Method for detecting and analyzing inorganic blockages in tiny glass capillary

Abstract

The invention provides a method for detecting and analyzing inorganic blockages in a tiny glass capillary tube, which comprises the following steps: driving the blockages in the tiny glass capillary tube to migrate by adopting high-pressure inert gas, so that the blockages gradually gather towards the port of the capillary tube to form an area to be analyzed, and after the blockages gather, detecting the inorganic blockages in the tiny glass capillary tube. According to the method, an FIB system is adopted to perform accurate cutting on the surface of a blockage object, an SEM observation mode is adopted to perform monitoring in the cutting process, morphology characterization is performed on the surface of a sample, so that the accuracy of an etching position is ensured, damage to a surrounding area is avoided, and in order to reduce pollution induced by ion beams, after FIB sample preparation is completed, an SEM EDS mode is switched, and therefore, the surface of the blockage object can be accurately cut. And performing component analysis on the surface of the sample. According to the detection method provided by the invention, accurate positioning, micro-area sample preparation and component-morphology combined characterization of the blockages in the micro glass capillary are realized, and reliable data support is provided for subsequent blockages source analysis and cleaning process optimization.

Description

Technical Field

[0001] This invention belongs to the field of materials testing and micro-area analysis technology, specifically relating to a method for detecting and analyzing inorganic blockages inside a tiny glass capillary. Background Technology

[0002] The core objective of detecting blockages inside glass tubes is to accurately identify the composition, state, concentration, and distribution of the internal substances without damaging the glass tube structure or minimizing interference. Currently, the main methods for detecting substances inside glass tubes can be divided into three categories: optical methods utilize the transparency of glass, achieving detection through the reflection, absorption, and scattering of light, including visual observation, ultraviolet-visible / infrared / Raman spectroscopy analysis, and imaging techniques such as microscopy and tomography; physical field methods leverage the interaction between the physical properties of the substance and external physical fields, such as ultrasonic testing, electromagnetic induction, and X-ray / CT scanning, suitable for opaque or thick-walled glass tubes; and invasive auxiliary methods involve minimally invasive procedures such as drilling holes in the glass tube wall for sampling or implanting sensors to access the substance, which requires disrupting the glass tube's seal.

[0003] However, existing methods for detecting substances inside glass tubes have many problems. Optical methods rely on the light transmittance of glass and are easily affected by scratches, stains, or dark or turbid substances. Furthermore, it is difficult to accurately distinguish components when the spectra of mixtures overlap, and the detection depth and spatial resolution are limited. Physical field methods have poor specificity and are difficult to distinguish substances with similar physical properties. X-ray / CT and other equipment are expensive and pose radiation risks. They are also easily affected by the external environment, and the results depend on the operator's experience. Invasive methods can damage the seal of the glass tube, which may lead to contamination, leakage, or changes in the original state of the substance. Moreover, sampling and analysis cannot be monitored in real time, and the results are easily distorted due to the volatilization and reaction of substances. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for detecting and analyzing inorganic blockages inside a tiny glass capillary.

[0005] To solve the above problems, the technical solution of the present invention is as follows:

[0006] A method for detecting and analyzing inorganic blockages inside a tiny glass capillary, characterized by the following steps:

[0007] Step S1, In-situ Focusing: A tiny glass capillary is sealed and connected to a pressure-controllable device. By applying a controllable gradient of inert gas flow, the dispersed inorganic blockages migrate in situ and accumulate at the end of the tiny glass capillary, forming a blockage accumulation area.

[0008] Step S2, Sample Preparation and Characterization: The end of the tiny glass capillary after step S1 is placed in the sample chamber of a focused ion beam (FIB) scanning electron microscope (SEM) system to locate the blockage accumulation area; the surface of the blockage accumulation area is slicing using the focused ion beam to expose its internal profile, while the scanning electron microscope is used for real-time imaging to monitor the slicing process and characterize the morphology of the internal profile;

[0009] Step S3, in-situ composition analysis: Without moving the sample, switch the working mode of the coupled system and use the energy dispersive spectroscopy (EDS) mode to perform qualitative and quantitative analysis of the elemental composition of the profile exposed in step S2, thereby obtaining compositional data corresponding to the morphological information.

[0010] Furthermore, the micro glass capillary is a tapered capillary glass tube.

[0011] Furthermore, the controllable gradient inert gas flow is controlled by high-purity argon gas via a pressure controller.

[0012] Furthermore, the depth of the layer cutting is precisely controlled to not exceed 20 μm.

[0013] Furthermore, in step S3, a spatial correspondence is established between the obtained elemental composition data and the morphological characterization data of the same cross section obtained in step S2, thereby realizing the joint analysis of composition and morphology.

[0014] Furthermore, by iteratively executing steps S2 and S3, that is, after the first component analysis, continuing to perform focused ion beam deburring at a specific depth, and again performing scanning electron microscopy morphology characterization and energy dispersive spectroscopy component analysis on the exposed new profile, the component distribution information of the inorganic blockage in three-dimensional space is obtained.

[0015] Furthermore, from step S1 to step S3, the tiny glass capillary itself is not damaged, maintaining the physical integrity of its structure.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0017] 1. This invention achieves precise localization, micro-area sample preparation, and joint characterization of composition and morphology of blockages in conical capillary glass tubes through a technical route from high-pressure drive to FIB micromachining-SEM monitoring and finally EDS analysis, providing reliable data support for subsequent analysis of blockage sources and optimization of cleaning processes.

[0018] 2. The glass capillary itself is not damaged throughout the process, thus preserving the integrity of the sample to the greatest extent. Simultaneously, by controlling the cutting depth of the FIB, the blockage can be "dissected layer by layer," overcoming the limitation of traditional EDS which can only analyze the outermost surface. This allows for the acquisition of information on the compositional distribution of the blockage in the depth direction, providing crucial data for analyzing the causes of blockage.

[0019] 3. The use of high-purity inert gas as the driving force prevents sample oxidation or contamination during pretreatment, ensuring the authenticity and reliability of the analytical results. Real-time monitoring of SEM ensures extremely high positional accuracy of FIB cutting, avoiding misoperation. On the same instrument platform (FIB-SEM-EDS), precise cutting, high-resolution morphology observation, and accurate component analysis are performed sequentially, achieving a complete and integrated characterization of blockages from macroscopic aggregation to microscopic morphology and nanoscale composition, providing unprecedented comprehensive analytical data. Attached Figure Description

[0020] Figure 1 A schematic diagram of internal blockage in a conical capillary glass tube;

[0021] Figure 2 This is a SEM morphology illustration of Embodiment 1 of the present invention;

[0022] Figure 3 This is a SEM morphology illustration of Embodiment 2 of the present invention;

[0023] Figure 4 This is a SEM morphology illustration of Embodiment 3 of the present invention; Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. Those skilled in the art should understand that these descriptions are merely exemplary and not intended to limit the scope of the present invention.

[0025] This invention provides a method for detecting and analyzing inorganic blockages inside tiny glass capillaries. By constructing a technical closed loop of in-situ aggregation, coupled sample preparation and characterization, and in-situ component analysis, the method achieves accurate, non-destructive, and in-depth analysis of blockages within a FIB-SEM-EDS coupled system.

[0026] The following example, using the analysis of white granular blockage inside a conical quartz capillary with an inner diameter of 50 μm, illustrates the implementation of the present invention in detail, specifically including the following steps:

[0027] Step S1: In-situ Accumulation: First, connect the wider end of the conical quartz capillary to a pressure controller supplied with high-purity argon gas, ensuring airtightness. Then, slowly turn on the gas source and precisely control the chamber pressure at 5 bar using the pressure controller, maintaining this position for 30 seconds. Under this pressure, high-purity argon gas flows into the capillary, effortlessly "pushing" the dispersed micron-sized blockages to the tube opening area. Figure 1 As shown, the originally dispersed particles migrate towards the port and accumulate under the drive of airflow, forming a microscopically visible, dense "region to be analyzed".

[0028] Step S2: Sample preparation and characterization: The capillary sample processed in step S1 is transferred to the sample chamber of the FIB.

[0029] First, at a low accelerating voltage of 5 kV, the "analytical region" at the capillary port was quickly located using SEM mode. Then, a platinum protective layer approximately 1 μm thick was deposited in situ on the surface of the selected region using FIB-assisted metal-organic vapor deposition to prevent damage to the original morphology from subsequent ion beam cutting. The ion beam current was set to 3 nA, and a "trenching" cut was performed above the protective layer to quickly remove some of the blockages, forming a preliminary profile. The ion beam current was then reduced to below 100 pA for fine polishing. During this process, SEM was used to image the post-cut region at an accelerating voltage of 5 kV in secondary electron mode (e.g., ...). Figure 2 , 3 (As shown in Figure 4). By comparing the SEM images before and after cutting, the amount of blockage removed and the density can be visually assessed. In this embodiment, the cutting depth is precisely controlled at approximately 8.85 μm by controlling the number of FIB scans and the time.

[0030] Step S3 In-situ component analysis: After completing the fine cutting in step S2 and obtaining a clear cross-sectional morphology, keep the sample position absolutely unchanged and switch the system working mode.

[0031] The accelerating voltage of the SEM was increased to 15 kV to excite characteristic X-rays of all possible elements in the blockage. The EDS detector was activated to perform a point-to-point surface scan of the same profile prepared in step S2, with an acquisition time of 10 seconds to ensure statistical significance. The EDS spectrum was analyzed to obtain the elemental composition of the profile at this depth.

[0032] Example 1

[0033] The surface of the aggregated blockage was cut to 4.7 μm using the FIB system, and its morphology and composition were analyzed.

[0034] The results are as follows Figure 2 As shown, Figure 2 SEM morphology of the sample after cutting 4.7 μm off the surface of the blockage, followed by... Figure 2 The components were analyzed using EDS mode, and the results are shown in Table 1. It can be seen that the main components of the blockage are C, O, Sn, Cr and Fe. Sn has the highest proportion, O has the lowest proportion, and Cr has the lowest number of elements.

[0035] Table 1. Results of Example 1, EDS Mode

[0036] Element Weight % Atomic % CK 2.5 19.7 OK 0.2 1.3 Cr K 0.4 0.8 Fe K 0.9 1.5 Sn L 96.0 76.7

[0037] Example 2

[0038] The surface of the aggregated blockage was cut to 8.85 μm using a FIB system, and its morphology and composition were analyzed.

[0039] The results are as follows Figure 3 As shown, Figure 3 SEM morphology of the sample after cutting 8.85 μm off the surface of the blockage, followed by... Figure 3 The wireframe section was analyzed using EDS mode, and the results are shown in Table 2. It can be seen that the main components of the blockage are C, O, Sn, Cr and Fe, with Sn having the highest proportion and Fe the lowest proportion.

[0040] Table 2. Results of EDS Mode in Example 2

[0041] Element Weight % Atomic % CK 8.4 42.6 OK 1.8 7.1 Cr K 3.3 3.8 Fe K 3.3 3.6 Sn L 83.3 42.9

[0042] Example 3

[0043] The surface of the aggregated blockage was cut to 18.85 μm using a FIB system, and its morphology and composition were analyzed.

[0044] The results are as follows Figure 4 As shown, Figure 4 SEM morphology of the sample after cutting 18.85 μm from the surface of the blockage, followed by... Figure 4 The components were analyzed using EDS mode, and the results are shown in Table 3. It can be seen that the main components of the blockage are C, Ca, O, Sn, Cr and Fe. Sn has the highest proportion, C has the highest number of elements, and Ca has the lowest proportion.

[0045] Table 3. Results of Example 3, EDS Mode

[0046] Element Weight % Atomic % CK 9.7 43.8 OK 2.2 7.6 Ca K 2.2 3.0 Cr K 6.2 6.5 Fe K 5.0 4.9 Sn L 74.7 34.3

[0047] The above description describes specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for detecting and analyzing inorganic blockages inside a micro glass capillary, characterized in that, Includes the following steps: Step S1, in-situ focusing: A tiny glass capillary is sealed and connected to a pressure-controllable device. By applying a controllable gradient of inert gas flow, the dispersed inorganic blockages migrate in situ and accumulate at the end of the tiny glass capillary, forming a blockage accumulation area. Step S2, Sample preparation and characterization: The end of the tiny glass capillary after step S1 is placed in the focused ion beam scanning electron microscope sample chamber to locate the blockage accumulation area; the surface of the blockage accumulation area is slicing with a focused ion beam to expose its internal profile, and the scanning electron microscope is used for real-time imaging to monitor the slicing process and characterize the morphology of the internal profile. Step S3, in-situ component analysis: Without moving the sample, switch the working mode of the coupled system and use the energy dispersive spectroscopy (EDS) mode to perform qualitative and quantitative analysis of the elemental composition of the exposed profile in step S2, thereby obtaining component data corresponding to the morphological information.

2. The method for detecting inorganic blockages inside a micro glass capillary according to claim 1, characterized in that: The micro glass capillary is a tapered capillary glass tube.

3. The method for detecting inorganic blockages inside a micro glass capillary according to claim 1, characterized in that: The controllable gradient inert gas flow is controlled by high-purity argon gas via a pressure controller.

4. The method for detecting inorganic blockages inside a micro glass capillary according to claim 1, characterized in that: The depth of the layer cutting is precisely controlled to not exceed 20 μm.

5. The method for detecting inorganic blockages inside a micro glass capillary according to claim 1, characterized in that: In step S3, a spatial correspondence is established between the obtained elemental composition data and the morphological characterization data of the same cross section obtained in step S2, thereby realizing the joint analysis of composition and morphology.

6. The method for detecting inorganic blockages inside a micro glass capillary according to claim 1, characterized in that: By iteratively executing steps S2 and S3, that is, after the first component analysis, continuing to perform focused ion beam deburring at a specific depth, and performing scanning electron microscopy morphology characterization and energy dispersive spectroscopy component analysis on the exposed new profile, the component distribution information of the inorganic blockage in three-dimensional space is obtained.

7. The method according to any one of claims 1-6, characterized in that, From step S1 to step S3, the tiny glass capillary itself is not damaged, maintaining the physical integrity of its structure.

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