CN108379657B - Sodium titanate nanorod array, sodium titanate/titanium alloy composite material, preparation and application - Google Patents
Sodium titanate nanorod array, sodium titanate/titanium alloy composite material, preparation and application Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention belongs to the technical field of nano bone repair materials, and particularly relates to a sodium titanate nanorod array, a sodium titanate/titanium alloy composite material, and preparation and application thereof. The invention mixes the ball-milled Na2O·2B2O3Different proportions of Na after particle or ball milling2O·2B2O3And Ca (OH)2The particle mixture is paved on the surface of the titanium substrate for heating and oxidation, and the nano rod sodium titanate array with adjustable size is obtained. The sodium titanate nanorod array grows regularly in a directional mode and is firmly combined with a matrix. The invention also provides a sodium titanate/titanium alloy composite material, the composite material takes titanium alloy as a matrix, the surface of the matrix comprises the sodium titanate nanorod array, the composite material effectively removes Al elements harmful to human bodies on the surface layer of the medical Ti6Al4V alloy, and provides a foundation for the application of the medical Ti6Al4V alloy in the fields of bone implantation, bone tissue repair biomedicine and the like.
Description
Technical Field
The invention belongs to the technical field of nano bone repair materials, and particularly relates to a sodium titanate nanorod array, a sodium titanate/titanium alloy composite material, and preparation and application thereof.
Background
The sodium titanate whisker has wide development prospect in a plurality of fields such as aerospace, bone tissue repair medical materials and the like due to excellent mechanical property, high chemical stability and drug delivery property endowed by a special tunnel structure and excellent biological activity. Compared with other biological surface modification layers, the array nanorod sodium titanate has higher surface area for further functional modification, which means that more active functional groups are available to form a biological surface active layer with higher biological activity. Because titanium and titanium alloy are biologically inert materials, after being implanted into a human body, the titanium and titanium alloy cannot be spontaneously connected with bone tissues, so that the implantation operation fails. The reason is that titanium and hydroxyapatite HAp which is similar to human bone in composition and has good biological activity have large difference of thermal expansion coefficients and cannot be well embedded. HAp has a coefficient of thermal expansion of about 15 × 10-6K-1The thermal expansion coefficient of the titanium alloy substrate is generally 8 to 9 x 10-6K-1The thermal expansion coefficients of the two are severely mismatched. Therefore, the thermal stress is concentrated at the interface of the oxide layer, so that the HAp coating on the implant falls off in the service process, and the failure phenomenon occurs. Na (Na)2O·2B2O3Has a coefficient of thermal expansion of 6.8X 10- 6K-1，TiO2Has a thermal expansion coefficient of 8.7X 10-6K-1The thermal expansion coefficient of the coating is similar to that of the matrix, and the strength of the coating is greatly improved. In the biomedical field of bone repair materials, pores with different sizes have great influence on the growth of bone tissues and the adhesion, proliferation and diffusion of cells. Therefore, the nanorod array sodium titanate with adjustable size is prepared on the surface of the medical Ti6Al4V alloy, so that the purpose of rapid osseointegration is achieved when the metal implant is implanted into a human body. Al is used as a main element causing senile dementia, and the removal of the Al element is particularly important in the aspect of application of medical Ti6Al4V alloy as implants and medical instruments.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary object of the present invention is to provide a method for preparing a sodium titanate nanorod array.
The invention also aims to provide the sodium titanate nanorod array prepared by the preparation method.
The invention also aims to provide application of the sodium titanate nanorod array.
The fourth object of the present invention is to provide a sodium titanate/titanium alloy composite material, which uses a titanium alloy as a matrix, and the surface of the matrix contains the sodium titanate nanorod array.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a sodium titanate nanorod array comprises the following steps:
(1) pretreating the titanium substrate to obtain a pretreated titanium substrate;
(2) mixing Na2O·2B2O3Ball milling to obtain Na with the particle size of 30-150 mu m2O·2B2O3Particles; or mixing Na2O·2B2O3And Ca (OH)2Respectively ball-milling to obtain Na with the particle size of 30-150 mu m2O·2B2O3Particles and Ca (OH)2Granulating, then adding Na2O·2B2O3Particles and Ca (OH)2The particles are mixed according to a molar ratio of 1: (0.01-1) uniformly mixing to obtain a mixture;
(3) na prepared in the step (2)2O·2B2O3Spreading the particles or the mixture on the surface of the titanium matrix pretreated in the step (1), and calcining for 2-7 h at 600-800 ℃;
(4) placing the titanium substrate calcined in the step (3) in water at the temperature of 60-80 ℃ for heating treatment for 3-5 h, and drying to obtain a sodium titanate nanorod array;
the titanium substrate in the step (1) is preferably a titanium alloy;
the titanium substrate in the step (1) is further preferably Ti6Al4V alloy;
the pretreatment in the step (1) is preferably to polish and polish the titanium substrate by using 2000-5000-mesh sand paper, wash the titanium substrate for 5-15 min by using acetone and then ultrasonically wash the titanium substrate in water;
ball-milled as described in step (2)Preferably, ethanol is used as a ball milling medium, and wet milling is carried out for 2-5 h at 200-240 r/min; the ethanol is used in an amount to cover Na2O·2B2O3And Ca (OH)2Preferably;
na described in step (3)2O·2B2O3The thickness of the particles or the mixture on the substrate is preferably 0.5-3 mm;
the calcination described in step (3) is preferably carried out in a muffle furnace;
the nano-rod size of the sodium titanate nano-rod array prepared in the step (4) is 200-800 nm;
a sodium titanate nanorod array, which is prepared by the preparation method;
the sodium titanate nanorod array is applied to the technical field of nano bone repair materials;
a sodium titanate/titanium alloy composite material takes titanium alloy as a matrix, and the surface of the matrix comprises the sodium titanate nanorod array;
the titanium alloy is preferably Ti6Al4V alloy;
the sodium titanate/titanium alloy composite material is applied to the technical field of nano bone repair materials;
the principle of the invention is as follows:
the porous metal biomaterial can reduce the elastic modulus of the metal material, so that the metal material is close to bone, and stress shielding is eliminated. For metal materials, the flexibility is mainly determined by the elastic modulus, and the elastic modulus of bone tissues is low, namely about 18-30 GPa (cortical bone). Therefore, in order to reduce damage to bone tissue caused by stress shielding phenomena, it is very important to lower the elastic modulus of the implant metal material. The porous metal material has unique net shape, no directivity and no rebound effect, so that the energy absorption performance is excellent, the corresponding impact resistance performance is superior to other materials, and the effects of shock absorption and impact resistance are achieved.
In the biomedical field of bone repair materials, pores of different sizes have different effects on the growth of bone tissues. The pore size distribution which is most beneficial to the growth of human bone tissues is 300-500 mu m. When the pore size is within the range of 100-600 μm, bone tissue can grow into the interior. Research in recent years shows that the nano-pore biomaterial is more beneficial to induce and guide the differentiation of stem cells. The composition of extracellular matrix and the distribution of integrins on cell membrane are influenced by the pore size of the nano tube on the surface of the implant, and synapses of osteoblasts prefer to grow into pores of the nano structure, so that the cell adhesion is increased and the biocompatibility of the implant is improved due to the fixation effect on cell bodies.
The invention is respectively to Na2O·2B2O3And Ca (OH)2Ball milling is carried out, and then the ball milled Na2O·2B2O3And Ca (OH)2Mixtures of (A) or Na alone2O·2B2O3And (3) paving the titanium substrate surface after pretreatment, then calcining, oxidizing, and washing impurities through heat treatment to obtain the sodium titanate nanorod array with adjustable size, wherein the size of the sodium titanate nanorod is 200-800 nm. Wherein, Ca (OH)2Plays a role of alkaline corrosion oxidation, promotes the removal of Al and Na2O·2B2O3Together as a catalyst, the reaction rate is improved. The sodium titanate nanorod array is used as a biological material with a nano aperture and is firmly combined with a metal material, so that the elastic modulus of a matrix metal material can be reduced, the matrix metal material is close to bone, stress shielding is eliminated, the differentiation of stem cells is induced, a cell body is fixed, cell adhesion is increased, and the biocompatibility of an implant is improved. In addition, when the nanorod sodium titanate array is prepared on the surface of the medical Ti6Al4V alloy which is a matrix material, Al elements harmful to human bodies on the surface layer of the medical Ti6Al4V alloy can be effectively removed, and the medical problem that the application range of the medical Ti6Al4V alloy is limited due to the fact that the surface of the medical Ti6Al4V alloy contains the Al elements is solved.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention obtains micron-sized Na by ball milling2O·2B2O3And Ca (OH)2Then, the mixture is mixed and paved on the surface of a matrix for heating and oxidation to obtain the nano rod sodium titanate array with adjustable size, and the nano rod sodium titanate array has the size of a sodium titanate nano rod200-800 nm, the elastic modulus of the metal material can be reduced to make it close to bone, eliminating stress shielding.
(2) The invention uses micron-sized Na2O·2B2O3And Ca (OH)2After being dried and mixed, the nano-rod sodium titanate powder is directly paved on a matrix, but not wet-ground into slurry, so that the influence of the powder particle size on the diameter of the nano-rod sodium titanate can be ensured.
(2) The sodium titanate nanorod array with the adjustable size, which is prepared by the invention, has good crystallization and is firmly combined with the Ti6Al4V alloy substrate, and the method effectively removes Al elements on the surface layer of the medical Ti6Al4V alloy, which are harmful to human bodies, and solves the medical problem that the application range of the medical Ti6Al4V alloy is limited because the surface of the medical Ti6Al4V alloy contains the Al elements.
(3) The invention has simple operation and easy industrialization, and can be widely applied to the fields of bone implantation, bone tissue repair biomedicine and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the nanorod array sodium titanate obtained in example 1.
FIG. 2 is a scanning electron micrograph of the nanorod array sodium titanate obtained in example 2.
FIG. 3 is a scanning electron micrograph of the nanorod array sodium titanate obtained in example 3.
FIG. 4 is a scanning electron micrograph of the Ti6Al4V alloy after calcination of the comparative example.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Grinding and polishing the surface of the medical Ti6Al4V alloy of the titanium substrate by using 2000-5000 meshes of sand paper, cleaning for 5min by using acetone, and then ultrasonically cleaning in deionized water to obtain a pretreated Ti6Al4V alloy;
(2) mixing Na2O·2B2O3Powder and Ca (OH)2Ball milling the powder respectively, wherein ethanol is used as a ball milling medium, wet milling is carried out for 3h at 220 r/min, and the amount of the ethanol is covered by Na2O·2B2O3And Ca (OH)2Preferably, Na having an average particle size of 50 μm is obtained2O·2B2O3Particles and Ca (OH)2Particles; then adding Na2O·2B2O3Particles and Ca (OH)2The particles are mixed according to a molar ratio of 1: 1, uniformly mixing to obtain a mixture;
(3) spreading the mixture prepared in the step (2) on the surface of the Ti6Al4V alloy pretreated in the step (1), wherein the thickness of the mixture on the Ti6Al4V alloy is 0.6 mm; then placing the Ti6Al4V alloy coated with the mixture in a corundum crucible and placing the corundum crucible in a 600 ℃ muffle furnace for calcining for 3 hours;
(4) and (3) placing the Ti6Al4V alloy calcined in the step (3) in deionized water at 80 ℃ for heating treatment for 3h, taking out, and drying to obtain a sodium titanate nanorod array (shown in figure 1), wherein the size of the nanorod is 200nm as shown in figure 1.
The sodium titanate nanorod array is well crystallized and firmly combined with Ti6Al4V alloy to form the sodium titanate/titanium alloy composite material.
Example 2
(1) Grinding and polishing the surface of the medical Ti6Al4V alloy of the titanium substrate by using 2000-5000 meshes of sand paper, cleaning for 5min by using acetone, and then ultrasonically cleaning in deionized water to obtain a pretreated Ti6Al4V alloy;
(2) mixing Na2O·2B2O3Powder and Ca (OH)2Ball milling the powder respectively, wherein ethanol is used as a ball milling medium, wet milling is carried out for 3h at 220 r/min, and the amount of the ethanol is covered by Na2O·2B2O3And Ca (OH)2Preferably, Na having an average particle size of 50 μm is obtained2O·2B2O3Particles and Ca (OH)2Particles; then adding Na2O·2B2O3Particles and Ca (OH)2The particles are mixed according to a molar ratio of 1: 0.5, mixing uniformly to obtain a mixture;
(3) spreading the mixture prepared in the step (2) on the surface of the Ti6Al4V alloy pretreated in the step (1), wherein the thickness of the mixture on the Ti6Al4V alloy is 0.6 mm; then placing the Ti6Al4V alloy coated with the mixture in a corundum crucible and placing the corundum crucible in a 600 ℃ muffle furnace for calcining for 3 hours;
(4) and (3) placing the Ti6Al4V alloy calcined in the step (3) in deionized water at 80 ℃ for heating treatment for 3h, taking out, and drying to obtain a sodium titanate nanorod array (shown in figure 2), wherein the size of the nanorod is 600 nm.
The sodium titanate nanorod array is well crystallized and firmly combined with Ti6Al4V alloy to form the sodium titanate/titanium alloy composite material.
Example 3
(1) Grinding and polishing the surface of the medical Ti6Al4V alloy of the titanium substrate by using 2000-5000 meshes of sand paper, cleaning for 5min by using acetone, and then ultrasonically cleaning in deionized water to obtain a pretreated Ti6Al4V alloy;
(2) mixing Na2O·2B2O3Ball milling the powder, wherein ethanol is used as a ball milling medium, wet milling is carried out for 3 hours at 220 r/min, and the amount of the ethanol is covered by Na2O·2B2O3Preferably, Na having an average particle size of 50 μm is obtained2O·2B2O3Particles;
(3) na prepared in the step (2)2O·2B2O3The particles are paved on the surface of the Ti6Al4V alloy pretreated in the step (1) and Na2O·2B2O3The thickness of the particles on the Ti6Al4V alloy is 0.6 mm; then covering with Na2O·2B2O3Placing the granular Ti6Al4V alloy in a corundum crucible, and placing the corundum crucible in a muffle furnace at 600 ℃ for calcining for 3 hours;
(4) and (3) placing the Ti6Al4V alloy calcined in the step (3) in deionized water at 80 ℃ for heating treatment for 3h, taking out, and drying to obtain a sodium titanate nanorod array (shown in figure 3), wherein the size of the nanorod is 800 nm.
The sodium titanate nanorod array is well crystallized and firmly combined with Ti6Al4V alloy to form the sodium titanate/titanium alloy composite material.
Example 4
(1) Grinding and polishing the surface of the medical Ti6Al4V alloy of the titanium substrate by using 2000-5000 meshes of sand paper, cleaning for 10min by using acetone, and then ultrasonically cleaning in deionized water to obtain a pretreated Ti6Al4V alloy;
(2) mixing Na2O·2B2O3Powder and Ca (OH)2Ball milling the powder respectively, wherein ethanol is used as a ball milling medium, wet milling is carried out for 2h at 240 r/min, and the amount of the ethanol is covered by Na2O·2B2O3And Ca (OH)2Preferably, Na having an average particle size of 30 μm is obtained2O·2B2O3Particles and Ca (OH)2Particles; then adding Na2O·2B2O3Particles and Ca (OH)2The particles are mixed according to a molar ratio of 1: 0.1, mixing uniformly to obtain a mixture;
(3) spreading the mixture prepared in the step (2) on the surface of the Ti6Al4V alloy pretreated in the step (1), wherein the thickness of the mixture on the Ti6Al4V alloy is 3 mm; then placing the Ti6Al4V alloy coated with the mixture in a corundum crucible and placing the corundum crucible in a muffle furnace at 800 ℃ for calcining for 2 hours;
(4) and (4) placing the Ti6Al4V alloy calcined in the step (3) in deionized water at 70 ℃ for heating treatment for 4h, taking out, and drying to obtain a sodium titanate nanorod array, wherein the sodium titanate nanorod array is well crystallized and firmly combined with the Ti6Al4V alloy to form the sodium titanate/titanium alloy composite material.
Example 5
(1) Grinding and polishing the surface of the medical Ti6Al4V alloy of the titanium substrate by using 2000-5000 meshes of sand paper, cleaning for 15min by using acetone, and then ultrasonically cleaning in deionized water to obtain a pretreated Ti6Al4V alloy;
(2) mixing Na2O·2B2O3Powder and Ca (OH)2Ball milling the powder respectively, wherein ethanol is used as ball milling medium, wet milling is carried out for 5h at 200 r/min, and the amount of ethanol is covered by Na2O·2B2O3And Ca (OH)2Preferably, Na having a particle size of 150 μm is obtained2O·2B2O3Particles and Ca (OH)2Particles; then adding Na2O·2B2O3Particles and Ca (OH)2The particles are mixed according to a molar ratio of 1: 0.01, and uniformly mixing to obtain a mixture;
(3) spreading the mixture prepared in the step (2) on the surface of the Ti6Al4V alloy pretreated in the step (1), wherein the thickness of the mixture on the Ti6Al4V alloy is 0.5 mm; then placing the Ti6Al4V alloy coated with the mixture in a corundum crucible and placing the corundum crucible in a muffle furnace at 700 ℃ for calcining for 7 hours;
(4) and (4) placing the Ti6Al4V alloy calcined in the step (3) in deionized water at 60 ℃ for heating treatment for 5h, taking out, and drying to obtain a sodium titanate nanorod array, wherein the sodium titanate nanorod array is well crystallized and firmly combined with the Ti6Al4V alloy to form the sodium titanate/titanium alloy composite material.
Comparative examples
(1) Grinding and polishing the surface of the medical Ti6Al4V alloy of the titanium substrate by using 2000-5000 meshes of sand paper, cleaning for 5min by using acetone, and then ultrasonically cleaning in deionized water to obtain a pretreated Ti6Al4V alloy;
(2) placing the Ti6Al4V alloy pretreated in the step (1) in a corundum crucible, and heating in a 600 ℃ muffle furnace for 3 hours;
(4) and (3) placing the Ti6Al4V alloy calcined in the step (2) in deionized water at 80 ℃ for heating treatment for 3h, taking out, drying, and observing the surface appearance. See fig. 4.
Effects of the embodiment
Scanning electron microscopy is adopted to detect the sodium titanate nanorod arrays prepared in the embodiments 1-3, and as can be seen from the figures 1-3, the sodium titanate nanorod arrays on the surface of the Ti6Al4V alloy effectively remove the surface harmful elements Al, Ca (OH)2Has the functions of alkaline corrosion and oxidation, promotes the reaction rate and the removal of Al, Na2O·2B2O3And Ca (OH)2The diameter and porosity of the sodium titanate nanorod generated by the mixture are easier to regulate and control due to mismatching of different atoms. Fig. 4 is a blank control, i.e. a morphology obtained without any addition of powder oxidation, which has not been removed of the surface detrimental element Al as it was not treated with the new method.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a sodium titanate nanorod array is characterized by comprising the following steps:
(1) pretreating the titanium substrate to obtain a pretreated titanium substrate;
(2) mixing Na2O·2B2O3Ball milling to obtain Na with the particle size of 30-150 mu m2O·2B2O3Particles; or mixing Na2O·2B2O3And Ca (OH)2Respectively ball-milling to obtain Na with the particle size of 30-150 mu m2O·2B2O3Particles and Ca (OH)2Granulating, then adding Na2O·2B2O3Particles and Ca (OH)2The particles are mixed according to a molar ratio of 1: (0.01-1) uniformly mixing to obtain a mixture;
(3) na prepared in the step (2)2O·2B2O3Spreading the particles or the mixture on the surface of the titanium matrix pretreated in the step (1), and calcining for 2-7 h at 600-800 ℃;
(4) and (4) placing the titanium substrate calcined in the step (3) in water at the temperature of 60-80 ℃ for heating treatment for 3-5 h, and drying to obtain the sodium titanate nanorod array.
2. The method for preparing a sodium titanate nanorod array according to claim 1, wherein:
the titanium substrate in the step (1) is Ti6Al4V alloy.
3. The method for preparing a sodium titanate nanorod array according to claim 1, wherein:
the pretreatment in the step (1) is to polish and polish the titanium substrate by using 2000-5000-mesh sand paper, wash the titanium substrate for 5-15 min by using acetone, and then ultrasonically wash the titanium substrate in water.
4. The method for preparing a sodium titanate nanorod array according to claim 1, wherein:
and (3) performing ball milling for 2-5 h at 200-240 r/min by using ethanol as a ball milling medium under the ball milling condition in the step (2).
5. The method for preparing a sodium titanate nanorod array according to claim 1, wherein:
na described in step (3)2O·2B2O3The thickness of the particles or the mixture on the substrate is 0.5 to 3 mm.
6. The method for preparing a sodium titanate nanorod array according to claim 1, wherein:
the nano-rod size of the sodium titanate nano-rod array prepared in the step (4) is 200-800 nm.
7. A sodium titanate nanorod array, characterized by being prepared by the preparation method of any one of claims 1-6.
8. The sodium titanate nanorod array of claim 7, in the technical field of preparation of nano bone repair materials.
9. A sodium titanate/titanium alloy composite material characterized in that a titanium alloy is used as a matrix, and the surface of the matrix comprises the sodium titanate nanorod array of claim 7.
10. The use of the sodium titanate/titanium alloy composite material of claim 9 in the technical field of preparing a nano bone repair material.
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