CN113358558B - Method for bonding nano material in-situ electron microscope - Google Patents
Method for bonding nano material in-situ electron microscope Download PDFInfo
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- CN113358558B CN113358558B CN202110601370.0A CN202110601370A CN113358558B CN 113358558 B CN113358558 B CN 113358558B CN 202110601370 A CN202110601370 A CN 202110601370A CN 113358558 B CN113358558 B CN 113358558B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N19/00—Investigating materials by mechanical methods
- G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
- G01N23/20025—Sample holders or supports therefor
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- Crystallography & Structural Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a method for bonding nano materials in an in-situ electron microscope, which utilizes the electron beam dosage of 15e/nm 2 And s, the adhesive is cured to realize the bonding of the nano materials. The adhesive is EMIMBr-AlCl 3 Ionic liquid prepared by reacting AlCl 3 Mixing the powder with EMIMBr in a molar ratio of 1.3, and magnetically stirring to obtain the EMIMBr powder. The method can be used for carrying out nondestructive bonding on the nano material under the low-dose electron beam irradiation, has wide application range, is particularly suitable for the nano material which is not resistant to electron beam irradiation and is not heat-resistant, and has simple use method and low cost.
Description
Technical Field
The invention belongs to the technical field of novel welding, and particularly relates to a method for bonding a nano material in an in-situ electron microscope.
Background
In recent years, along with the development and the rise of nano materials, people have more and more intensive researches on the performance of the nano materials, and the invention of a simple, effective and practical nano material adhesive has important significance for researching the mechanical property of a single nano material. In conventional research, the connection or fixation of nanomaterials often relies on advanced equipment such as focused ion beam welding and environmental electron microscope chemical reaction welding. The focused ion beam welding of the nanometer material has great damage to the nanometer material structure at the welding position, the welding point is easy to break, and the Pt for welding seriously pollutes the material. The welding method comprises the following steps that a nano material is welded by an environmental electron microscope, the nano material and a welding flux are subjected to chemical reaction under the irradiation of an electron beam to realize welding, and the electron beam irradiation and the reaction process release heat to cause the structural damage of the nano material. Moreover, both the focused ion beam and the environmental electron microscope are expensive large-scale equipment, the operation is complex, and the use difficulty is high.
Therefore, the method which is low in price, wide in application range and capable of performing nondestructive bonding on the nano material under low-dose electron beam irradiation has important practical value.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a method for bonding nanomaterials in situ under electron microscope irradiation with low dose of electron beam, wherein the adhesive is cured under low dose of electron beam irradiation, and there is no strong chemical reaction during the curing process.
In order to achieve the purpose, the invention provides the following scheme:
a method for adhering nano material in-situ electron microscope with electron beam dosage of 15e/nm 2 s, the adhesive is solidified to realize the bonding of the nano material; the adhesive is EMIMBr-AlCl 3 An ionic liquid.
Preferably, the dose in the electron beam is 0 to 2e/nm 2 s, contacting the nano material with the adhesive, and adjusting the electron beam dose to 15e/nm 2 And s, moving the electron beam to irradiate the contact position of the nano material and the adhesive.
Preferably, the preparation method of the adhesive comprises the following steps: mixing AlCl 3 Mixing with EMIMBr and stirring with magnetic stirrer.
Preferably, the AlCl is adopted 3 Molar ratio to EMIMBr 1.3.
Preferably, the time for magnetic stirring is 4h.
Preferably, the adhesive is prepared in an argon atmosphere and can be contacted with air when transferred into an in-situ electron microscope.
Preferably, the time for the adhesive to contact air when transferred into an in situ electron microscope is within 20 seconds.
Preferably, the in-situ electron microscope is an in-situ transmission electron microscope or an in-situ scanning electron microscope.
Compared with the prior art, the invention has the following beneficial effects:
1) The raw materials for preparing the adhesive are convenient to purchase, the price is low, the using amount is small, the adhesive is simple to prepare, the solidification time is short, especially the electron beam irradiation dose required by solidification is low, no violent reaction is generated in the solidification process, and the structure of the nano material at the adhesion part is completely preserved.
2) The invention can be used in a common transmission electron microscope without large-scale equipment with special functions, and is particularly suitable for nanometer materials which are not resistant to electron beam irradiation and are not heat-resistant.
3) The invention has simple use method, wide application range and low cost.
Drawings
FIG. 1 is a schematic diagram of the method for bonding nanomaterials in an in-situ electron microscope according to the present invention;
FIG. 2 is a TEM image after Au is snapped in example 2 of the present invention;
FIG. 3 is a TEM image after h-CNT is broken in example 3 of the present invention;
FIG. 4 is a TEM image after Cu breaking in inventive example 4.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The invention provides a method for bonding nano materials in an in-situ electron microscope, wherein the bonding agent used in the method is EMIMBr-AlCl 3 The ionic liquid is prepared by the following steps:
mixing aluminum trichloride (AlCl) 3 ) Two solid powders were mixed with brominated 1-ethyl-3-methylimidazolium salt (EMIMBr) in a molar ratio of 1.3 3 And mixing the mixture with EMIMBr uniformly to obtain a light yellow solution, namely the nano material adhesive.
In an in-situ electron microscope, when the nano material is contacted with the adhesive, the dosage of the electron beam is controlled to be less than 2e/nm 2 s, the adhesive is liquid and can be processed in situ without curing, and then the electron beam dose is adjusted to 15e/nm 2 And s, moving the contact position of the electron beam irradiation nanometer material and the adhesive, and quickly solidifying the adhesive (5 s) to complete good and stable adhesion.
The adhesive needs to be in an Ar atmosphere glove box (H) 2 O<0.01PPm,O 2 <0.01 PPm), when transferred into a transmission electron microscopeCan be contacted with air for a short time within 20 s.
Preparing an adhesive:
in a glove box under Ar atmosphere, 0.18g of AlCl is added 3 And 0.2g of EMIMBr were placed in a 5ml glass bottle and magnetically stirred for 4 hours to obtain a pale yellow viscous liquid, i.e., a binder.
Example 1
1) In an Ar atmosphere glove box, a CuO nanowire is adhered to a substrate on one side by silver glue, a copper bar with the thickness of 0.3mm is adopted as a substrate on the other side, a small amount of adhesive is dipped at the front end of the copper bar substrate, the copper bar substrate is assembled according to the figure 1 and is arranged in a transmission electron microscope sample rod, and then the transmission electron microscope is arranged.
2) At an electron beam intensity of 2e/nm 2 And s, moving the copper rod substrate to enable the adhesive to be in contact with the CuO nanowires, wherein the adhesive is liquid.
3) The electron beam intensity was adjusted to 15e/nm 2 And s, moving the electron beam to irradiate the contact position of the adhesive and the nanowire, so that the adhesive can be rapidly solidified.
4) The copper rod substrate is withdrawn, the nanowire can be broken, the fracture position can not occur at the bonding position, and the bonding process is proved not to damage the structure of the CuO nanowire.
Example 2
1) In an Ar atmosphere glove box, a gold rod with the diameter of 0.3mm is adopted as a substrate on one side, and a nanometer polycrystalline Au column with the diameter of 200nm and the length of 8 mu m is obtained by etching the front end by FIB (focused ion beam); and a 0.3mm copper rod is still used as the substrate on the other side, a small amount of adhesive is dipped, and the substrate is assembled and arranged in a transmission electron microscope sample rod according to the figure 1 and then arranged in a transmission electron microscope.
2) At an electron beam intensity of 2e/nm 2 And s, moving the copper rod substrate to enable the adhesive to be in contact with the front ends of the Au nanorods, wherein the adhesive is liquid.
3) The electron beam intensity was adjusted to 15e/nm 2 And s, moving the electron beam to irradiate the contact position of the adhesive and the nanowire, so that the adhesive can be rapidly solidified.
4) The Au nanorods can be broken by withdrawing the copper rod substrate, the fracture appears in the middle of the nanorods, and the fracture position does not occur at the bonding position, which proves that the bonding process does not damage the structure of the Au nanorods, as shown in FIG. 2.
Example 3
1) In an Ar atmosphere glove box, a semi-copper net with the diameter of 3mm is adopted as a substrate on one side, the upper half part of the semi-copper net is used for attracting the hollow carbon nano-tubes by static electricity, and the lower half part is dipped in an adhesive; and (3) adhering an AFM (atomic force microscope) probe on the other side substrate by using Ag, assembling and installing the AFM probe into a transmission electron microscope sample rod, and then installing the transmission electron microscope sample rod into the transmission electron microscope.
2) In transmission electron microscope, a small amount of adhesive is dipped by AFM tip and contacted with one end of hollow carbon nanotube with intensity of 15e/nm 2 s electron beam irradiation, adhesive solidification, AFM tip adhering single hollow carbon nanotube, contacting the other end of the hollow carbon nanotube with the adhesive in the lower half of the semi-copper mesh substrate with strength of 15e/nm 2 And(s) irradiating by electron beams, and solidifying the adhesive.
3) The substrate was withdrawn and the bond strength was measured to be > 1.5GPa, as shown in FIG. 3.
Example 4
1) Welding a Cu nanorod on an AFM probe by FIB, adhering the AFM probe to a substrate on one side, using a Cu rod with the thickness of 0.3mm as a substrate on the other side, dipping a small amount of adhesive on the copper rod substrate, assembling and loading the copper rod substrate into a transmission electron microscope sample rod according to the figure 1, and then loading the transmission electron microscope sample rod into the transmission electron microscope.
2) At an electron beam intensity of 2e/nm 2 s, moving the copper rod substrate to make the adhesive and the Cu nano rod contact, wherein the adhesive is liquid.
3) The electron beam intensity was adjusted to 15e/nm 2 And s, moving the electron beam to irradiate the contact position of the adhesive and the nanowire, so that the adhesive can be rapidly solidified.
4) The substrate was withdrawn and the bond strength was measured to be > 610Mpa, as shown in figure 4.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention made by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (6)
1. A method for bonding electron beam irradiation-intolerant and heat-intolerant nano materials in an in-situ electron microscope is characterized in that in the in-situ electron microscope, the dosage of electron beams is 15e/nm 2 s, the adhesive is cured to realize the adhesion of the nanometer material which is not resistant to electron beam irradiation and heat; the adhesive is EMIMBr-AlCl 3 An ionic liquid;
the preparation method of the adhesive comprises the following steps: mixing AlCl 3 Mixing with EMIMBr solid powder, and stirring with magnetic stirrer, wherein the AlCl is 3 Molar ratio to EMIMBr 1.3.
2. The method for bonding heat-labile nanomaterials incapable of withstanding electron beam irradiation in situ electron microscopy as claimed in claim 1, wherein the electron beam dose is in the range of 0 to 2e/nm 2 s, contacting the nano material with adhesive, and adjusting the electron beam dose to 15e/nm 2 And s, moving the electron beam to irradiate the contact position of the nano material and the adhesive.
3. The method for bonding the electron beam irradiation-intolerant and heat-intolerant nanomaterials in the in-situ electron microscope as claimed in claim 1, wherein the time for magnetic stirring is 4 hours.
4. The method for bonding the electron beam irradiation-intolerant and heat-intolerant nano-materials in the in-situ electron microscope according to claim 1 or 3, wherein the bonding agent is required to be configured in an argon atmosphere and can be in contact with air when being transferred into the in-situ electron microscope.
5. The method for bonding electron beam irradiation intolerant and heat intolerant nanomaterials in-situ electron microscopes according to claim 4, wherein the time for the adhesive to contact air when transferred into the in-situ electron microscope is within 20 s.
6. The method for bonding electron beam irradiation intolerant, heat-labile nanomaterials in an in-situ electron microscope according to claim 1, wherein the in-situ electron microscope is an in-situ transmission electron microscope or an in-situ scanning electron microscope.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105261784A (en) * | 2014-07-15 | 2016-01-20 | 北京理工大学 | Aluminum secondary battery |
| CN106086959A (en) * | 2016-08-03 | 2016-11-09 | 南京理工大学 | A kind of method that electrochemical reduction deposition of aluminum prepares thermite |
| CN110699020A (en) * | 2019-11-20 | 2020-01-17 | 湖南大学 | Polyion liquid adhesive and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5442417B2 (en) * | 2009-12-14 | 2014-03-12 | 株式会社日立ハイテクノロジーズ | Charged particle beam apparatus and sample observation method |
| CN103971951B (en) * | 2013-01-28 | 2017-02-01 | 海洋王照明科技股份有限公司 | Preparing method for supercapacitor |
| CN104008894A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene material, preparation method thereof, nitrogen-doped graphene electrode, and electrochemical capacitor |
| CN104008895A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene-ionic liquid composite electrode and preparation method thereof, and electrochemical capacitor |
| CN104792591B (en) * | 2015-04-10 | 2018-02-16 | 泽龙 | A kind of SEM EDX detection methods for making conductive processing agent with the methyl imidazolium tetrafluoroborate ionic liquid of 1 ethyl 3 |
| CN107132241B (en) * | 2017-04-24 | 2019-06-25 | 中国石油大学(北京) | A method of nano material is welded in Electronic Speculum in situ |
| CN107219243B (en) * | 2017-05-05 | 2019-10-11 | 大连理工大学 | A kind of transmission electron microscope in-situ nano mechanical stretch test sample adhering method |
| CN111518368B (en) * | 2020-05-07 | 2021-06-08 | 北京化工大学 | Fast-curing high-heat-resistance high-toughness resin matrix and preparation method thereof |
| CN111948231A (en) * | 2020-07-22 | 2020-11-17 | 中国科学院物理研究所 | In situ monitoring of AlF3Method for discharge process as positive electrode of lithium primary battery |
| CN112198175A (en) * | 2020-09-17 | 2021-01-08 | 燕山大学 | Method for researching electrochemistry of liquid battery under in-situ electron microscope |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105261784A (en) * | 2014-07-15 | 2016-01-20 | 北京理工大学 | Aluminum secondary battery |
| CN106086959A (en) * | 2016-08-03 | 2016-11-09 | 南京理工大学 | A kind of method that electrochemical reduction deposition of aluminum prepares thermite |
| CN110699020A (en) * | 2019-11-20 | 2020-01-17 | 湖南大学 | Polyion liquid adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electrodeposition of aluminum on magnesium from ionic liquid（EMIM）Br-AlCl3;张丽鹏;《Transactions of Nonferrous Metals Society of China》;20101230;全文 * |
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