CN110357451B - Relaxation-resistant coating, alkali metal air chamber and method - Google Patents

Relaxation-resistant coating, alkali metal air chamber and method Download PDF

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CN110357451B
CN110357451B CN201910466503.0A CN201910466503A CN110357451B CN 110357451 B CN110357451 B CN 110357451B CN 201910466503 A CN201910466503 A CN 201910466503A CN 110357451 B CN110357451 B CN 110357451B
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organic silane
organosilane
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房建成
池浩湉
全伟
周斌权
丁中亚
陆吉玺
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0075—Cleaning of glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions

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Abstract

An anti-relaxation coating, an alkali metal air chamber and a method, wherein an organosilane anti-relaxation material composite coating is plated on the surface of glass to compact the covering structure of the coating or increase the covering area, so that the quality of the anti-relaxation coating is improved, and the anti-relaxation effect of the alkali metal air chamber is further improved.

Description

Relaxation-resistant coating, alkali metal air chamber and method
Technical Field
The invention relates to an alkali metal air chamber relaxation-resistant technology, in particular to an anti-relaxation coating, an alkali metal air chamber and a method.
Background
The alkali metal air chamber is a core sensitive element of a plurality of research objects such as an atomic magnetometer, an atomic gyroscope and the like, and is composed of transparent quartz, high borosilicate silicon or aluminosilicate glass materials, and alkali metal atoms are filled in the air chamber. Once the polarized alkali metal atoms in the alkali metal gas chamber contact the exposed glass wall in the alkali metal gas chamber, the atoms are completely depolarized under the action of the larger magnetic field on the exposed glass wall, which is called wall relaxation of the alkali metal atoms. Wall relaxation is typically suppressed by filling the gas chamber with a buffer gas or plating an anti-relaxation coating. Although anti-relaxation coatings have many advantages over buffer gases, anti-relaxation coatings are not widely used as buffer gases due to limitations in the quality of the anti-relaxation coating and the operating temperature of the anti-relaxation coating. The materials forming the anti-relaxation coating at present are olefin materials, alkane materials, organochlorosilane materials and the like. The relaxation-resistant coating formed from the olefin material is best able to maintain the polarized alkali metal atoms 100 million collisions with the chamber wall without depolarization, however, the maximum operating temperature of this material is only 33 ℃. Paraffin, as a representative of anti-relaxation coating materials of alkanes, can maintain the number of collisions of polarized alkali metal atoms as high as 1 ten thousand, but the maximum working temperature of paraffin is 80 ℃, and the paraffin can not be applied to the field requiring high density of alkali metal atoms. The highest temperature at which octadecyltrichlorosilane in the organochlorosilane material can work is about 170 ℃, the highest recorded number of collisions at present is realized by Princeton university, the number of collisions is 2000, and the later people including the Princeton university can not reproduce 2000 times of alkali metal gas chambers with octadecyltrichlorosilane coatings. The inventor thinks that from the three types of anti-relaxation coating materials at present, the organosilanes represented by octadecyl trichlorosilane have potential space improvement and huge application prospects, and the improvement of the anti-relaxation performance of the organosilanes has great significance. Related studies have found that the resistance of the gas cell to relaxation is limited by the thickness and the area covered by the coating, with the thicker the coating thickness and the larger the area covered by the coating, the better the resistance of the coating to relaxation. At present, the problem of insufficient thickness of a single organic silane coating and insufficient compactness of a covering structure or too small covering area due to too many gaps exists in the single organic silane coating. The inventor imagines that if an organosilane relaxation-resistant composite coating is plated on the surface of glass, that is, short-chain organosilane is plated on the basis of long-chain organosilane plating, the coating thickness can be increased, the covering structure of the coating can be densified, or the covering area can be increased, on the premise of ensuring higher working temperature, the collision frequency of the alkali metal atoms for maintaining polarization can be increased, so that the quality of the relaxation-resistant coating can be improved, the relaxation resistance effect of an alkali metal gas chamber can be improved, and the application field of the alkali metal gas chamber with the relaxation-resistant coating can be expanded. In view of the above, the present inventors have completed the present invention.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides the anti-relaxation coating, the alkali metal air chamber and the method.
The technical scheme of the invention is as follows:
an anti-relaxation coating is characterized by comprising a glass substrate surface, wherein a first organic silane coating layer and a second organic silane coating layer are arranged on the surface, organic silane molecular chains of the first organic silane coating layer are longer than organic silane molecular chains of the second organic silane coating layer, and the first organic silane coating layer and the second organic silane coating layer form a composite coating.
The surface is also provided with a third organic silane coating layer, a fourth organic silane coating layer and a fifth organic silane coating layer, wherein an organic silane molecular chain of the third organic silane coating layer is shorter than that of the second organic silane coating layer, an organic silane molecular chain of the fourth organic silane coating layer is shorter than that of the third organic silane coating layer, and an organic silane molecular chain of the fifth organic silane coating layer is shorter than that of the fourth organic silane coating layer.
The organosilane plating layer adopts alkyl trichlorosilane, and the alkyl trichlorosilane reacts with hydrolytic water molecules to generate aquatic hydroxyl organochlorosilane or aquatic hydroxyl organosilane which reacts with surface hydroxyl on the surface of the glass substrate to form hydroxyl bonded silicon-oxygen bonds to form a covering film.
The organosilane plating layer adopts alkyl trichlorosilane, and the alkyl trichlorosilane reacts with hydrolytic water molecules to generate aquatic hydroxyl organochlorosilane or aquatic hydroxyl organosilane which reacts with hydroxyl which is not bonded at the tail end of the organosilane in the previous plating layer to form hydroxyl bonded silicon-oxygen bond so as to increase the thickness of the covering film.
The first organosilane plating layer adopts docosyltrichlorosilane, the second organosilane plating layer adopts eicosyl trichlorosilane, the third organosilane plating layer adopts octadecyl trichlorosilane, the fourth organosilane plating layer adopts hexadecyl trichlorosilane, and the fifth organosilane plating layer adopts tetradecyl trichlorosilane.
An alkali metal gas cell comprising a transparent glass housing, wherein the inner wall of the transparent glass housing is used as a glass substrate surface, and the glass substrate surface is provided with the anti-relaxation coating.
A method of making an anti-relaxation coating, comprising the steps of: step 1, carrying out primary cleaning, hydroxylation cleaning and third cleaning and drying on the surface of a glass substrate; step 2, plating a first organic silane plating layer on the surface of the hydroxylated glass substrate, wherein first water-borne hydroxyl organic silane generated by the reaction of the first organic silane and hydrolyzed water molecules reacts with surface hydroxyl on the surface of the glass substrate to form hydroxyl bonded silicon-oxygen bonds to form a first covering film; and 3, plating a second organic silane plating layer on the covering film, wherein the molecular chain of the second organic silane is shorter than that of the first organic silane, and second aquatic hydroxyl organic silane generated by the reaction of the second organic silane and the hydrolyzed water molecules reacts with hydroxyl on the surface, which is not bonded, of the glass substrate to form hydroxyl bonded silicon-oxygen bonds to form a second covering film, or reacts with hydroxyl on the tail end, which is not bonded, of organic silane in the first plating layer to form hydroxyl bonded silicon-oxygen bonds to increase the thickness of the covering film.
The coating method is characterized by further comprising the step of sequentially coating a third organic silane coating layer, a fourth organic silane coating layer and a fifth organic silane coating layer on the basis of the second organic silane coating layer, wherein an organic silane molecular chain of the third organic silane coating layer is shorter than that of the second organic silane coating layer, an organic silane molecular chain of the fourth organic silane coating layer is shorter than that of the third organic silane coating layer, and an organic silane molecular chain of the fifth organic silane coating layer is shorter than that of the fourth organic silane coating layer.
The preliminary cleaning adopts deionized water, the hydroxylation cleaning adopts glass surface hydroxylation cleaning liquid, the glass surface hydroxylation cleaning liquid comprises concentrated sulfuric acid and hydrogen peroxide solution, and the third cleaning adopts deionized water and methanol sequentially; the coating adopts a coating plating solution, the coating plating solution comprises an organosilane plating material and a solvent, and the organosilane plating material is docosyltrichlorosilane, eicosyl trichlorosilane, octadecyltrichlorosilane, hexadecyl trichlorosilane or tetradecyl trichlorosilane; the solvent is a preparation solution containing n-hexane, carbon tetrachloride and chloroform.
The surface of the glass substrate is the inner wall of the transparent glass shell of the alkali metal air chamber.
The invention has the following technical effects: the invention relates to an anti-relaxation coating, an alkali metal air chamber and a method, wherein coating materials with different molecular lengths are plated step by step to obtain a filling or thickening effect, for example, short-chain organosilane molecules sequentially fill gaps remained in a film forming process of long-chain organosilane molecules, so that the thickness of the anti-relaxation coating and the coverage area of the anti-relaxation coating are obviously increased, the quality of the anti-relaxation coating is improved, and the anti-relaxation performance of the alkali metal air chamber is further improved.
According to the invention, the composite coating consisting of five anti-relaxation coating materials with similar structures and different molecular chain lengths is arranged, and the plating sequence is from the long-chain material to the short-chain material in sequence, so that the short-chain material can fill the gap left by the long-chain material, and the coverage area of the anti-relaxation coating is increased. From long-chain to short-chain materials, e.g. by plating CH in sequence3(CH2)21SiCl3Docosyltrichlorosilane, CH3(CH2)19SiCl3Eicosyltrichlorosilane, CH3(CH2)17SiCl3Octadecyltrichlorosilane, CH3(CH2)15SiCl3Hexadecyltrichlorosilane, CH3(CH2)13SiCl3Tetradecyl trichlorosilane and the like, wherein the plating environment is atmospheric environment, so that the hydrolysis of the coating material and the bonding with hydroxyl on the surface of the glass are promoted by utilizing the moisture in the air, the thickness of the formed coating and the coverage area of the glass substrate are increased, the quality of the anti-relaxation coating can be greatly improved, and the anti-relaxation effect of the coating is further improved.
Drawings
FIG. 1 is a schematic representation of glass surface hydroxylation. For example, hydroxyl groups 5 can be generated when the inner wall of an alkali metal chamber (i.e., the inner wall of a transparent glass housing) is cleaned with piranha solution (a chamber cleaning solution or a so-called glass surface hydroxylation cleaning solution). The Piranha solution is usually made up of 98% by mass of concentrated sulfuric acid (H)2SO4) And 30% by mass of hydrogen peroxide solution (H)2O2) The volume ratio of the components is 3: 1.
FIG. 2 shows organosilanes (e.g., alkyltrichlorosilane) and hydrolyzed water molecules (e.g., atmospheric water molecules H)2O) to produce an aquatic hydroxyorganosilane. In FIG. 2, the terminal chlorine atom of the organosilane is replaced by a hydroxyl group, and the replaced chlorine atom forms a hydrogen chloride molecule.
FIG. 3 is a schematic representation of the reaction of a waterborne hydroxyorganosilane with surface hydroxyl groups on a glass surface to form hydroxyl-bonded siloxane bonds. In FIG. 3, every two hydroxyl groups are bonded to form a hydroxyl-bonded siloxane bond and an unhydrous molecule.
The reference numbers are listed below: 1-glass substrate surface (or glass wall or inner wall of gas chamber); 2-silicon atom (Si); 3-oxygen atom (O); 4-hydrogen atom (H); 5-surface hydroxyl (OH); 6-organosilanes or organochlorosilanes (organosilanes including organochlorosilanes and the like, e.g. CH)3(CH2)21SiCl3Docosyltrichlorosilane, CH3(CH2)19SiCl3Eicosyltrichlorosilane, CH3(CH2)17SiCl3Octadecyltrichlorosilane, CH3(CH2)15SiCl3Hexadecyltrichlorosilane, CH3(CH2)13SiCl3Tetradecyltrichlorosilane, etc.); 7-hydrolysis Water molecule (H)2O); 8-aquatic hydroxyorganosilanes or aquatic hydroxyorganochlorosilanes (e.g., organochlorosilanes in which the terminal chlorine atom is replaced by a hydroxyl group, the replaced chlorine atom forming a hydrogen chloride molecule); 9-hydrogen chloride molecule; a 10-terminal unbonded hydroxyl group; 11-unbound surface hydroxyl groups; 12-detachment of water molecule (H)2O); 13-hydroxy bonded siloxane bond (Si-OPerSi-OH-OH-Si ═ Si-O-Si + H2O formation).
Detailed Description
The invention is described below with reference to the accompanying drawings (fig. 1-3).
FIG. 1 is a schematic representation of glass surface hydroxylation. FIG. 2 shows organosilanes (e.g., alkyltrichlorosilane) and hydrolyzed water molecules (e.g., atmospheric water molecules H)2O) to produce an aquatic hydroxyorganosilane. FIG. 3 is a schematic representation of the reaction of a waterborne hydroxyorganosilane with surface hydroxyl groups on a glass surface to form hydroxyl-bonded siloxane bonds. Referring to fig. 1-3, an anti-relaxation coating includes a glass substrate surface 1 having a first organosilane (e.g., organochlorosilane 6) plating layer and a second organosilane plating layer thereon, the organosilane molecular chains of the first organosilane plating layer being longer than the organosilane molecular chains of the second organosilane plating layer, the first and second organosilane plating layers forming a composite coating. The surface is also provided with a third organic silane coating layer, a fourth organic silane coating layer and a fifth organic silane coating layer, wherein an organic silane molecular chain of the third organic silane coating layer is shorter than that of the second organic silane coating layer, an organic silane molecular chain of the fourth organic silane coating layer is shorter than that of the third organic silane coating layer, and an organic silane molecular chain of the fifth organic silane coating layer is shorter than that of the fourth organic silane coating layer. The organosilane plating layer adopts alkyl trichlorosilane, and the alkyl trichlorosilane reacts with hydrolyzed water molecules 7 to generate aquatic hydroxyl organochlorosilane or aquatic hydroxyl organosilane 8, and then reacts with surface hydroxyl 5 of the glass substrate surface 1 to form hydroxyl bonded silicon-oxygen bonds 13 to form a covering film. The aquatic hydroxyorganosilane 8 means that the terminal chlorine atom of the organochlorosilane is replaced by a hydroxyl group, and the replaced chlorine atom forms a hydrogen chloride molecule 9. The organosilane coating layer is made of alkyl trichlorosilane, and the alkyl trichlorosilane reacts with hydrolyzed water molecules 7 to generate aquatic hydroxyl organochlorosilane or aquatic hydroxyl organosilane 8 which is formed by reacting with hydroxyl 10 which is not bonded at the tail end in the organosilane of the previous coating layerThe hydroxyl group bonds to the silicon-oxygen bond to increase the thickness of the cover film. The first organosilane plating layer adopts docosyltrichlorosilane, the second organosilane plating layer adopts eicosyl trichlorosilane, the third organosilane plating layer adopts octadecyl trichlorosilane, the fourth organosilane plating layer adopts hexadecyl trichlorosilane, and the fifth organosilane plating layer adopts tetradecyl trichlorosilane.
An alkali metal gas cell comprising a transparent glass shell, characterized in that the inner wall of the transparent glass shell is used as a glass substrate surface 1, and the glass substrate surface 1 is provided with the above-mentioned relaxation-resistant coating.
A method of making an anti-relaxation coating, comprising the steps of: step 1, carrying out primary cleaning, hydroxylation cleaning and third cleaning and drying on the surface 1 of the glass substrate; step 2, plating a first organic silane plating layer on the surface 1 of the hydroxylated glass substrate, wherein first aquatic hydroxyl organic silane generated by the reaction of the first organic silane and hydrolyzed water molecules 7 reacts with surface hydroxyl 5 on the surface of the glass substrate to form hydroxyl bonded silicon-oxygen bonds 13 to form a first covering film; and 3, plating a second organic silane plating layer on the covering film, wherein the molecular chain of the second organic silane is shorter than that of the first organic silane, and second aquatic hydroxyl organic silane generated by the reaction of the second organic silane and the hydrolyzed water molecules reacts with hydroxyl 11 on the surface of the glass substrate 1, which is not bonded, to form hydroxyl-bonded silicon-oxygen bonds 13 to form the second covering film, or reacts with hydroxyl 10, which is not bonded, at the tail end of organic silane in the previous plating layer to form hydroxyl-bonded silicon-oxygen bonds 13 to increase the thickness of the covering film. The coating method is characterized by further comprising the step of sequentially coating a third organic silane coating layer, a fourth organic silane coating layer and a fifth organic silane coating layer on the basis of the second organic silane coating layer, wherein an organic silane molecular chain of the third organic silane coating layer is shorter than that of the second organic silane coating layer, an organic silane molecular chain of the fourth organic silane coating layer is shorter than that of the third organic silane coating layer, and an organic silane molecular chain of the fifth organic silane coating layer is shorter than that of the fourth organic silane coating layer.
The preliminary cleaning adopts deionized water, the hydroxylation cleaning adopts glass surface hydroxylation cleaning liquid, the glass surface hydroxylation cleaning liquid comprises concentrated sulfuric acid and hydrogen peroxide solution, and the third cleaning adopts deionized water and methanol sequentially; the coating adopts a coating plating solution, the coating plating solution comprises an organosilane plating material and a solvent, and the organosilane plating material is docosyltrichlorosilane, eicosyl trichlorosilane, octadecyltrichlorosilane, hexadecyl trichlorosilane or tetradecyl trichlorosilane; the solvent is a preparation solution containing n-hexane, carbon tetrachloride and chloroform. The surface of the glass substrate is the inner wall of the transparent glass shell of the alkali metal air chamber.
A method for making an anti-relaxation coating that is a hybrid coating capable of enhancing the anti-relaxation properties of alkali metal gas cells, comprising tetradecyltrichlorosilane (CH)3(CH2)13SiCl3) Hexadecyltrichlorosilane (CH)3(CH2)15SiCl3) Octadecyltrichlorosilane (CH)3(CH2)17SiCl3) Eicosyltrichlorosilane (CH)3(CH2)19SiCl3) Docosyltrichlorosilane (CH)3(CH2)21SiCl3) The five materials are plated in sequence according to the length of the molecular chain from long to short. The specific manufacturing steps comprise the following 3 steps:
step 1: and preparing a gas chamber cleaning solution and a coating plating solution. The gas chamber cleaning solution adopts piranha solution and consists of 98 percent concentrated sulfuric acid (H) by mass fraction2SO4) And 30% by mass of hydrogen peroxide solution (H)2O2) Preparing according to the volume ratio of 3: 1; the coating plating solution comprises five plating solutions consisting of solvent solution and coating material to be plated, wherein the coating material to be plated comprises tetradecyltrichlorosilane (CH)3(CH2)13SiCl3) Hexadecyltrichlorosilane (CH)3(CH2)15SiCl3) Octadecyl trichloro benzeneSilane (CH)3(CH2)17SiCl3) Eicosyltrichlorosilane (CH)3(CH2)19SiCl3) And behenyl trichlorosilane (CH)3(CH2)21SiCl3) The solvent solution is composed of 70-80% n-hexane (n-hexane) and 10-12% carbon tetrachloride CCl4And 15-18% chloroform (CHCl)3) Preparing, namely preparing the material to be plated and a solvent solution according to the concentration of 2 mM. The preparation process of the solution is carried out in an atmospheric environment at room temperature.
Step 2: firstly, deionized water is adopted to carry out 3-5 times of primary cleaning on the air chamber, and then piranha solution is injected into the alkali metal air chamber, so that hydroxyl groups which react with the solution to be plated can be generated while the air chamber is cleaned. The piranha solution in the chamber was allowed to remain for 1 hour, after 1 hour the piranha solution in the chamber was removed and deionized water and methanol (CH) were used3OH) are respectively cleaned for 3 to 5 times and then are placed in a vacuum oven to be dried for 60 minutes at the temperature of 100 ℃. The cleaning process is carried out in an atmospheric environment at room temperature.
And step 3: firstly plating docosyltrichlorosilane, and removing a docosyltrichlorosilane solution after the docosyltrichlorosilane solution is placed in a drying air chamber for 5 minutes; then plating eicosyl trichlorosilane, placing the eicosyl trichlorosilane solution in a drying air chamber for 5 minutes, and then removing the eicosyl trichlorosilane solution; and then, sequentially keeping an octadecyl trichlorosilane solution, a hexadecyltrichlorosilane solution and a tetradecyl trichlorosilane solution in an air chamber for 5 minutes, removing the solutions, finally cleaning the air chamber for 3-5 times by using chloroform, and drying the air chamber in a vacuum oven at the temperature of 200 ℃ for 24 hours. The coating plating process is carried out in an atmospheric environment at room temperature. And (3) filling alkali metal atoms in the dried alkali metal air chamber with the mixed coating to prepare the alkali metal air chamber with the mixed coating.
The invention relates to a method for preparing an anti-relaxation coating, which is a mixed coating capable of enhancing the anti-relaxation performance of an alkali metal air chamber, wherein the coating comprises five materials and is prepared by plating from long chains to short chains. After the first layer of material, namely the docosyltrichlorosilane is plated, gaps left by the docosyltrichlorosilane are further filled, meanwhile, because solution preparation and coating plating operation are carried out in the atmospheric environment, water molecules existing in the atmosphere can be fully utilized to promote the docosyltrichlorosilane and the docosyltrichlorosilane to form bonds, and then the octadecyl trichlorosilane is plated until the tetradecyl trichlorosilane is obtained. The plating method can increase the thickness and the coverage area of the coating, is beneficial to improving the quality of the coating and further improves the relaxation resistance of the alkali metal air chamber. The preparation method of an anti-relaxation coating is a mixed coating capable of enhancing the anti-relaxation performance of an alkali metal air chamber, and comprises a composite coating of five materials of tetradecyl trichlorosilane, hexadecyl trichlorosilane, octadecyl trichlorosilane, eicosyl trichlorosilane and docosyl trichlorosilane. And before coating, carrying out primary cleaning, hydroxylation cleaning and third-step cleaning and drying on the air chamber. The five plating materials are plated in sequence from long to short according to the length of a molecular chain. The short chain molecules fill gaps left by the long chain molecules, so that the coverage area of the coating is increased; and bonds with long-chain molecules under the action of water molecules, so that the thickness of the coating is increased.
The gas chamber cleaning solution adopts piranha solution and consists of 98 percent concentrated sulfuric acid (H) by mass fraction2SO4) And 30% by mass of hydrogen peroxide solution (H)2O2) The volume ratio of the components is 3: 1. The Piranha solution was placed in the air chamber for 1 hour, after which the Piranha solution was removed from the air chamber. After removing piranha solution, the air chamber is cleaned by deionized water and methanol for 3-5 times respectively, and then the mixture is dried in a vacuum oven for 60 minutes at the temperature of 100 ℃. The cleaning process is carried out in the atmospheric environment and at room temperature. The five plating materials are dissolved in solvent solution according to 70-80% n-hexane (n-hexane) and 10-12% carbon tetrachloride (CCl)4) And 15-18% chloroform (CHCl)3) The concentration of the five plating solutions is 2 mM. The five plating solutions are removed after being placed in an air chamber for 5 minutes, and after the tetradecyl trichlorosilane solution is plated, the air chamber is cleaned for 3 to 5 times by adopting chloroform and then is placed in a vacuum oven at 200 DEG CDrying for 24 hours under the condition. The plating process is carried out in atmospheric environment and at room temperature.
It is pointed out here that the above description is helpful for the person skilled in the art to understand the invention, but does not limit the scope of protection of the invention. Any such equivalents, modifications and/or omissions as may be made without departing from the spirit and scope of the invention may be resorted to.

Claims (7)

1. An anti-relaxation coating is characterized by comprising a glass substrate surface, wherein the surface is provided with a first organic silane coating layer and a second organic silane coating layer, organic silane molecular chains of the first organic silane coating layer are longer than organic silane molecular chains of the second organic silane coating layer, and the first organic silane coating layer and the second organic silane coating layer form a composite coating;
the surface is also provided with a third organic silane coating layer, a fourth organic silane coating layer and a fifth organic silane coating layer, wherein an organic silane molecular chain of the third organic silane coating layer is shorter than that of the second organic silane coating layer, an organic silane molecular chain of the fourth organic silane coating layer is shorter than that of the third organic silane coating layer, and an organic silane molecular chain of the fifth organic silane coating layer is shorter than that of the fourth organic silane coating layer;
the first organosilane plating layer adopts docosyltrichlorosilane, the second organosilane plating layer adopts eicosyl trichlorosilane, the third organosilane plating layer adopts octadecyl trichlorosilane, the fourth organosilane plating layer adopts hexadecyl trichlorosilane, and the fifth organosilane plating layer adopts tetradecyl trichlorosilane.
2. The anti-relaxation coating of claim 1, wherein the organosilane plating layer is alkyltrichlorosilane, and the alkyltrichlorosilane reacts with hydrolyzed water molecules to generate hydrobioxyorganochlorosilane or hydrohydroxyorganosilane, and then reacts with surface hydroxyls on the surface of the glass substrate to form hydroxyl-bonded siloxane bonds to form a cover film.
3. The anti-relaxation coating of claim 1, wherein the organosilane plating employs an alkyltrichlorosilane that reacts with hydrolyzed water molecules to form hydrobiohydroxychlorosilanes or hydrohydroxyorganosilanes that increase the thickness of the coating film by reacting with terminal unbound hydroxyl groups in the organosilane of the previous plating to form hydroxyl-bonded siloxane bonds.
4. An alkali metal gas cell comprising a transparent glass housing, characterized in that the inner wall of the transparent glass housing is provided as a glass substrate surface provided with an anti-relaxation coating as claimed in any one of the preceding claims 1 to 3.
5. A method of making an anti-relaxation coating, comprising the steps of: step 1, carrying out primary cleaning, hydroxylation cleaning and third cleaning and drying on the surface of a glass substrate; step 2, plating a first organic silane plating layer on the surface of the hydroxylated glass substrate, wherein first water-borne hydroxyl organic silane generated by the reaction of the first organic silane and hydrolyzed water molecules reacts with surface hydroxyl on the surface of the glass substrate to form hydroxyl bonded silicon-oxygen bonds to form a first covering film; step 3, plating a second organic silane plating layer on the covering film, wherein the molecular chain of the second organic silane is shorter than that of the first organic silane, and second aquatic hydroxyl organic silane generated by the reaction of the second organic silane and hydrolyzed water molecules reacts with hydroxyl on the surface, which is not bonded, of the glass substrate to form hydroxyl bonded silicon-oxygen bonds to form a second covering film, or reacts with hydroxyl on the tail end, which is not bonded, of organic silane in the first plating layer to form hydroxyl bonded silicon-oxygen bonds to increase the thickness of the covering film;
the preliminary cleaning adopts deionized water, the hydroxylation cleaning adopts glass surface hydroxylation cleaning liquid, the glass surface hydroxylation cleaning liquid comprises concentrated sulfuric acid and hydrogen peroxide solution, and the third cleaning adopts deionized water and methanol sequentially; the coating adopts a coating plating solution, the coating plating solution comprises an organosilane plating material and a solvent, and the organosilane plating material is docosyltrichlorosilane, eicosyl trichlorosilane, octadecyltrichlorosilane, hexadecyl trichlorosilane or tetradecyl trichlorosilane; the solvent is a preparation solution containing n-hexane, carbon tetrachloride and chloroform.
6. The method of forming an anti-relaxation coating layer as claimed in claim 5, further comprising sequentially plating a third organosilane plating layer, a fourth organosilane plating layer and a fifth organosilane plating layer on the second organosilane plating layer, wherein the organosilane molecular chain of the third organosilane plating layer is shorter than the organosilane molecular chain of the second organosilane plating layer, the organosilane molecular chain of the fourth organosilane plating layer is shorter than the organosilane molecular chain of the third organosilane plating layer, and the organosilane molecular chain of the fifth organosilane plating layer is shorter than the organosilane molecular chain of the fourth organosilane plating layer.
7. The method of claim 5, wherein the surface of the glass substrate is an inner wall of a transparent glass shell of an alkali metal gas cell.
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