CN112813404A

CN112813404A - Tantalum coating, preparation method thereof and dental implant

Info

Publication number: CN112813404A
Application number: CN202011616833.2A
Authority: CN
Inventors: 聂全新; 李小平; 张亚军; 杜领会; 任志东; 张静; 李积贤; 宿康宁; 雒敏; 黄浩; 胡瑞升
Original assignee: Ningxia Orient Tantalum Industry Co Ltd
Current assignee: Ningxia Orient Tantalum Industry Co Ltd
Priority date: 2020-12-30
Filing date: 2020-12-30
Publication date: 2021-05-18

Abstract

The invention relates to a tantalum plating layer, a preparation method thereof and a dental implant.

Description

Tantalum coating, preparation method thereof and dental implant

Technical Field

The invention relates to the field of surface treatment, in particular to a tantalum plating layer, a preparation method thereof and a dental implant.

Background

The preparation of tantalum coatings on the surfaces of medical metals (stainless steel, titanium and titanium alloys) and the clinical application trend thereof have become the future development trend. The titanium alloy has the characteristics of small specific gravity, high specific strength, low elastic modulus, easy processing and forming, rich raw material resources and the like, and is developed into a more ideal functional structure material for surgical implants. However, the complex environment in the human body can cause corrosion of metal materials to release toxic elements, so that the biocompatibility is reduced; in addition, the elastic modulus of the metal material is too different from that of human bone tissues, so that the stress shielding effect is easily generated, and the new bone growth and remodeling are not facilitated.

Disclosure of Invention

The inventor finds that the surface modification of the medical metal material to improve the comprehensive performance becomes a simple, convenient, quick and effective method. The tantalum coating is prepared on the surface of the medical metal material, the performance advantages of the material are utilized, the characteristic of good biocompatibility of the metal tantalum is exerted, and the high cost of completely using the metal tantalum is reduced.

The invention innovatively uses Chemical Vapor Infiltration (CVI) equipment to prepare the metal tantalum coating. The invention leads the inert gas and the tantalum target steam to diffuse into the reaction chamber together by introducing the inert gas into the target heating furnace, and forms the tantalum coating on the surface of the workpiece to be coated.

In some aspects, the present disclosure provides a method of Chemical Vapor Infiltration (CVI) producing a tantalum plating comprising the steps of:

(1) providing a Chemical Vapor Infiltration (CVI) device, wherein the CVI device comprises a reaction chamber for accommodating workpieces to be plated and a target heating furnace, and the target heating furnace is used for providing target steam to the reaction chamber;

(2) placing a workpiece to be plated in a reaction chamber, and vacuumizing the reaction chamber;

(3) preheating a workpiece to be plated;

(4) placing the tantalum target material in a target material heating furnace for heating so as to generate tantalum target material steam;

(5) and introducing inert gas into the target heating furnace, so that the inert gas and the tantalum target steam are diffused into the reaction chamber together, and forming a tantalum coating on the surface of the workpiece to be coated.

In some embodiments, in step (2), the reaction chamber is evacuated to 1 × 10^-3Pa or less.

In some embodiments, the temperature of the preheating in the step (3) is 500 to 700 ℃.

In some embodiments, in step (4), the tantalum target material is heated to 6000 to 6300 ℃.

In some embodiments, in the step (4), the purity of Ta of the tantalum target material is more than or equal to 99.99%, and each impurity element is less than 0.005ppm, wherein the impurity element is Al, Cr, U, Th, As, Hg or Pb.

In some embodiments, in step (5), the inert gas is argon.

In some embodiments, in step (5), the inert gas is introduced at a flow rate of 50 to 130 mL/min.

In some embodiments, the method of preparing a tantalum plating layer further comprises the step of preparing a tantalum target material comprising:

1) preparing tantalum ingots by adopting an electron beam furnace for smelting, wherein the purity of Ta of the tantalum ingots is more than or equal to 99.995%, each impurity element is less than 0.005ppm of high-purity ingots, and the impurity elements are Al, Cr, U, Th, As, Hg or Pb;

2) and forging, rolling and carrying out vacuum heat treatment on the tantalum cast ingot to obtain the tantalum target material.

In some embodiments, the method of preparing a tantalum plating further comprises the steps of:

preprocessing the workpiece to be plated before the workpiece to be plated is placed into the reaction chamber;

the pretreatment sequentially comprises the following operations: ultrasonic cleaning with distilled water, ultrasonic cleaning with a detergent, ultrasonic cleaning with isopropyl alcohol, ultrasonic cleaning with acetone, ultrasonic cleaning with distilled water, washing with distilled water and blow-drying.

In some embodiments, the composition of the workpiece to be plated is metal, ceramic, glass, or plastic;

in some embodiments, the composition of the workpiece to be plated is titanium metal, titanium alloy, or stainless steel.

In some embodiments, the workpiece to be plated is a dental implant.

In some aspects, the present disclosure provides a tantalum plating layer prepared by any one of the methods described above.

In some embodiments, the tantalum coating has a tantalum purity of 99.995% or greater and less than 0.005ppm of each of the heteroatoms, which is Al, Cr, U, Th, As, Hg, or Pb.

In some embodiments, the bonding strength of the coating and the workpiece to be coated is more than or equal to 20 MPa.

In some embodiments, the thickness of the coating is ≧ 10 μm.

In some aspects, the present disclosure provides a workpiece having a tantalum plating layer prepared by a method comprising: preparing a tantalum coating on the surface of a workpiece to be coated according to any one of the methods.

In some embodiments, the workpiece having a tantalum coating is a dental implant having a tantalum coating.

Description of terms:

the term "Chemical Vapor Infiltration (CVI)" is to be broadly interpreted as a process that includes the infiltration and deposition of species on the surface of a workpiece to be plated.

Advantageous effects

The invention develops a dental implant and a tantalum plating method, and is an innovative invention of new materials and new technologies. The method not only utilizes the performance advantages of titanium and titanium alloy, 316L stainless steel dental implant material, but also exerts the characteristic of excellent biocompatibility of metal tantalum, and simultaneously reduces the high cost of completely using the metal tantalum.

One or more technical schemes of the present disclosure have one or more of the following beneficial effects:

(1) the binding force is strong. When the target steam impacts the substrate in the heating state, a micro alloy layer is formed between the coating film and the substrate.

(2) The uniform plating capability is good. And introducing inert gas into the target heating furnace, so that the inert gas and the tantalum target steam are diffused into the reaction chamber together, and a tantalum coating is formed on the surface of the workpiece to be coated.

(3) The process has no pollution. Ion evaporation is a completely pollution-free method, and no harmful substances are generated in the whole process.

Drawings

FIG. 1 is a scanning electron micrograph of a cross section of a tantalum coating of an embodiment.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The medicines or instruments used are not indicated by manufacturers, and are all conventional products which can be obtained commercially.

1) Raw materials

A workpiece to be plated: dental implant with Ti-6Al-4V material and size

S10 RN; (φ 4.1 represents body diameter 4.1mm, S represents standard body, 10 represents implant length, RN represents conventional neck)

2) Preparation of target material

1) A1200 KW electron beam furnace is adopted to smelt high-purity ingot materials with Ta more than or equal to 99.995 percent, Al, Cr, U, Th, As, Hg, Pb and other human harmful elements less than 0.005 ppm.

2) The target material is prepared by pressure processing, which mainly comprises forging, rolling and vacuum heat treatment, wherein the forging processing rate is 82 percent, the rolling processing rate is 78 percent, the heat treatment temperature is 980 ℃, and the heat preservation time is 90 min.

3) Pretreatment of workpieces to be plated

Before the workpiece to be plated is put into a furnace, various dust, grease and sweat stains adhered to the surface of the workpiece, a surface oxidation film produced by the workpiece in humid air, adsorbed gas, burrs and the like are removed through pretreatment, so that the bonding strength and the purity of a plating layer are ensured.

The pretreatment comprises the following operations which are carried out in sequence: ultrasonic cleaning with distilled water for 20-30 min, ultrasonic cleaning with a detergent (Meishakelin) for 20-30 min, ultrasonic cleaning with isopropyl acetone for 10-25 min, ultrasonic cleaning with acetone for 10-20 min, ultrasonic cleaning with distilled water for 20-30 min, washing with distilled water and drying at low temperature.

4) A CVI (Chemical Vapor Infiltration) apparatus plates tantalum.

In this embodiment, the workpiece to be plated is a dental implant, the target material is a tantalum target material, and the working gas is argon gas (purity 99.99%).

The Chemical Vapor Infiltration (CVI) tantalum coating preparation process comprises the following steps:

(1) providing a pretreated workpiece to be plated;

(2) and opening a switch of circulating cooling water of the chemical vapor infiltration equipment for controlling the temperature of the target material, the substrate and each equipment component.

(3) Putting the workpiece to be plated into a reaction chamber, starting a vacuum pump, and vacuumizing to the vacuum degree of 1 multiplied by 10^-3Pa, setting the temperature of the workpiece to be plated to 600 ℃.

(4) The tantalum target material is put into a target material heating furnace, the temperature is set to be 6120 ℃, and the tantalum target material is heated to generate steam.

(5) Introducing inert gas into the target heating furnace, introducing working gas (argon) into the target heating furnace, wherein the flow range is 50-130ml/min, so that the working gas and tantalum target steam are diffused into the reaction chamber together, and starting tantalum permeation deposition, wherein the deposition time is 5 hours;

(6) and after the tantalum plating is finished, waiting for the vacuum furnace to cool to room temperature, closing the circulating cooling water, opening the furnace cover, taking out the sample, performing ultrasonic cleaning by using distilled water, and drying to obtain the dental implant with the tantalum plating layer.

Analytical testing

1) Component analysis (GDMS/YS/T897-2013)

The purity of Ta of the tantalum coating is more than or equal to 99.995 percent, and Al, Cr, U, Th, As, Hg and Pb are respectively less than 0.005 ppm.

2) Morphology analysis (SEM)

Scanning electron microscopy of the coating cross section was performed and figure 1 is a scanning electron micrograph of a cross section of the tantalum coating of example 1 showing an average tantalum layer thickness of 10.92 μm.

3) Analysis of binding Strength (GB-5270-

In size

The tantalum coating with the same thickness is deposited on the titanium test piece, the bonding strength is tested by adopting a pull-off method, and the bonding strength is more than or equal to 20 MPa.

While specific embodiments of the invention have been described in detail, those skilled in the art will understand that: various modifications may be made in the details within the teachings of the disclosure, and these variations are within the scope of the invention. The full scope of the invention is given by the appended claims and any equivalents thereof.

Claims

1. A method for preparing a tantalum coating by chemical vapor infiltration comprises the following steps:

(1) providing chemical vapor infiltration equipment, wherein the chemical vapor infiltration equipment comprises a reaction chamber for accommodating a workpiece to be plated and a target heating furnace, and the target heating furnace is used for providing target steam for the reaction chamber;

(3) preheating a workpiece to be plated;

(4) placing the tantalum target material in a target material heating furnace to be heated so as to generate tantalum target material steam;

2. The method of claim 1, characterized by one or more of the following:

-in step (2), the reaction chamber is evacuated to 1X 10^-3Pa below;

in the step (3), the preheating temperature is 500-700 ℃.

In the step (4), the tantalum target material is heated to 6000-6300 ℃;

in the step (4), the tantalum purity of the tantalum target material is more than or equal to 99.99%, each impurity element is less than 0.005ppm, and the impurity elements are Al, Cr, U, Th, As, Hg or Pb;

in step (5), the inert gas is argon.

3. The method of claim 1, further comprising the step of preparing a tantalum target comprising:

4. The method of claim 1, further comprising the steps of:

5. The method according to claim 1, wherein the component of the workpiece to be plated is metal, ceramic, glass or plastic;

preferably, the composition of the workpiece to be plated is titanium metal, titanium alloy or stainless steel.

6. The method of any one of claims 1 to 5, wherein the workpiece to be plated is a dental implant.

7. A tantalum plating layer prepared by the method of any one of claims 1 to 6.

8. The tantalum plating of claim 7 having one or more of the following characteristics:

-tantalum purity is greater than or equal to 99.995%, each impurity element is less than 0.005ppm, and the impurity elements are Al, Cr, U, Th, As, Hg or Pb;

the bonding strength of the coating and the workpiece to be coated is more than or equal to 20 MPa;

the thickness of the coating is greater than or equal to 10 μm.

9. A workpiece having a tantalum coating, prepared by the method comprising: a tantalum plating layer is prepared on the surface of a workpiece to be plated according to the method of any one of claims 1 to 6.

10. The workpiece of claim 9, which is a dental implant having a tantalum coating.