CN102589954A - Method using transmission electron microscope to observe ultra microstructure of inorganic high polymer material - Google Patents
Method using transmission electron microscope to observe ultra microstructure of inorganic high polymer material Download PDFInfo
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- CN102589954A CN102589954A CN2011100080252A CN201110008025A CN102589954A CN 102589954 A CN102589954 A CN 102589954A CN 2011100080252 A CN2011100080252 A CN 2011100080252A CN 201110008025 A CN201110008025 A CN 201110008025A CN 102589954 A CN102589954 A CN 102589954A
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Abstract
The invention belongs to the technical field of polymer materials, and relates to a method using a transmission electron microscope to observe ultra microstructure of inorganic high polymer material. The method includes following steps: placing the high polymer material into absolute ethanol solution or absolute acetone solution for eight hours for infiltration; then placing the high polymer material into mixed liquid of absolute ethanol and epoxy resin or mixed liquid of absolute acetone solution and epoxy resin for 2 to 7 days; placing the high polymer material into a 37 DEG C to 45 DEG C baking oven for 11 to 24 hours, so as to remove gaseous ethanol or gaseous acetone and store the high polymer material in pure epoxy resin; furthermore, adding the required amount of the pure epoxy resin to embedded blocks for 24-hour curing. The method provided by the invention can solve the problem that for a long time the embedded high polymer material can not or is difficult to acquire integral ultrathin sections, and performs the positive function for the three-dimensional reconstruction of the physical models inside the high polymer material particles. The method disclosed by the invention is further applied to study in other fields, and is widely applied in study fields such as medical treatment, space flight, and composition of the high polymer material.
Description
Technical field
The invention belongs to technical field of polymer materials; Relate to a kind ofly, be specifically related to a kind of method of the ultrastructure of inorganic polymer particulate material being cut into slices with transmission electron microscope with the Ultrastructural method of transmission electron microscope observation inorganic macromolecule material.
Background technology
Transmission electron microscope is generally used for biological and organic Observation on Ultrastructure; The ripe and extensively utilization of the preparing electron microscopy specimen of most organic-biological materials; And the preparing electron microscopy specimen of inorganic macromolecule material rests on the structure observation of molecule external model always, can't be through transmission electron microscope observation to the inner ultrastructure of macromolecule material particle; And along with macromolecular material in fields such as medical science, space flight application development constantly; Fine structure and synthetic understanding for macromolecular material; Demand has further been arranged; Seek new research method and operational means, and then more the fine structure of studying macromolecular material is understood on deep layer ground, very actively profound significance is arranged for practical application.
At present, usually adopt type negative staining technology to the inorganic polymer particulate material like SiO
2Particle; The multiprotein complex of C nano particle, C nanotube and other organic material particles carries out the electron microscopic observation analysis; This technology is when carrying out the Ultrastructural observation of electron microscope to the polymeric particles material; The result who is obtained is the formalness structure or the particle grain size of polymeric particles material, can't observe to obtain the inner structure of grain diameter.
Discover; Because the inorganic macromolecule material relative density is bigger; Need not equally with biological organization material fix, processing such as dehydration; But the machine macromolecular material is not supported because the parts of fine microstructure has epoxy resin to connect after pure epoxy resin 618 embedding liquid soak into, when carrying out ultra-thin section, is prone to the situation that part-structure is lost.
Summary of the invention
The objective of the invention is to overcome the defective and the deficiency of prior art, provide a kind of observation inorganic macromolecule material Ultrastructural method, especially use the Ultrastructural method of transmission electron microscope observation inorganic macromolecule material.This method improves the method for transmission electron microscope biological sample preparation commonly used, and transmission electron microscope capable of using is to the Ultrastructural observation of inorganic polymer particulate material and cut into slices.
The invention provides a kind of embedding method of independently macromolecular material; Under the effect of liquid-liquid-gas equilibrium principle; Macromolecule material particle or single tube inside the support of epoxy resin with link down; Form fixing polymkeric substance relative molecular mass, obtain the space diagram structure of narrow distribution, and can use the inside ultrastructure of the above-mentioned macromolecule material particle of conventional transmission electron microscope observation.
Particularly, of the present invention with the Ultrastructural method of transmission electron microscope observation inorganic macromolecule material, it is characterized in that it comprises step:
⑴ put into 100% straight alcohol or 100% pure acetone solution with macromolecular material, soaked into 8 hours;
⑵ put into ethanol or acetone and epoxy resin mixed liquor 2～7 days with macromolecular material;
⑶ be put into temperature with macromolecular material is to toast in 37 ℃～45 ℃ the baking oven, gets rid of ethanol or acetone gas, and macromolecular material is kept in the pure epoxy resin;
⑷ add the expense of pure epoxy resin to embedded block, solidified 24 hours.
Among the present invention, inorganic macromolecule material comprises: silicon dioxide (SiO
2), organic glass, CNT, carbon dust (C nano particle, C nanotube) etc.
Among the present invention, the ratio of ethanol or acetone and epoxy resin is 1 in the described mixed liquor of step (2)
:1 to 1
:4;
Among the present invention, the described stoving time of step (3) is 11～24 hours, and preferred stoving time is 12 hours.
Among the present invention, described acetone is the solution inflammable, volatile, that chemical property is more active, under certain temperature condition, volatilize with vapor form, and aggretion type epoxy resin 618 (E-51) is metastable solution; According to liquid-liquid-gas equilibrium principle; The intermiscibility solution that mixes with aggretion type epoxy resin 618 when acetone; Vaporization along with acetone; The mixed liquor of acetone and aggretion type epoxy resin 618 is in liquid-liquid-gas balance all the time, and aggretion type epoxy resin 618 concentration in the mixed liquor progressively improve, until aggretion type epoxy resin 618 purifying, curing.
When using the inventive method that macromolecular material is carried out embedding, slicing treatment, the result shows, the mixed liquor of acetone and aggretion type epoxy resin 618 is penetrated into SiO
2(polymethylmethacrylate, PMMA) in the macromolecular material high density granular inner structure, after acetone in acetone and aggretion type epoxy resin 618 mixed liquors vaporization volatilization, macromolecular material is like SiO for particle, C nano particle, C nanotube or organic glass
2Aggretion type epoxy resin 618 concentration in the high density slits such as particle, C nano particle, C nanotube are also thereupon than increasing; Until epoxy resin 618 purifying, curing; Cause macromolecule material particle interior detail microstructure to obtain the connection and the support of epoxy resin; Carry out ultra-thin section, make complete macromolecule material particle interior detail microstructure section; In one embodiment of the invention, (polymethylmethacrylate PMMA) carries out embedding, sectioning, can obtain complete section, need not vulcanize just and can carry out electron microscopic observation to the organic glass macromolecule transparent material.
Advantage with the Ultrastructural method of transmission electron microscope observation inorganic macromolecule material of the present invention is:
Adopt the embedding of method of the present invention, solve a difficult problem that can't or be difficult to obtain complete ultra-thin section after the macromolecular material embedding for a long time, solve macromolecular material deep structure research method more to macromolecular material nano particle electron microscope sample.Through the macromolecular material of this method embedding, in slicing processes, the injury tolerance of the diamond cutter edge of a knife of costliness is reduced to minimum; When carrying out the ultra-thin section of sample, obtain serial section, for the three-dimensional reconstruction of macromolecule material particle internal physical model has played positive effect.
Method of the present invention helps setting up the three-dimensional reconstruction model, and the three-dimensional reconstruction model is as micro-targeting vector in the medical treatment, for the treatment of particular patients ' unlimited meaning is arranged; The inventive method also is applied to the research in other field, is widely used in the research field such as compound of medical treatment, space industry, macromolecular material.
For the ease of understanding, through accompanying drawing and specific embodiment the present invention is carried out detailed description below.What need particularly point out is, specific embodiment and accompanying drawing only are in order to explain that obviously those skilled in the art can explain according to this paper, and the present invention is carried out various corrections or change, and these corrections and changing also will be included within the scope of the invention.
Description of drawings
Fig. 1 is that carbon granule drips chip architecture figure, shows the particle diameter and the configuration of surface that adopt the drop adsorption method can only obtain macromolecular material.
Fig. 2 is the silica dioxide granule structural drawing.
Fig. 3 is through obtaining the structural drawing of complete nano-carbon powder behind the embedded section.
Fig. 4 is the fine structure figure of CNT.
Fig. 5 is the structural drawing of the carbon pipe in the double-deck folder film.
But Fig. 6 is the outside drawing of serial section device.
Specific embodiment
Embodiment 1Observe the silica dioxide granule ultrastructure
Preparation SiO
2The electron microscope sample of particle macromolecule transparent material particle: grind to form the powder of micron utmost point with agate mortar, collect small quantities of powder and put 37
0The C baking oven is baked and banked up with earth the part of anhydrating, and a E618 epoxy resin adds 2 part of 100% ethanol or acetone is processed the embedding medium mixed liquor; Choose above-mentioned particulate material and place on a small quantity in the embedding mould, the embedding medium mixed liquor (embedding medium stoste is less than 100% pure acetone or ethanol) of preparation is measured in the adding mould on demand, carry out soaking into early stage curing after stirring with fine needle; Put 45 ℃ of baking ovens 12 hours; Pure embedding medium is filled it up with in injection in second day, puts 45 ℃ of baking ovens and continues to solidify in 24 hours the direct electron microscopic examination of section back; The result shows that this method can obtain good SiO
2The map architecture in particle macromolecule transparent material granule interior such as honeybee room (as shown in Figure 2).
Embodiment 2Observe C nano particle, C nanotube ultrastructure
⑵ material is a CNT, then needs a epoxy resin to add 4 part of 100% acetone and processes the embedding medium mixing
The electron microscope embedding sample of preparation macromolecular material C nano particle, C nanotube: for the electron microscope sample embedding of C nano particle and synthetic C nanotube; Because the moment absorption affinity of carbon is stopped up the high density passage of macromolecular material C nano particle, C nanotube easily; So; Before embedding to macromolecular material C nano particle, C nanotube, will be through 37
0C nano particle after the C baking oven is baked and banked up with earth or C nanotube are inserted and are injected a small amount of 100% acetone in the mould; According to liquid-liquid equilibrium principle; Pure 100% acetone is then introduced 1 part of epoxy resin and is added 4 part of 100% acetone mixed solution, makes it to reach balance, carries out soaking into early stage purifying, curing after stirring with fine needle; Put 45 ℃ of baking ovens 12 hours; Pure embedding medium is filled it up with in injection in second day, puts 45 ℃ of baking ovens and continues to solidify in 24 hours the direct electron microscopic examination of section back; The result shows, can obtain good macromolecular material C nano particle, the inner picture structure (as shown in Figure 3) of C nanotube.
Embodiment 3Observe organic glass macromolecule transparent material ultrastructure
The chemical name of the organic glass macromolecule transparent material of present embodiment is polymethylmethacrylate (PMMA), is formed by methyl methacrylate polymerization.Adopt embedding method of the present invention that polymethylmethacrylate (PMMA) is carried out specimen preparation: it is strong at first the organic glass of bulk to be made smooth with a file out powder on file, collects small quantities of powder and puts 37
0The C baking oven is baked and banked up with earth the part of anhydrating; Be difficult for being dissolved in ethanol owing to polymethylmethacrylate (PMMA) is dissolved in acetone, therefore, embedding medium can not be used acetone diluted and can only use 100% ethanol dilution; Selecting for use a E618 epoxy resin to add 2 ~ 3 part of 100% ethanol measures in the adding mould on demand; Carry out soaking into early stage after stirring with fine needle, purifying, curing, put 45 ℃ of baking ovens 12 hours, pure embedding medium is filled it up with in injection in second day; Put 45 ℃ of baking ovens and continue to solidify in 24 hours, cut into slices afterwards in double dish, to exert a gradual, corrupting influence on and carried out electron microscopic observation in 20-30 minutes with 2% osmic acid.
The present invention helps setting up the three-dimensional reconstruction model through experiment confirm, and the three-dimensional reconstruction model is as micro-targeting vector in the medical treatment, for the treatment of particular patients ' unlimited meaning is arranged; The present invention also can be used for the research in other field, is widely used in the research field such as compound of medical treatment, space industry, macromolecular material.
Claims (5)
1. one kind with the Ultrastructural method of transmission electron microscope observation inorganic macromolecule material, it is characterized in that it comprises step:
⑴ put into straight alcohol or pure acetone solution with macromolecular material, soaked into 8 hours;
⑵ put into ethanol or acetone and epoxy resin mixed liquor 2～7 days with macromolecular material;
⑶ be put into temperature with macromolecular material is in 37 ℃～45 ℃ the baking oven, toasts 11～24 hours, gets rid of ethanol or acetone gas, and macromolecular material is kept in the pure epoxy resin;
⑷ add the expense of pure epoxy resin to embedded block, solidified 24 hours.
2. by the described method of claim 1, it is characterized in that in the described step (1), straight alcohol or pure acetone solution are 100% straight alcohol or 100% pure acetone solution.
3. by the described method of claim 1, it is characterized in that in the described step (2), the ratio of ethanol or acetone and epoxy resin is 1
:1 to 1
:4.
4. by the described method of claim 1, it is characterized in that in the described step (3), stoving time is 12 hours.
5. by the described method of claim 1, it is characterized in that described inorganic macromolecule material is selected from silicon dioxide, organic glass, CNT or carbon dust.
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|---|---|---|---|
| CN201110008025.2A CN102589954B (en) | 2011-01-14 | 2011-01-14 | Method using transmission electron microscope to observe ultra microstructure of inorganic high polymer material |
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| CN102589954A true CN102589954A (en) | 2012-07-18 |
| CN102589954B CN102589954B (en) | 2014-06-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053178A (en) * | 2016-07-28 | 2016-10-26 | 广西医科大学 | Preparation method of boat-fruited sterculia seed scanning electron microscope samples |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003099222A2 (en) * | 2002-05-23 | 2003-12-04 | Invitrogen Corporation | Pseudo-tissues and uses thereof |
| US20040219588A1 (en) * | 2003-04-30 | 2004-11-04 | Masaru Furuta | Method for dispensing reagents onto biological samples and method for analyzing biological samples |
| CN1587959A (en) * | 2004-09-23 | 2005-03-02 | 上海交通大学 | Method for producing biolgoical sample embedded block based on atomic force microscope observation |
| JP2006058270A (en) * | 2004-08-24 | 2006-03-02 | Sumitomo Chemical Co Ltd | Analytical method for cross section of object to be inspected |
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2011
- 2011-01-14 CN CN201110008025.2A patent/CN102589954B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003099222A2 (en) * | 2002-05-23 | 2003-12-04 | Invitrogen Corporation | Pseudo-tissues and uses thereof |
| US20040219588A1 (en) * | 2003-04-30 | 2004-11-04 | Masaru Furuta | Method for dispensing reagents onto biological samples and method for analyzing biological samples |
| JP2006058270A (en) * | 2004-08-24 | 2006-03-02 | Sumitomo Chemical Co Ltd | Analytical method for cross section of object to be inspected |
| CN1587959A (en) * | 2004-09-23 | 2005-03-02 | 上海交通大学 | Method for producing biolgoical sample embedded block based on atomic force microscope observation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053178A (en) * | 2016-07-28 | 2016-10-26 | 广西医科大学 | Preparation method of boat-fruited sterculia seed scanning electron microscope samples |
| CN106053178B (en) * | 2016-07-28 | 2018-08-31 | 广西医科大学 | A kind of preparation method of sterculia seed scanning electron microscope example |
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| CN102589954B (en) | 2014-06-11 |
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Granted publication date: 20140611 Termination date: 20190114 |