CN108414423A - The scanning electron microscope imaging method of the micro-nano hole of rock - Google Patents
The scanning electron microscope imaging method of the micro-nano hole of rock Download PDFInfo
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- CN108414423A CN108414423A CN201810391119.4A CN201810391119A CN108414423A CN 108414423 A CN108414423 A CN 108414423A CN 201810391119 A CN201810391119 A CN 201810391119A CN 108414423 A CN108414423 A CN 108414423A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- G01N23/22—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 measuring secondary emission from the material
- G01N23/225—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 measuring secondary emission from the material using electron or ion
- G01N23/2251—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 measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N2015/0846—Investigating permeability, pore-volume, or surface area of porous materials by use of radiation, e.g. transmitted or reflected light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
Abstract
The invention discloses a kind of scanning electron microscope i mage analysis methods of the micro-nano hole of rock of noble metal nano particles label and its exclusive nano-particle and preparation method thereof, the imaging method to include：Noble metal nano particles are injected in the crack and hole of rock, the blowhole scanning electron microscope of noble metal nano particles filling is imaged.The preparation method of the nanoparticle probes includes：Precious metal salt is restored using reducing agent.It reacts, then centrifuges after the solution of reducing agent and precious metal salt is mixed.Using noble metal nano particles as hole probe, can ground really reflect the micro-nano hole gap structure of rock, target area is accurate and intuitive, and its sample preparation is simple, amplification factor is adjustable, range is wide, the high resolution of image, its is simple to operate, it is relatively low to accuracy of instrument requirement, solve the technical barrier that current scanline Electronic Speculum can not accurately identify the micro-nano hole of rock.
Description
Technical field
The present invention relates to geological resources and Geological Engineering field, in particular to a kind of sweeping for the micro-nano hole of rock
Retouch Electronic Speculum imaging method.
Background technology
Rock pore structure characterization is that the basis of fining description is carried out to geological resource, to correctly recognizing rock formation spy
Directiveness effect has been levied, meanwhile, it is correct to recognize geological resource and play a decisive role to its high efficient rational development.Existing characterization
The main method of rock pore structure is casting body flake analytic approach, and implementation process is under high pressure, by macromolecular probe-
The body of casting is injected among blowhole, then obtains pore structure by the position and its correlation of observing the body of casting under the microscope
Parameter, the percentage that the entire ken is accounted for using the body of casting calculate its porosity.
With the continuous adjustment of China's energy resource structure, unconventionaloil pool (such as shale oil gas and fine and close oil gas) exploration and development by
Deeply, the micro-nano hole characterization of rock becomes the critical issue of unconventionaloil pool research to step.However, scanning electron microscope is micro- as rock
The most frequently used most intuitive method always exists the problem that can not correctly identify hole in the characterizing method of nanoaperture.Due to tradition
Macromolecular hole probe limited by its physical size and cannot be introduced into the micro-nano hole of rock, the case where lacking probe instruction
Under, scanning electron microscope is identified dependent on simple gray scale, can not accurately and effectively distinguish hole and complicated Rock Matrix, it is even more impossible to
Accurately clearly describe pore shape, size and profile etc..
Invention content
First of the present invention is designed to provide a kind of scanning electron microscope imaging method of the micro-nano hole of rock, to realize
Correct identification to the micro-nano hole gap structure of rock.
Second object of the present invention is to provide a kind of noble metal nano particles fluid, so that being injected into rock pore
In gap, Rock Matrix can be clearly distinguishable from scanning electron microscope imaging to reflect the pore structure of rock.
Third object of the present invention is to provide a kind of preparation method of noble metal nano particles fluid, with by simple
Technique above-mentioned noble metal nano particles fluid is prepared.
The present invention solves its technical problem using following technical scheme to realize.
A kind of scanning electron microscope imaging method of the micro-nano hole of rock provided by the invention comprising：By noble metal nano
Particle injects in the crack and hole of rock, is imaged to the blowhole scanning electron microscope of noble metal nano particles filling.
The invention further relates to a kind of preparation method of noble metal nano particles, which is suitable for above-mentioned rock
The scanning electron microscope imaging method of the micro-nano hole of stone, as probe comprising：Precious metal salt is restored using reducing agent.
Optionally, it reacts, then centrifuges after the solution of reducing agent and precious metal salt being mixed.
The invention further relates to a kind of preparation method of noble metal nano particles fluid, which is suitable for note
Enter the micro-nano hole of rock comprising：Above-mentioned noble metal nano particles are scattered in organic solvent, optionally, organic solvent
Including at least one of ethyl alcohol, acetone and ethylene glycol.
The invention further relates to a kind of noble metal nano particles fluids, by the preparation side of above-mentioned noble metal nano particles fluid
Method is prepared.
By controlling the particle size of noble metal nano particles, surface modification state and fluid media (medium), make it easier to inject
To among the crack of rock and hole.Under the instruction of nano-probe, carrying out imaging using scanning electron microscope can be really intuitive
Ground reflects the micro-nano hole gap structure of rock, and its sample preparation is simple, amplification factor is adjustable, range is wide, the high resolution of image,
Scanning, Microanalysis, electron backscattered etc. can be combined as a whole, can be used for the size of hole in rock formation,
The research of distribution and basic porosity type, simple to operate, solving current scanline Electronic Speculum, can not to accurately identify rock micro-
The technical barrier of nanoaperture.
Description of the drawings
It, below will be to required use in embodiment in order to illustrate more clearly of the technical solution of embodiment of the present invention
Attached drawing be briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not to be seen as
It is the restriction to range, it for those of ordinary skill in the art, without creative efforts, can be with root
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the flow chart of the scanning electron microscope imaging method of the micro-nano hole of rock of embodiments of the present invention；
Fig. 2 is that hydrazine hydrate, hydroxylamine hydrochloride and ascorbic acid reduction gold nano obtained are respectively adopted in the embodiment of the present invention 1
The transmission electron microscope and scanning electron microscope (SEM) photograph of particle；
Fig. 3 is that the typical case for the blowhole that the gold nanoparticle probe in the embodiment of the present invention 1 with grain size minimum is filled sweeps
Retouch electromicroscopic photograph；
Fig. 4 is that nano silver made from 0.4g, 1.6g, 2.4g polyvinylpyrrolidone is respectively adopted in the embodiment of the present invention 2
Scanning electron microscope (SEM) photograph；
Fig. 5 is that the typical case for the blowhole that the Nano silver grain probe in the embodiment of the present invention 2 with grain size minimum is filled sweeps
Retouch electromicroscopic photograph；
Fig. 6 is that the typical case for the blowhole that the Nano silver grain probe in the embodiment of the present invention 2 with grain size minimum is filled sweeps
The Ag element power spectrums for retouching electromicroscopic photograph assist in identifying figure；
Fig. 7 is the energy spectrum diagram of Fig. 6 labeling positions in the embodiment of the present invention 2；
Fig. 8 is the stereoscan photograph of the positive stearylmercaptan nanogold of surface modification in the embodiment of the present invention 3；
Fig. 9 is in the embodiment of the present invention 3 with the blowhole of the positive stearylmercaptan gold nanoparticle probe filling of surface modification
Typical scan electromicroscopic photograph；
Figure 10 is in the embodiment of the present invention 3 with the blowhole of the positive stearylmercaptan gold nanoparticle probe filling of surface modification
Sjffle dE A typical spectrum Surface scan photo；
Figure 11 is that the scanning electron microscope of the nano silver of the different lower grain size minimums prepared of pH value control in the embodiment of the present invention 4 is shone
Piece；
Figure 12 is the typical scan electricity for the blowhole that the nanometer silver probe in the embodiment of the present invention 4 with grain size minimum is filled
Mirror photo；
Figure 13 is the stereoscan photograph of the Technique of Nano Pd prepared in the embodiment of the present invention 5；
Figure 14 is the typical scan electromicroscopic photograph for the blowhole filled with Technique of Nano Pd probe in the embodiment of the present invention 5；
Figure 15 is the stereoscan photograph of the Platinum Nanoparticles prepared in the embodiment of the present invention 6；
Figure 16 is the typical scan electromicroscopic photograph for the blowhole filled with Platinum Nanoparticles probe in the embodiment of the present invention 6.
Specific implementation mode
It, below will be to embodiment party of the present invention to keep the purpose, technical scheme and advantage of embodiment of the present invention clearer
Technical solution in formula is clearly and completely described.The person that is not specified actual conditions in embodiment or embodiment, according to routine
The condition that condition or manufacturer suggest carries out.Reagents or instruments used without specified manufacturer, being can be by commercially available purchase
Buy the conventional products of acquisition.
Scanning electron microscope imaging method to the micro-nano hole of the rock of embodiment of the present invention and suitable for above-mentioned below
Noble metal nano particles fluid of imaging method and preparation method thereof is specifically described.
Some embodiments of the present invention provide a kind of scanning electron microscope imaging method of the micro-nano hole of rock, packet
It includes：
Noble metal nano particles are injected in the crack and hole of rock；
Blowhole scanning electron microscope imaging to noble metal nano particles filling.
Since brightness is high under scanning electron microscope backscatter mode for noble metal nano particles, (especially have with Rock Matrix
Machine matter) luminance difference clearly, it is highly beneficial for the identification of hole and venturi, and noble metal nano particles can pass through
Synthesis control pattern obtains the single particle of shape size, is different from contour structures complexity more obviously under scanning electron microscope
Natural rock matrix.Therefore, by noble metal nano particles are injected rock crack and hole in after, can be directly using sweeping
It retouches Electronic Speculum and carries out imaging, you can accurately, easily reflect the pore structure of rock.
According to some embodiments, the grain size of noble metal nanoparticle is 2~200nm, such as noble metal nano particles
Grain size can be with 10~150nm, 10~100nm or 15~60nm etc..Nano-particle in above-mentioned particle size range can either meet
Noble metal nano particles can enter the demand in blowhole well, and disclosure satisfy that it under the observation of scanning electron microscope
Imaging can be carried out well to distinguish with rock matter.
According to some embodiments, noble metal nano particles include gold nanoparticle, Nano silver grain, nano platinum particle and
The combination of one or more of Pd nano particle, for example, noble metal nano particles can be gold nanoparticle, it can also
It is Nano silver grain or Pd nano particle, can also be gold nanoparticle, Nano silver grain, nano platinum particle and Pd nano particle
In two or three of nanoparticle mixture.
Some embodiments of the present invention further relate to the preparation method of above-mentioned noble metal nano particles comprising：Using also
Former agent restores precious metal salt.
According to some embodiments, reacted after the solution of reducing agent and precious metal salt is mixed, then centrifuge.It is logical
It crosses and reducing agent and precious metal salt are subjected to hybrid reaction in liquid form fully to contact between reactant, into
And the noble metal nano particles that can be needed.
According to some embodiments, reducing agent include sodium borohydride, potassium borohydride, vitamin C, hydroxylamine hydrochloride, tartaric acid,
Hydrazine hydrate, ethylene glycol, ethyl alcohol, sodium citrate, glucose, tannic acid, ascorbic acid, gallic acid, sodium hypophosphite and formaldehyde
One or more of combination.For example, reducing agent can select sodium borohydride, potassium borohydride, vitamin C, hydrochloric acid hydroxyl
Amine, tartaric acid, hydrazine hydrate, ethylene glycol, ethyl alcohol, sodium citrate, glucose, tannic acid, ascorbic acid, gallic acid, secondary phosphorous
One kind in sour sodium and formaldehyde can also select the mixture of such as ethylene glycol and ethyl alcohol, potassium borohydride and ascorbic mixing
The combination of two kinds of reducing agents such as object.It is of course also possible to be the combination of three kinds or three kinds or more of reducing agent in foregoing description.Together
When, it should be noted that in other embodiments, as long as disclosure satisfy that can make the reducing agent that precious metal salt restores
With, however it is not limited to the above-mentioned reducing agent enumerated.
According to some embodiments, the particle size of the nano material of acquisition can be controlled using different reducing agents.Example
Such as, with glucose, nano metal particles grain size made from this kind of weak reductant is larger, wider distribution, and pattern is not also advised
Then, spherical, strip, triangular shape and other shapes be there is；The nano metal made from this kind of strong reductant with hydrazine hydrate
Particle diameter is smaller, distribution is more uniform.During reducing agent restores precious metal salt, alkali has been additionally added to adjust
Reaction solution is alkalinity.In reaction process, pH value is bigger, and the nano metal particles grain size of synthesis is smaller, and stability is preferable.
According to some embodiments, during reducing agent restores precious metal salt, be additionally added protective agent and
Surface chemical modification agent.The nano-particle that can be avoided the formation of by protective agent is reunited, to reach to noble metal nano
The control of the grain size of particle.Therefore, when the mass ratio of protective agent and precious metal salt reduces, the nano metal particles of synthesis are reunited
It is more serious, and pattern is uneven, improves the mass ratio of protective agent and precious metal salt, can reduce the grain of noble metal nano particles
Diameter.
According to some embodiments, protective agent include trisodium citrate, chitosan, polyvinylpyrrolidone (PVP), poly- pair
Ethylene terephthalate (PET), stearic acid, gum arabic, hydroxypropyl methyl cellulose, sodium alginate, cetyl three
Methyl bromide ammonium (CTAB), lauryl sodium sulfate (SDS), neopelex (SDBS), polyvinyl alcohol (PVA), length
The combination of one or more of chain fatty acid, starch and lauryl mercaptan, it is preferable that protective agent be selected from trisodium citrate,
Polyvinylpyrrolidone, polyethylene terephthalate, stearic acid, gum arabic, hydroxypropyl methyl cellulose, alginic acid
Sodium, cetyl trimethylammonium bromide, lauryl sodium sulfate, neopelex, polyvinyl alcohol, long chain fatty acids,
Any one in starch and lauryl mercaptan, for example, protective agent can be polyvinylpyrrolidone, or cetyl three
Methyl bromide ammonium or sodium alginate or cetyl trimethylammonium bromide etc..
According to some embodiments, surface chemical modification agent includes one kind in cysteine, alkyl hydrosulfide and organic amine
Or two or more combination.For example, surface chemical modification agent can be cysteine, or alkyl hydrosulfide, or
Organic amine or surface chemical modification agent may be the mixture or organic amine and alkyl sulfide of cysteine and alkyl hydrosulfide
The mixture etc. of alcohol.Certainly, in other embodiment, it can also select other that can be modified noble metal particle surfaces
Coating material is not limited to above-mentioned several substances.
According to some embodiments, the change of the fluid media (medium) of nano-fluid by noble metal nano particles by being scattered in water
Or in organic solvent, optionally, organic solvent includes at least one of ethyl alcohol, acetone and ethylene glycol.According to some embodiment party
Formula characterizes the pattern and structure of noble metal nano particles, preferably noble metal is received after noble metal nano particles prepare
Rice corpuscles is spherical or spherical, so that its mobility is more preferable.The characterization of its pattern and structure can utilize scanning electron microscope, thoroughly
Radio mirror and X-ray diffraction are completed.
Size controlling, surface modification, fluid media (medium) and the particle of noble metal nano particles probe are realized by the above method
The parameter optimizations such as concentration realize that nano-fluid injects among rock to facilitate.
According to some embodiments, the porosity of rock is that noble metal nano particles are being injected rock generally 2~30%
Before in stone, rock is carried out
Mechanical polishing, it is preferable that it is Ra0.008~0.012 μm that rock surface, which is polished to its surface roughness,.
According to some embodiments, carried out after above-mentioned noble metal nano particles are prepared into noble metal nano particles fluid
It injects in rock.Therefore, in some embodiments, a kind of preparation method of noble metal nano particles fluid is further related to, it will be above-mentioned
Noble metal nano particles are scattered in water or organic solvent, it is preferable that organic solvent include in ethyl alcohol, acetone and ethylene glycol extremely
Few one kind.In some embodiments, a concentration of 1 × 10 of noble metal nano particles in fluid-2~1 × 10-5mol/L。
According to some embodiments, noble metal nano particles are noted using negative pressure saturation, low pressure displacement or the method for centrifugation
Enter into the crack and hole of rock.
It is different from the casting body flake method of conventional characterization rock pore structure, under the conditions of high pressure pouring and thin slice grind can pair
The original hole state of rock causes a degree of destruction, and the reagent injected is macromolecular material, even if in high pressure injection
Under the conditions of, it is still difficult to be injected into certain micropores, the complex manufacturing process and period is longer；In embodiments of the present invention
In, it is negative pressure saturation, positive pressure low pressure displacement that novel probe, that is, noble metal nano particles, which are filled into the mode in rock core hole,
Or centrifugation.In the method for negative pressure saturation, subnormal ambient is manufactured for Sandstone Cores, the original pore structure of sandstone will not be generated broken
It is bad；In positive pressure low pressure displacement process, filling of the nano-particle to Sandstone Cores hole, actuating pressure are completed by driving device
For environment under low pressure, inlet pressure and outlet pressure difference can also substantially reduce pressure to Sandstone Cores hole knot between 0-1MPa
The extent of the destruction of structure；Noble metal nano particles can carry out controllable surface modification, using surface modification change nano-fluid with
The wetability of rock greatlys improve migration of the nano-particle in blowhole, and it is micro-nano to make it easier to injection rock
Among hole.The control of nano-probe concentration can make nano-probe significantly be filled into sandstone pores in nano-fluid
In micropore and microcrack, show micro-nano hole gap structure to the greatest extent, and implementation process is simple and general experiment
Room can meet observation condition, avoid sample presentation link, shorten experimental period.
Specifically, the method for negative pressure saturation is rock to be soaked in the fluid of noble metal nano particles, then be placed in vacuum
Under environment, so that noble metal nano particles are entered with fluid in rock；Specifically, negative pressure saturation process is saturated using negative pressure
Device is put among rock core is soaked in nano particle fluid in vacuum tank, opens vacuum pump, and system is made to become vacuum shape
State, and then among making nano-particle enter the hole of rock with fluid using the pressure difference of vacuum and atmospheric pressure, complete to receive
Filling of the rice corpuscles to blowhole.
According to some embodiments, your gold is the method for low pressure displacement be the positive pressure difference using the inlet and outlet of driving device by
Belong to nano-particle with fluid displacement into rock, it is preferable that the inlet pressure of driving device is 1~1.5Mpa, and outlet pressure is
Atmospheric pressure.Specifically, displacement test is 1-1.5MPa by driving device, adjusting inlet pressure, and outlet pressure is for atmospheric pressure
0.1MPa.Using the pressure difference of the two, under the action of positive pressure difference, nano-particle is entered into rock core with fluid displacement, and most
The filling to blowhole is completed eventually.
According to some embodiments, the method for centrifugation is the accommodating case being placed in the rock of sheet on centrifugal pan
It is interior, and the fluid for having noble metal nano particles is filled in accommodating case, then centrifugal pan is rotated, it is preferable that centrifugal pan turns
It is fast gradually to increase, after increasing to 9000~11000r/min, keep 15~25min of maximum speed.Specifically, some embodiments
In, the sheet rock sample that diameter is greater than or equal to 0.2cm more than or equal to 0.5cm, length is drilled through, rock sample is cleaned up, is dried to
Rock sample is put into rock sample box by constant weight, and the nano-fluid of synthesis is filled in rock sample box, and rock sample box is packed into centrifugal pan,
From low speed gradually to running at high speed under experimental temperature, after last rotating speed reaches 10000r/min, centrifuge is persistently transported with the rotating speed
Turn 20min.
According to some embodiments rock is randomly selected using scanning electron microscope after injecting noble metal nano particles in rock
The hole and venturi of 30 or more the kens of stone are analyzed.It can be fully scientifically to rock by 30 or more the kens
Pore structure reflected so that the final result is more accurate.
Referring to attached drawing 1, the scanning electron microscope imaging method of the micro-nano hole of rock provided in some embodiments of the invention,
Synthesis and the characterization of noble metal nano particles probe are first carried out, probe is then dispersed in acquisition nanometer stream in suitable fluid
Then body uses low pressure displacement or negative pressure saturation or the method for centrifugation right by probe injection rock core hole, then under scanning electron microscope
Observation is identified in noble metal nano particles filling region, and supplementing analysis by power spectrum determines noble metal nano particles fill area
Domain, to obtain the pore structure of rock.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
0.02mol/L hydrazine hydrates, hydroxylamine hydrochloride and the ascorbic acid solution of 1.0mL Fresh are diluted to respectively
34mL.In the case where being sufficiently stirred, it is rapidly added 1.25mL HAuCl thereto4Storing solution.Solution continues stirring 10 minutes, during which molten
Liquid color will be changed into navy blue rapidly by light yellow.The nanogold of different-grain diameter, such as Fig. 2 is prepared.It is minimum to choose grain size
The gold nanoparticle that is prepared as hole probe, that is, hydrazine hydrate reduction of gold nanoparticle.Hydrazine hydrate reduction is prepared
Nanogold (average grain diameter is 8nm or so) be scattered in ethylene glycol obtain nanoparticle concentration be 3 × 10-4The nanometer of mol/L
Fluid.
Rock core to be analyzed is polished using sand paper manual polishing, is first polished rock sample out-of-flatness place with coarse sandpaper, then successively
With the sand paper of 800 mesh, 2000 mesh, 5000 mesh, rock sample is polishing to surface roughness is 0.008 μm of Ra.Then, by driving device
Inlet outlet pressure differential displacement pressure be adjusted to 1.5MPa, confining pressure is adjusted to 3.0MPa, since to be present in ethylene glycol molten for nano-particle
In liquid, in displacement process, under pressure, during nano-particle displacement enters sandstone pores, ethylene glycol also enters
To Sandstone Cores and occupy the hole of certain volume, so in order to enable the filling effect of sandstone pores is best, using displacement+baking
It after dry method, i.e. displacement to outlet section drain, is dried 6 hours at a temperature of 50 DEG C, is further continued for the experimental method of displacement, repeated
Several times so that loading reaches maximum.
After being cleaned out the nano-probe of excess surface with cotton ball soaked in alcohol, the blowhole of gold nanoparticle filling is swept
Retouch Electronic Speculum imaging.It is conductive since the nano-particle of injection is metallic element, therefore present and highlight under scanning electron microscope mirror,
It can directly be carried out under the microscope in scanning electron microscope, such as Fig. 3.It randomly selects 30 regions to be observed, utilizes gray scale automatic identification
Calculate, obtain rock be averaged Areal porosity be 21.6%.
Embodiment 2
0.4g, 1.6g, 2.4g polyvinylpyrrolidine are taken respectively by the grain size for protecting the dosage of reagent to control nano-particle
Ketone (PVP) is dissolved in 100ml deionized waters, is used in combination ultrasonic disperse instrument that it is made all to dissolve.Appropriate silver nitrate (AgNO is taken again3)、
Potassium borohydride (KBH4), sodium hydroxide (NaOH) solution of a concentration of 0.01mol/l is respectively prepared.4mL 0.01mol/l are taken again
AgNO3It is added in polyvinylpyrrolidone (PVP) solution, and stirs.Then, the KBH of 1mL 0.01mol/l is taken4It is added to
In the NaOH of 4mL 0.01mol/l, and stir；Later, by AgNO3It is added to KBH at a slow speed with the mixed liquor of PVP4With mixing for NaOH
It closes in liquid, and is kept stirring, solution colour in adition process can be observed and gradually change；Finally, reaction half is small under stirring condition
When, nano silver is prepared.
The molecular structure and grain size of obtained nano-particle are characterized using the method for scanning electron microscope.From scanning
From the point of view of Electronic Speculum result, the grain size of synthesizing nano-particle has reached expected requirement between 15-60nm.As shown in figure 4, respectively
Using the scanning electron microscope (SEM) photograph of nano silver made from 0.4g, 1.6g, 2.4g polyvinylpyrrolidone.Choose the silver nanoparticle of grain size minimum
Particle is as hole probe.Nano silver (average grain diameter is 20nm or so) dispersion that 0.4g polyvinylpyrrolidones are prepared
It is 3 × 10 that nanoparticle concentration is obtained in ethyl alcohol-3The nano-fluid of mol/L.
Rock core to be analyzed is polished using sand paper manual polishing, is first polished rock sample out-of-flatness place with coarse sandpaper, then successively
With the sand paper of 800 mesh, 2000 mesh, 5000 mesh, rock sample is polishing to surface roughness is 0.008 μm of Ra.Then, by driving device
Inlet outlet pressure differential displacement pressure be adjusted to 1MPa, confining pressure is adjusted to 2.5MPa, since nano-particle is present in ethanol solution,
In displacement process, under pressure, during nano-particle displacement enters sandstone pores, ethyl alcohol also enters sandstone rock
The heart and the hole for occupying certain volume, so in order to enable the filling effect of sandstone pores is best, using the side of displacement+drying
After method, i.e. displacement to outlet section drain, is dried 6 hours at a temperature of 50 DEG C, is further continued for the experimental method of displacement, is repeated several times,
So that loading reaches maximum.
After being cleaned out the nano-probe of excess surface with cotton ball soaked in alcohol, the blowhole of Nano silver grain filling is swept
Retouch Electronic Speculum imaging.It is conductive since the nano-particle of injection is metallic element, therefore present and highlight under scanning electron microscope mirror,
It can directly be carried out under the microscope in scanning electron microscope, such as Fig. 5.It randomly selects 30 regions to be observed, calculates Areal porosity average value
It is 7.6%.Due to rock texture complexity, the brightness under Electronic Speculum of some mineral is higher, when can not carry out gray scale automatic identification hole,
Can power spectrum supplement analysis further can be carried out in the doubtful filling region of nano-particle, obtain the element composition in the region, due to
Content of the silver element in rock and its small, is such as found that gold element enrichment, then the region is set to nano-scale gold particle in the region
The pore region of son filling.Rock pore structure feature, such as Fig. 6 can be obtained to analyze the silver element in the region,
Corresponding power spectrum elemental analysis is as a result, such as Fig. 7.
Embodiment 3
Take 6mL 0.01mol/L HAuCl4It is added in 150mL deoxidation ultra-pure waters, is put into 60 degrees Celsius of thermostat water baths, and
It is vigorously stirred, rapidly joins excessive 0.2M NH2OHHCl, react 10 minutes, solution becomes bronzing from light yellow, continues anti-
It after answering 30 minutes, is cooled to room temperature, with ultra-pure water and each centrifuge washing of ethyl alcohol 3 times, is dispersed in 200mL alcohol, 4mL is added
The positive stearylmercaptans of 0.0125M react 4 hours, and centrifuge washing is scattered in ethyl alcohol that obtain nanoparticle concentration be 3 for 3 times in ethanol
×10-4The nano-fluid of mol/L.The positive stearylmercaptan nanogold of surface modification being prepared is as hole probe, such as Fig. 8.
Rock core to be analyzed is polished using sand paper manual polishing, is first polished rock sample out-of-flatness place with coarse sandpaper, then successively
With the sand paper of 800 mesh, 2000 mesh, 5000 mesh, rock sample is polishing to surface roughness is 0.008 μm of Ra.Rock core is soaked in again
Among nano-particle solution, be put into vacuum tank, open vacuum pump, make system become vacuum state, and then using vacuum with
The pressure difference of atmospheric pressure makes nano-particle be entered with solution among the hole of rock, completes nano-particle to blowhole
Filling.
Rock sample is dried 6 hours at a temperature of 50 DEG C, is cleaned out the nano-probe of excess surface with cotton ball soaked in alcohol
Afterwards, it can directly be carried out under the microscope in scanning electron microscope, such as Fig. 9.It randomly selects 33 regions to be observed, it is average to calculate Areal porosity
Value is 3.9%.
Due to rock texture complexity, the brightness under Electronic Speculum of some mineral is higher, can be into when can not carry out gray scale automatic identification
One step can carry out power spectrum supplement analysis in the doubtful filling region of nano-particle, the element composition in the region be obtained, due to gold dollar
Content of the element in rock and its small, is such as found that gold element enrichment, then the region is set to nano Au particle and fills out in the region
The pore region filled.Rock pore structure feature, such as Figure 10 can be obtained to analyze the gold element in the region.
Embodiment 4
First, it takes 0.4g trisodium citrates to be dissolved in 100ml deionized waters, ultrasonic disperse instrument is used in combination that it is made all to dissolve.
Take appropriate silver nitrate, sodium borohydride, sodium hydroxide (NaOH) that the solution of a concentration of 0.01mol/l is respectively prepared again.It takes again
4mL0.01mol/l AgNO3It is added in citric acid three sodium solution, and stirs.Then, the sodium borohydride of 1mL0.01mol/l is taken
It is added separately in the NaOH of 0.5mL, 2mL and 4mL0.01mol/l, and stirs；Pass through NaOH addition control ph.Then
By AgNO3It is added at a slow speed in the mixed liquor of sodium borohydride and NaOH, and is kept stirring with the mixed liquor of trisodium citrate, it is considerable
Solution colour in adition process is observed to gradually change；Finally, half an hour is reacted under stirring condition, different pH controls is prepared
Nano silver.The Nano silver grain of selection grain size minimum is added NaOH as hole probe (average grain diameter is 50nm or so) and is
An example of 4mL0.01mol/l, such as Figure 11, it is 3 × 10 to be scattered in acquisition nanoparticle concentration in ethyl alcohol-5The nanometer stream of mol/L
Body.Rock core to be measured using sand paper manual polishing polish, first rock sample out-of-flatness place is polished with coarse sandpaper, then successively with 800 mesh,
2000 mesh, 5000 mesh sand paper by rock sample be polishing to surface roughness be 0.012 μm of Ra.Rock core is soaked in nano-particle again
It among solution, is put into vacuum tank, opens vacuum pump, so that system is become vacuum state, and then utilize vacuum and atmospheric pressure
Pressure difference makes nano-particle be entered with solution among the hole of rock, completes filling of the nano-particle to blowhole.
Rock sample is dried 6 hours at a temperature of 50 DEG C, is cleaned out the nano-probe of excess surface with cotton ball soaked in alcohol
Afterwards, it can directly be carried out under the microscope in scanning electron microscope, such as Figure 12.It randomly selects 33 regions to be observed, it is flat to calculate Areal porosity
Mean value is 18.8%.
Embodiment 5
It takes 0.4g trisodium citrates to be dissolved in 100ml deionized waters, ultrasonic disperse instrument is used in combination that it is made all to dissolve.It takes again suitable
The solution of a concentration of 0.01mol/l is respectively prepared in amount palladium bichloride, sodium borohydride, sodium hydroxide (NaOH).4mL is taken again
The PdCl of 0.01mol/l2It is added in citric acid three sodium solution, and stirs.Then, the sodium borohydride of 1mL0.01mol/l is taken to be added
Into the NaOH of 4mL0.01mol/l, and stir；Later, by PdCl2It is added to boron hydrogen at a slow speed with the mixed liquor of trisodium citrate
It in the mixed liquor for changing sodium and NaOH, and is kept stirring, solution colour in adition process can be observed and gradually change；Finally, it stirs
Under the conditions of react half an hour, nano-probe, such as Figure 13 is prepared.It after centrifugation, distributes it in ethanol solution, is obtained
Nanoparticle concentration is 3 × 10-4The Technique of Nano Pd fluid of mol/L.
Then, the sheet rock sample that diameter is greater than or equal to 0.2cm more than or equal to 0.5cm, length is drilled through, using sand paper people
Work sanding and polishing is first polished rock sample out-of-flatness place with coarse sandpaper, then successively will with the sand paper of 800 mesh, 2000 mesh, 5000 mesh
It is 0.010 μm of Ra that rock sample, which is polishing to surface roughness,.Rock sample is cleaned up, drying to constant weight, rock sample is put into rock sample box
It is interior, and fill in rock sample box the nano-fluid of synthesis, rock sample box is packed into centrifugal pan, under experimental temperature from low speed gradually to
It runs at high speed, after last rotating speed reaches 10000r/min, centrifuge is with rotating speed continuous running 20min.Complete nano-particle pair
The filling of blowhole.
Rock sample is dried 6 hours at a temperature of 50 DEG C, is cleaned out the nano-probe of excess surface with cotton ball soaked in alcohol
Afterwards, it can directly be carried out under the microscope in scanning electron microscope, such as Figure 14.Finally, 35 regions are randomly selected to be observed, face is calculated
Rate average value is 11.2%.
Embodiment 6
It takes 0.4g trisodium citrates to be dissolved in 100ml deionized waters, ultrasonic disperse instrument is used in combination that it is made all to dissolve.It takes again suitable
The solution of a concentration of 0.01mol/l is respectively prepared in amount platinum chloride, sodium borohydride, sodium hydroxide (NaOH).4mL is taken again
The PtCl of 0.01mol/l4It is added in citric acid three sodium solution, and stirs.Then, the sodium borohydride of 1mL0.01mol/l is taken to be added
Into the NaOH of 4mL0.01mol/l, and stir；Later, by PtCl4It is added to boron hydrogen at a slow speed with the mixed liquor of trisodium citrate
It in the mixed liquor for changing sodium and NaOH, and is kept stirring, solution colour in adition process can be observed and gradually change；Finally, it stirs
Under the conditions of react half an hour, platinum nano-probe, such as Figure 15 is prepared.It after centrifugation, distributes it in ethanol solution, is received
Miboplatin fluid.
Then, the sheet rock sample that diameter is greater than or equal to 0.2cm more than or equal to 0.5cm, length is drilled through, using sand paper people
Work sanding and polishing is first polished rock sample out-of-flatness place with coarse sandpaper, then successively will with the sand paper of 800 mesh, 2000 mesh, 5000 mesh
It is 0.010 μm of Ra that rock sample, which is polishing to surface roughness,.Rock sample is cleaned up, drying to constant weight, rock sample is put into rock sample box
It is interior, and fill in rock sample box the nano-fluid of synthesis, rock sample box is packed into centrifugal pan, under experimental temperature from low speed gradually to
It runs at high speed, after last rotating speed reaches 10000r/min, centrifuge is with rotating speed continuous running 20min.Complete nano-particle pair
The filling of blowhole.
Rock sample is dried 6 hours at a temperature of 50 DEG C, is cleaned out the nano-probe of excess surface with cotton ball soaked in alcohol
Afterwards, it can directly be carried out under the microscope in scanning electron microscope, such as Figure 16.Finally, 30 kens bored sample at random using scanning electron microscope
Hole and venturi, it is 3.8% to calculate Areal porosity average value.
In conclusion since brightness is high under scanning electron microscope backscatter mode for noble metal nano particles, with Rock Matrix
Luminance difference clearly, it is highly beneficial for the identification of hole and venturi, and noble metal nano particles can pass through synthesis
It controls pattern and obtains the single particle of shape size, be different from natural rock matrix more obviously under scanning electron microscope；Nanometer
Particle can carry out controllable surface modification, and the electriferous state of control surface and polarity etc. help to improve nano-fluid and rock
The state of interface of stone facilitates nano-particle to inject among blowhole；Only need nano-particle, negative pressure full in embodiment of the present invention
Sample making can be completed with instrument and conventional driving device or centrifuge, recycle scanning electron microscopic observation.Implemented
Journey is simple and common laboratory can meet observation condition, avoids sample presentation link, shortens experimental period.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of scanning electron microscope imaging method of the micro-nano hole of rock, which is characterized in that it includes：
Noble metal nano particles are injected in the crack and hole of rock；
Blowhole scanning electron microscope imaging to noble metal nano particles filling.
2. the scanning electron microscope imaging method of the micro-nano hole of rock according to claim 1, which is characterized in that your gold
The grain size for belonging to nanoparticle is 2~200nm, preferably 10~100nm, more preferable 15~60nm, it is preferable that the noble metal nano
Particle includes the combination of one or more of gold nanoparticle, Nano silver grain, nano platinum particle and Pd nano particle.
3. the scanning electron microscope imaging method of the micro-nano hole of rock according to claim 1, which is characterized in that will be described expensive
Metal nanoparticle is injected into using negative pressure saturation, low pressure displacement or the method for centrifugation in the crack and hole of rock.
4. the scanning electron microscope imaging method of the micro-nano hole of rock according to claim 3, which is characterized in that the negative pressure
The method of saturation be the rock is soaked in the fluid of the noble metal nano particles, then be placed under vacuum environment so that
The noble metal nano particles are entered with fluid in the rock；
The method of the low pressure displacement be using driving device inlet and outlet positive pressure difference by the noble metal nano particles with
Fluid displacement is into the rock, it is preferable that the inlet pressure of the driving device is 1~1.5Mpa, and outlet pressure is air
Pressure；
The method of the centrifugation is that the columnar rock is placed in the accommodating case on centrifugal pan, and the accommodating case
Inside filling has the fluid of the noble metal nano particles, then the centrifugal pan is rotated, it is preferable that the centrifugal pan turns
It is fast gradually to increase, after increasing to 9000~11000r/min, keep 15~25min of maximum speed.
5. according to the scanning electron microscope imaging method of the micro-nano hole of Claims 1 to 4 any one of them rock, feature exists
In the porosity of the rock is 2~30%, it is preferable that is injected before the noble metal nano particles, to the table of the rock
Face is mechanically polished, it is preferable that it is Ra0.008~0.012 μm that the rock surface, which is polished to its surface roughness,；
Preferably, the hole and venturi that 30 or more the kens of the rock are randomly selected using scanning electron microscope are analyzed.
6. a kind of preparation method of noble metal nano particles, which is characterized in that the noble metal nano particles are wanted suitable for right
Seek the scanning electron microscope imaging method of 1~5 micro-nano hole of any one of them rock comprising：Using reducing agent to noble metal
Salt is restored；Preferably, it reacts, then centrifuges after the solution of the reducing agent and the precious metal salt being mixed.
7. the preparation method of noble metal nano particles according to claim 6, which is characterized in that the reducing agent includes boron
Sodium hydride, potassium borohydride, vitamin C, hydroxylamine hydrochloride, tartaric acid, hydrazine hydrate, ethylene glycol, ethyl alcohol, sodium citrate, glucose, list
The combination of one or more of peaceful acid, ascorbic acid, gallic acid, sodium hypophosphite and formaldehyde.
8. the preparation method of the noble metal nano particles described according to claim 6 or 7, which is characterized in that in the reducing agent
During being restored to the precious metal salt, it is additionally added protective agent and surface chemical modification agent；
Preferably, the protective agent includes trisodium citrate, chitosan, polyvinylpyrrolidone, polyethylene terephthalate
Ester, stearic acid, gum arabic, hydroxypropyl methyl cellulose, sodium alginate, cetyl trimethylammonium bromide, dodecyl
One or more of sodium sulphate, neopelex, polyvinyl alcohol, long chain fatty acids, starch and lauryl mercaptan
Combination；
Preferably, the surface chemical modification agent includes one or more of cysteine, alkyl hydrosulfide and organic amine
Combination.
9. a kind of preparation method of noble metal nano particles fluid, which is characterized in that will be according to the system described in claim 6~8
The noble metal nano particles that Preparation Method is prepared are scattered in organic solvent, it is preferable that the noble metal nano particles it is dense
Degree is 1 × 10-2~1 × 10-5Mol/L, it is preferable that the organic solvent includes at least one of ethyl alcohol, acetone and ethylene glycol.
10. a kind of noble metal nano particles fluid, which is characterized in that it is by the noble metal nano particles stream described in claim 9
The preparation method of body is prepared.
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| CN112296348B (en) * | 2020-08-20 | 2022-11-04 | 成都理工大学 | Hydrophobic noble metal nano tracer liquid, preparation method and application |
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| CN112304999B (en) * | 2020-09-16 | 2023-09-15 | 宜宾学院 | Quantitative statistical method for shale micro-nano pore characteristics of scanning electron microscope |
| CN113433038A (en) * | 2021-05-31 | 2021-09-24 | 昆明理工大学 | Novel method for selecting mixed nano fluid particle combination |
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