CN112095104A

CN112095104A - Method for preparing composite film on titanium surface, composite material and application

Info

Publication number: CN112095104A
Application number: CN202010929323.4A
Authority: CN
Inventors: 吕宇鹏; 陈歆; 刘冰; 肖桂勇
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2020-09-07
Filing date: 2020-09-07
Publication date: 2020-12-18
Anticipated expiration: 2040-09-07
Also published as: CN112095104B

Abstract

The invention relates to a method for preparing a composite film layer on a titanium surface, a composite material and application. The method comprises the following specific steps: and sequentially carrying out acid etching and alkali washing on the titanium sample, carrying out induction heating treatment in a nitrogen atmosphere, and cooling in the nitrogen atmosphere to obtain the titanium product with the composite film layer. The frequency of induction heating is 0.5-27MHz, and the rated power of induction heating is 2-50 KW. The hardness, wear resistance and corrosion resistance of the surface of the sample can be obviously improved. The titanium oxide is mainly anatase phase, and can improve the biocompatibility and the bioactivity of the high-purity titanium implant.

Description

Method for preparing composite film on titanium surface, composite material and application

Technical Field

The invention belongs to the technical field of surface modification of biomedical metal materials, and particularly relates to a method for preparing a composite film on a titanium surface, a composite material and application.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

Titanium and titanium alloy have low density, high specific strength, elastic modulus similar to human bone and good biocompatibility, and have wide application in the biomedical fields of orthopedics, dentistry and the like, but the bioactivity, corrosion resistance and wear resistance of the titanium and titanium alloy still need to be further improved so as to meet the requirements of early integration and long-term safety of the implant. Many surface modification techniques can improve the wear resistance, bioactivity, and biocompatibility of titanium and titanium alloy surfaces by altering morphology, composition, roughness, and the like. Among them, the alkali heat treatment is a surface modification method which is widely studied and has been proved to be excellent in promoting the deposition of hydroxyapatite on the surface, but the abrasion resistance thereof is still required to be further improved.

The titanium oxide film layer is obtained on the titanium surface, so that the deposition of hydroxyapatite can be induced, and the combination of the film layer and the substrate is realized.

Disclosure of Invention

In view of the problems in the prior art, the invention aims to provide a method for preparing a composite film layer on a titanium surface, a composite material and application. The composite film layer of sodium titanate, titanium oxide and titanium nitride is obtained by high-temperature nitridation. And forming a porous composite film layer rich in sodium titanate, anatase phase titanium oxide and titanium nitride on the surface of the pure titanium.

In order to solve the technical problems, the technical scheme of the invention is as follows:

in a first aspect, a method for preparing a composite film on a titanium surface comprises the following specific steps:

and sequentially carrying out acid etching and alkali washing on the titanium sample, carrying out induction heating treatment in a nitrogen atmosphere, and cooling in the nitrogen atmosphere to obtain the titanium product with the composite film layer.

The induction heating is electromagnetic induction heating. Under the induction heating and nitrogen atmosphere, a sodium titanate film layer, a titanium oxide film layer and a titanium nitride film layer can be formed on the surface of the titanium, and the titanium oxide is in an anatase phase. The composite film layer of sodium titanate, titanium oxide and titanium nitride is uniformly distributed on the surface of titanium. The composite film layer has strong binding force with the titanium surface, and is beneficial to improving the hardness and the wear resistance.

After alkali washing, a porous structure with a micro-nano scale is formed on the surface of the titanium, which is beneficial to the performance of the composite film layer.

In a second aspect, the composite material obtained by the method for preparing the composite film layer on the surface of titanium comprises titanium, a sodium titanate, titanium nitride and titanium oxide composite film layer on the surface of titanium, wherein titanium oxide is an anatase phase.

In a third aspect, the method for preparing the composite film on the surface of the titanium is applied to the biomedical field.

One or more technical schemes of the invention have the following beneficial effects:

by utilizing the method for preparing the sodium titanate, titanium oxide and titanium nitride composite film on the surface of titanium, the sodium titanate, titanium oxide and titanium nitride composite film can be obtained on the surface of pure titanium under the condition of high-temperature induction heating, and the hardness, wear resistance and corrosion resistance of the surface of a sample can be obviously improved.

The film prepared by the method for preparing the titanium oxide and titanium nitride composite film on the titanium surface has a porous structure with a micro-nano scale, and the obtained titanium oxide is mainly anatase phase, so that the biocompatibility and the bioactivity of the high-purity titanium implant can be improved.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.

FIG. 1 is an XRD curve of a composite film layer of titanium oxide and titanium nitride on the surface of pure titanium prepared by induction heating in different atmospheres in example 1 and comparative example 1; wherein nitrogen-IHT represents example 1, and air-IHT represents comparative example 1;

FIG. 2 is a scanning electron microscope image of field emission of a composite film of porous sodium titanate, titanium oxide and titanium nitride on the surface of pure titanium prepared by induction heating in nitrogen atmosphere in example 1;

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

The induction heating is electromagnetic induction heating. Under the induction heating mode, a composite film layer of sodium titanate, titanium nitride and titanium oxide is obtained, the titanium nitride film layer is beneficial to improving the hardness and the wear resistance of the titanium surface, and the titanium nitride has good biocompatibility and osteogenic activity.

The anatase phase titanium oxide has a crystal structure that allows for atomic arrangement that facilitates the epitaxy of the apatite crystal and a lower degree of mismatching that facilitates the deposition of apatite than rutile phase titanium oxide.

The obtained composite material with the composite film layer has better capability of inducing hydroxyapatite, so that the bonding capability of the film layer and the matrix is stronger.

In some embodiments of the invention, the titanium sample is pure titanium or a titanium alloy.

In some embodiments of the invention, the titanium sample is grit blasted prior to acid etching. The sand blasting is mainly used for cleaning the titanium surface and obtaining a certain roughness on the titanium surface.

In some embodiments of the invention, the blasting uses 60-80 mesh alumina particles.

In some embodiments of the invention, the pressure of the blasting is 0.1 to 1MPa for a period of 10 to 60s, and the distance of the lance from the sample surface is 1 to 5 cm. Preferably, the pressure of the sand blasting is 0.8-1MPa, the time is 50-60s, and the distance between the spray gun and the surface of the sample is 4-5 cm.

In some embodiments of the present invention, the method of acid etching treatment is: soaking a titanium sample in a hydrofluoric acid solution; preferably, the mass concentration of the hydrofluoric acid solution is 2-4%; preferably, the soaking time is 30-60 s.

In some embodiments of the invention, the method of alkali washing treatment is to put a titanium sample into a sodium hydroxide solution; preferably, the concentration of the sodium hydroxide solution is 5-10 mol/L; preferably, the temperature of the alkali washing is 50-70 ℃, and the time of the alkali washing treatment is 12-24 h.

In some embodiments of the invention, the alkali washed sample is subjected to a water wash.

In some embodiments of the invention, the frequency of the induction heating is 0.5-27MHz, and the rated power of the induction heating is 2-50 KW; preferably, the frequency of the induction heating is 30-100KHz, and the rated power of the induction heating is 20-50 KW. The frequency is inversely proportional to the heating depth, and 30-100KHz is from ultrasonic frequency to high frequency, so that a micro-nano porous structure can be generated; the power is in direct proportion to the heating speed, if the power is lower, the heating speed is slow, the thermal oxidation time is longer, and the generation of anatase phase titanium oxide is not facilitated; if the power is too large, the heating speed is very fast, and the time of thermal oxidation and nitridation is too short, which is not favorable for the generation of titanium nitride. Therefore, the composite film layer with the optimal micro-nano porous structure and the phase composition of anatase titanium oxide and titanium nitride can be obtained in the range.

In some embodiments of the invention, the induction heating is performed for a time period of 10 to 60 seconds.

In some embodiments of the invention, the induction heating time is started 90s after the nitrogen gas is introduced into the atmosphere box. Nitrogen is firstly introduced to meet the nitrogen condition.

In some embodiments of the invention, the cooling is natural cooling, cooling to room temperature conditions.

The sodium titanate is a product after alkali washing, and a large number of experiments prove that the sodium titanate can perform ion exchange with calcium phosphorus plasma in a body fluid environment, so that the deposition of hydroxyapatite on the surface of a sample is promoted.

The invention will be further illustrated by the following examples

Example 1

The method for preparing a composite film on a titanium surface described in this embodiment includes the following specific steps:

(1) under the condition of room temperature, carrying out sand blasting on the surface of pure titanium, wherein the sand blasting adopts 60-mesh alumina particles, the pressure is 0.8MPa, the time is 60s, and the distance between a spray gun and the surface of a sample is 5 cm;

(2) ultrasonically cleaning the sample obtained in the step (1), and soaking the sample in a 4% hydrofluoric acid solution at room temperature for acid etching for 60 s;

(3) ultrasonically cleaning the sample obtained in the step (2), and soaking the sample in 5M sodium hydroxide solution for alkaline washing for 24 hours under the condition of constant-temperature water bath at 60 ℃;

(4) washing the sample obtained in the step (3) for a plurality of times by using deionized water, and placing the sample in a drying box for drying;

(5) placing the sample obtained in the step (4) at the heating position of an induction coil in an atmosphere box, introducing nitrogen for 90s until the atmosphere box is filled with the nitrogen, and starting induction heating, wherein the rated power is 50kW, the frequency is 44KHZ, and the time is 15 s;

(6) and (5) placing the sample obtained in the step (5) in a nitrogen atmosphere, and cooling to room temperature to obtain the product.

As can be seen from fig. 2, the porous film layer of the sample obtained in example 1 was relatively uniform, the large pit size was around 5 μm, and the pore size was about 500 nm.

Comparative example 1

(5) placing the sample obtained in the step (4) at a heating position of an induction coil, and carrying out induction heating in air, wherein the rated power is 50kW, the frequency is 44KHZ, and the time is 15 s;

(6) and (5) placing the sample obtained in the step (5) in air to be cooled to room temperature, and obtaining the product.

As can be seen from fig. 1, the sample obtained in comparative example 1, except for the matrix titanium, was mainly rutile phase titanium oxide on the surface of the sample inductively heated in air; the sample obtained in example 1 had a surface that was induction-heated in nitrogen gas, mainly anatase-phase titanium oxide and titanium nitride, and sodium titanate.

Example 2

(1) under the condition of room temperature, carrying out sand blasting on the surface of pure titanium, wherein the sand blasting adopts 80-mesh alumina particles, the pressure is 0.1MPa, the time is 10s, and the distance between a spray gun and the surface of a sample is 1 cm;

(2) ultrasonically cleaning the sample obtained in the step (1), and soaking the sample in a 2% hydrofluoric acid solution at room temperature for acid etching for 60 s;

(3) ultrasonically cleaning the sample obtained in the step (2), and soaking the sample in 1M sodium hydroxide solution for alkaline washing for 24 hours under the condition of constant-temperature water bath at 80 ℃;

(5) placing the sample obtained in the step (4) at the heating position of an induction coil in an atmosphere box, introducing nitrogen for 90s until the atmosphere box is filled with the nitrogen, and starting induction heating, wherein the rated power is 50kW, the frequency is 20KHZ, and the time is 20 s;

Example 3

(1) under the condition of room temperature, carrying out sand blasting on the surface of pure titanium, wherein the sand blasting adopts 60-mesh alumina particles, the pressure is 0.5MPa, the time is 30s, and the distance between a spray gun and the surface of a sample is 5 cm;

(2) ultrasonically cleaning the sample obtained in the step (1), and soaking the sample in a 6% hydrofluoric acid solution for acid etching for 90s at room temperature;

(3) ultrasonically cleaning the sample obtained in the step (2), and soaking the sample in 10M sodium hydroxide solution for alkaline washing for 24 hours under the condition of constant-temperature water bath at 80 ℃;

(5) placing the sample obtained in the step (4) at the heating position of an induction coil in an atmosphere box, introducing nitrogen for 90s until the atmosphere box is filled with the nitrogen, and starting induction heating, wherein the rated power is 50kW, the frequency is 80KHZ, and the time is 10 s;

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a composite film layer on the surface of titanium is characterized in that: the method comprises the following specific steps:

2. The method for preparing a composite film on a titanium surface according to claim 1, wherein: the titanium sample is pure titanium or a titanium alloy.

3. The method for preparing a composite film on a titanium surface according to claim 1, wherein: and carrying out sand blasting treatment on the titanium sample before acid etching.

4. The method for preparing a composite film on a titanium surface according to claim 3, wherein: the sand blasting adopts 60-80 mesh alumina particles;

preferably, the pressure of the sand blasting is 0.1-1MPa, the time is 10-60s, and the distance between the spray gun and the surface of the sample is 1-5 cm;

further preferably, the pressure of the blasting is 0.8-1MPa, the time is 50-60s, and the distance between the spray gun and the sample surface is 4-5 cm.

5. The method for preparing a composite film on a titanium surface according to claim 1, wherein: the acid etching treatment method comprises the following steps: soaking a titanium sample in a hydrofluoric acid solution; preferably, the mass concentration of the hydrofluoric acid solution is 2-4%; preferably, the soaking time is 30-60 s.

6. The method for preparing a composite film on a titanium surface according to claim 1, wherein: the alkali washing treatment method comprises the steps of putting a titanium sample into a sodium hydroxide solution; preferably, the concentration of the sodium hydroxide solution is 5-10 mol/L; preferably, the temperature of alkali washing is 50-70 ℃, and the time of alkali washing treatment is 12-24 h;

or washing the sample after alkali washing with water.

7. The method for preparing a composite film on a titanium surface according to claim 1, wherein: the frequency of induction heating is 0.5-27MHz, and the rated power of induction heating is 2-50 KW; preferably, the frequency of the induction heating is 30-100KHz, and the rated power of the induction heating is 20-50 KW.

8. The method for preparing a composite film on a titanium surface according to claim 1, wherein: the induction heating time is 10-60 s;

or, the induction heating time is started after nitrogen is introduced into the atmosphere box for 90 s;

or, the cooling is natural cooling and is cooled to the room temperature.

9. The composite material prepared by the method for preparing the composite film layer on the titanium surface according to any one of claims 1 to 9, wherein the method comprises the following steps: comprises titanium, a titanium oxide composite film layer, titanium nitride and titanium titanate on the surface of the titanium, wherein the titanium oxide is anatase.

10. Use of the method of any of claims 1 to 9 for the preparation of a composite film on a titanium surface in the biomedical field.