CN111482600B - Method for constructing micro/nano structure on surface of pure titanium or titanium alloy based on additive manufacturing technology and application - Google Patents
Method for constructing micro/nano structure on surface of pure titanium or titanium alloy based on additive manufacturing technology and application Download PDFInfo
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- CN111482600B CN111482600B CN202010176194.6A CN202010176194A CN111482600B CN 111482600 B CN111482600 B CN 111482600B CN 202010176194 A CN202010176194 A CN 202010176194A CN 111482600 B CN111482600 B CN 111482600B
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- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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Abstract
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology and application thereof. The construction method comprises the following steps: step one, obtaining a pure titanium or titanium alloy substrate material through 3D printing; placing the substrate obtained in the step one in a hydrothermal reaction kettle, and carrying out hydrothermal reaction under an alkaline condition to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is more than or equal to 110 ℃, and the hydrothermal time is more than or equal to 6 hours; during hydrothermal reaction, the concentration of hydroxide ions in the system is more than 0.1 mol/L; step three, cleaning the obtained hydrothermal reaction product; then drying and heat treatment are carried out; obtaining a titanium material with a micro/nano structure on the surface; the temperature of the heat treatment is 300-700 ℃. The product constructed by the invention is used as a biomedical orthopedic implant. The construction method of the invention is not limited by the condition of surface flatness; the operation is simple, convenient and controllable; the obtained product has excellent performance; is convenient for large-scale application.
Description
Technical Field
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology and application thereof; belongs to the technical field of biological material preparation.
Background
As a transition metal, the outermost layer of titanium is not completely filled with electrons. The density of titanium is low, only 4.5g/cm 3 It is about 60% of steel. The light weight can reduce the burden of the patient and enhance the comfort and the activity function of the patient. Elastic modulus coordination between implant and natural bone for prolonged implantationThe service life of the implant is very important. Compared with cobalt alloy and stainless steel, the elasticity modulus of titanium and titanium alloy is closest to that of human bones, so that stress shielding can be reduced, and local bone absorption is prevented.
However, since the titanium-based metal material is biologically inert, the bone formation speed is slow after the titanium-based metal material is implanted into a body, and the wrapping behavior of fibrous tissues can be caused, so that the implantation effect is influenced. The morphological structure of the surface of the orthopedic implant can significantly influence the protein adsorption behavior, the in vitro cell-related behavior and the in vivo osteogenesis behavior. According to the scale characteristics, the morphology structure of the material surface can be mainly divided into a nano structure and a micro structure. The proper nano-structure and the micro-structure can promote the osteogenic differentiation of stem cells and the osteogenic effect in vivo. Compared with the surface with single-scale structural features, the micro-nano structure surface with nano-scale and micro-scale structural features can further improve the biological performance of the material.
Due to the special biological performance of the micro-nano structure, people carry out a great deal of research on the micro-nano structure. In terms of the preparation method, people try to obtain a micro-nano composite structure by taking medical pure titanium or titanium alloy as a raw material and combining sand blasting treatment and/or laser etching, alkali liquor-acid treatment and hydrothermal treatment; such as patent CN 201210223080.8; micro-arc oxidation and hydrothermal treatment have also been attempted to construct micro/nano structures, such as "Huang Q, Elkhooly T A, Liu X, Zhang R, Yang X, Shen Z, Feng Q. effects of thermal micro/nano-topographies on the morphology, promotion and differentiation of organism-like cells, colloids and Surfaces B: Biointerfaces,2016,145: 37-45"; however, the methods have the problems that the methods can only be constructed on a flat surface, are not suitable for complex structures, have poor film adhesion and the like. However, no report of constructing the micro/nano structure by using 3D printing, hydrothermal treatment and thermal treatment has been found so far.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and provide a titanium metal material with a micro-nano dual structure on the surface and a micro/nano structure construction method and application thereof, which are not limited by the condition of surface flatness.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; the selective laser melting technology, the hydrothermal technology, the ion exchange technology and the annealing technology are effectively matched; the micro/nano structure with strong adaptability and excellent performance is obtained. The substrate for constructing the micro/nano structure in the invention is medical pure titanium or titanium alloy prepared by 3D printing technology.
As the refinement of the technical conception, the invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; the method comprises the following steps:
step one
Obtaining a pure titanium or titanium alloy substrate material through 3D printing;
step two
Placing the substrate obtained in the step one in a hydrothermal reaction kettle, and carrying out hydrothermal reaction under an alkaline condition to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is more than or equal to 110 ℃, preferably 110-200 ℃, and the time of the hydrothermal reaction is more than or equal to 6 hours, preferably 6-24 hours; during hydrothermal reaction, the concentration of hydroxide ions in the system is more than 0.1 mol/L;
step three
Cleaning the hydrothermal reaction product obtained in the second step; after cleaning, drying and heat treatment; obtaining a titanium material with a micro/nano structure on the surface; the temperature of the heat treatment is 300-700 ℃.
As a preferred scheme, the invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; when the hydrothermal reaction solution contains at least one ion of magnesium ions, calcium ions and strontium ions, cleaning the hydrothermal reaction product obtained in the second step; after cleaning, drying and heat treatment are carried out; obtaining a titanium material with titanate on the surface and a micro/nano structure; the temperature of the heat treatment is 300-700 ℃. The titanate is selected from at least one of calcium titanate, magnesium titanate and strontium titanate.
As a preferred scheme, the invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; when the water is heatedWhen the reaction solution does not contain magnesium ions, calcium ions and strontium ions, cleaning the hydrothermal reaction product obtained in the second step; will use 0.5-3mol/LHCl or HNO 3 Soaking in the solution for 5-20min, preferably 10-15min for ion exchange; then washing the substrate by using a large amount of deionized water, and drying the substrate in a vacuum drying oven at the temperature of below 60 ℃ after washing; finally, carrying out heat treatment; obtaining a titanium material with a micro/nano structure and titanium dioxide on the surface; the temperature of the heat treatment is 300-700 ℃.
In the present invention, 0.5 to 3mol/LHCl and HNO are used 3 When the solution is soaked in the hydrothermal product, the hydrothermal product is difficult to obtain if the time is too long; or the binding force of the obtained product to the substrate is extremely poor.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; placing pure titanium or titanium alloy powder into a powder box of selective laser melting equipment, vacuumizing the selective laser melting equipment, and melting, sintering and forming by using a high-energy laser beam after filling argon to obtain a pure titanium or titanium alloy substrate material; the pure titanium or titanium alloy powder is spherical powder, the particle diameter of the powder is 20-60 mu m, the laser power is 300-500W, preferably 350-450W, the scanning speed is 800-2000mm/s, preferably 1000mm/s-1800mm/s, the scanning interval is 0.08-0.15mm, preferably 0.085-0.12mm, and the powder layer thickness is 0.02-0.06mm, preferably 0.03-0.05 mm.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; after the 3D printed substrate is obtained, ultrasonic cleaning is respectively carried out for 10 min/time by using deionized water, absolute ethyl alcohol and acetone, and then the substrate is placed in a vacuum drying oven for drying; the temperature is controlled to be less than or equal to 100 ℃ during drying.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; when hydrothermal reaction is carried out under alkaline conditions, the medium contains sodium hydroxide and/or potassium hydroxide. In order to endow the product with some special performance, the medium for hydrothermal reaction may also contain at least one of calcium ion, magnesium ion and strontium ion. As a further preferred variant, the calcium ions, magnesium ions, strontium ions are provided by the corresponding nitrates and/or hydrochlorides.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; when hydrothermal reaction is carried out under alkaline condition, the loading amount of the inner lining of the reaction kettle is 30-80 v%.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; before the hydrothermal reaction under alkaline conditions, a hydrochloride or nitrate may be added to the medium. However, the concentration of hydroxide ions in the system must be controlled to be more than 0.1 mol/L.
Preferably, before the hydrothermal reaction is carried out under alkaline conditions; the concentration of the hydroxide ion in the system is 0.1 to 10mol/L, more preferably 0.5 to 5 mol/L.
Further preferably, the drying treatment is carried out in a vacuum drying oven at 60 ℃ or lower for 3 to 6 hours.
When the hydrothermal reaction is carried out, calcium, magnesium and strontium are not introduced; the micro/nano structure comprises rutile phase mainly containing titanium and oxygen.
When the hydrothermal reaction is carried out, any one or more of calcium, magnesium and strontium are introduced; the micro/nano structure mainly contains a titanic acid M phase of titanium, M and oxygen elements; and M is at least one selected from calcium, magnesium and strontium.
For further optimization, the temperature of the heat treatment is 300-700 ℃, and the time of the heat treatment is 30-120 min.
The invention relates to a method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology; the constructed product is used for biomedical orthopedic implants.
Principles and advantages
Firstly, obtaining a pure titanium or titanium alloy substrate material by adopting 3D printing; obtaining a titanium-based metal table with a micrometer-scale structure through 3D printing; then combining a hydrothermal method and a short-time ion exchange method or combining hydrothermal reaction of adding calcium, magnesium and strontium ions; and obtaining a preformed product, and performing heat treatment on the preformed product to obtain a product which has a micro-nano structure and a surface layer of titanium dioxide or magnesium titanate, calcium titanate and strontium titanate.
The method has the advantages of simple process flow, capability of personalized customization, time and economic cost saving, stable and controllable constructed micro-nano structure and the like.
Drawings
The invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a microscopic picture of the surface of a pure titanium metal block prepared by selective laser melting, wherein the scale is 500 μm.
FIG. 2 is a surface X-ray diffraction pattern of a sample after surface treatment according to an embodiment of the present invention.
FIG. 3 is a photomicrograph of the topography of the surface of a sample after a surface treatment according to an embodiment of the present invention, with the scale being 1 μm.
FIG. 4 is a photomicrograph of the surface topography of the sample after surface treatment according to the second embodiment of the present invention, wherein the scale is 1 μm.
FIG. 5 is a photomicrograph of the surface topography of a sample after surface treatment according to the third embodiment of the present invention, wherein the ruler is 1 μm.
FIG. 6 is a photomicrograph of the surface topography of a sample after surface treatment in accordance with an embodiment of the present invention, with the scale being 1 μm.
FIG. 7 is a graph showing results of calcein staining on the first, third and fifth days after the experimental group and the pure titanium group were seeded with SaOS-2 cells;
as can be seen from fig. 1, the surface of the pure titanium bulk material prepared by the laser melting technology is regular fish-scale shape, and the structure scale of the pure titanium bulk material is in micron scale.
As can be seen from fig. 2, XRD results on the surface of the sample show the presence of α -titanium and strontium titanate, indicating that the strontium titanate is formed on the surface of the sample by hydrothermal and post-heat treatment of the pure titanium bulk material formed by the selective laser melting technique with a mixed solution of strontium chloride and sodium hydroxide.
As can be seen from FIG. 3, the mixed solution of strontium chloride and sodium hydroxide is used to perform hydrothermal and subsequent heat treatment on the pure titanium bulk material formed by the selective laser melting technology, and a layer of near-spherical particles of strontium titanate with the size of-300 nm are uniformly grown on the surface of the sample.
As can be seen from FIG. 4, by subjecting the pure titanium bulk material formed by the selective laser melting technique to hydrothermal and subsequent heat treatment using 30ml of 1mol/L NaOH solution, the sample surface had flaky titanium dioxide with dentate edges, and the width of the titanium dioxide was about 1 μm and the thickness of the titanium dioxide was less than 100 nm.
As can be seen from FIG. 5, by subjecting the pure titanium bulk material formed by the selective laser melting technique to hydrothermal and subsequent heat treatment using 60ml of 0.5mol/LNaOH solution, flaky titanium dioxide was formed on the surface of the sample, the width of which was about 1-2 μm, and the thickness of which was less than 100 nm.
As can be seen from FIG. 6, by subjecting the pure titanium bulk material formed by the selective laser melting technique to hydrothermal and subsequent heat treatment using 60ml of 5mol/L NaOH solution, the sample surface had flaky titanium dioxide with serrated edges, and the diameter of the flaky titanium dioxide was less than 50 nm.
In fig. 7, an experiment in which a final product obtained in the first embodiment of the present invention was used as a treatment object a and SaOS-2 cells were planted on the surface of the treatment object a was defined as an experiment group; defining a pure titanium sample which is formed by selective laser melting and is not subjected to hydrothermal treatment in the first embodiment of the invention as a treatment object B, sequentially grinding the treatment object B by 240-mesh, 400-mesh, 800-mesh, 1000-mesh, 1500-mesh and 2000-mesh abrasive paper step by step, polishing by using diamond polishing cloth to obtain a pure titanium experimental material, and planting SaOS-2 cells on the surface of the pure titanium experimental material to obtain a pure titanium group; as can be seen from FIG. 7, the number of SaOS-2 cells in the experimental group was significantly greater than that in the pure titanium group at the same time; the micro-nano composite structure surface constructed by the embodiment I of the invention has the function of promoting osteoblast proliferation and can improve the biocompatibility of pure titanium.
Detailed Description
And adopting selective laser melting to form a pure titanium block material, and constructing a micro-nano structure on the surface of the pure titanium by hydrothermal treatment.
A pure titanium block material with the thickness of 14 multiplied by 3mm is prepared by adopting a selective laser melting technology, and the direct laser acting surface is the front surface. The grain diameter of the adopted powder is 20-60 mu m, the laser power is 400W, the powder spreading thickness is 0.04mm, the laser scanning interval is 0.09mm, and the laser scanning speed is 1700 mm/s. Cutting the pure titanium block into 7 × 7 × 3mm by linear cutting, ultrasonic cleaning with acetone, ethanol and deionized water sequentially for 10 min/time, and oven drying at 50 deg.C in a vacuum drying oven. A strontium chloride solution (0.1 mol/L) was prepared as solution A, a NaOH solution (1 mol/L) was prepared as solution B, and A, B solutions were mixed uniformly in the same volume to prepare a mixed solution. The sample is placed in a lining of a 100ml polytetrafluoroethylene hydrothermal reaction kettle containing 60ml of mixed solution with the right side facing upwards and reacts for 6 hours at the temperature of 110 ℃. Then taking out, and ultrasonically cleaning twice with deionized water for 10 min/time. And (3) drying the cleaned sample in a vacuum drying oven at 50 ℃. Then, a muffle furnace is used for annealing treatment, the temperature rise rate is set to be 5 ℃/min, the temperature is raised from 20 ℃ to 300 ℃, then the temperature is kept for 1h, and the furnace is cooled.
The surface of the pure titanium block material formed by selective laser melting is in a regular fish scale shape (see figure 1), the surface is generated with strontium titanate (see figure 2) after hydrothermal treatment, and the surface has dense and uniform nano spherical particles under high power, so that a micro-nano composite structure is successfully constructed on the titanium surface.
The contact angle of the pure titanium sample which is formed by selective laser melting and is not subjected to hydrothermal treatment is 70.3 degrees, and after the nano granular strontium titanate is constructed on the surface of the pure titanium sample through hydrothermal treatment, the contact angle is less than 10 degrees, and the sample shows super-hydrophilicity. In vitro cell experiment results show that the micro-nano composite structure surface formed after the nano-granular strontium titanate is constructed has the effect of promoting osteoblast proliferation and can improve the biocompatibility of pure titanium (see figure 7).
Example II
And adopting selective laser melting to form a pure titanium block material, and constructing a micro-nano structure on the surface of the pure titanium by hydrothermal treatment.
A pure titanium block material with the thickness of 14 multiplied by 3mm is prepared by adopting a selective laser melting technology, and the direct laser acting surface is the front surface. The grain diameter of the adopted powder is 20-60 mu m, the laser power is 400W, the powder spreading thickness is 0.04mm, the laser scanning interval is 0.09mm, and the laser scanning speed is 1700 mm/s. Cutting the pure titanium block into 7 × 7 × 3mm by linear cutting, ultrasonic cleaning with acetone, ethanol and deionized water sequentially for 10 min/time, and oven drying at 50 deg.C in a vacuum drying oven. The sample is placed in a lining of a polytetrafluoroethylene hydrothermal reaction kettle which is filled with 30ml of 1mol/LNaOH solution and is placed with the front side facing upwards, and the reaction is carried out for 16 hours at the temperature of 200 ℃. Then taking out, and ultrasonically cleaning twice with deionized water for 10 min/time. Then, the mixture is soaked in 1mol/LHCl solution for 10min for ion exchange, washed clean by a large amount of deionized water and placed in a vacuum drying oven for drying at 50 ℃ for 4 h. Then, a muffle furnace is used for annealing treatment, the temperature rise rate is set to be 5 ℃/min, the temperature is raised from 20 ℃ to 600 ℃, then the temperature is kept for 2h, and the furnace is cooled.
The surface of the pure titanium block material formed by selective laser melting is in a regular fish scale shape, titanium dioxide is generated on the surface after hydrothermal treatment, and the surface of the pure titanium block material is provided with dense and uniform nano sheets with dentate edges under high power. Therefore, the micro-nano composite structure is successfully constructed on the titanium surface.
The contact angle of the pure titanium sample which is formed by selective laser melting and is not subjected to hydrothermal treatment is 70.3 degrees, and after the nano-dentate flaky titanium dioxide is constructed on the surface of the pure titanium sample by the hydrothermal treatment, the contact angle is 24.28 degrees, and the pure titanium sample is hydrophilic. In vitro cell experiment results show that the micro-nano composite structure surface formed after the nano dentate flaky titanium dioxide is constructed has the effect of promoting osteoblast proliferation and can improve the biocompatibility of pure titanium.
Example three
And adopting selective laser melting to form a pure titanium block material, and constructing a micro-nano structure on the surface of the pure titanium by hydrothermal treatment.
A pure titanium block material with the thickness of 14 multiplied by 3mm is prepared by adopting a selective laser melting technology, and the direct laser acting surface is the front surface. The grain diameter of the adopted powder is 20-60 mu m, the laser power is 400W, the powder spreading thickness is 0.04mm, the laser scanning interval is 0.09mm, and the laser scanning speed is 1700 mm/s. Cutting the pure titanium block into 7 × 7 × 3mm by linear cutting, ultrasonic cleaning with acetone, ethanol and deionized water sequentially for 10 min/time, and oven drying at 50 deg.C in a vacuum drying oven. The sample was placed with its front side facing up in a 100ml inner liner of a polytetrafluoroethylene hydrothermal reaction vessel containing 60ml of a 0.5mol/LNaOH solution and reacted at 200 ℃ for 16 hours. Then taking out, and ultrasonically cleaning twice with deionized water for 10 min/time. Then, the mixture is soaked in 1mol/LHCl solution for 10min for ion exchange, washed clean by a large amount of deionized water and placed in a vacuum drying oven for drying at 50 ℃ for 4 h. Then, a muffle furnace is used for annealing treatment, the temperature rise rate is set to be 5 ℃/min, the temperature is raised from 20 ℃ to 600 ℃, then the temperature is kept for 2h, and the furnace is cooled.
The surface of the pure titanium block material formed by selective laser melting is in a regular fish scale shape, titanium dioxide is generated on the surface after hydrothermal treatment, and the surface of the pure titanium block material is provided with compact and uniform nano sheets under high power. Therefore, the micro-nano composite structure is successfully constructed on the surface of the titanium.
The contact angle of the pure titanium sample which is formed by selective laser melting and is not subjected to hydrothermal treatment is 70.3 degrees, and after the nano flaky titanium dioxide is constructed on the surface of the pure titanium sample by the hydrothermal treatment, the contact angle is 19.7 degrees, and the pure titanium sample is hydrophilic. In vitro cell experiment results show that the micro-nano composite structure surface formed after the nano flaky titanium dioxide is constructed has the effect of promoting osteoblast proliferation and can improve the biocompatibility of pure titanium.
Example four
And adopting selective laser melting to form a pure titanium block material, and constructing a micro-nano structure on the surface of the pure titanium by hydrothermal treatment.
A pure titanium block material with the thickness of 14 multiplied by 3mm is prepared by adopting a selective laser melting technology, and the direct laser acting surface is the front surface. The grain diameter of the adopted powder is 20-60 mu m, the laser power is 400W, the powder spreading thickness is 0.04mm, the laser scanning interval is 0.09mm, and the laser scanning speed is 1700 mm/s. Cutting the pure titanium block into 7 × 7 × 3mm by linear cutting, ultrasonic cleaning with acetone, ethanol and deionized water sequentially for 10 min/time, and oven drying at 50 deg.C in a vacuum drying oven. The sample is placed in a lining of a polytetrafluoroethylene hydrothermal reaction kettle which is filled with 60ml of 5mol/LNaOH solution and is placed with the front side facing upwards, and the reaction is carried out for 16 hours at the temperature of 200 ℃. Then taking out, and ultrasonically cleaning the glass substrate twice for 10 min/time by using deionized water. Then, the mixture is soaked in 1mol/LHCl solution for 10min for ion exchange, washed clean by a large amount of deionized water and placed in a vacuum drying oven for drying at 50 ℃ for 4 h. Then, a muffle furnace is used for annealing treatment, the temperature rise rate is set to be 5 ℃/min, the temperature is raised from 20 ℃ to 600 ℃, then the temperature is kept for 2h, and the furnace is cooled.
The surface of the pure titanium block material formed by selective laser melting is in a regular fish scale shape, titanium dioxide is generated on the surface after hydrothermal treatment, and dense and uniform nano wires are arranged on the surface under high power. Therefore, the micro-nano composite structure is successfully constructed on the titanium surface.
The contact angle of the pure titanium sample subjected to selective laser melting forming and not subjected to hydrothermal treatment is 70.3 degrees, and after the nano flaky titanium dioxide is constructed on the surface of the pure titanium sample subjected to hydrothermal treatment, the contact angle is 26.78 degrees, and the pure titanium sample is hydrophilic. In vitro cell experiment results show that the micro-nano composite structure surface formed after the nano linear titanium dioxide is constructed has the effect of promoting osteoblast proliferation and can improve the biocompatibility of pure titanium.
Comparative example 1
And adopting selective laser melting to form a pure titanium block material, and constructing a micro-nano structure on the surface of the pure titanium by hydrothermal treatment.
A pure titanium block material with the thickness of 14 multiplied by 3mm is prepared by adopting a selective laser melting technology, and the direct laser acting surface is the front surface. The grain diameter of the adopted powder is 20-60 mu m, the laser power is 400W, the powder spreading thickness is 0.04mm, the laser scanning interval is 0.09mm, and the laser scanning speed is 1700 mm/s. Cutting the pure titanium block into 7 × 7 × 3mm by linear cutting, ultrasonic cleaning with acetone, ethanol and deionized water sequentially for 10 min/time, and oven drying at 50 deg.C in a vacuum drying oven. The sample is placed in a lining of a polytetrafluoroethylene hydrothermal reaction kettle which is filled with 30ml of 1mol/LNaOH solution and is placed with the front side facing upwards, and the reaction is carried out for 16 hours at the temperature of 200 ℃. Then taking out, and ultrasonically cleaning twice with deionized water for 10 min/time. Then, soaking the mixture for 180min by using 1mol/LHCl solution for ion exchange, washing the mixture by using a large amount of deionized water, and drying the mixture for 4h at 50 ℃ in a vacuum drying oven. Then, a muffle furnace is used for annealing treatment, the temperature rise rate is set to be 5 ℃/min, the temperature is raised from 20 ℃ to 600 ℃, then the temperature is kept for 2h, and the furnace is cooled.
In the embodiment, the surface of the pure titanium block material formed by selective laser melting is in a regular fish scale shape, after the pure titanium block material is soaked in 1mol/LHCl solution for 180min for ion exchange, a film layer on the surface of a sample is dissolved and falls off, and XRD results show that the surface of the sample has no titanium dioxide, and the experiment fails.
Comparative example 2
A micro-nano structure is constructed on the surface of pure titanium by adopting a commercial pure titanium block material and hydrothermal treatment.
The commercially pure titanium bulk material was cut into a pure titanium bulk material of 7 × 7 × 3mm by wire cutting, and then sanded with 240 mesh, 400 mesh, 800 mesh, 1000 mesh, 1500 mesh, 2000 mesh sandpaper in this order, and polished with a diamond polishing cloth. The sample is placed in a 100ml polytetrafluoroethylene hydrothermal reaction kettle lining containing 30ml of 1mol/LNaOH solution with the polished surface facing upwards, and reacts for 16h at the temperature of 200 ℃. Then taking out, and ultrasonically cleaning twice with deionized water for 10 min/time. Then, the mixture is soaked in 1mol/LHCl solution for 10min for ion exchange, washed clean by a large amount of deionized water and placed in a vacuum drying oven for drying at 50 ℃ for 4 h. Then, a muffle furnace is used for annealing treatment, the temperature rise rate is set to be 5 ℃/min, the temperature is raised from 20 ℃ to 600 ℃, then the temperature is kept for 2h, and the furnace is cooled.
This example uses commercially pure titanium bulk material, after hydrothermal treatment, at high power. Only the nano flaky titanium dioxide is generated, which indicates that the construction of the micro-nano composite structure fails.
Comparative example 3
And adopting selective laser melting to form a pure titanium block material.
A pure titanium block material with the thickness of 14 multiplied by 3mm is prepared by adopting a selective laser melting technology, and the direct laser acting surface is the front surface. The grain diameter of the adopted powder is 20-60 mu m, the laser power is 300W, the powder spreading thickness is 0.04mm, the laser scanning interval is 0.15mm, and the laser scanning speed is 1800 mm/s. Cutting the pure titanium block into 7 × 7 × 3mm by linear cutting, ultrasonic cleaning with acetone, ethanol and deionized water sequentially for 10 min/time, and oven drying at 50 deg.C in a vacuum drying oven.
The pure titanium block material formed by selective laser melting has serious surface spheroidization, is not suitable for subsequent construction of a nano structure, and fails in experiments.
Claims (5)
1. A method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on an additive manufacturing technology is characterized in that; the method comprises the following steps:
step one
Placing pure titanium or titanium alloy powder into a powder box of selective laser melting equipment, vacuumizing the selective laser melting equipment, and melting, sintering and forming by using a high-energy laser beam after filling argon to obtain a pure titanium or titanium alloy substrate material; the pure titanium or titanium alloy powder is spherical powder, the particle size of the powder is 20-60 mu m, the laser power is 350-450W, the scanning speed is 1000-1800mm/s, the scanning interval is 0.085-0.12mm, and the powder layer thickness is 0.03-0.05 mm;
step two
Placing the substrate obtained in the step one in a hydrothermal reaction kettle, and carrying out hydrothermal reaction under an alkaline condition to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is more than or equal to 110 ℃, and the time of the hydrothermal reaction is more than or equal to 6 h; during hydrothermal reaction, the concentration of hydroxide ions in the system is 0.1-10 mol/L;
step three
When the hydrothermal reaction solution contains at least one ion of magnesium ions, calcium ions and strontium ions, cleaning the hydrothermal reaction product obtained in the second step; after cleaning, drying and heat treatment are carried out; obtaining a titanium material with titanate on the surface and a micro/nano structure; the temperature of the heat treatment is 300-700 ℃, and the time is 30-120 min; the titanate is selected from at least one of calcium titanate, magnesium titanate and strontium titanate;
when the hydrothermal reaction solution does not contain magnesium ions, calcium ions and strontium ions, 0.5-3mol/LHCl or HNO is used before the hydrothermal reaction product obtained in the step two is cleaned 3 Soaking in the solution for 5-20min for ion exchange; then washing with deionized water, and drying in a vacuum drying oven at below 60 deg.C for 3-6 h; finally, carrying out heat treatment; obtaining titanium material with rutile phase titanium dioxide on the surface and micro/nano structure; the temperature of the heat treatment is 300-700 ℃, and the time is 30-120 min.
2. The method for constructing the micro/nano structure on the surface of the pure titanium or the titanium alloy based on the additive manufacturing technology according to claim 1; the method is characterized in that: after the 3D printed substrate is obtained, ultrasonic cleaning is respectively carried out for 10 min/time by using deionized water, absolute ethyl alcohol and acetone, and then the substrate is placed in a vacuum drying oven for drying; the temperature is controlled to be less than or equal to 100 ℃ during drying.
3. The method for constructing the micro/nano structure on the surface of the pure titanium or the titanium alloy based on the additive manufacturing technology according to claim 1; the method is characterized in that: when hydrothermal reaction is carried out under alkaline conditions, the medium contains sodium hydroxide and/or potassium hydroxide.
4. The method for constructing the micro/nano structure on the surface of the pure titanium or the titanium alloy based on the additive manufacturing technology according to claim 1; the method is characterized in that: when hydrothermal reaction is carried out under alkaline condition, the loading amount of the inner lining of the reaction kettle is 30-80 v%.
5. Use of a product constructed by the method for constructing a micro/nano structure on the surface of pure titanium or titanium alloy based on additive manufacturing technology according to any one of claims 1 to 4; the method is characterized in that: the constructed product is used for biomedical orthopedic implants.
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