CN115584470A - Through Zr/Zr 2 Method for improving corrosion and abrasion resistance of titanium alloy surface by N/ZrN multilayer coating - Google Patents
Through Zr/Zr 2 Method for improving corrosion and abrasion resistance of titanium alloy surface by N/ZrN multilayer coating Download PDFInfo
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Abstract
The invention relates to the technical field of coating preparation, in particular to Zr/Zr-passing coating 2 The Zr intermediate layer can reduce the defects of the coating, improve the compactness of the coating, preferentially generate a passive film, hinder the diffusion of corrosive media and improve the corrosion resistance of the coating; meanwhile, the Zr metal layer can inhibit crack propagation, the abrasion performance of the medical titanium alloy coating in a corrosive environment is improved by jointly improving corrosion and toughness, and the abrasion rate of the Zr/Zr2N/ZrN multilayer coating on the surface of the titanium alloy is (4.69 multiplied by 10) ‑6 mm 3 (Nm) ‑1 ) Compared to a single layer coating (1.46X 10) ‑5 mm 3 (Nm) ‑1 ) One order of magnitude lower, and the average current density of the multilayer coating (1.19 x 10) when simulating corrosion by human body fluids ‑8 A/cm 2 ) Compared with a single-layer coating (3.19X 10) ‑8 A/cm 2 ) 3 times lower, and the corrosion resistance of the multilayer coating is obviously better than that of a single-layer coating.
Description
Technical Field
The invention relates to the technical field of coating application, in particular to Zr/Zr-passing coating 2 A method for improving the corrosion and abrasion resistance of the surface of titanium alloy by using an N/ZrN multilayer coating.
Background
Titanium alloy (Ti-6 Al-4V) is one of three biomedical metals, and compared with stainless steel and Co-Cr-Mo alloy, the Young modulus of the titanium alloy is only half of that of the stainless steel and the Co-Cr-Mo alloy, so that the titanium alloy is more suitable for cortical bone. In addition, the titanium alloy has good mechanical property and biocompatibility, and a compact oxide film generated on the surface can effectively deal with corrosion caused by a human body fluid environment. At present, artificial joint prostheses, internal fracture fixators and orthopedic instruments which are made of titanium alloy as a base material are used in large quantities in clinic, and become the most representative biomedical metal materials. However, titanium alloy is corroded by body fluid in human environment and faces to-and-fro friction between bone implants, and the surface of titanium alloy is seriously worn under the interaction of corrosion and friction. And Al and V ions released by the titanium alloy can generate certain toxic and side effects on surrounding tissues. Therefore, for practical significance of safe use of titanium alloy in human body, it is very important to improve the corrosion resistance and the friction resistance of the titanium alloy.
At present, the preparation of hard coating on the surface of titanium alloy is one of the most effective methods for solving the problems of low surface hardness and poor wear resistance of titanium alloy. As a metal without biotoxicity, corrosion resistance and good cell compatibility, zr is widely applied to biomedicine all the time. The ZrN coating prepared by the Physical Vapor Deposition (PVD) technology has good performance in practical application. However, PVD coatings have a high number of structural defects which tend to cause localized corrosion, particularly pitting. The pits or recesses formed by pitting cause great damage to the coating.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problem of the structure in the ZrN coating on the surface of the titanium alloyThe defects are more, local corrosion is easy to cause, particularly, pitting corrosion is easy to occur, and small pits or deep holes formed by the pitting corrosion can cause great damage to the coating, and the Zr/Zr-containing coating is provided 2 A method for improving the corrosion and abrasion resistance of the surface of titanium alloy by using an N/ZrN multilayer coating.
In order to achieve the above object, the present invention discloses a method for producing Zr/Zr 2 The method for improving the corrosion and abrasion resistance of the surface of the titanium alloy by the N/ZrN multilayer coating comprises the following steps:
s1, carrying out ultrasonic cleaning on a titanium alloy sample, and drying;
s2, placing the titanium alloy pattern processed in the step S1 on a substrate rotating stand, heating and vacuumizing, introducing argon, starting a Ti target, performing ion bombardment on the surface of the base material, performing ion etching to clean the surface of the base material, and activating the base material;
s3, after the ion etching in the step S2 is finished, keeping the deposition temperature and the pressure of the furnace chamber unchanged, starting a Zr target, and depositing a metal Zr layer;
s4, after the Zr metal layer deposition in the step S3 is finished, keeping the deposition temperature unchanged, closing argon, introducing nitrogen, and depositing Zr 2 An N transition layer;
s5, waiting for Zr in the step S4 2 After the deposition of the N transition layer is finished, keeping the deposition temperature unchanged, continuously introducing nitrogen, and depositing a ZrN layer;
s6, repeating the steps S3 to S5, and alternately depositing Zr metal layers and Zr 2 Obtaining Zr/Zr deposited on the surface of the N transition layer and the ZrN layer 2 Titanium alloy of N/ZrN multilayer coating.
In the step S2, the argon flow is 200-600 sccm, the negative bias of the substrate is-200V, and the ion etching time is 40min.
In the step S3, the bias voltage of the base material is-60 to-80V, the target current of the metal Zr target is 100 to 130A, and the deposition time is 5 to 10min.
The pressure of the nitrogen gas introduced in the step S4 is 1-2 Pa, the flow rate of the nitrogen gas is 100-300 sccm, and the deposition time is 2-4 min.
After the nitrogen is continuously introduced in the step S5, the pressure intensity is 2-5Pa 2 The flow rate is 400-800 sccm, and deposition is carried outThe time is 10-15 min.
Alternately depositing Zr metal layer and Zr in the step S6 2 The number of times of the N transition layer and the ZrN layer was 7.
The pressure of the nitrogen gas introduced in the step S3 is 1-2 Pa, the flow rate of the nitrogen gas is 100-300 sccm, and the deposition time is 2-4 min.
After the nitrogen is continuously introduced in the step S4, the pressure intensity is 2-5Pa 2 The flow rate is 400-800 sccm, and the deposition time is 10-15 min.
In the step S5, zr metal layers and Zr are alternately deposited 2 The number of times of the N transition layer and the ZrN layer was 7.
Zr/Zr in said step S6 2 The N/ZrN multilayer coating comprises a plurality of Zr/Zr 2 A N/ZrN coating unit, said Zr/Zr 2 The N/ZrN coating unit comprises a metal Zr layer and Zr 2 An N transition layer and a ceramic ZrN layer, the Zr/Zr 2 The thickness of the N/ZrN coating unit was 3 μm.
The thickness ratio of the metal Zr layer to the ceramic ZrN layer is 1:3, and the thickness of a single metal Zr layer is 110nm.
Compared with the prior art, the invention has the beneficial effects that:
1. Zr/Zr on surface of titanium alloy prepared by the invention 2 Compared with a single-layer ZrN coating, the N/ZrN multilayer composite coating has a more compact coating structure, the addition of the metal Zr layer interrupts the columnar growth of ZrN crystals, and the diffusion channel of corrosive media is reduced, so that the corrosion resistance of the surface of the titanium alloy can be improved.
2、Zr/Zr 2 ZrO formed by metal Zr intermediate layer in N/ZrN multilayer composite coating 2 The passivation film can inhibit further diffusion of corrosive media, and can block the defects of cracks, holes and the like in the coating, so that the corrosive media are prevented from penetrating into the titanium alloy matrix, and the corrosion resistance of the coating is greatly improved;
3. the multilayer structure releases the internal stress of the coating, the softer metal Zr layer and the hard ceramic ZrN layer have synergistic effect, excellent friction resistance is shown, a corrosion product generated by the metal Zr layer participates in the friction process, a certain lubricating effect is achieved, and compared with a single-layer coating, the corrosion wear rate of the multilayer coating is greatly reduced.
Drawings
FIG. 1 is a schematic view of a multilayer composite coating of the present invention;
FIG. 2 is a FESEM picture of a cross section of a single layer coating and a multi-layer composite coating;
FIG. 3 is an XRD pattern of a single layer coating and a multilayer composite coating;
FIG. 4 is (a) an impedance spectrum and (b) a Bode plot of a single-layer coating and a multi-layer composite coating;
FIG. 5 is a potentiodynamic polarization curve for a single-layer coating and a multi-layer composite coating;
FIG. 6 is a signal spectrum of secondary ion mass spectrometry after electrochemical experiments of a single-layer coating and a multi-layer composite coating;
FIG. 7 shows the open circuit potential and the friction coefficient of the single-layer coating and the multi-layer composite coating in the corrosion friction test;
FIG. 8 is a three-dimensional topography of wear scar measured after corrosion rubbing experiments for (a) single layer coatings and (b) multi-layer coatings;
FIG. 9 is a graph of the average coefficient of friction and wear rate of single and multi-layer composite coatings after corrosive rubbing;
FIG. 10 is a TEM image of a multilayer composite coating of the present invention after wear failure.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
(1) Carrying out ultrasonic cleaning on the Ti-6Al-4V titanium alloy material after grinding and polishing for a certain time, washing with deionized water, and drying for later use;
(2) Placing the processed titanium alloy pattern on a substrate rotating stand, heating to 380 deg.C, and vacuumizing to 10 deg.C -4 Introducing Ar gas with the flow rate of 400sccm under Pa, starting the Ti target, controlling the negative bias to be-200V, and performing ion bombardment etching cleaning for 40min;
(3) Keeping the deposition temperature constant and further increasing N 2 Gas, changing the pressure to be 5Pa 2 Depositing a ZrN layer with the flow of 800sccm. The deposition time is 100min, and the deposition of the ZrN layer is completed.
Example 2
(1) Carrying out ultrasonic cleaning on the Ti-6Al-4V titanium alloy material after grinding and polishing for a certain time, washing with deionized water, and drying the sample for later use;
(2) Placing the processed titanium alloy pattern on a substrate rotating stand, heating to 380 deg.C, and vacuumizing to 10 deg.C -4 Pa, introducing Ar gas with the flow of 400sccm, starting the Ti target, controlling the negative bias voltage to-200V, and performing ion bombardment etching cleaning for 40min;
(3) Keeping the deposition temperature, starting a Zr target, and depositing a metal Zr layer; the substrate bias voltage is-60, and the target current of the metal Zr target is 130A, and the deposition is finished after 5min.
(4) Keeping the deposition temperature unchanged, closing Ar gas, and introducing a small amount of N 2 Gas, changing the pressure to 1Pa 2 Flow rate of 100sccm, deposit Zr 2 And an N transition layer. The deposition time is 2min;
(5) Keeping the deposition temperature constant and further increasing N 2 Gas, changing the pressure to be 5Pa 2 Depositing a ZrN layer with the flow rate of 800 sccm. The deposition time is 15min, and the deposition of the ZrN layer is completed.
(6) Repeating the process, and alternately depositing Zr metal layers and Zr 2 The N transition layer and the ZrN layer are arranged 7 times.
FIG. 1 is a schematic view of a multilayer composite coating of the present invention, wherein the coating comprises Zr and Zr 2 N, zrN a multilayer structure.
FIGS. 2 (a) and 2 (b) are the ZrN single layer coating and the Zr/Zr prepared respectively 2 FESEM picture of the section of the N/ZrN multilayer coating shows that Zr/Zr 2 The structure of the N/ZrN multilayer coating is more compact, the defects in the coating are greatly reduced, and the coating quality is obviously superior to that of a single-layer coating.
FIG. 3 is an XRD pattern of a single layer coating versus a multilayer coating, from which it can be seen that in addition to the metallic Zr and ZrN phases, zr is present in the multilayer coating 2 And (4) N phase. Zr 2 The existence of the N phase improves the binding force between the metal Zr intermediate layer and the ceramic ZrN layer, and the coating has stronger toughness. In addition, a multi-layer coating phaseCompared with a single-layer coating, the peak intensity of the ZrN (200) surface is reduced and the ZrN surface shifts to a high angle, so that the grains of the multi-layer coating are refined, the internal stress of the coating is released, and the coating can better adapt to the corrosive friction environment in a human body.
FIGS. 4 (a) and 4 (b) are the electrochemical impedance spectrum and Bode plot of a single-layer coating and a multi-layer coating, respectively, and it can be seen that the Nyquist curve capacitance arc diameter of the multi-layer coating is significantly larger than that of the single-layer coating, and that the phase angle of the Bode plot is closer to 90 and the value of | Z | is higher. This all indicates that the multilayer coating has a greater resistance value than the single layer coating, and has better corrosion resistance in the face of SBF solution corrosion.
Fig. 5 is a potentiodynamic polarization curve of a single-layer coating and a multi-layer coating, wherein the current density of the anode area of the single-layer coating is increased sharply, which represents that the coating is dissolved by an anode in an SBF solution, and the corrosion resistance of the coating is poor. While the multilayer coating had a distinct passivation region and the multilayer coating (1.19X 10) -8 A/cm 2 ) Average current density of (3.19X 10) compared to a single layer coating -8 A/cm 2 ) 3 times lower, and the corrosion resistance of the multilayer coating is obviously better than that of a single-layer coating.
FIG. 6 is a depth profile of secondary mass spectrometry of a single layer coating and a multi-layer coating after electrochemical testing. By comparing O of the two coatings - And Cl - It can be seen that the single-layer coating has O because of the relatively large number of defects in the coating, and the SBF solution reaches the depth of the coating through these internal passages, causing corrosion damage in the coating - And Cl - The signal is still largely detectable within the single layer coating. This is because a single layer coating has a high number of corrosion holes inside it and this corrosion behavior is catastrophic to the coating. Improved Zr/Zr for Zr intermediate layer 2 For the N/ZrN multilayer coating, in a corrosion experiment for simulating a human body environment, the multilayer coating optimizes the coating structure due to the insertion of the metal Zr layer, so that compact tissues and fewer defects are obtained, the passing of electrolyte is effectively blocked, and meanwhile, the Zr metal layer can preferentially generate ZrO 2 Passive film, barrier to the diffusion of corrosive media, and little or no O inside the coating - And Cl - Signal, which has a positive effect on the corrosion resistance of the coating.
Fig. 7 shows the change of open circuit potential OCP and COF values of the coefficient of friction during corrosive rubbing for single-layer and multi-layer coatings. FIG. 8 is a three-dimensional topography of wear scars measured after single-layer and multi-layer coating corrosion friction experiments. FIG. 9 shows the average coefficient of friction and wear rate measured after single and multi-layer coating corrosion abrasion tests. As can be seen from FIGS. 7, 8 and 9, the single layer coating exhibited a higher average coefficient of friction (0.72) and wear rate (1.46X 10) -5 mm 3 (Nm) -1 ) And Zr/Zr with improved Zr interlayer 2 The N/ZrN multilayer coating has low average friction coefficient (0.51) and wear rate (4.69 x 10) -6 mm 3 (Nm) -1 )。
Fig. 8 is an inset showing that the single-layer coating has deep grinding marks because the coating has loose texture and more defects, and is easy to form block-shaped falling under the interaction of corrosion and friction, and massive hard coating particles cannot be discharged in time due to the deep grinding pits, so that serious abrasive wear is caused in the grinding pits. And the multilayer coating has compact structure, better wear resistance and shallower grinding pit, and the abrasive dust generated in the friction process is easier to discharge.
FIG. 10 is a cross-sectional TEM image of a multilayer coating after corrosion rubbing. It can be seen that the multilayer coating had little wear and a passive film was formed on the surface of the coating, which was formed by the metallic Zr layer immediately adjacent to the ZrN layer. It can be seen that a portion of the metallic Zr layer is "consumed" by the corrosive liquid penetrating the metallic Zr through the gaps or cracks in the ZrN of the top layer. Anodic dissolution of the Zr metal layer destroys the integrity of the coating, but at the same time the ZrO formed 2 A layer of passive film is generated on the surface of the coating, and the barrier coating is contacted with the corrosive liquid, so that the corrosion resistance of the coating is improved. ZrO (ZrO) 2 When the coating is involved in a friction process, the coating also plays a certain role in lubrication, so that the multi-layer coating has lower wear rate and friction coefficient.
In a multilayer system, the presence of a metal layer can reduce corrosion of the nitride layer, and the hard nitride layer provides a strong support against friction, which cooperate with each other. Due to the addition of the transverse interface, cracks can grow selectively and horizontally under the catalysis of load stress. The corrosion medium is blocked on the Zr/ZrN interlayer surface, the interlayer surface crack is enlarged due to the anode dissolution of the Zr metal layer, and the Zr/ZrN layer on the top of the coating falls off along with the aggravation of corrosion and continuous reciprocating mechanical friction. The previous process was repeated with exposure of the fresh Zr/ZrN layer to a corrosive rubbing environment. The failure behavior similar to self-healing delays the time that corrosive liquid spreads to a matrix, greatly prolongs the service life of the titanium alloy, and has very important practical significance on biomedical instruments.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be appreciated by those skilled in the art that many variations, modifications, and equivalents may be made thereto without departing from the spirit and scope of the invention as defined in the claims.
Claims (8)
1. Through Zr/Zr 2 The method for improving the corrosion and abrasion resistance of the titanium alloy surface by the N/ZrN multilayer coating is characterized by comprising the following steps:
s1, carrying out ultrasonic cleaning on a titanium alloy sample, and drying;
s2, placing the titanium alloy pattern processed in the step S1 on a substrate rotating stand, heating and vacuumizing, introducing argon, starting a Ti target, performing ion bombardment on the surface of the base material, performing ion etching to clean the surface of the base material, and activating the base material;
s3, after the ion etching in the step S2 is finished, keeping the deposition temperature and the pressure of the furnace chamber unchanged, starting a Zr target, and depositing a metal Zr layer;
s4, after the Zr metal layer deposition in the step S3 is finished, keeping the deposition temperature unchanged, closing argon, introducing nitrogen, and depositing Zr 2 An N transition layer;
s5, waiting for Zr in the step S4 2 After the deposition of the N transition layer is finished, keeping the deposition temperature unchanged, continuously introducing nitrogen, and depositing a ZrN layer;
s6, repeating the steps S3 to S5, and alternately depositing Zr metal layers and Zr 2 Obtaining Zr/Zr deposited on the surface of the N transition layer and the ZrN layer 2 Titanium alloy of N/ZrN multilayer coating.
2. A process of claim 1 for the preparation of Zr/Zr 2 The method for improving the corrosion and abrasion resistance of the titanium alloy surface by the N/ZrN multilayer coating is characterized in that in the step S2, the argon flow is 200-600 sccm, the negative bias of the base material is-200V, and the ion etching time is 40min.
3. A Zr/Zr transition metal oxide as claimed in claim 1 2 The method for improving the corrosion and abrasion resistance of the titanium alloy surface by the N/ZrN multilayer coating is characterized in that in the step S3, the bias voltage of the base material is-60 to-80V, the target current of the metal Zr target is 100 to 130A, and the deposition time is 5 to 10min.
4. A Zr/Zr transition metal oxide as claimed in claim 1 2 The method for improving the corrosion and abrasion resistance of the surface of the titanium alloy by the N/ZrN multilayer coating is characterized in that the pressure after the nitrogen is introduced in the step S4 is 1-2 Pa, the flow rate of the nitrogen is 100-300 sccm, and the deposition time is 2-4 min.
5. A Zr/Zr transition metal oxide as claimed in claim 1 2 The method for improving the corrosion and abrasion resistance of the surface of the titanium alloy by the N/ZrN multilayer coating is characterized in that the pressure intensity is 2-5Pa after the nitrogen is continuously introduced in the step S5 2 The flow rate is 400-800 sccm, and the deposition time is 10-15 min.
6. A Zr/Zr transition metal oxide as claimed in claim 1 2 The method for improving the corrosion and abrasion resistance of the surface of the titanium alloy by the N/ZrN multilayer coating is characterized in that a Zr metal layer and Zr are alternately deposited in the step S6 2 The number of times of the N transition layer and the ZrN layer was 7.
7. A Zr/Zr transition metal oxide as claimed in claim 1 2 The method for improving the corrosion and abrasion resistance of the surface of the titanium alloy by the N/ZrN multilayer coating is characterized in that Zr/Zr in the step S6 2 The N/ZrN multilayer coating comprises a plurality of Zr/Zr 2 A N/ZrN coating unit, said Zr/Zr 2 The N/ZrN coating unit comprises a metal Zr layer and Zr 2 An N transition layer and a ceramic ZrN layer, the Zr/Zr 2 The thickness of the N/ZrN coating units was 3 μm.
8. A Zr/Zr transition metal oxide as claimed in claim 7 2 The method for improving the corrosion and abrasion resistance of the titanium alloy surface by the N/ZrN multilayer coating is characterized in that the thickness ratio of the metal Zr layer to the ceramic ZrN layer is 1:3, and the thickness of a single metal Zr layer is 110nm.
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| US5071693A (en) * | 1989-09-11 | 1991-12-10 | Union Carbide Coatings Service Technology Corporation | Multilayer coating of a nitride-containing compound and method for producing it |
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