Coating method of nanocrystalline ZrN coating Hall material
By controlling parameters such as negative bias of the substrate, nanocrystalline ZrN coatings are prepared, which solves the problem of coating performance regulation in the prior art, and achieves precise control of coating performance and the development of high-performance Hall materials.
Patent Information
- Application Number
- CN202510366749.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-26
- Publication Date
- 2025-07-11
AI Technical Summary
It is difficult for the prior art to accurately regulate key parameters such as grain size, growth orientation and residual stress of nanocrystalline ZrN coatings, affecting the overall performance of the coating.
Through the substrate pretreatment, presputtering and ZrN coating deposition processes, parameters such as negative bias of the substrate are controlled, nanocrystalline ZrN coatings with different grain sizes are prepared, and the performance is characterized by tools such as X-ray diffraction and field emission scanning electron microscopy to achieve accurate regulation of coating hardness and other properties.
The authenticity of the anti-Hall-Petch effect in nanocrystalline ZrN coatings is clarified, and nanocrystalline ZrN coatings with specific microstructures can be prepared to achieve precise control of coating performance and provide theoretical guidance to develop high-performance Hall material coatings.
Smart Images
Figure CN120291017A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the technical field of material surface treatment, and particularly relates to a coating method for nanocrystalline ZrN-coated Hall materials. Background Art
[0002] In the field of materials science, it is of great significance to study the influence of grain size on the properties of materials such as hardness. Traditional materials follow the classical Hall-Petch equation, and as the grain size decreases, the hardness increases. However, when the grain size is reduced to the nanoscale, the inverse Hall-Petch effect appears in some materials, that is, the hardness decreases as the grain size decreases. In the research of nanocrystalline hard coatings, the understanding of the inverse Hall-Petch effect is not yet perfect, and there are many problems in previous studies. For example, it is not clear whether this effect is an inherent property of nanocrystalline hard coatings, and other factors affecting the coating hardness are not fully considered, which limits the development and application of high-performance Hall material coatings. At the same time, the existing coating preparation methods have deficiencies in controlling the microstructure and properties of coatings, and it is difficult to accurately regulate key parameters such as the grain size, growth orientation, and residual stress of coatings, thus affecting the comprehensive performance of coatings as Hall materials. Summary of the Invention
[0003] The purpose of this application is to provide a coating method for nanocrystalline ZrN-coated Hall materials to solve the technical problem in the prior art that it is difficult to accurately regulate key parameters such as the grain size, growth orientation, and residual stress of coatings.
[0004] To achieve the above purpose, the technical solution adopted in this application is: to provide a coating method for nanocrystalline ZrN-coated Hall materials, which specifically includes the following steps:
[0005] (1) Substrate pretreatment: The substrate material is ultrasonically cleaned in acetone and ethanol in sequence, and then dried to obtain the target.
[0006] (2) Pre-sputtering treatment: The target is placed in an argon atmosphere, and the sputtering power and gas pressure are set for pre-sputtering to remove impurities on the target surface and obtain the pre-sputtered target.
[0007] (3) ZrN coating deposition: The pre-sputtered target is placed in a mixed atmosphere of argon and nitrogen, the substrate pressure, deposition gas pressure, and DC power are adjusted and applied to the zirconium target; the deposition temperature and nitrogen flow ratio are set, and nanocrystalline ZrN coatings with different grain sizes are prepared by changing the substrate negative bias voltage.
[0008] In one embodiment,
[0009] Coating characterization and property regulation of nanocrystalline ZrN coating are carried out. The specific steps are as follows: measure the thickness of the nanocrystalline ZrN coating to ensure it remains within 1.0 - 1.2 μm; determine the composition of the coating using electron probe microanalysis, analyze the crystal structure and texture coefficient of the coating by X-ray diffraction, measure the residual stress of the coating by the conventional sin2ψ method using Co radiation as the X-ray source, observe the cross-sectional morphology of the coating with a field emission scanning electron microscope, and measure the coating hardness using a nanoindentation instrument with Oliver-Pharr technique; according to the measurement results, analyze the relationship between the microstructure and properties of the coating under different substrate negative biases, and realize the regulation of properties such as coating hardness by adjusting process parameters such as the negative bias.
[0010] In one embodiment,
[0011] The time for ultrasonic cleaning in step (i) is 10 min.
[0012] In one embodiment,
[0013] The time for pre-sputtering in step (ii) is 30 min.
[0014] In one embodiment,
[0015] The sputtering power in step (ii) is 200 W and the gas pressure is 1.0 Pa.
[0016] In one embodiment,
[0017] The purity of argon and nitrogen is 99.999%.
[0018] In one embodiment,
[0019] The substrate pressure in step (iii) is 8.0×10 -4 Pa, the deposition gas pressure is 0.5 Pa, and the DC power is 250 W.
[0020] In one embodiment,
[0021] The purity of the zirconium target in step (iii) is 99.99%.
[0022] In one embodiment,
[0023] The deposition temperature in step (iii) is 300 °C, the nitrogen flow ratio is 20%, and the substrate negative bias is 0 - 150 V.
[0024] In one embodiment,
[0025] The calculation formula for the nitrogen flow ratio in step (iii) is N2 / (N2 + Ar).
[0026] The present application provides a coating method for a nanocrystalline ZrN-coated Hall material. The present application systematically studies the influence of various factors on the coating hardness, eliminates the interference of factors such as porosity, multiphase, chemical composition, texture, and residual stress on the inverse Hall-Petch effect, clarifies the authenticity of the inverse Hall-Petch effect in the nanocrystalline ZrN coating, and provides an experimental basis for deeply understanding the performance of nanocrystalline hard coatings; by precisely controlling parameters such as the substrate negative bias voltage during the magnetron sputtering process, nanocrystalline ZrN coatings with different microstructures can be prepared, and key factors such as the grain size, growth orientation, and residual stress of the coating can be effectively regulated, thereby realizing precise control of the performance such as the hardness of the coating; based on the nanocrystalline ZrN coating prepared in the present application, through the proposed theoretical model based on the dislocation pile-up mechanism, the critical grain size for the transformation between the Hall-Petch effect and the inverse Hall-Petch effect in the coating can be calculated, providing theoretical guidance for the design and preparation of Hall material coatings with specific properties, and helping to develop high-performance Hall material coatings that meet different application requirements. Description of the Drawings
[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.
[0028] Figure 1 It is a flowchart of the coating method. Detailed Embodiments
[0029] In order to make the technical problems to be solved, technical solutions, and beneficial effects of the present application clearer and more understandable, the present application will be further described in detail. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
[0030] Embodiment 1
[0031] As Figure 1 shown, a coating method for a nanocrystalline ZrN-coated Hall material specifically includes the following steps:
[0032] (1). Substrate pretreatment: The mirror-polished cemented carbide substrate material is ultrasonically cleaned in acetone and ethanol for 10 minutes in sequence, dried, and the target is obtained;
[0033] (2). Pre-sputtering treatment: The target is placed in an argon atmosphere with a purity of 99.999%, the sputtering power is set to 200 W, and the gas pressure is 1.0 Pa for pre-sputtering for 30 minutes to remove impurities on the target surface, and the pre-sputtered target is obtained;
[0034] (III) ZrN Coating Deposition: Place the pre-sputtered target in a mixed atmosphere of argon and nitrogen with a purity of 99.999%. Adjust the base pressure to 8.0×10 -4 Pa, the deposition gas pressure to 0.5 Pa, the DC power to 250 W, and apply it to a zirconium target with a purity of 99.99%. Set the deposition temperature to 300 °C, the nitrogen flow ratio to 20%, and the base negative bias voltage to 0 V. A coating with a grain size of 45 nm is obtained, having a certain porosity, and the growth orientation is mainly in the (200) direction;
[0035] (IV) Coating Characterization and Property Regulation: Measure the thickness of the nanocrystalline ZrN coating to be 1.1 μm. Use electron probe microanalysis to determine the composition of the coating, use X-ray diffraction to analyze the crystal structure and texture coefficient of the coating, measure the residual stress of the coating to be 0.50 GPa by the conventional sin2ψ method using Co radiation as the X-ray source, observe the cross-sectional morphology of the coating with a field emission scanning electron microscope, and measure the hardness of the coating to be 19.74 ± 1.25 GPa using the Oliver-Pharr technique with a nanoindentation instrument; at this time, the hardness of the coating conforms to the classical Hall-Petch effect, that is, as the subsequent negative bias voltage increases, the hardness shows an upward trend.
[0036] Example 2
[0037] The difference between this example and Example 1 is that the base negative bias voltage is adjusted to 50 V, and the other operations are the same. After characterization, the coating thickness is still 1.1 μm, the grain size is reduced to about 31.5 nm, the porosity is reduced, the growth orientation begins to change to a random direction, the residual stress increases to 0.90 GPa, and the hardness is increased to 22.60 ± 0.22 GPa; at this stage, the increase in the coating hardness is due to the combined action of various factors such as grain refinement, structural densification, orientation change, and increase in residual stress.
[0038] Example 3
[0039] The difference between this example and Example 1 is that the base negative bias voltage is adjusted to 100 V, and the other operations are the same. After characterization, the deposited coating thickness is 1.1 μm, the grain size is reduced to 19.0 nm, the structure is more dense, the growth orientation is mainly in the (111) direction, the residual stress reaches 4.24 GPa, and the hardness reaches 34.11 ± 0.66 GPa; within the negative bias voltage range of 0 - 100 V, the coating hardness continues to increase, and the enhancing effect of each factor on the hardness is obvious.
[0040] Example 4
[0041] The difference between this example and Example 1 is that the substrate negative bias voltage is adjusted to 125 V, and the remaining operations are the same. After characterization, the coating thickness is 1.1 μm, the grain size is 14.2 nm, presenting a dense equiaxed crystal structure, the residual stress is 7.95 GPa, and the hardness drops to 31.47 ± 0.50 GPa; at this time, the inverse Hall-Petch effect begins to appear. Although the residual stress and the (111) texture coefficient are still increasing, the hardness decreases due to the decrease in grain size.
[0042] Example 5
[0043] The difference between this example and Example 1 is that the substrate negative bias voltage is adjusted to 150 V, and the remaining operations are the same. After characterization, the coating thickness is 1.1 μm, the grain size is about 10 nm, the structure is a dense equiaxed crystal, the residual stress is as high as 13.28 GPa, the hardness further drops to 30.51 ± 0.71 GPa, and the inverse Hall-Petch effect is more significant.
[0044] By comparing Examples 1-5, the influence law of the substrate negative bias voltage on the microstructure and properties of the nanocrystalline ZrN coating can be clearly observed, verifying the effectiveness of the coating method of the present invention in regulating the coating properties.
[0045] The present application provides a coating method for a nanocrystalline ZrN-coated Hall material, specifically including: Substrate pretreatment: The substrate material is ultrasonically cleaned in acetone and ethanol in sequence, and then dried to obtain the target; Pre-sputtering treatment: The target is placed in an argon atmosphere, and the sputtering power and gas pressure are set for pre-sputtering to remove impurities on the surface of the target, obtaining the pre-sputtered target; ZrN coating deposition: The pre-sputtered target is placed in a mixed atmosphere of argon and nitrogen, the substrate pressure, deposition gas pressure, and DC power are adjusted and applied to the zirconium target; The deposition temperature and nitrogen flow ratio are set, and nanocrystalline ZrN coatings with different grain sizes are prepared by changing the substrate negative bias voltage; The present application systematically studies the influence of various factors on the coating hardness, excludes the interference of factors such as porosity, multiphase, chemical composition, texture, and residual stress on the inverse Hall-Petch effect, clarifies the authenticity of the inverse Hall-Petch effect in the nanocrystalline ZrN coating, and provides an experimental basis for deeply understanding the performance of nanocrystalline hard coatings; By precisely controlling parameters such as the substrate negative bias voltage during the magnetron sputtering process, nanocrystalline ZrN coatings with different microstructures can be prepared, and key factors such as the grain size, growth orientation, and residual stress of the coating can be effectively regulated, thereby achieving precise control of the coating properties such as hardness; Based on the nanocrystalline ZrN coating prepared in the present application, through the proposed theoretical model based on the dislocation pile-up mechanism, the critical grain size for the transition between the Hall-Petch effect and the inverse Hall-Petch effect in the coating can be calculated, providing theoretical guidance for designing and preparing Hall material coatings with specific properties, and helping to develop high-performance Hall material coatings that meet different application requirements.
[0046] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present application, "a plurality" means two or more unless otherwise specifically defined.
[0047] The above are only the preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present application shall be included within the protection scope of the present application.
Claims
1. A coating method for a nanocrystalline ZrN-coated Hall material, characterized in that, Specifically, it includes the following steps: (1). Substrate pretreatment: Ultrasonically clean the substrate material successively in acetone and ethanol, and then dry it to obtain the target; (2). Pre-sputtering treatment: Place the target in an argon atmosphere, set the sputtering power and gas pressure for pre-sputtering to remove impurities on the surface of the target and obtain the pre-sputtered target; (3). ZrN coating deposition: Place the pre-sputtered target in a mixed atmosphere of argon and nitrogen, adjust the substrate pressure, deposition gas pressure, DC power and apply it to the zirconium target; Set the deposition temperature and nitrogen flow ratio, and prepare nanocrystalline ZrN coatings with different grain sizes by changing the substrate negative bias voltage.
2. The coating method of a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, Conduct coating characterization and property regulation on the nanocrystalline ZrN coating. The specific steps are as follows: Measure the thickness of the nanocrystalline ZrN coating, and the thickness is 1.0 - 1.2 μm; Use electron probe microanalysis to determine the composition of the coating, X-ray diffraction to analyze the crystal structure and texture coefficient of the coating, use the conventional sin2ψ method with Co radiation as the X-ray source to measure the residual stress of the coating, use a field emission scanning electron microscope to observe the cross-sectional morphology of the coating, and use a nanoindentation instrument with Oliver-Pharr technology to measure the hardness of the coating; According to the measurement results, analyze the relationship between the microstructure and properties of the coating under different substrate negative bias voltages, and realize the regulation of properties such as the hardness of the coating by adjusting process parameters such as the negative bias voltage.
3. The coating method of a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, The time for ultrasonic cleaning in step (1) is 10 min.
4. A coating method for a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, The time for pre-sputtering in step (2) is 30 min.
5. The coating method of a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, The sputtering power in step (2) is 200 W, and the gas pressure is 1.0 Pa.
6. A coating method for a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, The purity of the argon and nitrogen is 99.999%.
7. A coating method for a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, The base pressure in step (III) is 8.0×10 -4 Pa, the deposition gas pressure is 0.5 Pa, and the DC power is 250 W.
8. A coating method for a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that The purity of the zirconium target in step (3) is 99.99%.
9. A coating method for a nanocrystalline ZrN-coated Hall material according to claim 1, characterized in that, The deposition temperature in step (3) is 300 °C, the nitrogen flow ratio is 20%, and the substrate negative bias voltage is 0 - 150 V.
10. The coating method of a nanocrystalline ZrN-coated Hall material according to claim 9, characterized in that, The calculation formula for the nitrogen flow ratio in step (3) is N2 / (N2 + Ar).