阅读说明：本技术 透射电镜检测用复型样品的制作方法、凝胶液及应用方法 (Manufacturing method of replica sample for transmission electron microscope detection, gel liquid and application method ) 是由 金传伟 吴园园 胡显军 于 2020-07-28 设计创作，主要内容包括：本发明揭示了一种透射电镜检测用复型样品的制作方法、凝胶液及应用方法。透射电镜检测用复型样品的制作方法包括：将乙酸纤维素、石墨烯和丙酮按照1:1:3-1:1:5范围的体积比混合,之后密封静置,得到凝胶液；将试样按照金相制样处理,得到具有腐蚀表面的金相试样；在所述金相试样的腐蚀表面均匀涂敷所述凝胶液,之后干燥成凝胶薄膜；将所述凝胶薄膜从金相试样剥离下来,之后向所述凝胶薄膜的有效表面喷碳,得到复合薄膜；将所述复合薄膜放入丙酮中浸泡直至呈卷曲状态,用载网捞出后烘干,得到碳膜即所述复型样品。解决了现有技术中的气泡问题以及复型样品上残留污染物的问题,效率高、成功率高且所得复型样品质量佳。(The invention discloses a preparation method of a replica sample for transmission electron microscope detection, a gel liquid and an application method. The preparation method of the replica sample for transmission electron microscope detection comprises the following steps: mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1:5, and then sealing and standing to obtain gel liquid; processing the sample according to a metallographic phase sample preparation to obtain a metallographic phase sample with a corroded surface; uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and then drying to form a gel film; stripping the gel film from the metallographic sample, and then spraying carbon on the effective surface of the gel film to obtain a composite film; and (3) soaking the composite film in acetone until the composite film is in a curled state, fishing out the composite film by using a net, and drying to obtain a carbon film, namely the replica sample. The method solves the problems of air bubbles and residual pollutants on the replica sample in the prior art, and has the advantages of high efficiency, high success rate and good quality of the replica sample.)

1. A method for manufacturing a replica sample for transmission electron microscope detection is characterized by comprising the following steps:

mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1:5 to obtain gel liquid;

sequentially polishing, corroding, washing and blow-drying the sample according to metallographic phase sample preparation to obtain a metallographic sample with a corroded surface;

uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and then standing until the gel liquid is naturally dried into a gel film;

stripping the gel film from the corroded surface of the metallographic specimen, and then spraying carbon on the effective surface of the gel film in a vacuum coating instrument to obtain a composite film, wherein the effective surface is originally contacted with the corroded surface before the stripping process;

and (3) soaking the composite film in acetone until the composite film is in a curled state, fishing out the composite film by using a net, and drying to obtain a carbon film, namely the replica sample.

2. The method for preparing a replica sample for transmission electron microscopy detection according to claim 1, wherein the step of mixing cellulose acetate, graphene and acetone in a volume ratio ranging from 1:1:3 to 1:1:5 is a volume ratio under free stacking.

3. The method for preparing the replica sample for transmission electron microscope detection according to claim 1, wherein the gel liquid is obtained by mixing cellulose acetate, graphene and acetone at a volume ratio of 1:1:3 to 1:1:5, performing magnetic stirring and ultrasonic dispersion treatment in sequence, and then sealing and standing.

4. The method for preparing a replica sample for transmission electron microscopy according to claim 1, wherein in the step of "polishing, corroding, washing and drying the sample in sequence according to metallographic phase preparation", the sample is subjected to the corrosion treatment by using 4% nitric acid and ethanol until the sample is yellow, and then the washing treatment is immediately performed by using water and ethanol in sequence.

5. The method for preparing a replica sample for transmission electron microscopy detection according to claim 1, wherein in the step of "uniformly applying the gel solution to the corroded surface of the metallographic specimen", a layer of acetone is applied to the corroded surface of the metallographic specimen, and the gel solution is uniformly applied to the corroded surface carrying the layer of acetone.

6. The method for preparing a replica sample for transmission electron microscopy according to claim 1, wherein the gel film is peeled off from the corroded surface of the metallographic specimen and fixed on a cover glass with the effective surface facing upward, and then carbon is sprayed on the effective surface in a vacuum coater.

7. The method for manufacturing a replica sample for transmission electron microscopy according to claim 1, wherein in the step of "spraying carbon on the effective surface of the gel film in a vacuum coater", the distance between the effective surface and the sputtering electrode of the vacuum coater is not less than 45 mm.

8. A method for manufacturing a replica sample for transmission electron microscope detection is characterized by comprising the following steps:

mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1:5 to obtain gel liquid;

sequentially polishing, corroding, washing and blow-drying the sample according to metallographic phase sample preparation to obtain a metallographic sample with a corroded surface;

uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and standing for 5 minutes to obtain a gel film;

stripping the gel film from the corroded surface of the metallographic specimen, and then spraying carbon on the effective surface of the gel film in a vacuum coating instrument to obtain a composite film, wherein the effective surface is originally contacted with the corroded surface before the stripping process;

and putting the composite film into acetone for soaking to dissolve the cellulose acetate of the composite film, fishing out the rest part of the composite film by using a net, and drying to obtain a carbon film, namely the replica sample.

9. The gel liquid is characterized by being prepared by mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1: 5.

10. A method of using the gel liquid according to claim 9, comprising,

uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and then standing until the gel liquid is naturally dried to form a gel film;

stripping the gel film from the corroded surface, and then spraying carbon to the effective surface of the gel film to obtain a composite film, wherein the effective surface is originally contacted with the corroded surface before the stripping process;

and (3) soaking the composite film in acetone until the composite film is in a curled state, fishing out the composite film by using a net, and drying to obtain a replica sample for transmission electron microscope detection.

Technical Field

The invention belongs to the technical field of material preparation, and relates to a gel liquid and an application method of the gel liquid, in particular to an application method of the gel liquid in the preparation of a replica sample for transmission electron microscope detection, and a preparation method of the replica sample for transmission electron microscope detection.

Background

The size of precipitated phase in steel sample is usually from several nanometers to several hundred nanometers, and at present, the precipitated phase is mainly analyzed by preparing a replica sample and detecting the replica sample under a transmission electron microscope. Therefore, the quality of the replica sample can directly influence the detection result of the transmission electron microscope, and further influence the analysis of the steel sample. The existing method for manufacturing replica samples for transmission electron microscope detection is mainly divided into a first-stage replica method and a second-stage replica method.

The first-order replica method is roughly: after the steel sample is corroded, a thin carbon film is sprayed on the surface to be detected, the carbon film is taken down from the surface of the sample by corroding the steel sample substrate, and the carbon film is fished out to form a replica sample for transmission electron microscope detection. The disadvantages of this method are: (1) when the carbon film is taken down by corroding the sample substrate, corrosion products are easily brought onto the carbon film together, and further the detection result is adversely affected by the corrosion products; (2) for a sample of small crystal grains having a size of less than 500nm or large crystal grains having a size of more than 100 μm, the carbon film is difficult to adhere and extremely easy to break, thereby causing failure in preparation of a replica sample.

The two-stage replica method is roughly: after the steel sample is corroded, laying and dissolving cellulose acetate paper on the surface to be detected, and naturally drying the dissolved cellulose acetate paper into an organic film; stripping the organic film from the surface of the sample, and spraying carbon to form a composite film with an organic film and a carbon film; and finally, soaking the composite film in an organic solvent to dissolve the organic film, and fishing out the carbon film to form a composite sample for transmission electron microscope detection. The disadvantages of this method are: (1) when the acetate fiber paper is laid and dissolved on the surface of the sample, air bubbles between the acetate fiber paper and the surface of the sample are difficult to be completely discharged, so that an organic film is difficult to be completely attached to the surface of the sample, and the finally prepared replica sample cannot accurately replica the surface of the sample, thereby causing inaccurate detection results; (2) when the cellulose acetate paper is dissolved on the surface of a sample, the naked eye is difficult to judge whether the dissolution is complete, cellulose acetate paper particles are easy to remain due to incomplete dissolution, the particles can be wrapped by a carbon film when carbon is sprayed, and then when the composite film is soaked by an organic solvent, the organic solvent is difficult to contact the particles, so that the cellulose acetate paper remains in a final replica sample (namely a final carbon film), and the detection result of a transmission electron microscope is adversely affected; (3) further, in order to avoid the occurrence of the acetate fiber paper remaining in the replica sample, it is necessary to prolong the soaking time as much as possible in the process of finally soaking the composite film with acetone, and even prolong the soaking time in the process of initially dissolving the acetate fiber paper and preparing the organic film, however, on one hand, the time duration is only blindly prolonged depending on experience due to the difficulty in judgment by naked eyes, so that the whole preparation process of the replica sample is time-consuming, inefficient and uncontrollable, and on the other hand, even if the time duration is prolonged, the existence of the particles makes it difficult to ensure that the acetate fiber paper does not remain in the final replica sample.

Disclosure of Invention

In order to solve at least one of the above technical problems, the present invention provides a gel solution and a method for using the same.

One embodiment of the invention provides a gel liquid, which is prepared by mixing cellulose acetate, graphene and acetone according to a volume ratio of 1:1:3-1:1: 5.

An embodiment of the present invention further provides an application method of the gel liquid, including:

uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and then standing until the gel liquid is naturally dried to form a gel film;

stripping the gel film from the corroded surface, and then spraying carbon to the effective surface of the gel film to obtain a composite film, wherein the effective surface is originally contacted with the corroded surface before the stripping process;

and (3) soaking the composite film in acetone until the composite film is in a curled state, fishing out the composite film by using a net, and drying to obtain a replica sample for transmission electron microscope detection.

In order to solve at least one of the above problems, an object of the present invention is to provide a method for manufacturing a replica sample for transmission electron microscope inspection.

An embodiment of the present invention provides a method for manufacturing a replica sample for transmission electron microscope detection, including:

mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1:5 to obtain gel liquid;

sequentially polishing, corroding, washing and blow-drying the sample according to metallographic phase sample preparation to obtain a metallographic sample with a corroded surface;

uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and then standing until the gel liquid is naturally dried into a gel film;

stripping the gel film from the corroded surface of the metallographic specimen, and then spraying carbon on the effective surface of the gel film in a vacuum coating instrument to obtain a composite film, wherein the effective surface is originally contacted with the corroded surface before the stripping process;

and (3) soaking the composite film in acetone until the composite film is in a curled state, fishing out the composite film by using a net, and drying to obtain a carbon film, namely the replica sample.

As a further refinement of an embodiment of the invention, in the step "mixing cellulose acetate, graphene and acetone in a volume ratio in the range of 1:1:3 to 1:1: 5", the volume ratio is the volume ratio under free stacking ".

As a further modification of an embodiment of the present invention, the gel liquid is obtained by mixing cellulose acetate, graphene and acetone at a volume ratio in the range of 1:1:3 to 1:1:5, and performing magnetic stirring and ultrasonic dispersion treatment in this order, followed by sealing and standing.

As a further improvement of one embodiment of the invention, in the step of sequentially polishing, corroding, washing and drying the sample according to metallographic phase sample preparation, the sample is corroded by nitric acid and alcohol with the concentration of 4% until the sample is yellow, and then the washing treatment is sequentially performed by water and alcohol.

In a further improvement of an embodiment of the present invention, in the step "uniformly applying the gel liquid to the corroded surface of the metallographic specimen", the layer of acetone is first applied to the corroded surface of the metallographic specimen, and the gel liquid is uniformly applied to the corroded surface having the layer of acetone.

In a further improvement of an embodiment of the present invention, the gel film is peeled off from the corroded surface of the metallographic specimen, fixed on a cover glass with the effective surface facing upward, and then carbon is sprayed on the effective surface in a vacuum coating apparatus.

As a further improvement of an embodiment of the present invention, in the step of "spraying carbon to the effective surface of the gel film in a vacuum coater", a distance between the effective surface and a sputtering electrode of the vacuum coater is not less than 45 mm.

The embodiment of the invention also provides a manufacturing method of the replica sample for transmission electron microscope detection, which comprises the following steps:

mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1:5 to obtain gel liquid;

sequentially polishing, corroding, washing and blow-drying the sample according to metallographic phase sample preparation to obtain a metallographic sample with a corroded surface;

uniformly coating the gel liquid on the corroded surface of the metallographic specimen, and standing for 5 minutes to obtain a gel film;

stripping the gel film from the corroded surface of the metallographic specimen, and then spraying carbon on the effective surface of the gel film in a vacuum coating instrument to obtain a composite film, wherein the effective surface is originally contacted with the corroded surface before the stripping process;

and putting the composite film into acetone for soaking to dissolve the cellulose acetate of the composite film, fishing out the rest part of the composite film by using a net, and drying to obtain a carbon film, namely the replica sample.

Compared with the prior art, beneficial effect lies in:

(1) the gel liquid can be in complete contact with the corroded surface of the metallographic specimen with proper fluidity, so that no air bubbles are left between the gel film and the corroded surface, the problem that the air bubbles are difficult to discharge and stay in the prior art is solved, and the gel film can be ensured to be completely and accurately reshaped out of the corroded surface;

(2) through the addition of the graphene, bubbles can be further ensured not to be left between the gel film and the corroded surface; meanwhile, the graphene can prevent bubbles from remaining in the gel film, so that the gel film is homogenized at all positions, and the gel film can keep stable in form when being impacted during carbon spraying, so that a replica sample capable of accurately replicating the corroded surface of the sample can be obtained finally (otherwise, if bubbles exist in the gel film, the bubbles can cause the surface of the gel film to collapse due to the impact of the carbon spraying, and further the corroded surface of the sample cannot be accurately replicated by the carbon film);

(3) when the gel solution is used on a corroded surface, the problem that acetate fiber paper particles are remained due to insufficient dissolution of the acetate fiber paper in the prior art is solved, so that the cellulose acetate in the composite film can effectively contact acetone and be separated from a carbon film, and the obtained replica sample can completely remove the interference of pollutants such as cellulose acetate and the like;

(4) in addition, as the graphene is a nano material and a carbon material, when the composite film is soaked in acetone to remove the gel film, even if the graphene remains on the surface of the carbon film, the application of the carbon film in the transmission electron microscope detection cannot be interfered;

(5) based on the effect that the cellulose acetate can effectively contact with acetone and be separated from the carbon film, when the gel liquid is applied to the preparation of the replica sample for the detection of the transmission electron microscope, compared with the prior art, the preparation time of the replica sample can be greatly reduced, the quality of the replica sample is ensured, the efficiency is improved, and the time controllability of production is realized;

(6) further, through optimizing the ratio of cellulose acetate, graphite alkene and acetone in the gel liquid, can further guarantee the mobility of gel liquid for when satisfying mobile demand in order to discharge sample surface bubble, still guaranteed can dry into the gel film in the short time, raise the efficiency.

Drawings

FIG. 1 is a diagram showing the results of transmission electron microscopy examination of a replica sample obtained in example 4 of the present invention;

FIG. 2 is a diagram showing the results of transmission electron microscopy examination of the replica samples obtained in example 5 of the present invention;

FIG. 3 is a transmission electron microscope examination result chart of the replica samples obtained in example 6 of the present invention.

Detailed Description

First embodiment

In a first embodiment of the present invention, there is provided a gel liquid comprising cellulose acetate, graphene and acetone mixed in a volume ratio of 1:1:3 to 1:1: 5. The gel liquid can be applied to the manufacturing of the replica sample for the transmission electron microscope detection, and specifically can replace the cellulose acetate paper in the prior art to be applied to the two-stage replica manufacturing method of the replica sample for the transmission electron microscope detection, or can replace the cellulose acetate paper in the prior art to be used for preparing an organic film in the two-stage replica manufacturing method of the replica sample for the transmission electron microscope detection.

Compared with the prior art, beneficial effect lies in:

(1) the gel liquid can be in complete contact with the corroded surface of the metallographic specimen with proper fluidity, so that no air bubbles are left between the gel film and the corroded surface, the problem that the air bubbles are difficult to discharge and stay in the prior art is solved, and the gel film can be ensured to be completely and accurately reshaped out of the corroded surface;

(2) by adding the graphene, bubbles can be further prevented from remaining between the gel film and the corroded surface; meanwhile, the graphene can prevent bubbles from remaining in the gel film, so that the gel film is homogenized at all positions, and the gel film can keep stable in form when being impacted during carbon spraying, so that a replica sample capable of accurately replicating the corroded surface of the sample can be obtained finally (otherwise, if bubbles exist in the gel film, the bubbles can cause the surface of the gel film to collapse due to the impact of the carbon spraying, and further the corroded surface of the sample cannot be accurately replicated by the carbon film);

(3) when the gel solution is used on a corroded surface, the problem that acetate fiber paper particles are remained due to insufficient dissolution of the acetate fiber paper in the prior art is solved, so that the cellulose acetate in the composite film can effectively contact acetone and be separated from a carbon film, and the obtained replica sample can completely remove the interference of pollutants such as cellulose acetate and the like;

(4) in addition, as the graphene is a nano material and a carbon material, when the composite film is soaked in acetone to remove the gel film, even if the graphene remains on the surface of the carbon film, the application of the carbon film in the transmission electron microscope detection cannot be interfered;

(5) based on the effect that the cellulose acetate can effectively contact with acetone and be separated from the carbon film, when the gel liquid is applied to the preparation of the replica sample for the detection of the transmission electron microscope, compared with the prior art, the preparation time of the replica sample can be greatly reduced, the quality of the replica sample is ensured, the efficiency is improved, and the time controllability of production is realized;

(6) further, through optimizing the ratio of cellulose acetate, graphite alkene and acetone in the gel liquid, can further guarantee the mobility of gel liquid for when satisfying the surface bubble of mobile demand with the discharge sample, still guaranteed can dry into the gel film in the short time, raise the efficiency.

The present embodiment also provides a method for preparing the gel solution, including: mixing cellulose acetate, graphene and acetone according to the volume ratio of 1:1:3-1:1:5 to obtain gel liquid.

In this embodiment, the volume ratio of the cellulose acetate, the graphene and the acetone preferably refers to a volume ratio under free stacking.

Further, in the preparation method, cellulose acetate, graphene and acetone are mixed according to the volume ratio of 1:1:3-1:1:5, magnetic stirring and ultrasonic dispersion treatment are sequentially adopted, and then the mixture is sealed and kept stand to obtain the gel liquid.

The gel liquid and the method of preparing the same according to the first embodiment of the present invention will be described in detail with reference to specific preferred examples 1 to 3.