A hydrogen barrier wear-resistant coating and a preparation method and application thereof

Abstract

The present application relates to hydrogen protection technical field, especially to a kind of hydrogen barrier wear-resistant coating and its preparation method and application.The present application provides a kind of hydrogen barrier wear-resistant coating, from bottom to top, including the Zr metal bonding layer, periodic nanometer multilayer and chromium nitride top layer that are sequentially stacked;The periodic nanometer multilayer includes CrN ceramic layer and Zr metal layer that are sequentially and alternately stacked on the surface of the Zr metal bonding layer;The material of the Zr metal bonding layer is Zr.The hydrogen barrier wear-resistant coating simultaneously has excellent hydrogen barrier performance and wear resistance.

Description

Technical Field

[0001] This invention relates to the field of hydrogen protection technology, and in particular to a hydrogen-blocking and wear-resistant coating, its preparation method, and its application. Background Technology

[0002] Hydrogen atoms readily diffuse and penetrate into the interior of materials, causing hydrogen damage phenomena such as hydrogen embrittlement, blistering, and corrosion. This not only reduces the service performance and lifespan of hydrogen energy equipment and its key components (such as gas cylinders, pipelines, compressors, valves, and sealing components), but may also lead to destructive failures and pose serious safety hazards.

[0003] Surface coating technology is one of the most economical and effective methods to address hydrogen damage in materials. Applying a multifunctional hydrogen-barrier coating of a certain thickness to the surface of hydrogen-sensitive materials serves as a protective barrier, not only slowing down or preventing hydrogen atom penetration and thus preventing hydrogen embrittlement, but also enhancing the material's wear and corrosion resistance, and improving its suitability for complex hydrogen environments. Currently, hydrogen-barrier coatings mainly include metal (alloy) coatings, metal oxide coatings, metal nitride coatings, and their composite coatings. Commonly used preparation methods include magnetron sputtering, cathodic arc ion plating, plasma spraying, embedding aluminizing, and hot-dip galvanizing. Coatings prepared using existing technologies all exhibit significant hydrogen-barrier protection effects; their actual hydrogen-barrier performance mainly depends on the coating's chemical composition, microstructure, and preparation method.

[0004] The integrity of hydrogen-barrier coatings is crucial for their protective function. In hydrogen environments, surface protection of moving parts requires coatings with not only excellent hydrogen barrier properties but also strong wear resistance and damage resistance to ensure continued protection after friction and wear. Currently, most research focuses on improving the hydrogen barrier properties of coatings, and effective solutions are still lacking for the multifunctional protection required for moving parts surfaces that combine hydrogen barrier and wear resistance. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a hydrogen-blocking and wear-resistant coating, its preparation method and application, wherein the hydrogen-blocking and wear-resistant coating has both excellent hydrogen-blocking performance and wear resistance performance.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a hydrogen-barrier and wear-resistant coating, which, from bottom to top, includes a Zr metal bonding layer, a periodic nano-multilayer layer, and a chromium nitride sealing layer stacked sequentially.

[0008] The periodic nanomultilayer comprises CrN ceramic layers and Zr metal layers alternately stacked sequentially on the surface of the Zr metal bonding layer;

[0009] The Zr metal bonding layer is made of Zr.

[0010] Preferably, the thickness of the Zr metal bonding layer is 8~200 nm;

[0011] The thickness of the chromium nitride sealing layer is 50~300nm;

[0012] The thickness of each CrN ceramic layer in the periodic nanomultilayer is independently 16~300nm;

[0013] The thickness of each Zr metal layer in the periodic nanomultilayer is independently 8~100 nm;

[0014] The total thickness of the periodic nanomultilayer is 0.5~5.0 μm.

[0015] Preferably, the thickness ratio of adjacent CrN ceramic layers and Zr metal layers in the periodic nanomultilayer is (2~15):1, the sum of the thicknesses of two adjacent layers is 24~400nm, and the number of periods is 5~20.

[0016] The present invention also provides a method for preparing the hydrogen-resistant and wear-resistant coating described in the above technical solution, comprising the following steps:

[0017] The hydrogen-barrier and wear-resistant coating is obtained by sequentially sputtering a Zr metal bonding layer, a periodic nanolayer, and a chromium nitride sealing layer on the substrate surface using a high-power pulsed magnetron sputtering method.

[0018] Preferably, the sputtering conditions for sputtering the Zr metal bonding layer are as follows: using zirconium metal as the sputtering target, sputtering power of 3~10kW, argon flow rate of 50~150sccm, substrate pulse bias voltage of -50~-200V, and sputtering time of 5~25min.

[0019] Preferably, the sputtering conditions for sputtering the CrN ceramic layer in the periodic nanomultilayer are as follows: using metallic chromium as the sputtering target, sputtering power of 4~10kW, argon flow rate of 20~150sccm, nitrogen flow rate of 40~100sccm, substrate pulse bias voltage of -50~-200V, and sputtering time of 3~45min.

[0020] Preferably, the sputtering conditions for sputtering the Zr metal layer in the periodic nanomultilayer are as follows: using zirconium metal as the sputtering target, sputtering power of 3~10kW, argon flow rate of 50~150sccm, substrate pulse bias voltage of -50~-200V, and sputtering time of 1~12min.

[0021] Preferably, the sputtering conditions for sputtering the chromium nitride capping layer are as follows: using metallic chromium as the sputtering target, sputtering power of 4~10kW, argon flow rate of 20~150sccm, nitrogen flow rate of 40~100sccm, substrate pulse bias voltage of -50~-200V, and sputtering time of 1~45min.

[0022] Preferably, before sputtering the Zr metal bonding layer, the substrate is further subjected to ion source etching;

[0023] The surface roughness of the substrate is 0.04~0.15μm;

[0024] The etching conditions for the ion source are as follows: argon flow rate of 50~200 sccm, substrate pulse bias voltage of -400~-800V, ion source power of 4~8kW, and etching time of 30~120min.

[0025] The present invention also provides the application of the hydrogen-resistant and wear-resistant coating described in the above technical solution or the hydrogen-resistant and wear-resistant coating prepared by the preparation method described in the above technical solution in the field of surface protection of hydrogen energy equipment components.

[0026] This invention provides a hydrogen-barrier and wear-resistant coating.

[0027] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0028] 1. The hydrogen-resistant and wear-resistant coating of this invention is composed of alternating Zr layers (soft metal layers) and CrN layers (hard ceramic layers), and its interlayer interfaces effectively prevent crack initiation and propagation. Compared with a single CrN layer, this multi-layer structure has higher strength and toughness due to its higher spacing, and can maintain structural integrity under stress, significantly improving the coating's damage resistance in harsh environments;

[0029] 2. The Zr layer in the hydrogen-blocking nano-coating of the present invention can act as a hydrogen trap to capture permeated hydrogen atoms and block their diffusion path to the substrate; at the same time, the multilayer interface can effectively extend the hydrogen atom diffusion path and further enhance the hydrogen-blocking effect.

[0030] 3. Under the action of mechanical stress and frictional heat, the metallic Zr in the hydrogen-resistant and wear-resistant coating of the present invention reacts with hydrogen atoms in situ at the friction interface to generate a self-lubricating ε-ZrH2 phase, which can reduce the interfacial friction and further inhibit the diffusion of hydrogen atoms, thus realizing the synergistic effect of "capture-utilization" of hydrogen atoms.

[0031] The present invention also provides a method for preparing the hydrogen-barrier and wear-resistant coating described in the above technical solution.

[0032] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0033] 1. The preparation method described in this invention uses high-power pulsed magnetron sputtering to overcome the shortcomings of traditional DC magnetron sputtering in forming columnar crystal structures, and solves the problem of large particles being generated by arc ion plating. The resulting coating has a dense and uniform structure with significantly reduced porosity and defects, greatly reducing hydrogen atom diffusion channels and enabling the coating to exhibit superior hydrogen barrier performance.

[0034] 2. The preparation method of the present invention uses high-power pulsed magnetron sputtering to prepare the hydrogen-blocking and wear-resistant coating. The conditions and parameters are controllable, the process is stable, and high-quality coatings can be prepared. Moreover, the entire preparation process is green and environmentally friendly, with no pollutant emissions. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the hydrogen-barrier and wear-resistant coating described in this invention;

[0036] Figure 2 The images show the surface SEM image (a) and cross-sectional SEM image (b) of the hydrogen-resistant and wear-resistant coating described in Example 1.

[0037] Figure 3 The images show the XRD patterns of the hydrogen-resistant and wear-resistant coating described in Example 1 and the hydrogen-resistant and wear-resistant coatings described in Comparative Examples 1 and 2.

[0038] Figure 4 The electrochemical hydrogen permeation curves of the hydrogen-barrier and wear-resistant coating described in Example 1 and the hydrogen-barrier and wear-resistant coatings described in Comparative Examples 1 and 2, and the stainless steel substrate;

[0039] Figure 5 The wear rate of the hydrogen-barrier and wear-resistant coatings described in Example 1 and Comparative Examples 1-2 before and after hydrogen charging by an electrochemical method. Detailed Implementation

[0040] like Figure 1 As shown, the present invention provides a hydrogen-barrier and wear-resistant coating, which, from bottom to top, includes a Zr metal bonding layer, a periodic nano-multilayer layer, and a chromium nitride sealing layer (CrN sealing layer) stacked sequentially.

[0041] The periodic nanomultilayer comprises CrN ceramic layers and Zr metal layers alternately stacked sequentially on the surface of the Zr metal bonding layer;

[0042] The Zr metal bonding layer is made of Zr.

[0043] In this invention, the thickness of the Zr metal bonding layer is preferably 8~200 nm, more preferably 8 nm, 40 nm, 80 nm, 120 nm, 160 nm or 200 nm. In an embodiment of this invention, the thickness of the Zr metal bonding layer can be 8 nm.

[0044] In this invention, the advantage of controlling the thickness of the Zr metal bonding layer within the above-mentioned range is that it has excellent adhesion between the coating and the substrate.

[0045] In this invention, the thickness of the chromium nitride sealing layer is preferably 50-300 nm, more preferably 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, or 300 nm. In an embodiment of this invention, the thickness of the chromium nitride sealing layer can be 100 nm.

[0046] In this invention, the advantage of controlling the thickness of the chromium nitride sealing layer within the above-mentioned range is that it simultaneously possesses excellent wear resistance and hydrogen barrier properties.

[0047] In this invention, the thickness of each CrN ceramic layer in the periodic nanomultilayer is preferably 16-300 nm, more preferably 16 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, or 300 nm; the thickness of each Zr metal layer in the periodic nanomultilayer is preferably 8-100 nm, more preferably 8 nm, 20 nm, 40 nm, 60 nm, 80 nm, or 100 nm; the total thickness of the periodic nanomultilayer is preferably 0.5-5.0 μm. In embodiments of this invention, the thickness of each CrN ceramic layer in the periodic nanomultilayer can be 100 nm, the thickness of each Zr metal layer in the periodic nanomultilayer can be 8 nm, 16 nm, or 24 nm; the total thickness of the periodic nanomultilayer can be 108 nm, 116 nm, or 124 nm.

[0048] In this invention, the advantage of controlling the thickness of each CrN ceramic layer and Zr metal layer in the periodic nanomultilayer within the above-mentioned range is that it has excellent hydrogen barrier properties, mechanical properties and bonding strength.

[0049] In this invention, the thickness ratio of adjacent CrN ceramic layers and Zr metal layers in the periodic nanomultilayer is preferably (2~15):1, more preferably 2:1, 4.17:1, 6.25:1, 8:1, 10:1, 12.5:1, 14:1 or 15:1; the sum of the thicknesses of two adjacent layers is preferably 24~400 nm, more preferably 24 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm or 400 nm; the number of periods is preferably 5~20. In embodiments of this invention, the thickness ratio of CrN ceramic layers and Zr metal layers in the periodic nanomultilayer can be 4.17:1, 6.25:1 or 12.5:1, the sum of the thicknesses of two adjacent layers can be 108 nm, 124 nm or 116 nm, and the number of periods can be 6 or 7.

[0050] In this invention, the advantage of controlling the thickness ratio, the sum of the thicknesses of two adjacent layers, and the number of cycles within the above-mentioned range is that it generates a synergistic enhancement effect and optimizes the coating performance.

[0051] The present invention also provides a method for preparing the hydrogen-resistant and wear-resistant coating described in the above technical solution, comprising the following steps:

[0052] The hydrogen-barrier and wear-resistant coating is obtained by sequentially sputtering a Zr metal bonding layer, a periodic nanolayer, and a chromium nitride sealing layer on the substrate surface using a high-power pulsed magnetron sputtering method.

[0053] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0054] In this invention, the substrate is preferably a stainless steel substrate. This invention does not impose any special limitations on the type of stainless steel substrate; any type well-known to those skilled in the art can be used.

[0055] Before sputtering the Zr metal bonding layer, the present invention preferably performs the following steps sequentially: grinding, polishing, cleaning, drying, and ion source etching on the substrate. In this invention, the grinding is preferably performed by mechanically grinding the substrate with silicon carbide sandpaper of 200 grit, 400 grit, 800 grit, 1600 grit, and 3000 grit. In this invention, the polishing is preferably performed by sequentially polishing with velvet polishing cloth and diamond polishing fluid. The present invention does not impose any special limitations on the conditions and parameters of the mechanical grinding and polishing; conditions and parameters well known to those skilled in the art are sufficient to achieve a surface roughness of the substrate within the range of 0.04~0.15 μm. In this invention, the cleaning preferably includes ultrasonic cleaning for 30 minutes each with ultrapure water, acetone, and anhydrous ethanol. In this invention, the drying is preferably vacuum drying, with the vacuum drying temperature preferably at 60°C and the drying time preferably at 5 hours.

[0056] In this invention, the preferred etching conditions for the ion source are: argon flow rate preferably 50~200 sccm, more preferably 50 sccm, 100 sccm, 150 sccm or 200 sccm; substrate pulse bias preferably -400~-800V, more preferably -400V, -500V, -600V, -700V or -800V; ion source power preferably 4~8kW, more preferably 4kW, 5kW, 6kW, 7kW or 8kW; etching time preferably 30~120min, more preferably 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min. In an embodiment of this invention, the argon flow rate can be 80 sccm, the substrate pulse bias can be -450V, the ion source power is 6kW, and the etching time is 30min.

[0057] In an embodiment of the present invention, the specific process of the ion source etching can be as follows: clamp the substrate on the rotating frame, turn on the vacuum pump system of mechanical pump + Roots pump + molecular pump to pump the gas pressure in the vacuum chamber to below 5×10-3 Pa, heat the vacuum chamber to 200°C at the same time, introduce argon gas into the vacuum chamber, apply bias voltage to the substrate, turn on the ion source power supply, set the ion source power, and use high-energy argon ions to bombard and etch the substrate.

[0058] In this invention, the ion source etching is used to remove the oxide layer on the surface of the substrate.

[0059] In this invention, the sputtering conditions for sputtering the Zr metal bonding layer are preferably as follows: using zirconium metal as the sputtering target, the sputtering power is preferably 3~10kW, more preferably 3kW, 4kW, 5kW, 6kW, 7kW, 8kW, 9kW, or 10kW; the argon flow rate is preferably 50~150sccm, more preferably 50sccm, 80sccm, 110sccm, 130sccm, or 150sccm; the substrate pulse bias voltage is preferably -50~-200V, more preferably -50V, -80V, -110V, -140V, -170V, or -200V; and the sputtering time is preferably 5~25min, more preferably 5min, 10min, 15min, or 20min. In an embodiment of this invention, the sputtering conditions for sputtering the Zr metal bonding layer can be: a sputtering power of 5kW, an argon flow rate of 100sccm, a substrate pulse bias voltage of -100V, and a sputtering time of 1min.

[0060] In an embodiment of the present invention, the process of sputtering the Zr metal bonding layer can be as follows: turn off the ion source of the anode layer, adjust the flow rate of the introduced argon gas to the above-mentioned flow rate range, apply a bias voltage to the substrate, turn on the high-power pulsed magnetron sputtering Zr target power supply, set the sputtering power, and perform sputtering.

[0061] In this invention, the advantage of setting the sputtering conditions of the Zr metal bonding layer within the above-mentioned range is that it forms a dense, defect-free structure.

[0062] In this invention, the sputtering conditions for sputtering the CrN ceramic layer in the periodic nanomultilayer are preferably as follows: using metallic chromium as the sputtering target, the sputtering power is preferably 4~10kW, more preferably 4kW, 5kW, 6kW, 7kW, 8kW, 9kW or 10kW; the argon flow rate is preferably 20~150sccm, more preferably 20sccm, 40sccm, 60sccm, 80sccm, 100sccm, 120sccm, 140sccm or 150sccm; the nitrogen flow rate is preferably 40~1 The sputtering voltage is preferably 40 sccm, 60 sccm, 80 sccm, or 100 sccm; the substrate pulse bias voltage is preferably -50 to -200V, more preferably -50V, -70V, -90V, -110V, -130V, -150V, -170V, -190V, or -200V; the sputtering time is preferably 3 to 45 min, more preferably 3 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, or 40 min. In an embodiment of the present invention, the sputtering power for sputtering the CrN ceramic layer is 5 kW, the argon flow rate is 100 sccm, the nitrogen flow rate is 100 sccm, the substrate pulse bias voltage is -100V, and the sputtering time can be 15 min.

[0063] In this invention, the advantage of setting the sputtering conditions of the CrN ceramic layer within the above-mentioned range is that it ensures the high purity of the coating's chemical composition.

[0064] In this invention, the sputtering conditions for sputtering the Zr metal layer in the periodic nanomultilayer are preferably as follows: using zirconium metal as the sputtering target, the sputtering power is preferably 3~10kW, more preferably 3kW, 4kW, 5kW, 6kW, 7kW, 8kW, 9kW or 10kW; the argon flow rate is preferably 50~150sccm, more preferably 50sccm, 60sccm, 70sccm, 80sccm, 90sccm, 100sccm, 110sccm, 120sccm, 130sccm, 140sccm or 150sccm; the substrate pulse bias voltage is preferably -50~-200V, more preferably -50V, -100V, -150V or -200V; and the sputtering time is preferably 1~12min, more preferably 1min, 2min, 4min, 6min, 8min, 10min or 12min. In an embodiment of the present invention, the sputtering power of the Zr metal layer is 5kW, the argon flow rate is 100sccm, the substrate pulse bias voltage is -100V, and the sputtering time can be 1min, 2min or 3min.

[0065] In this invention, the advantage of controlling the sputtering conditions of the Zr metal layer within the above-mentioned range is that it effectively controls the crystal structure of the metal layer, which is beneficial to inducing the preferential growth of the subsequent ceramic layer.

[0066] After obtaining the Zr metal layer by sputtering, the present invention preferably includes repeating the above-described process of sputtering the CrN ceramic layer and the Zr metal layer. The number of repetitions is preferably 4 to 19, more preferably 4, 6, 7, 10, 12, 14, 16, 18, or 19. In embodiments of the present invention, the number of repetitions can be 6 or 7.

[0067] In this invention, the sputtering conditions for sputtering the chromium nitride capping layer are preferably as follows: using metallic chromium as the sputtering target, the sputtering power is preferably 4~10kW, more preferably 4kW, 6kW, 8kW or 10kW; the argon flow rate is preferably 20~150sccm, more preferably 20sccm, 40sccm, 60sccm, 80sccm, 100sccm, 120sccm, 140sccm or 150sccm; the nitrogen flow rate is preferably 40~100sccm, more preferably 40sccm, 60sccm, 80sccm or 100sccm; the substrate pulse bias voltage is preferably -50~-200V, more preferably -50V, -100V, -150V or -200V; and the sputtering time is preferably 8~45min, more preferably 8min, 10min, 15min, 20min, 25min, 30min, 35min, 40min or 45min. In an embodiment of the present invention, the sputtering power of the chromium nitride capping layer is 5kW, the argon flow rate is 100sccm, the nitrogen flow rate is 100sccm, the substrate pulse bias voltage is -100V, and the sputtering time is 15min.

[0068] In this invention, the advantage of controlling the sputtering conditions of the chromium nitride sealing layer within the above-mentioned range is that it enables the optimization of surface functional properties.

[0069] This invention also provides the application of the hydrogen-resistant and wear-resistant coating described in the above-described technical solutions, or the hydrogen-resistant and wear-resistant coating prepared by the preparation method described in the above-described technical solutions, in the field of surface protection of hydrogen energy equipment components. This invention does not impose any special limitations on the method of application; any method well-known to those skilled in the art can be used.

[0070] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0071] Example 1

[0072] The stainless steel substrate (SS316L) was mechanically polished stepwise using silicon carbide sandpaper of 200 grit, 400 grit, 800 grit, 1600 grit and 3000 grit. The stainless steel substrate was polished to a mirror finish (roughness less than 0.15 μm) using velvet polishing cloth and diamond polishing liquid. Then, the polished stainless steel substrate was ultrasonically cleaned for 30 min each using ultrapure water, acetone and anhydrous ethanol respectively. It was then vacuum dried at 60℃ for 5 h to obtain the pretreated substrate.

[0073] The pretreated matrix is ​​clamped onto the rotating frame, and the vacuum pumping system consisting of a mechanical pump, a Roots pump, and a molecular pump is turned on to pump the air pressure in the vacuum chamber to 5 × 10⁻⁶. -3 Below Pa, the vacuum chamber is heated to 200°C, 80 sccm of argon gas is introduced into the vacuum chamber, a pulse bias voltage of -450V is applied to the substrate, the ion source power is turned on, the ion source power is set to 6kW, and the substrate is etched by high-energy argon ions for 30 minutes to remove the surface oxide layer.

[0074] Turn off the ion source of the anode layer, increase the flow rate of the introduced argon gas to 100 sccm, apply a pulse bias voltage of -100V to the substrate, turn on the high-power pulsed magnetron sputtering Zr target power supply, set the sputtering power to 5kW, and sputter on the substrate surface for 1 min to obtain a metal Zr bonding layer (thickness of 8nm).

[0075] Turn off the Zr sputtering target, maintain the substrate bias voltage at -100V, maintain 100sccm of argon gas, and introduce 100sccm of nitrogen gas. Turn on the high-power pulsed magnetron sputtering Cr target power supply, set the sputtering power to 5kW, and perform reaction sputtering on the metal Zr bonding layer for 15min to obtain a CrN ceramic layer (thickness of 100nm).

[0076] Turn off the Cr sputtering target, turn on the high-power pulsed magnetron sputtering Zr target power supply, set the sputtering power to 5kW, maintain the argon flow rate at 100sccm, maintain the pulse bias voltage of -100V, sputter for 1min, and obtain a Zr metal layer (thickness of 8nm).

[0077] The CrN ceramic layer and Zr metal layer are taken as one cycle. The above sputtering process of CrN ceramic layer and Zr metal layer is repeated 7 times. The thickness ratio of CrN ceramic layer and Zr metal layer is 12.5:1. The sum of the thickness of two adjacent layers is 108 nm, forming a periodic nanomultilayer.

[0078] With the Zr sputtering target turned off, the substrate pulse bias voltage was maintained at -100V, the argon flow rate at 100sccm, and the nitrogen flow rate at 100sccm. The high-power pulsed magnetron sputtering power supply for the Cr target was turned on, and the sputtering power was set to 5kW. Sputtering was performed for 15 minutes to obtain a chromium nitride capping layer (100nm thick), ultimately resulting in a hydrogen-barrier and wear-resistant coating.

[0079] Figure 2 The images shown are the surface SEM image (a) and cross-sectional SEM image (b) of the hydrogen-barrier and wear-resistant coating. Figure 2 It can be seen that the surface of the chromium nitride capping layer is flat and dense, and the cross-sectional structure of the periodic nano-multilayer is dense, with obvious cross-sectional structure and no columnar crystal structure.

[0080] Example 2

[0081] Referring to Example 1, the difference is that the sputtering time of the Zr metal layer is 2 minutes, and the resulting Zr metal layer (thickness is 16 nm) is obtained; the above sputtering process of CrN ceramic layer and Zr metal layer is repeated 6 times, the thickness ratio of CrN ceramic layer to Zr metal layer is 6.25:1, and the sum of the thicknesses of adjacent layers is 116 nm, forming a periodic nano-multilayer, and finally a hydrogen-barrier and wear-resistant coating is obtained.

[0082] Example 3

[0083] Referring to Example 1, the difference is that the sputtering time of the Zr metal layer is 3 minutes, and the resulting Zr metal layer (thickness is 24 nm) is obtained; the above sputtering process of CrN ceramic layer and Zr metal layer is repeated 6 times, the thickness ratio of CrN ceramic layer and Zr metal layer is 4.17:1, and the sum of the thicknesses of adjacent layers is 124 nm, forming a periodic nano-multilayer, and finally a hydrogen-barrier and wear-resistant coating is obtained.

[0084] Comparative Example 1

[0085] Referring to Example 1, the difference is that the metal Zr bonding layer is replaced with a metal Ti bonding layer (thickness of 8 nm), the zirconium target is replaced with a titanium target during the preparation process, and the sputtering time is 3 min; a Ti metal layer (thickness of 8 nm) is sputtered on the surface of the CrN ceramic layer, the Zr target is replaced with a Ti target during the preparation process, and the sputtering time is 3 min; by repeating the above sputtering process of the CrN ceramic layer and the Ti metal layer 7 times, the thickness ratio of the CrN ceramic layer and the Zr metal layer is 12.5:1, and the sum of the thicknesses of the two adjacent layers is 108 nm, forming a periodic nanomultilayer, and finally a hydrogen-barrier and wear-resistant coating is obtained.

[0086] Comparative Example 2

[0087] Referring to Example 1, the difference is that the metal Zr bonding layer is replaced with a metal Cr bonding layer (thickness of 8 nm), the zirconium target is replaced with a Cr target during the preparation process, and the sputtering time is 40 s; a Cr metal layer (thickness of 8 nm) is sputtered on the surface of the CrN ceramic layer, the Zr target is replaced with a Cr target during the preparation process, and the sputtering time is 40 s; by repeating the above sputtering process of the CrN ceramic layer and the Cr metal layer 7 times, the thickness ratio of the CrN ceramic layer and the Cr metal layer is 12.5:1, and the sum of the thicknesses of the two adjacent layers is 108 nm, forming a periodic nanolayer, and finally a hydrogen-barrier and wear-resistant coating is obtained.

[0088] Figure 3 The images shown are XRD patterns of the hydrogen-resistant and wear-resistant coating described in Example 1 and the hydrogen-resistant and wear-resistant coatings described in Comparative Examples 1 and 2. Figure 3 It can be seen that the CrN ceramic layer in the hydrogen-barrier and wear-resistant coating described in Example 1 and the hydrogen-barrier and wear-resistant coating described in Comparative Examples 1 and 2 are both face-centered CrN ceramics. In addition, the reason why no metal layer was observed in XRD is that the content of the metal layer is less than 10% of the coating.

[0089] Figure 4 The electrochemical hydrogen permeation curves of the hydrogen-blocking and wear-resistant coating described in Example 1 and the hydrogen-blocking and wear-resistant coatings described in Comparative Examples 1 and 2, and the stainless steel substrate, are obtained from... Figure 4 It can be seen that the hydrogen-blocking composite coatings described in Example 1 and Comparative Examples 1-2 all reduced the steady-state current density of the stainless steel substrate. However, the steady-state current density of Example 1 is smaller than that of Comparative Examples 1-2, which proves that the hydrogen-blocking wear-resistant coating described in this invention has better hydrogen-blocking performance.

[0090] The hydrogen-barrier and wear-resistant coatings described in Example 1 and Comparative Examples 1-2 were subjected to a 0.2 mol / L NaOH + 3 g / L CH4N2S solution at a flow rate of 100 mA / cm². 2 After electrochemical hydrogenation at a current density of 24 h, a tribological test was conducted. The friction pair consisted of an alumina ball with a diameter of φ6 mm, the load was 5 N, and the test time was 60 min.

[0091] Figure 5 The wear rate of the hydrogen-barrier and wear-resistant coatings described in Example 1 and Comparative Examples 1-2 before and after hydrogen charging by an electrochemical method is given by... Figure 5 It can be seen that the wear rate of the hydrogen-blocking and wear-resistant coating described in Example 1 after hydrogenation is lower than that of Comparative Examples 1 and 2, indicating that the hydrogen-blocking and wear-resistant coating described in this invention has good wear resistance.

[0092] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A hydrogen barrier wear resistant coating, characterized in that, From bottom to top, comprising Zr metal bonding layer, periodic nanometer multilayer and chromium nitride capping layer which are sequentially stacked; The periodic nanometer multilayer comprises CrN ceramic layers and Zr metal layers which are sequentially and alternately stacked on the surface of the Zr metal bonding layer; The material of the Zr metal bonding layer is Zr; The thickness of the Zr metal bonding layer is 8-200 nm; The thickness of the chromium nitride capping layer is 50-300 nm; The thickness of each CrN ceramic layer in the periodic nanometer multilayer is independently 16-300 nm; The thickness of each Zr metal layer in the periodic nanometer multilayer is independently 8-100 nm; The total thickness of the periodic nanometer multilayer is 0.5-5.0 μm; The thickness ratio of adjacent CrN ceramic layer and Zr metal layer in the periodic nanometer multilayer is (4.17-12.5):1, the sum of the thickness of adjacent two layers is 24-400 nm, and the number of periods is 6-7; The preparation method of the hydrogen-resistant wear-resistant coating is high-power pulsed magnetron sputtering method.

2. The method of claim 1 wherein the hydrogen barrier wear resistant coating is prepared by, The method comprises the following steps: The Zr metal bonding layer, the periodic nanometer multilayer and the chromium nitride capping layer are sequentially sputtered on the surface of the substrate by high-power pulsed magnetron sputtering method to obtain the hydrogen-resistant wear-resistant coating.

3. The production method according to claim 2, wherein The sputtering conditions of the Zr metal bonding layer are as follows: using metal zirconium as sputtering target material, sputtering power is 3-10 kW, argon flow rate is 50-150 sccm, substrate pulse bias is -50--200 V, and sputtering time is 5-25 min.

4. The production method according to claim 2, wherein The sputtering conditions of the CrN ceramic layer in the periodic nanometer multilayer are as follows: using metal chromium as sputtering target material, sputtering power is 4-10 kW, argon flow rate is 20-150 sccm, nitrogen flow rate is 40-100 sccm, substrate pulse bias is -50--200 V, and sputtering time is 3-45 min.

5. The production method according to claim 2, wherein The sputtering conditions of the Zr metal layer in the periodic nanometer multilayer are as follows: using metal zirconium as sputtering target material, sputtering power is 3-10 kW, argon flow rate is 50-150 sccm, substrate pulse bias is -50--200 V, and sputtering time is 1-12 min.

6. The production method according to claim 2, wherein The sputtering conditions of the chromium nitride capping layer are as follows: using metal chromium as sputtering target material, sputtering power is 4-10 kW, argon flow rate is 20-150 sccm, nitrogen flow rate is 40-100 sccm, substrate pulse bias is -50--200 V, and sputtering time is 8-45 min.

7. The method according to any one of claims 2 to 6, wherein the method is carried out at a temperature of from 20 to 100°C. Before sputtering the Zr metal bonding layer, the method further comprises ion source etching the substrate; The surface roughness of the substrate is 0.04-0.15 μm; The conditions of the ion source etching are as follows: argon flow rate is 50-200 sccm, substrate pulse bias is -400--800 V, ion source power is 4-8 kW, and etching time is 30-120 min.

8. The hydrogen-resistant wear-resistant coating of claim 1 or the hydrogen-resistant wear-resistant coating prepared by the method of any one of claims 2-7 is applied in the field of surface protection of hydrogen energy equipment components.

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