Preparation method of SiO2 and Al2O3 composite hydrogen-resistant coating for hydrogen delivery pipeline based on radio frequency magnetron sputtering

Abstract

The invention belongs to the technical field of hydrogen resistance of hydrogen conveying pipelines, and particularly relates to a preparation method of a SiO2 and Al2O3 composite hydrogen resistance coating for a hydrogen conveying pipeline based on radio frequency magnetron sputtering. According to the preparation method, the SiO2 and alpha-Al2O3 composite hydrogen-resistant coating is prepared on the surface of a hydrogen conveying pipeline base material through a radio frequency magnetron sputtering method. The preparation method of the composite coating provided by the invention is simple and easy to implement and low in preparation cost, and the prepared composite hydrogen-resistant coating is uniform in particle, compact in structure, excellent in hydrogen-resistant performance and tight in interface bonding, and can be prepared by modifying various materials and utilizing radio frequency magnetron sputtering.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogen barrier for hydrogen transmission pipelines, and specifically relates to a method for preparing a SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering. Background Art

[0002] Hydrogen storage and transportation technology is a key link in the utilization of hydrogen energy. At present, the main methods of hydrogen transportation include long-tube trailer gas transportation, pipeline transportation, solid transportation and liquid hydrogen transportation. Among them, pipeline transportation is the safest, most efficient and economical method. Hydrogen has a strong permeability and can quickly penetrate almost all metal materials and cause hydrogen embrittlement, resulting in unpredictable brittle fracture of materials under conditions far below the design strain, bringing immeasurable accident hazards to human life safety, property safety, ecological environment, etc. Therefore, in view of the current situation that the hydrogen permeation rate of existing pipeline steel materials is high and hydrogen embrittlement is prone to occur, it is of great practical significance to cover the surface with hydrogen-barrier ceramic coating to solve the problems of hydrogen permeation and hydrogen embrittlement.

[0003] At present, the development of anti-hydrogen embrittlement and hydrogen barrier coatings is still in its infancy. The solution to hydrogen embrittlement in hydrogen pipelines is to use low-grade pipeline steel to replace high-grade pipeline steel for small-caliber, low-pressure transportation, which cannot meet the needs of large-scale hydrogen transportation and use in the future. Therefore, it is very important to find a method to resist hydrogen and block hydrogen for high-grade pipeline steel.

[0004] The present invention aims to develop a safe, reliable, economical, hydrogen-barrier coating with excellent hydrogen barrier properties and tight interface bonding, which can change the problems of high hydrogen permeation rate and high hydrogen embrittlement sensitivity of traditional high-grade steel pipelines, and can ensure that hydrogen pipelines do not suffer from hydrogen embrittlement fractures. This not only greatly saves manpower, material and financial resources, but also ensures the service safety of hydrogen pipelines. Summary of the invention

[0005] In order to solve the deficiencies of the prior art, the present invention provides a method for preparing a composite hydrogen barrier coating of SiO2 and Al2O3 for hydrogen transmission pipelines based on radio frequency magnetron sputtering. The preparation method of the composite coating provided by the present invention is simple and easy, with low preparation cost. The prepared composite hydrogen barrier coating has uniform particles, dense structure, excellent hydrogen barrier performance, and tight interface bonding. It can be prepared by modifying a variety of materials and using radio frequency magnetron sputtering.

[0006] The technical solution provided by the present invention is as follows:

[0007] A method for preparing a SiO2 and Al2O3 composite hydrogen barrier coating for a hydrogen pipeline based on radio frequency magnetron sputtering comprises the following steps: preparing a SiO2 and α-Al2O3 composite hydrogen barrier coating on the surface of a hydrogen pipeline substrate by radio frequency magnetron sputtering.

[0008] The above technical solution uses the radio frequency magnetron sputtering method to prepare a SiO2 and α-Al2O3 composite hydrogen barrier coating on the surface of the hydrogen pipeline substrate, which can form a sandwich composite structure of substrate material-SiO2-α-Al2O3. The composite hydrogen barrier coating prepared by this method has uniform particles, dense structure, excellent hydrogen barrier performance, and tight interface bonding.

[0009] The preparation method of the SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen pipeline based on radio frequency magnetron sputtering specifically comprises the following steps:

[0010] 1) The pipe to be treated is ground and polished before coating is prepared, and then the pipe is ultrasonically cleaned with acetone and alcohol, and then dried;

[0011] 2) preparing SiO2 coating on the base material of the tube by radio frequency magnetron sputtering method;

[0012] 3) Prepare α-Al2O3 coating on SiO2 coating using radio frequency magnetron sputtering method.

[0013] Specifically, in the RF magnetron sputtering method: the target materials are Si target materials with a purity of 99.99% and Al target materials with a purity of 99.99%, the ignition gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%.

[0014] Specifically, in the RF magnetron sputtering method, the RF power source adopts a SY type RF power source with a power of 150 to 200 W, and the vacuum degree is ≥ 4*10 -3 Pa, sputtering power is 50-160W, sputtering gas pressure is 0.25-2Pa, O2 / Ar gas mixing ratio is in the range of 1:10-1:5, and the heating temperature of the tube substrate is 400-600℃.

[0015] Preferably, in the step 2):

[0016] The SiO2 coating is prepared on the base material of the tube by using the radio frequency magnetron sputtering method. The target material is a Si target with a purity of 99.99%, the ignition gas is an Ar gas with a purity of 99.99%, and the reaction gas is an O2 gas with a purity of 99.99%.

[0017] Vacuum degree ≥4*10 -3 Pa, sputtering power 70 ~ 120W, sputtering gas pressure 0.25 ~ 1.5Pa, O2 / Ar gas mixing ratio in the range of (1:10) ~ (1:5), tube substrate heating temperature 400 ~ 500 ℃;

[0018] The deposition rate of the SiO2 coating is 150nm / h~253nm / h, and the thickness of the prepared SiO2 is 50-122nm.

[0019] Preferably, in the step 3):

[0020] The α-Al2O3 coating was prepared on the SiO2 coating by radio frequency magnetron sputtering. The target material was an Al target with a purity of 99.99%, the ignition gas was an Ar gas with a purity of 99.99%, and the reaction gas was an O2 gas with a purity of 99.99%.

[0021] Vacuum degree ≥4*10 -3 Pa, sputtering power 50 ~ 160W, sputtering gas pressure is 1 ~ 2Pa, O2 / Ar gas mixing ratio is in the range of 1:10) ~ (1:5), and the heating temperature of the tube substrate is 500 ~ 600℃;

[0022] The deposition rate of the α-Al2O3 coating is 89nm / h-140nm / h, and the thickness of the prepared α-Al2O3 is 120-172nm.

[0023] Specifically, the hydrogen pipeline is selected from X52 carbon pipeline steel, X65 carbon pipeline steel, X70 carbon pipeline steel, X80 carbon pipeline steel, 304 stainless steel pipeline or 316 stainless steel pipeline.

[0024] Based on the above technical solution, SiO2 and Al2O3 composite hydrogen barrier coatings can be formed on hydrogen pipelines made of various materials based on radio frequency magnetron sputtering, which has a wide range of applications.

[0025] The present invention also provides a hydrogen transmission pipeline prepared according to the above preparation method.

[0026] Specifically, the structure of the pipeline includes a base material, a SiO2 layer deposited on the base material, and an α-Al2O3 layer deposited on the SiO2 layer.

[0027] Specifically, the composite hydrogen barrier coating has a dense structure, a close bond between the base material and SiO2, and between SiO2 and α-Al2O3 interfaces, and a membrane-base bonding force of 8.5 to 16 N. The hydrogen permeation activation energy is 146.2 to 177.9 kJ. / mol, and the hydrogen permeation pressure index is 0.73 to 0.91.

[0028] The beneficial effects of the present invention are:

[0029] The present invention provides a method for preparing a composite hydrogen barrier coating of SiO2 and Al2O3 for hydrogen pipelines based on radio frequency magnetron sputtering, which is simple and easy to prepare with low preparation cost. The composite hydrogen barrier coating has a dense structure, and the interface between the base material and SiO2, and between SiO2 and α-Al2O3 is tightly bonded, and the membrane-base bonding force can reach more than 8.5N. The hydrogen permeation activation energy is 146.2-177.9 kJ. / mol, and the hydrogen permeation pressure index is 0.73-0.91, which can greatly reduce the hydrogen permeation and hydrogen embrittlement problems of hydrogen pipelines, and ensure the service safety of hydrogen pipelines. DETAILED DESCRIPTION

[0030] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0031] Example 1

[0032] This embodiment provides a specific preparation process of a SiO2 coating:

[0033] The SiO2 coating is prepared on the X80 pipeline steel substrate by radio frequency magnetron sputtering. The target material is Si (99.99%) target, the ignition gas is 99.99% pure Ar gas, and the reaction gas is 99.99% pure O2 gas. Vacuum degree ≥ 4*10 -3 Pa, sputtering power 80W, sputtering pressure 1Pa, O2 / Ar gas mixing ratio 1:10, tube substrate heating temperature 400°C. The deposition rate of SiO2 coating is 150nm / h, and the prepared SiO2 thickness is 62nm.

[0034] Example 2

[0035] This embodiment provides a specific preparation process of a SiO2 coating:

[0036] The SiO2 coating is prepared on the X52 pipeline steel substrate by radio frequency magnetron sputtering. The target material is Si (99.99%) target, the ignition gas is 99.99% pure Ar gas, and the reaction gas is 99.99% pure O2 gas. Vacuum degree ≥ 4*10 -3 Pa, sputtering power 100W, sputtering pressure 1.5Pa, O2 / Ar gas mixing ratio 1:10, tube substrate heating temperature 500℃. The deposition rate of SiO2 coating is 174nm / h, and the prepared SiO2 thickness is 97nm.

[0037] Example 3

[0038] This embodiment provides a specific preparation process for preparing an α-Al2O3 coating on the surface of L360QS ground gathering and transportation pipeline steel after coating the SiO2 coating on the surface:

[0039] The α-Al2O3 coating is prepared on the SiO2 coating by radio frequency magnetron sputtering. The target material is Al (99.99%) target, the ignition gas is 99.99% pure Ar gas, and the reaction gas is 99.99% pure O2 gas. Vacuum degree ≥4*10 -3 Pa, sputtering power 120W, sputtering pressure 2Pa, O2 / Ar gas mixing ratio 1:5, tube substrate heating temperature 600°C. The deposition rate of α-Al2O3 coating is 89nm / h, and the thickness of prepared α-Al2O3 is 125nm.

[0040] Example 4

[0041] This embodiment provides a specific preparation process for preparing an α-Al2O3 coating on the surface of an X80 pipeline steel by coating a SiO2 coating:

[0042] The α-Al2O3 coating is prepared on the SiO2 coating by radio frequency magnetron sputtering. The target material is Al (99.99%) target, the ignition gas is 99.99% pure Ar gas, and the reaction gas is 99.99% pure O2 gas. Vacuum degree ≥4*10 -3 Pa, sputtering power 145W, sputtering pressure 1.8Pa, O2 / Ar gas mixing ratio 1:5, tube substrate heating temperature 550°C. The deposition rate of α-Al2O3 coating is 92nm / h, and the thickness of the prepared α-Al2O3 is 139nm.

[0043] Example 5

[0044] Preparation process of SiO2 / α-Al2O3 composite hydrogen barrier coating in this embodiment:

[0045] For Examples 3 and 4, after the composite coating is prepared, the sandwich composite structure of the substrate material-SiO2-α-Al2O3 is subjected to stress relief annealing at 200°C for 1h. The prepared composite coating has a dense structure, and the substrate material and SiO2, SiO2 and α-Al2O3 interfaces are tightly bonded. The scratching method is used for testing, and the membrane-base bonding force is about 8.5N respectively. The hydrogen permeation activation energy is 146.2-177.9 kJ. / mol, and the hydrogen permeation pressure index is 0.73-0.91.

[0046] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A preparation method of a SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering, characterized in that, It includes the following steps: Prepare a SiO2 and α-Al2O3 composite hydrogen-blocking coating on the surface of the hydrogen transmission pipeline substrate by radio frequency magnetron sputtering.

2. The preparation method of the SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering according to claim 1, characterized in that, Specifically, it includes the following steps: 1) Grind and polish the pipeline to be treated before coating preparation, then ultrasonically clean the pipe material with acetone and alcohol, and then perform drying treatment; 2) Prepare a SiO2 coating on the matrix material of the pipe by radio frequency magnetron sputtering; 3) Prepare an α-Al2O3 coating on the SiO2 coating by radio frequency magnetron sputtering.

3. The preparation method of the SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering according to claim 2, characterized in that, In the radio frequency magnetron sputtering method: the target materials are Si target with a purity of 99.99% and Al target with a purity of 99.99%, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%.

4. The preparation method of the SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering according to claim 2, characterized in that, In the radio frequency magnetron sputtering method: an SY type radio frequency power source with a power of 150 - 200 W is used for the radio frequency power supply, the vacuum degree is ≥ 4 * 10 -3 Pa, the sputtering power is 50 - 160 W, the sputtering gas pressure is 0.25 - 2 Pa, the O2 / Ar gas mixing ratio is in the range of 1:10 - 1:5, and the heating temperature of the pipe substrate is 400 - 600 °C.

5. The preparation method of the SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering according to claim 2, characterized in that, In step 2): Prepare a SiO2 coating on the matrix material of the pipe by radio frequency magnetron sputtering. The target material is Si target with a purity of 99.99%, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%; Vacuum degree ≥ 4 * 10 -3 Pa, sputtering power 70 - 120 W, sputtering gas pressure 0.25 - 1.5 Pa, O2 / Ar gas mixing ratio in the range of (1:10) - (1:5), and the heating temperature of the pipe substrate is 400 - 500 °C; The deposition rate of the SiO2 coating is 150nm / h - 253nm / h, and the prepared SiO2 thickness is 50 - 122nm.

6. The preparation method of the SiO2 and Al2O3 composite hydrogen barrier coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering according to claim 2, characterized in that, In step 3): Prepare an α-Al2O3 coating on the SiO2 coating by radio frequency magnetron sputtering. The target material is Al target with a purity of 99.99%, the starting gas is Ar gas with a purity of 99.99%, and the reaction gas is O2 gas with a purity of 99.99%; Vacuum degree ≥ 4*10 -3 Pa, sputtering power 50 - 160 W, sputtering gas pressure 1 - 2 Pa, O2 / Ar gas mixing ratio in the range of (1:10) - (1:5), heating temperature of the pipe substrate 500 - 600 °C; The deposition rate of the α-Al2O3 coating is 89nm / h - 140nm / h, and the prepared α-Al2O3 thickness is 120 - 172nm.

7. The preparation method of the SiO2 and Al2O3 composite hydrogen-blocking coating for hydrogen transmission pipelines based on radio frequency magnetron sputtering according to any one of claims 1 to 6, characterized in that: The hydrogen transmission pipeline is selected from X52 carbon pipeline steel, X65 carbon pipeline steel, X70 carbon pipeline steel, X80 carbon pipeline steel, 304 stainless steel pipeline or 316 stainless steel pipeline.

8. A hydrogen transmission pipeline prepared by the preparation method according to any one of claims 1 to 7.

9. The hydrogen transmission pipeline according to claim 8, wherein: The structure of the pipeline includes a matrix material, a SiO2 layer deposited on the matrix material, and an α-Al2O3 layer deposited on the SiO2 layer.

10. The hydrogen transmission pipeline according to claim 8, wherein: The film-substrate bonding force is 8.5 - 16N; the hydrogen permeation activation energy is 146.2 - 177.9kJ. / mol; the hydrogen permeation pressure index is 0.73 - 0.91.