relatively smooth, and a large number of scratches and pits (shown in FIG. 1) can be seen on the surface under a high-power SEM; the surface of the stent is covered with a coating after phosphorylation treatment, the coating is a fiber network structure formed by random accumulation of countless nanorods, the structure is similar to the surface of natural bone after demineralization and absorption of osteoclasts, and the average diameter of fibers in the fiber network structure is 100-300nm through statistics, and the surface of the fibers is smooth (as shown in figure 2); after the second hydrothermal calcification treatment, the HR-Ti64 scaffold surface coating still maintains the porous fiber network structure, but uniformly covers a layer of granular protrusions with the diameter of 100-200nm on the fiber surface, which is supposed to be formed by calcium salt deposition (as shown in FIG. 3). As shown in FIG. 4, the HR-Ti64 stent surface coating mainly comprises Ti, O, P, Ca and C elements, and the elements are uniformly distributed on the surface of the stent pore wall, which indicates that bioactive elements Ca and P are successfully doped in the coating, and the doping amounts are respectively Ca 7.2 wt% and P3.5 wt%.

As shown in FIG. 5, at 0.5W/cm²Ti64 in 1 minute under the irradiation of near-infrared laserThe temperature of the bracket can be quickly increased to 42.5 ℃, and the temperature is increased to 60.2 ℃ within 5 minutes; after the two-step hydrothermal coating treatment, the photo-thermal performance of the HR-Ti64 stent is improved, and the temperature is rapidly increased to 72.5 ℃ within 5 minutes. Before and after the coating treatment, the support material has obvious absorption and stronger photothermal conversion capability at the near infrared light, and lays a foundation for the subsequent application of the support material in the aspects of photothermal antitumor.

As shown in FIGS. 6-8, HR-Ti64 scaffolds were placed in neodymium nitrate hexahydrate (Nd (NO) at a concentration of 0.025g/mL₃)₃·6H₂O) after constant temperature oscillation treatment in the water solution, the surface of the bracket is still formed by disorderly stacking a porous fiber rod-shaped structure and a spherical structure (shown in figure 6); EDS component analysis shows that the surface coating of the Nd-doped 0.025Nd-HR-Ti64 support not only contains Ti, O, P and Ca elements, but also has an obvious Nd element peak, and a semi-quantitative result shows that the doping amount of the surface Nd element is 2.5 wt%; the element surface scanning pictures show that the Nd element is uniformly distributed on the surface of the bracket, which indicates the successful doping of the lanthanide rare earth element Nd (as shown in FIG. 7). Under the excitation of near infrared light of 808nm, the 0.025Nd-HR-Ti64 bracket not only has improved photo-thermal performance (as shown in figures 8(a) and (b)), but also can emit infrared fluorescence, and trivalent Nd appears in an emission spectrum (as shown in figure 8 (c))³⁺Characteristic fluorescence emission peaks (881nm and 892 nm: (881 nm)⁴F_3/2→⁴F_9/2)；1062nm(⁴F_3/2→⁴F_11/2)；1336nm(⁴F_3/2→⁴F_13/2) The material lays a foundation for becoming a dual-function material with photo-thermal and fluorescence temperature measurement characteristics.

Example 2

The steps of this example are as follows:

hydrofluoric acid, nitric acid and water are prepared according to the volume ratio of 2:4:5 to prepare an acid etching treatment solution.

Performing acid etching treatment on the 3D printed porous titanium alloy Ti64 support in an acid etching treatment solution for 2min, and sequentially using acetone, absolute ethyl alcohol and ultrapure waterUltrasonic cleaning for 20min, drying, and placing in 50mL H₂O₂And H₃PO₄In a mixed aqueous solution of (wherein H)₂O₂Mass concentration of 20%, H₃PO₄10 percent of mass concentration), performing hydrothermal reaction for 22 hours at 210 ℃ and 110kPa, cleaning and drying, and then placing in 50mL of CaCl with the concentration of 0.4g/mL₂And carrying out secondary hydrothermal reaction for 6h at 110 ℃ under 80kPa in the solution, cleaning and drying to obtain the coated HR-Ti64 stent.

(2) Doping of rare earth element neodymium (Nd):

the coated HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) with a concentration of 0.05g/mL₃)₃·6H₂O) in the water solution, carrying out constant-temperature oscillation reaction for 6h at the temperature of 30 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy bracket with the photo-thermal and temperature control warning functions, namely the 0.05Nd-HR-Ti64 alloy bracket.

The experimental results are as follows: as shown in FIGS. 9-11, in this example, the HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) at a concentration of 0.05g/mL₃)₃·6H₂O) after constant temperature oscillation treatment in aqueous solution, the surface of the bracket is still formed by disorderly stacking porous fiber rod-shaped structures and spherical structures (shown in figure 9); EDS component analysis shows that the doping amount of the Nd element is obviously increased and is 7.3 wt%; as can be seen from the element surface scanning pictures, the Nd element was successfully doped and uniformly distributed on the surface of the stent (as shown in fig. 10). Under the excitation of 808nm laser, the photothermal property and the fluorescence property of the 0.05Nd-HR-Ti64 bracket are improvedTrivalent Nd in spectrogram³⁺Characteristic fluorescence emission peaks (881nm and 892 nm: (881 nm)⁴F_3/2→⁴F_9/2)；1062nm(⁴F_3/2→⁴F_11/2)；1336nm(⁴F_3/2→⁴F_13/2) The peak intensity of the Nd element is obviously enhanced along with the increase of the content of the Nd element, which lays a foundation for the Nd element to become a dual-functional material with photothermal and fluorescence temperature measurement characteristics (as shown in figures 11 (a-c)).

Example 3

The steps of this example are as follows:

hydrofluoric acid, nitric acid and water are prepared according to the volume ratio of 2:3:5 to prepare an acid etching treatment solution.

Carrying out acid etching treatment on the 3D printed porous titanium alloy Ti64 support for 3min, respectively carrying out ultrasonic cleaning on the support by acetone, absolute ethyl alcohol and ultrapure water in sequence for 30min, drying the support, and placing the support into 50mL of H₂O₂And H₃PO₄In a mixed aqueous solution of (wherein H)₂O₂Mass concentration of 3%, H₃PO₄9 percent of mass concentration), performing hydrothermal reaction for 24 hours at 220 ℃ under the condition of 120kPa, cleaning, drying, and then placing in 50mL of CaCl with the concentration of 0.6g/mL₂Carrying out secondary hydrothermal reaction for 8h at 120 ℃ under the condition of 90kPa in the solution, cleaning and drying to obtain the HR-Ti64 stent after coating treatment.

(2) Doping of rare earth element neodymium Nd:

the coated HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) with a concentration of 0.1g/mL₃)₃·6H₂O) in the water solution, carrying out constant-temperature oscillation reaction for 12h at 35 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy bracket with photo-thermal and temperature control warning functions, namely the 0.1Nd-HR-Ti64 alloy bracket.

The experimental results are as follows: as shown in FIGS. 12-14, the HR-Ti64 stent was placed in a 0.1g/mL concentration of neodymium nitrate hexahydrate (Nd (NO)₃)₃·6H₂O) after constant temperature oscillation treatment in the water solution, the morphology structure of the stent surface formed by disorderly stacking porous fiber rod-shaped and spherical structures is basically unchanged (as shown in figure 12); EDS component analysis shows that the doping amount of Nd is further increased to 9.2 wt%; the elemental surface scan pictures show that Nd element was successfully doped and uniformly distributed on the surface of the stent (as shown in fig. 13). Under the excitation of 808nm laser, the photothermal and fluorescent properties of the 0.1Nd-HR-Ti64 bracket are further improved, and trivalent Nd in an emission spectrum diagram³⁺Characteristic fluorescence emission peaks (881nm and 892 nm: (881 nm)⁴F_3/2→⁴F_9/2)；1062nm(⁴F_3/2→⁴F_11/2)；1336nm(⁴F_3/2→⁴F_13/2) The peak intensity of the Nd element is further enhanced along with the increase of the content of the Nd element, which lays a foundation for the double-function material with the temperature measurement characteristics of photo-thermal and fluorescence (as shown in figures 14 (a-c)).

Example 4

The steps of this example are as follows:

hydrofluoric acid, nitric acid and water are prepared according to the volume ratio of 1:4:5 to prepare an acid etching treatment solution.

Carrying out acid etching treatment on the 3D printed porous titanium alloy Ti64 support for 4min, respectively carrying out ultrasonic cleaning on the support by using acetone, absolute ethyl alcohol and ultrapure water in sequence for 40min, drying the support, and placing the support into 50mL of H₂O₂And H₃PO₄Mixed aqueous solution ofWherein (H)₂O₂Mass concentration of 3%, H₃PO₄3% by mass), performing hydrothermal reaction at 230 ℃ and 130kPa for 26h, cleaning, drying, and placing in 50mL of CaCl with the concentration of 0.8g/mL again₂Carrying out secondary hydrothermal reaction for 10h at 130 ℃ under the condition of 100kPa in the solution, cleaning and drying to obtain the HR-Ti64 stent after coating treatment.

(2) Doping of rare earth element neodymium Nd:

the coated HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) with a concentration of 0.2g/mL₃)₃·6H₂O) in the water solution, carrying out constant-temperature oscillation reaction for 24h at 40 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy bracket with photo-thermal and temperature control warning functions, namely the 0.2Nd-HR-Ti64 alloy bracket.

The experimental results are as follows: as shown in FIGS. 15-17, in this example, the HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) at a concentration of 0.2g/mL₃)₃·6H₂O) after constant temperature oscillation treatment in the water solution, the morphology structure of the stent surface formed by disorderly stacking porous fiber rod-shaped and spherical structures is basically unchanged (as shown in FIG. 15); EDS component analysis shows that the doping amount of Nd is further increased to 13.7 wt%; the elemental surface scan pictures show that Nd element was successfully doped and uniformly distributed on the surface of the stent (as shown in fig. 16). And under the excitation of 808nm laser, the 0.2Nd-HR-Ti64 bracket presents excellent photo-thermal and fluorescence characteristics, and trivalent Nd in an emission spectrum diagram³⁺Characteristic fluorescence emission peaks (881nm and 892 nm: (881 nm)⁴F_3/2→⁴F_9/2)；1062nm(⁴F_3/2→⁴F_11/2)；1336nm(⁴F_3/2→⁴F_13/2) The peak intensity of the Nd element is obviously enhanced along with the increase of the content of the Nd element, which lays a foundation for the Nd element to become a dual-functional material with photothermal and fluorescence temperature measurement characteristics (as shown in fig. 17 (a-c)).

Example 5

The steps of this example are as follows:

Carrying out acid etching treatment on the 3D printed porous titanium alloy Ti64 support for 5min, respectively carrying out ultrasonic cleaning on the support by using acetone, absolute ethyl alcohol and ultrapure water in sequence for 50min, drying, and placing the support in 50mL of H₂O₂And H₃PO₄In a mixed aqueous solution of (wherein H)₂O₂Mass concentration of 20%, H₃PO₄10% by mass), hydrothermal reaction at 240 ℃ under 140kPa for 28h, washing, drying, and placing in 50mL of 1.0g/mL CaCl₂Carrying out secondary hydrothermal reaction for 12h at 140 ℃ under 110kPa in the solution, cleaning and drying to obtain the HR-Ti64 stent after coating treatment.

(2) Doping of rare earth element neodymium Nd:

the coated HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) with a concentration of 0.4g/mL₃)₃·6H₂O) in the water solution, carrying out constant-temperature oscillation reaction for 36h at the temperature of 45 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy bracket with the photo-thermal and temperature control warning functions, namely the 0.4Nd-HR-Ti64 alloy bracket.

The experimental results are as follows: as shown in FIGS. 18-20, the HR-Ti64 stent of this example was exposed to neodymium nitrate hexahydrate (Nd (NO) (concentration 0.4 g/mL)₃)₃·6H₂O) after constant temperature oscillation treatment in water solution, the shape structure of the stent surface formed by disorderly stacking porous fiber rod-shaped and spherical structures is basically unchanged, and the structure surface is obviously covered with a layer of flaky substances which are supposed to be deposited by doped neodymium salt (as shown in FIG. 18); EDS component analysis shows that the doping amount of the Nd element is further increased obviously and is 21.5 wt%; the elemental surface scan pictures show that Nd element was successfully doped and uniformly distributed on the surface of the stent (as shown in fig. 19). Under the excitation of 808nm laser, the photothermal and fluorescent properties of the 0.4Nd-HR-Ti64 bracket are further greatly improved, and trivalent Nd in an emission spectrum diagram³⁺Characteristic fluorescence emission peaks (881nm and 892 nm: (881 nm)⁴F_3/2→⁴F_9/2)；1062nm(⁴F_3/2→⁴F_11/2)；1336nm(⁴F_3/2→⁴F_13/2) The peak intensity of the Nd element is obviously enhanced along with the increase of the content of the Nd element, which lays a foundation for the Nd element to become a dual-functional material with photothermal and fluorescence temperature measurement characteristics (as shown in figures 20 (a-c)).

Example 6

The steps of this example are as follows:

Carrying out acid etching treatment on the 3D printed porous titanium alloy Ti64 support for 6min, respectively carrying out ultrasonic cleaning on the support by using acetone, absolute ethyl alcohol and ultrapure water in sequence for 60min, drying the support, and placing the support into 50mL of H₂O₂And H₃PO₄In a mixed aqueous solution of (wherein H)₂O₂Mass concentration of 20%, H₃PO₄10 percent of mass concentration), performing hydrothermal reaction for 30 hours at 250 ℃ under the condition of 150kPa, cleaning, drying, and placing in 50mL of CaCl with the concentration of 1.2g/mL₂In the solution, after carrying out secondary hydrothermal reaction for 14h at 150 ℃ and 120kPa, cleaning and drying to obtain the HR-Ti64 stent after coating treatment.

(2) Doping of rare earth element neodymium Nd:

the coated HR-Ti64 stent was placed in neodymium nitrate hexahydrate (Nd (NO) with a concentration of 0.8g/mL₃)₃·6H₂O) in the water solution, carrying out constant-temperature oscillation reaction for 48h at 50 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy bracket with the photo-thermal and temperature control warning functions, namely the 0.8Nd-HR-Ti64 alloy bracket.

The experimental results are as follows: as shown in FIGS. 21-23, the HR-Ti64 stent of this example was exposed to neodymium nitrate hexahydrate (Nd (NO) at a concentration of 0.8g/mL₃)₃·6H₂O) after constant temperature oscillation treatment in aqueous solution, the surface of the stent is almost completely covered by a layer of flaky substances, which are supposed to be deposited by doped neodymium salt, wherein the surface of the morphological structure is formed by disorderly stacking porous fiber rod-shaped and spherical structures (as shown in FIG. 21); EDS component analysis shows that the doping amount of Nd is further increased obviously and is 27.6 wt%; the elemental surface scan pictures show that Nd element was successfully doped and uniformly distributed on the surface of the stent (as shown in fig. 22). Under the excitation of 808nm laser, the photothermal and fluorescent properties of the 0.8Nd-HR-Ti64 bracket are further greatly improved, and trivalent Nd in an emission spectrum diagram³⁺Characteristic fluorescence emission peaks (881nm and 892 nm: (881 nm)⁴F_3/2→⁴F_9/2)；1062nm(⁴F_3/2→⁴F_11/2)；1336nm(⁴F_3/2→⁴F_13/2) The peak intensity of the Nd element is greatly enhanced along with the increase of the content of the Nd element, which lays a foundation for the double-function material with the temperature measurement characteristics of photo-thermal and fluorescence (as shown in fig. 23 (a-c)).

The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims

1. A construction method of a 3D printing titanium alloy support with photo-thermal and temperature control warning functions is characterized by comprising the following steps:

carrying out acid etching treatment, cleaning and drying on the 3D printed porous titanium alloy Ti64 bracket, and then placing the bracket in H₂O₂And H₃PO₄The mixed aqueous solution is subjected to hydrothermal reaction for 20 to 30 hours at the temperature of 200 ℃ and 250 ℃ and the pressure of 100kPa, washed and dried, and then placed in CaCl₂In the solution, carrying out a second hydrothermal reaction at the temperature of 100-150 ℃ and under the condition of 70-120kPa, reacting for 4-14h, cleaning and drying to obtain the HR-Ti64 stent after coating treatment;

(2) doping of rare earth element neodymium Nd:

placing the coated HR-Ti64 stent in a neodymium nitrate hexahydrate aqueous solution, carrying out constant-temperature oscillation reaction for 3-48h at the temperature of 25-50 ℃, and then cleaning and drying to obtain the 3D printing titanium alloy stent with the photo-thermal and temperature control warning functions;

in step (1), the CaCl₂The concentration of the solution is 1.2 g/mL; in the step (2), the concentration of the neodymium nitrate hexahydrate aqueous solution is 0.8 g/mL.

2. The method for constructing the 3D printing titanium alloy bracket with the photothermal and temperature control warning functions according to claim 1, wherein in the step (1), the H is₂O₂And H₃PO₄In the mixed aqueous solution of (1), H₂O₂Has a mass concentration of 3-27%, H₃PO₄The mass concentration of (A) is 3-27%.

3. The method for constructing the 3D printing titanium alloy bracket with the photothermal and temperature control warning functions according to claim 1, wherein in the step (1), the H is₂O₂And H₃PO₄H in the mixed aqueous solution of₂O₂And H₃PO₄The mass ratio of (1-9) to (1-3).

4. The method for constructing a 3D printing titanium alloy bracket with photothermal and temperature control warning functions according to claim 1, wherein in the step (1), the treatment solution for the acid etching treatment is a mixed solution of hydrofluoric acid, nitric acid and water according to a volume ratio of (1-2) to (3-4) to 5, and the time for the acid etching treatment is 1-6 min.

5. The method for constructing the 3D printing titanium alloy bracket with the photothermal and temperature control warning functions according to claim 1, wherein in the step (1), after the acid etching treatment, ultrasonic cleaning is sequentially performed by acetone, absolute ethyl alcohol and ultrapure water, and the cleaning time is 10-60min each time.

6. 3D printing titanium alloy support with photothermal and temperature control warning functions obtained by the construction method according to any one of claims 1-5.