A method for preparing and using a zirconium (N) solid solution structured coating
Patent Information
- Application Number
- CN202611129938.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-28
- Publication Date
- 2026-10-27
AI Technical Summary
虽然上述陶瓷涂层具有较高硬度，但其本征脆性较强，在高应力条件下容易产生裂纹扩展及灾难性断裂，导致涂层失效
本发明采用高功率脉冲磁控溅射进行涂层薄膜的沉积，并通过精确控制氮气流量和峰值电流密度，实现氮原子在α-Zr晶格中的过饱和间隙固溶，并有效抑制脆性ZrN相的形成，从而获得以α-Zr(N)固溶体为主导的，兼具高硬度、高强度、优异变形容忍性及耐腐蚀性能的Zr(N)薄膜单相结构涂层。具体有益效果如下：
Smart Images
Figure CN122979842A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of thin film and surface engineering technology, and specifically relates to a method for preparing and applying a Zr(N) solid solution structure coating. Background Technology
[0002] Zirconium (Zr) and its alloys are widely used in nuclear industry, chemical industry, biomedicine and marine engineering due to their excellent corrosion resistance, low thermal neutron absorption cross section and good biocompatibility. However, pure Zr films have relatively low hardness and strength, and are prone to wear, plastic deformation and local failure in complex service environments, making it difficult to meet the requirements of high load, high corrosion and long service life.
[0003] Currently, researchers typically enhance the hardness and wear resistance of Zr-based thin films by preparing ceramic coatings such as ZrN, ZrC, and ZrCN. While these ceramic coatings exhibit high hardness, they are inherently brittle and prone to crack propagation and catastrophic fracture under high stress conditions, leading to coating failure. Furthermore, traditional stoichiometric ZrN coatings generally suffer from poor deformation tolerance and insufficient impact resistance.
[0004] Therefore, providing a method for preparing a Zr(N) solid solution (a supersaturated interstitial solid solution of nitrogen atoms in the α-Zr lattice) structure coating that can achieve nitrogen supersaturated solid solution strengthening and suppress the formation of brittle ZrN is of great significance for obtaining Zr-based protective coatings with high strength, high hardness, corrosion resistance and deformation tolerance. Summary of the Invention
[0005] The present invention aims to solve one or more technical problems existing in the prior art, and at least provide a beneficial alternative. Specifically, the present invention provides a method for preparing a Zr(N) solid solution structure coating, which can achieve nitrogen supersaturated solid solution strengthening and inhibit the formation of brittle ZrN, thereby obtaining a Zr(N) solid solution structure coating.
[0006] The inventive concept of this invention: The preparation method of the Zr(N) solid solution structure coating of this invention includes the following steps: in a nitrogen-containing mixed atmosphere, using a Zr target as the sputtering target, a coating is deposited on a substrate by high-power pulsed magnetron sputtering; the nitrogen flow rate in the nitrogen-containing mixed atmosphere is 0.1-0.2 sccm; during the coating deposition process using high-power pulsed magnetron sputtering, the peak current density of the sputtering target is 0.2-1.0 A / cm. 2 .
[0007] In traditional DC magnetron sputtering processes, the low metal ionization rate and limited ion energy control make it difficult to precisely control the nitrogen solid solution behavior, easily leading to the formation of a large amount of brittle ZrN phase. This invention employs high-power pulsed magnetron sputtering (HiPIMS) for coating film deposition. HiPIMS features high plasma density, high metal ionization rate, and strong ion-assisted deposition, effectively controlling film growth kinetics and improving film density and interfacial bonding. Simultaneously, by precisely controlling the nitrogen flow rate and peak current density, nitrogen atoms can enter the α-Zr hexagonal close-packed lattice in an interstitial solid solution form, achieving supersaturated interstitial solid solution of nitrogen atoms in the α-Zr lattice, forming an α-Zr(N) solid solution structure, and effectively suppressing the formation of the brittle ZrN phase. This results in a single-phase Zr(N) thin film coating dominated by the α-Zr(N) solid solution, exhibiting high hardness, high strength, excellent deformation tolerance, and corrosion resistance.
[0008] Therefore, a first aspect of the present invention provides a method for preparing a Zr(N) solid solution structure coating.
[0009] Specifically, the preparation method of the Zr(N) solid solution structure coating includes the following steps: In a nitrogen-containing mixed atmosphere, a coating is deposited on the substrate using a Zr target as the sputtering target and high-power pulsed magnetron sputtering. In the nitrogen-containing mixed atmosphere, the flow rate of nitrogen is 0.1-0.2 sccm; During coating deposition using high-power pulsed magnetron sputtering, the peak current density of the sputtering target is 0.2-1.0 A / cm³. 2 .
[0010] Preferably, the Zr(N) solid solution structure coating comprises an α-Zr(N) solid solution.
[0011] Specifically, the Zr(N) solid solution structure coating is mainly composed of α-Zr(N) solid solution, meaning that nitrogen atoms exist in the α-Zr lattice in an interstitial solid solution form. This is achieved when the N2 flow rate is controlled around 0.2 sccm and the peak current density of the sputtering target is controlled at 0.6 A / cm. 2 When the target area is nearby, an optimized structure with both high strength and high deformation tolerance can be obtained.
[0012] Preferably, the nitrogen-containing mixed atmosphere further includes an inert gas with a flow rate of 5-7 sccm.
[0013] Preferably, the inert gas includes at least one of He, Ne, Ar, and Kr.
[0014] Preferably, the purity of the Zr target material is not less than 99.9%.
[0015] Preferably, the power supply for the high-power pulsed magnetron sputtering includes any one of a unipolar high-power pulsed magnetron sputtering power supply and a bipolar high-power pulsed magnetron sputtering power supply.
[0016] Preferably, when using a bipolar high-power pulsed magnetron sputtering power supply, the number of targets is 2N, where N is an integer.
[0017] Preferably, during the coating deposition process using high-power pulsed magnetron sputtering, the average power density of the sputtering target is 2-20 W / cm². 2 .
[0018] Specifically, the peak current density is determined by I MAX / S T The calculated average power density is derived from P M / S T Calculations show that I MAX P M S T These represent the maximum current value of the cathode target (i.e., sputtering target), the average cathode power, and the surface area of the cathode target, respectively.
[0019] Preferably, the working gas pressure is 0.2-3.0 Pa during the coating deposition process using high-power pulsed magnetron sputtering; more preferably, the working gas pressure is 0.3-0.6 Pa.
[0020] Preferably, the coating deposition time is 85-95 minutes.
[0021] Preferably, the substrate comprises any one of cemented carbide, silicon wafer, and Zr alloy.
[0022] Preferably, the Zr alloy comprises a Zr-3 alloy.
[0023] Preferably, the bias voltage of the substrate is 0 to -300V.
[0024] Preferably, the temperature of the substrate is room temperature - 500°C.
[0025] Preferably, the substrate undergoes glow discharge cleaning before coating deposition.
[0026] Preferably, during glow discharge cleaning, the deposition chamber is evacuated to a background vacuum level below 5.0 × 10⁻⁶. -4 Pa.
[0027] Preferably, an Ar atmosphere is used in the glow discharge cleaning process.
[0028] Preferably, during the glow discharge cleaning process, the substrate bias voltage is -850~-950V, and the cleaning time is 4-6 minutes.
[0029] Preferably, ultrasonic cleaning is performed before glow discharge cleaning.
[0030] Preferably, ultrasonic cleaning is first performed in water containing metal detergent, followed by ultrasonic cleaning in ethanol.
[0031] Specifically, the present invention does not particularly limit the type of metal detergent; any conventional metal detergent in the art can be used.
[0032] The second aspect of the present invention provides an application of the Zr(N) solid solution structure coating prepared by the preparation method described in the first aspect of the present invention in wear-resistant and corrosion-resistant protection of metal surfaces.
[0033] Compared with the prior art, the beneficial effects of the technical solution provided by the present invention are as follows: This invention employs high-power pulsed magnetron sputtering for coating film deposition. By precisely controlling the nitrogen flow rate and peak current density, supersaturated interstitial solid solution of nitrogen atoms in the α-Zr lattice is achieved, effectively suppressing the formation of the brittle ZrN phase. This results in a single-phase Zr(N) thin film coating dominated by the α-Zr(N) solid solution, exhibiting high hardness, high strength, excellent deformation tolerance, and corrosion resistance. Specific beneficial effects are as follows: (1) Nitrogen atoms were supersaturated in α-Zr by HiPIMS high ionization deposition, which suppressed the formation of a large amount of brittle ZrN phase. The prepared Zr(N) film has a dense nanocolumnar structure, which significantly reduces columnar grain boundary defects. At the same time, the film has both high hardness and excellent deformation tolerance, which can avoid the catastrophic brittle failure of traditional ZrN ceramic coatings. It also has excellent corrosion resistance and can effectively reduce corrosion current density.
[0034] (2) The Zr(N) solid solution structure coating prepared by the present invention can be widely used in the fields of nuclear industry, marine engineering, biomedicine and surface protection of high-end equipment. Attached Figure Description
[0035] Figure 1 The X-ray diffraction patterns are those of the coating films obtained in Examples 1-5 and Comparative Examples 1-3 of this invention. Figure 2 These are scanning electron microscope (SEM) images of the cross-sections of the coated thin films in Examples 1 and 3-5 of the present invention. Figure 3 These are scanning electron microscope (SEM) images of the cross-sections of the coating films in Embodiment 1 and Comparative Examples 1-3 of the present invention. Figure 4 These are hardness and elastic modulus diagrams of the coating films in Examples 1, 3-5, and Comparative Examples 1-3 of the present invention; Figure 5 The image shows the compression test results of the coated film micropillar in Example 3 of this invention. Detailed Implementation
[0036] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.
[0037] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.
[0038] Example 1 This embodiment provides a method for preparing a Zr(N) solid solution structure coating on a Zr-3 alloy substrate, the specific steps of which are as follows: (1) Matrix pretreatment: The Zr-3 alloy substrate was first ultrasonically cleaned in deionized water with added metal detergent for 30 minutes, then ultrasonically cleaned in anhydrous ethanol for 30 minutes, dried and placed in the deposition chamber. In a pure Ar atmosphere, the deposition chamber pressure was controlled at 0.9 Pa, and the deposition chamber was evacuated to a background vacuum of 5.0 × 10⁻⁶ Pa. -4 Pa, set the substrate bias voltage to -900V, and perform glow discharge cleaning on the substrate for 5 minutes; (2) Preparation of Zr(N) solid solution structure coating (i.e. Zr(N) thin film) HiPIMS technology was employed, with the total working gas pressure controlled at 0.4 Pa, Ar flow rate at 7 sccm, N2 flow rate at 0.2 sccm, and peak current density of the cathode target at 0.4 A / cm². 2 The substrate bias voltage was -100V, the substrate temperature was 300℃, and the deposition time was 90min.
[0039] Example 2 The only difference between Example 2 and Example 1 is that the peak current density of the cathode target in Example 2 is 0.2 A / cm². 2 The rest is the same as in Example 1.
[0040] The resulting film exhibits a distinct columnar structure and low density.
[0041] Example 3 The only difference between Example 3 and Example 1 is that the peak current density of the cathode target in Example 3 is 0.6 A / cm². 2 The rest is the same as in Example 1.
[0042] The resulting film exhibits a distinct columnar structure, and its density is enhanced compared to Example 1.
[0043] Example 4 The only difference between Example 4 and Example 1 is that the peak current density of the cathode target in Example 4 is 0.8 A / cm². 2 The rest is the same as in Example 1.
[0044] The resulting film exhibits a distinct columnar structure, and although its density is enhanced, localized inhomogeneity is observed.
[0045] Example 5 The only difference between Example 5 and Example 1 is that the peak current density in Example 5 is 1.0 A / cm². 2 The rest is the same as in Example 1.
[0046] The resulting film exhibits a distinct columnar structure, with more pronounced localized inhomogeneities.
[0047] Comparative Example 1 Comparative Example 1: ZrN thin films were prepared on a Zr-3 alloy substrate using HiPIMS technology. The specific steps are as follows: (1) Matrix pretreatment: The Zr-3 alloy substrate was first ultrasonically cleaned in deionized water with added metal detergent for 30 minutes, then ultrasonically cleaned in anhydrous ethanol for 30 minutes, dried and placed in the deposition chamber. In a pure Ar atmosphere, the pressure in the deposition chamber was controlled at 0.9 Pa, and the chamber was evacuated to a background vacuum of 5.0 × 10⁻⁶ Pa. -4 Pa, set the substrate bias voltage to -900V, and perform glow discharge cleaning on the substrate for 5 minutes; (2) Preparation of ZrN thin films: HiPIMS technology was employed, with the total working gas pressure controlled at 0.3 Pa, Ar flow rate at 7 sccm, N2 flow rate at 0.3 sccm, and peak current density of the cathode target at 0.4 A / cm². 2 The substrate bias voltage was -100V, the substrate temperature was 300℃, and the deposition time was 90min.
[0048] The resulting thin film is mainly a face-centered cubic zirconium nitride (fcc-ZrN) structure with no metallic phase present.
[0049] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that the N2 flow rate in Comparative Example 2 is 0.4 sccm, while the rest is the same as in Example 1.
[0050] The resulting film is dominated by the ZrN phase, and the film structure is more compact, but the brittleness is enhanced.
[0051] Comparative Example 3 The only difference between Comparative Example 3 and Example 1 is that the N2 flow rate in Comparative Example 3 is 0.5 sccm, while the rest is the same as in Example 1.
[0052] The resulting film is still dominated by the ZrN phase, and the density of the film structure is reduced.
[0053] Performance testing 1. X-ray diffraction analysis The coating films obtained in Examples 1-5 and Comparative Examples 1-3 were analyzed using conventional X-ray diffraction scanning at angles of 30°-70° and a rate of 5° / min. The X-ray diffraction patterns are shown below. Figure 1 As shown. Among them, Figure 1 Figure (a) shows the X-ray diffraction patterns of the coating films obtained in Example 1 and Comparative Examples 1-3. Figure 1 Figure (b) is an X-ray diffraction pattern of the coating film obtained in Examples 1-5.
[0054] Depend on Figure 1 It can be seen that in Examples 1-5, under low N2 flow conditions, nitrogen mainly exists in the α-Zr lattice in the form of interstitial solid solution. As the N2 flow rate increases, ZrN diffraction peaks begin to appear in the film obtained in Comparative Example 1, and the film structure gradually changes from solid solution-dominated to nitride-dominated. In the film obtained in Comparative Example 2, the ZrN phase is dominant, that is, as the N2 flow rate increases, the ZrN phase gradually forms.
[0055] 2. Scanning electron microscopy observation The cross-sections of the coating films prepared under peak current density in Examples 1 and 3-5 were observed using scanning electron microscopy, and the results are as follows: Figure 2 As shown.
[0056] The cross-sections of the coating films prepared in Examples 1 and Comparative Examples 1-3 under different nitrogen flow rates were observed using scanning electron microscopy. The results are as follows: Figure 3 As shown.
[0057] Depend on Figure 2 It can be seen that the film obtained in Example 3 exhibits a distinct columnar structure, with enhanced density compared to Example 1; the film obtained in Example 4 also exhibits a distinct columnar structure, with enhanced density but localized inhomogeneity; the film obtained in Example 5 exhibits a distinct columnar structure, with even more pronounced localized inhomogeneity. This indicates that as the peak current density increases, the film gradually transforms from a loose columnar structure to a dense structure, but when the peak current density further increases, localized inhomogeneity will occur.
[0058] Depend on Figure 3 It can be seen that as the N2 flow rate increases, the film gradually transforms from a loose columnar structure to a dense structure, but when the N2 flow rate increases further, the density of the film structure decreases.
[0059] 3. Mechanical property testing Hardness and elastic modulus of the coated films obtained in Comparative Examples 1-3, Example 1, and Examples 3-5 were analyzed using a nanoindentation testing machine (TTX-NHT2, Anton Parr, Australia), with a Berkovich diamond indenter having a vertex angle of 142.3°. Hardness (H) and elastic modulus (E) values were determined according to the Oliver-Fal method. To ensure accurate data acquisition, a simple matrix method was used to obtain nine data points, removing the maximum and minimum values and retaining the average.
[0060] The hardness and elastic modulus results of the coated films obtained in Examples 1, 3-5, and Comparative Examples 1-3 are as follows: Figure 4 As shown. Figure 4 Figure (a) in the figure is a comparison of the hardness and elastic modulus results of the coated films of Example 1 and Comparative Examples 1-3. Figure 4 Figure (b) shows the hardness and elastic modulus results of the coating films in Examples 1 and 3-5.
[0061] Simultaneously, micropillar compression tests were performed on the film obtained in Example 3. First, a compression test was conducted under linear loading with a fixed strain of 40%. Based on the results of the first test, the second experiment (curve scale at 20%) was adjusted, and deliberately interrupted at approximately 20% strain to capture the intermediate deformation morphology before final failure. The micropillar compression test results of the coated film in Example 3 are as follows: Figure 5 As shown. Among them, Figure 5 Figure (a) in the diagram is a stress-strain curve. Figure 5 Figures (b), (c), and (d) are compression deformation morphology diagrams at preset strains of 0%, 20%, and 40%, respectively.
[0062] Depend on Figure 5 It can be seen that the two batches of tests exhibited similar stress-strain responses in the initial stage. As the strain increased, the stress rose rapidly and reached a maximum compressive stress of about 5.5 GPa at about 8.5% strain. This indicates that the Zr(N) film has a high load-bearing capacity.
[0063] Combination Figure 4 , 5 It can be seen that the Zr(N) films prepared in the embodiments of the present invention possess high hardness, high compressive strength, and good deformation tolerance. Although the hardness of the comparative examples is higher than that of the examples, due to the formation of ZrN ceramic films, the toughness is insufficient, and it cannot simultaneously possess high hardness and good deformation tolerance. The hardness of the film in Example 3 is 13.8 ± 1.6 GPa, and the elastic modulus is 261 GPa.
[0064] 4. Electrochemical corrosion test. A three-electrode testing system was used to conduct electrochemical tests on the thin films of Examples 1-5, Comparative Examples 1-3, and Zr-3 alloy substrates in a simulated 3.5wt% NaCl solution. The potential dynamics test range was -0.6~0.8V, and the scan rate was 2mV / s.
[0065] The electrochemical corrosion results of the thin films and Zr-3 alloy substrates in Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.
[0066] Table 1: Electrochemical corrosion results of thin films and Zr-3 alloy substrates in Examples 1-5 and Comparative Examples 1-3
[0067] As can be seen from Table 1, the films of Examples 1-5 of the present invention have low corrosion current density and good corrosion resistance.
[0068] In Comparative Examples 1-3, the nitrogen flow rate was not in the range of 0.1-0.2 sccm, which made the corrosion resistance of the film worse than that of Example 1. Furthermore, it could not have both high hardness and deformation tolerance, and could not be used under the combined conditions of electrochemical corrosion and stress corrosion.
[0069] In summary, this invention employs high-power pulsed magnetron sputtering to deposit a coating film, and by precisely controlling the nitrogen flow rate and peak current density, achieves supersaturated interstitial solid solution of nitrogen atoms in the α-Zr lattice, effectively suppressing the formation of brittle ZrN phase, thereby obtaining a single-phase Zr(N) thin film coating dominated by α-Zr(N) solid solution, which possesses high hardness, high strength, excellent deformation tolerance, and corrosion resistance.
[0070] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for preparing a Zr(N) solid solution structure coating, characterized in that, The preparation method includes the following steps: In a nitrogen-containing mixed atmosphere, a coating is deposited on the substrate using a Zr target as the sputtering target and high-power pulsed magnetron sputtering. In the nitrogen-containing mixed atmosphere, the flow rate of nitrogen is 0.1-0.2 sccm; During coating deposition using high-power pulsed magnetron sputtering, the peak current density of the sputtering target is 0.2-1.0 A / cm³. 2 .
2. The preparation method according to claim 1, characterized in that, The Zr(N) solid solution structure coating is composed of α-Zr(N) solid solution.
3. The preparation method according to claim 1, characterized in that, The nitrogen-containing mixed atmosphere also includes an inert gas with a flow rate of 5-7 sccm.
4. The preparation method according to claim 3, characterized in that, The inert gas includes at least one of He, Ne, Ar, and Kr.
5. The preparation method according to claim 1, characterized in that, The power supply for the high-power pulsed magnetron sputtering includes either a unipolar high-power pulsed magnetron sputtering power supply or a bipolar high-power pulsed magnetron sputtering power supply.
6. The preparation method according to claim 1, characterized in that, During coating deposition using high-power pulsed magnetron sputtering, the average power density of the sputtering target is 2-20 W / cm². 2 .
7. The preparation method according to claim 1, characterized in that, During the coating deposition process using high-power pulsed magnetron sputtering, the working gas pressure is 0.2-3.0 Pa; And / or, the coating deposition time is 85-95 min.
8. The preparation method according to claim 1, characterized in that, The substrate includes any one of cemented carbide, silicon wafer, and Zr alloy.
9. The preparation method according to claim 1, characterized in that, The substrate has a bias voltage of 0 to -300V; and / or the substrate has a temperature of room temperature to 500°C.
10. The application of the Zr(N) solid solution structure coating prepared by the preparation method according to any one of claims 1-9 in the wear-resistant and corrosion-resistant protection of metal surfaces.