CN110014167A - The detection method of furfural in auri ping-pong ball surface enhanced material and transformer oil - Google Patents
The detection method of furfural in auri ping-pong ball surface enhanced material and transformer oil Download PDFInfo
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- CN110014167A CN110014167A CN201910322173.8A CN201910322173A CN110014167A CN 110014167 A CN110014167 A CN 110014167A CN 201910322173 A CN201910322173 A CN 201910322173A CN 110014167 A CN110014167 A CN 110014167A
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- auri
- ping
- surface enhanced
- pong ball
- ball surface
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 240000006409 Acacia auriculiformis Species 0.000 title claims abstract description 39
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims description 68
- 238000001514 detection method Methods 0.000 title claims description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229960004756 ethanol Drugs 0.000 claims abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000001509 sodium citrate Substances 0.000 claims abstract description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- 238000001069 Raman spectroscopy Methods 0.000 claims description 38
- 239000003921 oil Substances 0.000 claims description 34
- 238000001237 Raman spectrum Methods 0.000 claims description 17
- 230000003287 optical effect Effects 0.000 claims description 17
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 230000005284 excitation Effects 0.000 claims description 10
- 230000002708 enhancing effect Effects 0.000 claims description 5
- 241000931526 Acer campestre Species 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 230000010354 integration Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 2
- 238000007664 blowing Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- JBPWDTQELHPIPV-UHFFFAOYSA-N n-(3,6-dihydro-2h-pyridin-1-yl)pyridine-4-carboxamide Chemical compound C=1C=NC=CC=1C(=O)NN1CCC=CC1 JBPWDTQELHPIPV-UHFFFAOYSA-N 0.000 description 11
- 229920001469 poly(aryloxy)thionylphosphazene Polymers 0.000 description 11
- 230000003595 spectral effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004624 confocal microscopy Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000023004 detection of visible light Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010616 electrical installation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- -1 methoxyl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- 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
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N2021/653—Coherent methods [CARS]
- G01N2021/655—Stimulated Raman
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
Auri ping-pong ball surface enhanced material, it is that silver nano-grain is assembled in made from golden film surface as coupling agent as chemical preparation process using 4- aminothiophenol, it is prepared especially by following steps: (1) synthesizing silver sol solution: after the silver nitrate aqueous solution of 1mM is heated to boiling, the sodium citrate aqueous solution that mass fraction is 1% is added, continues heating 1h and solution is kept to be in fluidized state；(2) golden film is modified: by golden film respectively in deionized water and dehydrated alcohol after ultrasound 20min at room temperature with being dried with nitrogen, then it is placed at room temperature in the ethanol solution of 4- aminothiophenol and deposits 4-10h, the 4- aminothiophenol molecule that surface is not bound with is washed after taking-up；And (3) in golden film surface-assembled silver nano-grain: modified golden film being impregnated at least 10h with being dried with nitrogen to be placed in silver sol solution, is washed out, is stored for future use at room temperature with after being dried with nitrogen.
Description
Technical field
The invention belongs to insulation of electrical installation on-line monitoring and fault diagnosis fields, and in particular to a kind of auri ping-pong ball surface
Reinforcing material and using auri ping-pong ball surface enhanced material as the detection of furfural in the transformer oil of surface enhanced base material
Method.
Background technique
Transformer is in During Process of Long-term Operation, due to the effect by factors such as temperature, electric field, moisture and oxygen, absolutely
Cellulose chain fracture generates furan derivative and is dissolved in transformer oil in edge paper, and wherein furfural content highest, is to comment at present
Estimate one of most common index of paper oil insulation degree of aging.
Surface enhanced Raman spectroscopy (Surface-enhanced Raman Scattering, SERS) technology is enhancement solution
One of most common method of body sample Raman signal, it can obtain target with six orders of magnitude or higher intensification factor in principle
The finger-print of substance.Preprocessing process of the Surface enhanced Raman spectroscopy technology using laser as detection means, without complexity
Quick, the lossless in situ detection that can realize target substance in mixing liquid dissolves aging character object in transformer oil
Detection field has a good application prospect.
But due in operating transformer oil complicated component, furfural content it is lower, Furfural Molecule Raman signal is dissolved in oil
Relative intensity it is weaker.Therefore.Need to develop a kind of enhancing substrate that can effectively enhance and dissolve Furfural Molecule Raman signal in oil
The Raman spectra detection process of furfural in material and corresponding transformer oil.
Summary of the invention
In view of problems of the prior art, one aspect of the present invention provides a kind of auri ping-pong ball surface enhanced material, institute
Stating auri ping-pong ball surface enhanced material is to pass through chemical preparation process for silver nano-grain group by coupling agent of 4- aminothiophenol
Made from golden film surface.
Preferably, range of the size of the silver nano-grain in 50-60nm.
Preferably, the golden film be plated in silicon chip substrate with a thickness of 100nm, having a size of 0.5cm × 0.5 cm
Golden film.
Preferably, the auri ping-pong ball surface enhanced material is prepared by following steps: (1) synthesizing silver sol solution: will
Concentration is that 1/50 quality point that volume is silver nitrate aqueous solution volume is added after the silver nitrate aqueous solution of 1mM is heated to boiling
The sodium citrate aqueous solution that number is 1% continues heating 1h and solution is kept to be in fluidized state；(2) golden film is modified: will be golden
Film respectively in deionized water and dehydrated alcohol after ultrasound 20min at room temperature with being dried with nitrogen, then at room temperature by golden film
It is placed in the ethanol solution of 4- aminothiophenol and deposits 4-10h, rushed repeatedly after being drawn off with deionized water and dehydrated alcohol
It washes, removes the 4- aminothiophenol molecule that surface is not bound with；And (3) in golden film surface-assembled silver nano-grain: will be
Modified golden film impregnates at least 10 with being dried with nitrogen to be placed in step (1) in prepared silver sol solution in step (2)
H is stored for future use with after being dried with nitrogen at room temperature then with alternately washing at least four times of dehydrated alcohol and deionized water.
Preferably, in the ethanol solution of the 4- aminothiophenol concentration of 4- aminothiophenol molecule in 0.05-
The range of 0.2mol/L.
Preferably, the concentration of 4- aminothiophenol molecule is 0.1 mol/L in the ethanol solution of the 4- aminothiophenol.
On the other hand, the present invention also provides furfural situ Raman Spectroscopy detection method in a kind of oil, the method is with above-mentioned
Auri ping-pong ball surface enhanced material is as surface enhanced base material, comprising the following steps: (1) increases auri ping-pong ball surface
Strong material is put into transformer oil to be detected, connects the auri ping-pong ball surface enhanced material sufficiently with transformer oil to be detected
Touching；(2) transformer oil to be detected that placed auri ping-pong ball surface enhanced material in step (1) is appropriate relative to excitation light source
Ground is placed, so that focus laser energy is in the upper surface of the auri ping-pong ball surface enhanced material；(3) under single optical maser wavelength into
Row in situ detection simultaneously acquires raman spectrum.
Preferably, the optical maser wavelength selection 532nm, laser power 100mW, time of integration 3s, integral number of times are
100, slit width is 50 μm, selects 600l/500nm type grating, and Raman spectrum detection range is 250-2500cm-1。
Preferably, characteristic peak of the furfural in Surface enhanced Raman spectroscopy detection is chosen to be in the transformer oil
1662cm-1, minimum detectable concentration 1.06mg/L.
Furfural in oil is carried out as surface enhanced substrate using auri ping-pong ball surface enhanced material provided by the present invention
When situ Raman Spectroscopy detects, the characteristic peak of furfural is chosen to be 1662cm in oil-1, the sensitivity of detection is significantly improved, especially
It is compared with the gold enhancing substrate that team where inventor developed in 2016 using multilayer coupling method, and minimum detection is dense
Degree is reduced to 1.06mg/L by 4.8mg/L.
Detailed description of the invention
Fig. 1 is the preparation flow figure of auri ping-pong ball surface enhanced material of the invention.
Fig. 2 is the sem image of auri ping-pong ball surface enhanced material prepared in the embodiment of the present invention.
Fig. 3 is the composition schematic diagram of Confocal laser-scanning microscopy detection platform used in one embodiment of the invention.
Fig. 4 is spectrogram, and wherein curve (a) is the SERS spectra figure of 100mg/L furfural transformer oil solution, curve (b)
It is the SERS spectra figure of individual auri ping-pong ball surface enhanced base material, curve (c) is the Raman spectrogram of pure furfural.
Specific embodiment
A specific embodiment of the invention is described in detail below in conjunction with attached drawing.
Embodiment 1: the preparation of auri ping-pong ball surface enhanced material
The preparation of auri ping-pong ball surface enhanced material generallys include three steps: (1) synthesizing silver sol solution；(2) to gold
Film surface is modified；And (3) in golden film surface-assembled silver nano-grain.It is specific as follows.
(1) silver sol solution is synthesized
After the silver nitrate aqueous solution that 200ml concentration is 1mM is heated to boiling, addition volume is silver nitrate aqueous solution volume
The sodium citrate aqueous solution that the mass fraction of 1/50 (that is, 4ml) is 1%, continuing heating 1h makes solution keep fluidized state, molten
Liquid color gradually becomes milky and bit greenish from colorless and transparent state.
(2) golden film surface is modified
Will with a thickness of 100nm, the golden film having a size of 0.5cm × 0.5cm respectively in deionized water and dehydrated alcohol it is ultrasonic
Golden film is placed in the 4- aminothiophenol of 0.1mol/L then at room temperature with being dried with nitrogen by 20min at room temperature later
(PATP) 4-10h is deposited in ethanol solution, and deionized water and dehydrated alcohol repeated flushing are used after taking-up, removes surface and does not tie
The PATP molecule of conjunction.Wherein, sedimentation time of the golden film in the ethanol solution of 4- aminothiophenol is preferably 5h.
(3) in golden film surface-assembled silver nano-grain
Modified golden film in step (2) is placed in step (1) in prepared silver sol solution with being dried with nitrogen
Continue to impregnate 12h, then with alternately washing at least four times of dehydrated alcohol and deionized water, be stored at room temperature with after being dried with nitrogen
It is spare.
Fig. 2 is to make coupling agent auri ping-pong ball surface enhanced material prepared by self assembly Nano silver grain in golden film with PATP
The SEM electron microscope of material, it can be seen that Nano silver grain is relatively uniform in the distribution of golden film surface, in golden film surface unit area
The silver nanoparticle ball of absorption is more.It is closed this is because being bonded between PATP molecule and golden film substrate with Au-S, meanwhile, in PATP molecule
Since the presence of phenyl ring makes it have higher rigidity, almost all of terminal amino is all far from substrate upward rather than to surface
Inclination or bending.With coupling agent 3- aminopropyl commonly used in the prior art-trimethoxy silane (APTMS) molecule methoxyl group water
The hydroxy combining of Xie Houyu silicon chip surface is compared, more stable with the combination of Au-S key between PATP molecule and golden film substrate.This
Outside, APTMS molecule is more flexible, and terminal amino is easier to tilt or be bent, to hinder between Nano silver grain and amino
Electrostatic Absorption.
Embodiment 2: the Raman in situ detection of furfural is dissolved in oil
Using auri ping-pong ball surface enhanced material prepared by embodiment 1 as surface enhanced base material, pass through copolymerization
Burnt Raman spectrum detection platform detects the furfural in transformer oil, obtains and dissolves furfural Raman spectrum in oil, determines chaff
Aldehyde characteristic peak.
Confocal laser-scanning microscopy detection platform is by excitation light source module, filtration module, optical path guidance system, spectrometer and spy
It surveys the part such as device to form, as shown in Figure 3.
Excitation light source is mainly used for providing the Raman diffused light of narrow linewidth, and the Raman of excited species is used for as incident light
Scatter light.The excitation light source of Confocal laser-scanning microscopy detection platform used in the present embodiment has selected Cobolt company 04-
01SambaTMSerial 532nm type solid-state semiconductor continuous wave laser is further provided with RGB as excitation light source
The Novapro series 785nm compact continuous conductor laser of Lasersystems company alternately excitation light source.
Filtration module can be such that the scattering light in particular range of wavelengths passes through, and then filter out the interference such as Rayleigh scattering light letter
Number, mainly by a series of filter sets at.It has been installed additional at 532nm and 785nm laser exit by Semrock company
Interference-type optical filter and Edge Filter bandpass-type filter set at filter set, so as to filter out laser sending other
Miscellaneous line.Filter set has been installed additional respectively for two wavelength of 532nm and 785nm in the preceding optical path of entrance slit, to realize filter
Except incident laser, pass through the function of Raman diffused light.Every road filter set is filtered by two panels semrock company edge filter type
Mating plate composition: it is a piece of to be fixed with low-angle, can further improving laser reflection efficiency；Another adjustable angle, can
To meet the acquisition demand to different range lower wave number Raman signal, two panels filter plate mutually tunes the suppression guaranteed to incident laser
System is than being greater than OD8.Two groups of optical filters are fixed on disk, can be by between rotating circular disc completion two optical paths of 532nm and 785nm
Switching.
Optical path guidance system is mainly used for by incident laser collimated illumination in sample to be tested, while to the drawing that sample generates
Graceful scattering light is collected and imports subsequent filtration module.Surface enhanced Raman spectroscopy detection platform used herein uses
Micro- optical path form, selecting Leica DM2700 type just setting microscope is main component, is simplified to confocal microscopy
Built confocal microscopy light path, wherein equipped with 10 × and 100 × high-performance fluorite objective, 50 × dark field object lens and
50 × object lens of focal length.90 ° of horizontal adapters have been designed and produced according to object lens mirror holder head.Equipped with reflective dark field in microscope
Attachment is further provided with color cmos surveillance camera, can be by focus point and the image transmitting on detectable substance surface to computer screen
It is observed.Objective table is furnished with XYZ manual sample platform, and accuracy of reading reaches 0.01mm, and three-dimensional continuous moving observation may be implemented；
Incident laser is directed immediately into micro- optical axis, increases point of irradiation hot spot, reduces costs and optical path is to mechanical stability
Demand.Under 532nm laser irradiation, transverse spatial resolution and longitudinal space resolution ratio can respectively reach 1 μm and 2 μm.
Raman spectrometer has selected the SR-500i color dispersion-type Raman spectrometer of Andor company, which is equipped with
Three blocks of 600l/mm type, 1200l/mm type and 1800l/mm type gratings, by select the grating of different grooves can meet wide spectrum,
Three kinds of detection demands of near-infrared and high-resolution.With good throughput and spectral sensitivity, three rank of monocrystalline silicon is detected
The signal-to-noise ratio of Raman signal is higher than 30:1；Two entrance slits are equipped with, side is as confocal elliptical waveguide optical path entrance, the other side
F/# adaptation F-matcher is then installed, the fiber Raman optical path entrance that the later period builds is reserved as；Under 532nm laser excitation
Spectral region is up to 50-8000cm-1, spectral region is then 50-5000cm under 785nm laser excitation-1, can satisfy various
The range requirement of liquid substance detection.
Raman optical signal after light splitting can be switched to electric signal by detector, and import data analysis module in the form of spectrogram into
Row processing and analysis.Confocal laser-scanning microscopy detection platform used in the present embodiment is due to having selected 532 and 785nm two-way
Laser need to complete the quick detection of visible light all band Raman scattering signal.Therefore, the iDus-416 of Andor company is selected
Type CCD is installed on Raman spectrometer interface as detector.This CCD chip is reached having a size of 3.8 × 30mm, resolution ratio
To 256 × 2000, sensitivity with higher, spectral detection range is 200-1100nm, be can satisfy ultraviolet to near-infrared
The detection demand of Raman scattering signal, dark noise are less than 0.0006e/s/pixel, and minimum reachable -95 DEG C of cryogenic temperature, reading is made an uproar
Sound is less than 5e/pixel, has good signal-to noise ratio to faint Raman signal is detected；Quantum efficiency within the scope of 500-870nm is not
Lower than 80%, its detection sensitivity can be further promoted.
Using the Raman spectrogram of above-mentioned Confocal laser-scanning microscopy detection platform test sample, optical maser wavelength is selected
532nm, laser power 100mW, time of integration 3s, integral number of times 100, slit width are 50 μm, select 600l/
500nm type grating, acquires the Raman spectrum of respective sample, is determined according to Raman frequency shift locating for the raman characteristic peak of Furfural Molecule
Raman spectrum detection range is 250-2500cm-1。
Based on above-mentioned Surface enhanced Raman spectroscopy detection platform, with the auri silver nanoparticle ball enhancing prepared according to embodiment 1
Material is determined in transformer oil using the transformer oil sample of the furfural containing 100mg/L as surface enhanced substrate and dissolves Furfural Molecule
Surface-enhanced Raman characteristic peak and transformer oil in dissolve furfural minimum concentrations.The following institute of concrete operations process
It states.
Firstly, carrying out spectrum correction, with high-purity silicon wafer, it is based on its 521cm-1It is inclined to spectrum on the basis of the Raman signal at place
Shifting amount is corrected.
Next, surface enhanced base material and liquid to be detected are placed in quartz colorimetric utensil, liquid to be detected sample
After filling cuvette, a period of time is stood, it is ensured that surface enhanced base material comes into full contact with liquid to be detected sample.
Next, choosing test point, the quartz colorimetric utensil equipped with sample to be tested is placed horizontally on microscope carrier,
Objective table height is adjusted by Z axis, so that laser is focused on the upper surface of surface enhanced substrate, is in conjunction with CMOS surveillance camera
Existing image selectes test point position by adjusting X-Y axis.
Then, detection parameters are set, select 532nm laser as excitation light source, 50 × telephoto lens, 600l/mm type light
Grid, slit width are 100 μm, time for exposure 1s, are integrated 10 times, laser power 25mW.
Finally, handling the spectrogram obtained in detection process, the raman spectrum that will acquire carries out baseline, noise reduction etc.
Then pretreatment operation selectes characteristic peak and carries out qualitative and quantitative analysis.
Meanwhile using individual auri ping-pong ball surface enhanced material and pure furfural as experimental control, theirs are acquired respectively
Surface enhanced Raman spectroscopy figure or Raman spectrogram.
Fig. 4 is collected spectrogram in detection process, and wherein curve (a) is 100mg/L furfural transformer oil solution
Surface enhanced Raman spectroscopy figure, curve (b) are the Surface enhanced Raman spectroscopy figures of individual auri ping-pong ball surface enhanced material, bent
Line (c) is the Raman spectrogram of pure furfural.
Comparative analysis curve (a), (b) and (c), have carried out preliminary ownership to the main Raman peaks source in curve (a), bent
In line (a) and curve (b) 1072,1139,1183,1386,1431,1570cm-1 Raman peaks belong to is coupling molecule PATP
Characteristic peak.Since PATP is for connecting silver nano-grain and golden film, by the effect by electromagnetic coupling between the two, make its drawing
Graceful signal enhancing, therefore occur the very strong Raman signal of PATP molecule in spectrogram.
Meanwhile with (c) comparison it can be found that these Raman signals are Chong Die with furfural raman spectra serious, to furfural detection
Bring severe jamming.1229,1272,1570,1662cm-1This everywhere raman spectra from furfural, with the 1224 of pure furfural,
1281、1569、1670cm-1Raman spectra compares everywhere for this, the results showed that in golden film prepared by self assembly silver nanoparticle ball
Surface enhanced substrate can effectively enhance in transformer oil dissolve furfural Raman signal.
When carrying out the detection of compounding substances, each substance could be carried out accurately to determine by selecting correct Characteristic Raman spectral peak
Property and quantitative analysis, the Characteristic Raman spectral peak of each substance according to the prior art determine each substance Characteristic Raman spectrum
Peak.The Characteristic Raman spectral peak of selected substance, it should not with the peak overlap of other compositions, intensity with higher, and draw
In graceful spectrometer detection range.
According to the selection principle of the above Raman signatures spectral peak, 1570cm-1Locate raman spectra and substrate itself Raman signal weight
It is folded, 1229cm-1、1272cm-1With 1662cm-1It is relatively independent to locate raman spectra, but 1662cm-1It is higher to locate raman spectra intensity,
Therefore 1662cm is chosen-1As in transformer oil dissolve Furfural Molecule Surface enhanced Raman spectroscopy detection in feature spectral peak,
So that better detection sensitivity can be obtained.In the present invention, with 1662cm-1Place's raman spectra is as dissolving chaff in transformer oil
Feature spectral peak of the aldehyde molecule in Surface enhanced Raman spectroscopy detection, can be realized minimum detectable concentration is 1.06mg/L.
By embodiment 1 and embodiment 2 it is found that golden film is sunk in PATP ethanol solution when PATP concentration is 0.1mol/L
The particle arrangement on auri silver nanoparticle ball reinforcing material surface prepared under the conditions of immersion 12h is uniform, tight in product 5h, silver sol
Close, no particle cluster has best reinforcing effect, shows good homogeneity and consistency.With the auri silver nanoparticle ball
Reinforcing material, can be low with the minimum detectable concentration that Surface enhanced Raman spectroscopy method detects furfural as surface enhanced substrate
To 1.06mg/L.
While there has been shown and described that some exemplary embodiments of the invention, those skilled in the art should manage
It, can be right in the case where solution, the principle of the invention limited in without departing substantially from claim and their equivalent scheme and spirit
These exemplary embodiments make variation.Without departing from the scope and spirit of illustrated each embodiment, for this
Many modifications and changes are obvious for the those of ordinary skill of technical field.The selection of term used herein,
It is intended to best explain the principle of each embodiment, practical application or to the technological improvement in market, or makes the art
Other those of ordinary skill can understand each embodiment disclosed herein.
Claims (9)
1. a kind of auri ping-pong ball surface enhanced material, it is characterised in that: the auri ping-pong ball surface enhanced material is with 4- amino
Benzenethiol is that silver nano-grain is assembled in made from golden film surface by coupling agent as chemical preparation process.
2. auri ping-pong ball surface enhanced material according to claim 1, it is characterised in that: the size of the silver nano-grain
In the range of 50-60nm.
3. auri ping-pong ball surface enhanced material according to claim 1 or 2, it is characterised in that: the golden film is to be plated on
In silicon chip substrate with a thickness of 100nm, having a size of the golden film of 0.5cm × 0.5cm.
4. oil auri ping-pong ball surface enhanced material according to claim 1, it is characterised in that:
The auri ping-pong ball surface enhanced material is prepared by following steps:
(1) synthesize silver sol solution: after the silver nitrate aqueous solution that concentration is 1mM is heated to boiling, addition volume is silver nitrate
The sodium citrate aqueous solution that the mass fraction of aqueous solution volume 1/50 is 1% continues heating 1h and solution is kept to be in fluidized state；
(2) golden film is modified: golden film is used into nitrogen after ultrasound 20min in deionized water and dehydrated alcohol respectively at room temperature
Air-blowing is dry, is then placed in golden film at room temperature in the ethanol solution of 4- aminothiophenol and deposits 4-10h, uses after being drawn off
Deionized water and dehydrated alcohol repeated flushing remove the 4- aminothiophenol molecule that surface is not bound with；And
(3) in golden film surface-assembled silver nano-grain: modified golden film will be placed on step with being dried with nitrogen in step (2)
(1) at least 10h is impregnated in prepared silver sol solution in, then with the alternately washing at least four of dehydrated alcohol and deionized water
It is secondary, it is stored for future use at room temperature with after being dried with nitrogen.
5. auri ping-pong ball surface enhanced material according to claim 4, it is characterised in that: the second of the 4- aminothiophenol
Range of the concentration of 4- aminothiophenol molecule in 0.05-0.2mol/L in alcoholic solution.
6. auri ping-pong ball surface enhanced material according to claim 4, it is characterised in that: the second of the 4- aminothiophenol
The concentration of 4- aminothiophenol molecule is 0.1mol/L in alcoholic solution.
7. the detection method of furfural in a kind of transformer oil, which is characterized in that the method is with any one of claim 1-6 institute
The auri ping-pong ball surface enhanced material stated is as surface enhanced base material, comprising the following steps:
(1) the auri ping-pong ball surface enhanced material is put into transformer oil to be detected, makes the auri ping-pong ball surface enhanced
Material comes into full contact with transformer oil to be detected；
(2) transformer oil to be detected that placed auri ping-pong ball surface enhanced material in step (1) is suitable relative to excitation light source
Locality is placed, so that focus laser energy is in the upper surface of the auri ping-pong ball surface enhanced material；
(3) Raman spectrogram of in situ detection and collection surface enhancing is carried out under single optical maser wavelength.
8. the detection method of furfural in transformer oil according to claim 7, it is characterised in that: the excitation light source swashs
It is 50 μm that optical wavelength, which selects 532nm, laser power 100mW, time of integration 3s, integral number of times 100, slit width, choosing
With 600l/500nm type grating, Raman spectrum detection range is 250-2500cm-1。
9. the detection method of furfural in transformer oil according to claim 8, it is characterised in that: chaff in the transformer oil
Characteristic peak of the aldehyde in Surface enhanced Raman spectroscopy detection is chosen to be 1662cm-1, minimum detectable concentration 1.06mg/L.
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