CN102109584B - Reagent and method for measuring magnetic field intensity by using magneto discoloration - Google Patents
Reagent and method for measuring magnetic field intensity by using magneto discoloration Download PDFInfo
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- CN102109584B CN102109584B CN 201010589426 CN201010589426A CN102109584B CN 102109584 B CN102109584 B CN 102109584B CN 201010589426 CN201010589426 CN 201010589426 CN 201010589426 A CN201010589426 A CN 201010589426A CN 102109584 B CN102109584 B CN 102109584B
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Abstract
The invention provides a reagent and a method for measuring magnetic field intensity by using magneto discoloration. The reagent is a three-phase material system consisting of superparamagnetic nano colloid clusters (CNCs), liquid solvent, and a liquid resin; each CNCs consists of a plurality of single-domain Fe3O4 magnetic nanoparticles coated by silicon dioxide; the method comprises the following steps that: 1, the reagent is placed in an external magnetic field, the magnetic attraction caused by the superparamagnetic nano colloid clusters, and electrostatic repulsion and solvating power are leveled off under the action of the magnetic field so as to form chain structures along a magnetic line of force, and a large number of chain structures are uniformly distributed so as to form photonic crystal; and 2, the lattice constant of the photonic crystal determines the color of diffraction beams, different colors of the reagent are displayed according to different magnetic field intensities, and the corresponding magnetic field intensity can be obtained by looking up a color-magnetic field intensity comparison table according to the corresponding relation between the color and the magnetic field intensity.
Description
Technical field
The present invention relates to a kind of reagent and method thereof of measuring magnetic field intensity, refer in particular to a kind of reagent and method thereof of utilizing magneto discoloration to measure magnetic field intensity.
Background technology
In current engineering application and scientific research, usually need measure the size of magnetic field intensity, for invariant in time D.C. magnetic field (steady magnetic field), surveying instrument commonly used has 7 kinds at present: moment magnetometer, fluxmeter and ballistic galvanometer, rotation coil magnetometer, flux-gate magnetometer, Hall effect magnetometer, nucleus-magnetism-resonance magnetometer and magnetic potentiometer.
Moment magnetometer: be called for short magnetometer.Utilize the stress effect measurement magnetic field intensity in magnetic field or the magnetization of material.
Fluxmeter and ballistic galvanometer (seeing galvanometer): be used for ballistic method (seeing the soft magnetic material measurement) and measure magnetic flux and magnetic flux density.During measurement, the magnetic flux in the magnetic test coil is changed.
Rotation coil magnetometer: in tested stationary magnetic field, place a little magnetic test coil, and make it do at the uniform velocity rotation.By the electromotive force of measuring coil, can calculate magnetic flux density or magnetic field intensity.Measurement range is that 0.1 milli is special to 10 spies.Error is 0.1～1%.Also can or move on to fast field-free region with suddenly upset of magnetic test coil, measure magnetic flux density by the ballistic method principle.
Flux-gate magnetometer: the iron core of being made by the high magnetic permeability soft magnetic material is subjected to alternation and constant two kinds of magnetic fields simultaneously, because magnetization curve is non-linear, and the asymmetric district that is operated in curve unshakable in one's determination, contain even-order harmonic component, particularly second harmonic so that be wrapped in the voltage that the magnetic test coil on the iron core inducts.This harmonic voltage and stationary magnetic field intensity are proportional.By measuring the harmonic voltage of magnetic test coil, calculate magnetic field intensity.The theory structure of flux-gate magnetometer as shown in the figure.Two iron cores in the probe are made with the high magnetic permeability magnetically soft alloy.Respectively be wound with the AC excitation coil on each iron core, and magnetic test coil is on two iron cores.By the oscillator power supply, the magnetic field intensity that produces in two iron cores is Δ H after the series connection of two AC excitation coils, but opposite direction.The first-harmonic of inducting in the magnetic test coil like this, and odd harmonic voltage are cancelled out each other.Be H when probe is in intensity
0Tested stationary magnetic field in the time, two iron cores are subject to respectively H
0+ Δ H and H
0-Δ H is the superposition of alternation and stationary magnetic field, thereby produces even-order harmonic voltage in magnetic test coil, through frequency-selecting amplification and synchronous detection link, gets its second harmonic voltage, its reading and tested stationary magnetic field intensity H
0Proportional.The sensitivity of flux-gate magnetometer is very high, and it is special that resolving power reaches 100 skins.Be mainly used in measuring low-intensity magnetic field.Be widely used in geology, ocean and the space technology.The optically pumped magnetometer that 60～seventies of 20th century is developed into and the superconducting quantum magnetometer that utilizes superconducting quantum interference device (squid) to make, sensitivity is higher, and resolving power reaches respectively 10
-7With 10
-9Peace/rice.
Hall effect magnetometer: the semiconductor rectangular tab is placed in the magnetic field vertical with the thin slice plane (magnetic flux density is B), if between the opposite end surface of thin slice, pass to DC current I, then between the respective point of other both ends of the surface, produce electromotive force E (being Hall effect).When I is constant, the proportional relation of E and B, the width b of scale-up factor and thin slice, length l is relevant with thickness d and material therefor.This specific character of material is called again magnetic sensitive characteristic.The magnetometer that utilizes Hall effect to make can be measured the flux density value of 1 little tesla in 10 tesla's scopes.Error is 0.1%～5%.Hall plate can be done to get Bao Erxiao, can stretch in the close clearance and measure, also can be in order to measure non-uniform magnetic-field.The device that magnetic sensitive characteristic is arranged also has bismuth spiral, magnetodiode etc. except Hall plate.
Nucleus-magnetism-resonance magnetometer: nuclear magnetic moment will be around the magnetic direction precession under the effect of magnetic flux density B, its precession frequency f
0=γ B (γ is gyromagnetic ratio, and for certain material, it is a constant) is if apply a little alternating magnetic field in the direction perpendicular to B, as its frequency and f
0When equating, will produce the resonance absorption phenomenon, i.e. nuclear magnetic resonance.Can calculate exactly magnetic flux density or magnetic field intensity by resonant frequency.The measurement range of this magnetometer is that 0.1 milli is special to 10 spies.Accuracy is very high, and error is lower than 10
-4～10
-5, commonly used to provide standard Magnetic Field and as the verification standard.
Magnetic potentiometer: be used for the magnetic difference of potential of measurement space a, b point-to-point transmission, as be uniform magnetic field, can convert out the magnetic field intensity at this place.Magnetic potentiometer also can be used to measure the magnetic field intensity of material internal.Because magnetic material magnetic field intensity tangential component at the interface equates, therefore in the magnetic field intensity of locating along the material surface space to record with magnetic potentiometer, is exactly the inner magnetic field intensity tangential component in this place of material.The structure of magnetic potentiometer be with thin insulated conductor evenly on non magnetic soft band or hard sheet, the former claims soft magnetic potentiometer; The latter claims hard magnetic potentiometer.Measurement instrument adopts ballistic galvanometer or fluxmeter.For the stationary magnetic field, the magnetic flux that magnetic potentiometer institute chain is closed changes.Such as survey be uniform magnetic field, then convert out magnetic field intensity by the magnetic difference of potential.Magnetic potentiometer can be demarcated in the standard uniform magnetic field, by the field strength values scale.
The magnetic-field measurement instrument that these are commonly used, its design are generally all complicated, need Power supply or magnetizing coil, and volume is larger, and it is convenient not to carry, and price is higher.
Magnetic Fe
3O
4The preparation method of nano particle is relatively ripe, can be divided into liquid phase method and solid phase method generally.The complex of solid phase method Chang Yitie such as iron pentacarbonyl [Fe (CO) 5] or ferrocene [FeCP2] are raw material, under more violent reaction conditions, raw material is decomposed make.Solid phase method has that technological process is short, and product quality is high, granular superfine, evenly, the characteristics such as good dispersion, but its technical difficulty is large, the structure of equipment and material is required high, application surface is narrower.
The Liquid preparation methods magnetic Nano material has the characteristics such as reaction conditions gentleness, raw material cheaply are easy to get, easy and simple to handle, particle diameter is controlled, is superparamagnetic Fe
3O
4The main preparation methods of nano particle.Below will be according to the requirement of using, to magnetic Fe commonly used
3O
4The preparation method of nano particle carries out brief review.
1. coprecipitation (Coprecipitation)
Coprecipitation is to prepare the most frequently used, the easiest method of superparamag-netic iron oxide, also is the main production method of commercialization superparamagnetic contrast medium.In non-oxidizing atmosphere, excessive precipitation agent such as ammoniacal liquor or NaOH etc. are joined (stoichiometric proportion is Fe in the aqueous solution that contains ferric ion and ferrous ion
3+/ Fe
2+=2: 1), when the pH of solution value precipitation reaction has occured during for 8-14, formed the magnetic Fe_3O_4 nano particle of black.The chemical equation of coprecipitation reaction is as follows:
2Fe
3++Fe
2++8OH
-→Fe
3O
4+4H
2O
The factor that affects coprecipitated product comprises: Fe in the consumption of alkali and adding mode, the reactant
3+/ Fe
2+The ratio of amount of substance, the structure of spreading agent and consumption, temperature of reaction and product curing time etc.The magnetic nanoparticle of coprecipitation method preparation has that particle diameter is little, surface hydrophilicity, can be in advantages such as water dispersions, and preparation technology is simple, starting material are cheap and easy to get, is fit to industrialized production.But, form Fe in coprecipitation
3O
4In the process of nano particle, because reaction velocity is very fast, follow slowly crystal growing process after the fulminant nucleation, so that nucleation is difficult to separate with crystallization process, cause that the particle monodispersity is poor, out-of-shape, and be difficult to Fe
3O
4The particle diameter of particle is regulated and control.In order to satisfy the needs of using in the magnetic resonance imaging body, obtain the more uniform Fe of particle diameter
3O
4Nano particle often needs the Fe to the coprecipitation preparation
3O
4Nano particle carries out stage trapping, not only take time and effort, and productive rate is not high yet.In addition, owing to Fe in the coprecipitation reaction
3O
4Mainly by kinetic factor control, temperature is lower than 100 ℃ when carrying out in aqueous solution and react, and causes the Fe that forms in the formation of nano particle
3O
4The crystallization degree of particle is low, and is a little less than the magnetization, little on the impact of proton relaxation.Therefore, need to use the Fe of higher concentration
3O
4Nano particle could produce enough tissue contrasts in magnetic resonance imaging.The defective of above-mentioned two aspects has hindered the Fe of coprecipitation preparation
3O
4The application of nano particle in the magnetic resonance Enhanced Imaging, exploitation can prepare that monodispersity is good, crystallization degree is high, the Fe of water stably dispersing
3O
4The new method of nano particle is the needs of magnetic resonance imaging, also is the challenge that the nano material worker faces.
2. microemulsion method (Microemulsion method)
Microemulsion method is a kind of common methods for preparing the dispersed nano particle.Microemulsion is Thermodynamically stable, isotropy, appearance transparent or the dispersed system translucent, particle diameter 1-100nm that is formed under the spreading agent effect by two kinds of immiscible liquid.Microemulsion method (or being called reverse micelle method) is to utilize microemulsion (microemulsion) or claim the short space that forms in the reversed phase micelle (reversed micelle) to prepare a kind of method of nano particle as reaction tank.Because nano particle reacts formation in reaction tank, the growth of crystal is subjected to the control of reaction tank size and structure, therefore the character such as the form by " reaction tank " in control micella and the micella, structure, polarity just can be controlled size, the structure of particle.The employing microemulsion methods such as Y.Lee have prepared the good Fe of monodispersity
3O
4Nano particle by the relative concentration of control presoma, surfactant and solvent, has obtained the Fe of particle diameter 2～10nm
3O
4Nano particle.The Fe of microemulsion method preparation
3O
4The nano particle monodispersity is good, and particle diameter is controlled, but because micella thermally-stabilised relatively poor, the temperature of reaction of preparation nano particle is lower, and the common crystallization degree of the particle that obtains is low, and crystal formation is imperfect, the Fe that its magnetization and coprecipitation prepare
3O
4Nano particle is very nearly the same.And the surfactant that adds in the microemulsion method is difficult to remove after easily being adsorbed on the surface of nano particle, has affected Fe
3O
4The biocompatibility of nano particle has limited its in vivo application in the imaging.
3. solvent heat decomposition method (Thermo Decomposition)
Because the Fe of coprecipitation and microemulsion method preparation
3O
4The nano particle crystallization degree is low, and a little less than the magnetization, the solvent heat decomposition method single Fe3O4 of dispersion nano particle of preparing high magnetic intensity has received researcher's concern in recent years.The solvent heat decomposition method is with the complex of iron such as FeCup
3, Fe (CO)
5Fe (acac)
3Deng being dissolved in the high boiling organic solvent (as: diphenyl ether etc.) and it at high temperature decomposed rapidly, form a large amount of nucleus (explosive forming core) in short time, nucleus obtains the Fe of surface hydrophobic through the high temperature crystal growth stage under the effect of reductive agent
3O
4Nano particle.Because above-mentioned reaction is at high temperature carried out, and is conducive to the crystallization of product, and Fe
3O
4Nucleation process separate with crystal growing process, therefore the growth time of crystal grain is almost identical, can prepare crystallinity and the good Fe of monodispersity
3O
4Particle.In addition, can regulate and control accurately the particle size of product by crystal seed mediating growth mode, the nano particle of preparation particle diameter from several nanometers to tens nanometers.Also can be to Fe by changing the means such as surfactant structure and consumption
3O
4The pattern of nano particle is regulated and control, the Fe of preparation class ball-type, Cubic, the different-shape such as star-like
3O
4Nano particle.
But the employed solvent of the method and surfactant are hydrophobic molecule, so that the magnetic Fe of preparation
3O
4Nano grain surface is hydrophobicity, understands spontaneous reunion in aqueous solution, can't adapt to the needs of magnetic resonance in-vivo imaging.In order to obtain the nano particle of surface hydrophilicity, need to again modify the nano particle of preparation, process is more loaded down with trivial details, and the surface dispersant molecule also is difficult to be unfavorable for biologic applications, particularly the application in the biosome from the surface rejecting.
In order to prepare surperficial hydrophilic magnetic Fe by single step reaction
3O
4Nano particle has prepared Fe take the stronger 2-pyrrolinone of polarity as solvent
3O
4Nano particle, and use it for the magnetic resonance imaging of liver, kidney, confirm the Fe of preparation
3O
4Nano particle is enriched in the positions such as liver, spleen after entering in the body, can significantly reduce the magnetic resonance signal intensity of these histoorgans.Use the stronger pyrrolinone molecule of polarity to substitute the non-polar solvents such as diphenyl ether, so that the magnetic Fe of preparation
3O
4Nano grain surface has certain water wettability, but still more traditional coprecipitation is poor in the dispersiveness of aqueous phase, and the monodispersity of particle also not as the front mention with diphenyl ether make solvent, the particle for preparing when oleic acid/oleyl amine is made spreading agent is good.In addition, pyrrolinone has stronger toxicity, is combined in magnetic Fe
3O
4Be difficult to behind the nano grain surface remove, just may be used for the magnetic resonance imaging in the biosome after must it being replaced with the molecule of other good biocompatibility.
4. hydro-thermal method (Hydrothermal method)
Hydro-thermal method refers in special closed reactor (autoclave), adopt aqueous solution as reaction system, by reaction system is heated, pressurizes (or spontaneous vapor pressure), create the reaction environment of a relatively-high temperature, high pressure, so that usually indissoluble or insoluble substance dissolves and recrystallization and carry out a kind of effective ways of inorganic preparation and material processed.Under hydrothermal condition, water is not only as solvent but also as mineralizer, at liquid state or gaseous state or the medium of transmission of pressure, thereby simultaneously since under high pressure most reactants all can be partially dissolved in water and impel reaction in liquid phase or gas phase, to carry out.Hydro-thermal method has been widely used in preparations of nanomaterials in recent years, compares with other preparation method, and the purity that hydro-thermal prepares nano material is high, crystal grain is grown, and has avoided the impurity and the fault of construction that cause because of subsequent treatment such as high-temperature calcination and ball millings.Adopt hydro-thermal method, make spreading agent with water and ethanol as mixed solvent, oleic acid/sodium oleate, under 180 ℃, enclosed high pressure condition, prepared all better Fe of monodispersity and crystallinity
3O
4Nano particle.
But because synthetic particle surface combines the organic dispersing agents such as oleic acid, Fe
3O
4Particle surface is hydrophobicity, is restricted in the application of biomedical aspect, therefore, preparation surface hydrophilicity, the magnetic Fe that particle diameter is controlled, crystallization degree is good
3O
4Nano particle remains the challenge that material supplier author faces.
5. polyvalent alcohol method (Polyol method)
Many pure methods (Polyol) are a kind of important method of preparation metal and metal oxide nanoparticles.The method utilizes the more much higher unit's alcohol of boiling point (mainly being dibasic alcohol) as solvent and reductive agent, under stirring, slaine is dissolved in polyol solvent, such as ethylene glycol (EG), diethylene glycol or polyglycol (PEG) etc., polyvalent alcohol generates metal simple-substance with the metallic ion direct-reduction under hot conditions, or alcoholysis forms metal oxide.The nano particle diameter narrow distribution of polyol reduction method preparation, and because the polyvalent alcohol boiling point is higher, for preparation feedback provides higher temperature of reaction, be conducive to improve the degree of crystallization of nano particle.Because polyvalent alcohol has stronger polarity, be adsorbed on behind the nano grain surface that reaction forms so that product has preferably water wettability.Another advantage of the method is that the week reduction atmosphere that polyvalent alcohol forms can separate the nano particle of formation and extraneous oxidizing atmosphere, prevents the nano particle oxidation by air.Therefore, from the These characteristics of polyvalent alcohol method, it is suitable for preparing surface hydrophilicity, the magnetization is high, monodispersity is good Fe very much
3O
4Nano particle has very large potentiality in the preparation of superparamagnetic contrast medium.
A plurality of single domain Fe for coated with silica
3O
4The magnetic microsphere preparation of magnetic nanoparticle, the diameter of the magnetic microsphere that biomedical sector uses is generally in 30～1000nm scope, in order to keep microballoon superparamagnetism at room temperature, usually consisted of by particle diameter 10nm left and right sides magnetic-particle and propping material, such magnetic microsphere has preferably magnetic responsiveness, and can avoid left magnetic effect to cause reunion between microballoon.The magnetic-particle that wherein adopts is generally γ-Fe
2O
3, Fe
3O
4, ferrocobalt etc.Owing to metal material easy oxidation in air loses magnetism, limited its application, and the iron oxide magnetic stability of material is good, therefore use also extensive.The propping material that adopts comprises inorganic material and macromolecular material, and the inorganic material that wherein the most often adopts is silicon dioxide, and macromolecular material is polystyrene etc.The preparation method front of magnetic nanoparticle mentions, here the magnetic microsphere preparation method of the different clads of article.
Generally by the sol-gel process preparation, it is that the magnetic nanoparticle that will prepare first is dispersed in ethyl orthosilicate (TEOS) solution to silicon dioxide microsphere, makes the TEOS hydrolysis form monox by acid/salt catalytic reaction, is coated on Fe
3O
4Nano grain surface forms magnetic microsphere.The magnetic microsphere of preparation mostly is monox and coats single magnetic-particle or a few particle; this preparation method's advantage is that the microballoon list is scattered; the monox thickness of the shell is controlled; shortcoming be the magnetisable material content in the microballoon very low (＜10wt%); saturation magnetization only is 7.5emu/g; cross low saturation magnetization and be unfavorable for improving magnetic microsphere to the enhancement effect of proton relaxation, be difficult to satisfy the needs of magnetic resonance Enhanced Imaging.If the concentration of magnetic nanoparticle in the increase reactant increases the granule number that coats in the microballoon, it is irregular that the magnetic microsphere pattern becomes again, and particle diameter is heterogeneity very, can't satisfy application demand.
Summary of the invention
The problem to be solved in the present invention is for the deficiency that existing Static magnetic field measuring technique exists, to provide a kind of reagent and method thereof of utilizing magneto discoloration to measure magnetic field intensity.Comprise and provide a kind of easy to use, need not Power supply, need not magnetizing coil, Miniaturized, but large tracts of land, and the reagent of the lower measurement magnetic field intensity of cost of manufacture, and the method for utilizing this reagent measuring magnetic field intensity, namely utilize the different colours of this reagent in magnetic field, judge the size of magnetic field intensity.
In order to address the above problem, the invention provides a kind of reagent that utilizes magneto discoloration to measure magnetic field intensity, it is characterized in that, the three-phase material system that it is comprised of superparamagnetic nano-colloid cluster (CNCs), liquid flux and liquid resin, each CNCs is by a plurality of single domain Fe of coated with silica
3O
4Magnetic nanoparticle forms, and when not having externally-applied magnetic field, the CNCs random dispersion is in liquid resin.
During enforcement, described Fe
3O
4The single domain magnetic nanoparticle is to utilize a kind of method in coprecipitation, microemulsion method, solvent heat decomposition method, hydro-thermal method and the polyvalent alcohol method to be prepared from.
During enforcement, described Fe
3O
4The single domain magnetic nanoparticle is dispersed in ethyl orthosilicate (TEOS) solution, makes the TEOS hydrolysis form monox by acid/salt catalytic reaction, is coated on Fe
3O
4The magnetic nanoparticle surface forms superparamagnetic nano-colloid cluster (CNCs).
During enforcement, utilize the colourless transparent material such as plastic sheeting that described three-phase material system sealed package is formed a kind of test paper of measuring magnetic field intensity.
The present invention also provides a kind of method of utilizing reagent measuring magnetic field intensity claimed in claim 1, it is characterized in that, comprises the steps:
Step 1: described reagent is placed the external magnetic field, CNCs is under magnetic fields, the magnetic attraction that is caused by superparamagnetic nano-colloid cluster and electrostatic repulsion and solvation power reach balance, form the chain structure along the magnetic line of force, a large amount of chain structures formation photonic crystal that evenly distributes;
Step 2: the grating constant of described photonic crystal determines the color of diffraction light, the color of described reagent shows different colors because magnetic field intensity is different, according to the corresponding relation of color and magnetic field intensity, search " color-magnetic field intensity table of comparisons " and can draw corresponding magnetic field intensity.
During enforcement, also can utilize spectrometer accurately to measure the reflectance spectrum of test paper, obtain magnetic field intensity by the analytical calculation (or computing machine comparison) to reflectance spectrum.
During enforcement, described " color-magnetic field intensity table of comparisons " records corresponding reagent color under known standard Magnetic Field intensity, thereby draws " color-magnetic field intensity table of comparisons ".
Beneficial effect of the present invention is: simple to operate, easy to use, need not Power supply, environmental protection and energy saving, use safety, large I freely designs, but ultra-thin micro or large tracts of land, and observation is directly perceived, cost of manufacture is relatively low, each instrument and equipment that it is relevant in magnetic field, engineering use and the various fields such as scientific research in, the potentiality that all are widely used with have huge marketable value.
Description of drawings
Fig. 1 is the side view of test paper that the reagent sealed package of measurement magnetic field intensity of the present invention is formed in the colourless transparent material such as plastic sheeting;
Fig. 2 measures magnetic field intensity process schematic diagram.
Embodiment
Below in conjunction with accompanying drawing, technical characterictic of the present invention and advantage are described in more detail.
Fig. 1 is the structural representation of test paper that the reagent sealed package of measurement magnetic field intensity of the present invention is formed in the colourless transparent material such as plastic sheeting.
The invention provides a kind of reagent 1 that utilizes magneto discoloration to measure magnetic field intensity, i.e. a kind of three-phase material system that is formed by superparamagnetic nano-colloid cluster 11 (CNCs), liquid flux 12 alcohols solvents such as () ethanol and liquid resin 13.Each CNCs11 is by a plurality of single domain Fe of coated with silica
3O
4Nano particle forms.When not having externally-applied magnetic field, the CNCs11 random dispersion presents sepia in liquid resin 13, and this color also is the intrinsic color of tri-iron tetroxide.
The above-mentioned three-phase material system sealed package surface of colourless transparent material 14 (or above-mentioned three-phase material system is applied to by rubbing method) to the surface of colourless transparent material 14 has been formed a kind of test paper of measuring magnetic field intensity, utilize this test paper can measure magnetic field intensity, be convenient to preserve and carry through the test paper that above-mentioned processing is made, so that more convenient and quick in the practical application.Used colourless transparent material 14 normal transparent plastics as long as can play the effect of enclosing liquid, all can not use with the transparent material of reagent generation chemical reaction simultaneously, such as all industrial transparent plastic films such as PE film, PET film, PVC film, BOPP films.
In the present invention, with the standby superparamagnetic single domain Fe of polyvalent alcohol legal system
3O
4Nano particle is raw material, has prepared the CNCs11 with high magnetic intensity by sol-gel process, and magnetisable material content surpasses 40wt%, and its preparation process is as follows: with the superparamagnetic single domain Fe for preparing first
3O
4Nano particle (the Fe that namely utilizes the polyvalent alcohol method to prepare
3O
4The single domain magnetic nanoparticle) is dispersed in ethyl orthosilicate (TEOS) solution, makes the TEOS hydrolysis form monox by acid/salt catalytic reaction, be coated on Fe
3O
4Nano grain surface forms CNCs11 (concrete grammar and document " artificial lens journal " " it is nanocrystalline that microemulsion method prepares coated with silica ZnS:Mn/CdS ", Yao Yuan, Li Dongmei, Sang Wenbin fetes just the 35th volume, the 2nd phase, in April, 2006, the 400-403 page or leaf is identical.Above-mentioned superparamagnetic single domain Fe
3O
4The raw material of nano particle also can be by routine the method such as coprecipitation, microemulsion method, solvent heat decomposition method, hydro-thermal method prepare.The UV light-cured resin that the liquid resin that liquid resin 13 employing UV light-cured resins of the present invention or heat reactive resin etc. can solidify can be used is as shown in table 1.
Table 1
Solidify this liquid resin 13 during measurement, by solidifying the structure of this liquid resin 13, thus color that can fixating reagent, reagent still keeps its color constant after leaving magnetic field, has made things convenient for next step color measuring; Liquid resin 13 also can adopt the common liq resin, the liquid resin that namely can not solidify, but test paper must be in the magnetic field all the time when measuring magnetic field, and after breaking away from magnetic field, reagent recovers original sepia.This liquid resin can be the liquid resin of this area routine, such as various epoxy liquid resins, phenolics, chlorine ammonia resin, aldehyde ketone resin, vinyl chloride-vinyl acetate resin etc.
In addition, the invention provides a kind of method of utilizing mentioned reagent to measure magnetic field intensity.Its step is as follows: during measurement, place the external magnetic field with mentioned reagent or with the test paper that obtains after the reagent encapsulation, and hand-holdable during use, also available other support clamping.CNCs11 is under magnetic fields, and the magnetic attraction that is caused by superparamagnetic nuclear reaches balance with electrostatic repulsion and solvation power, forms the chain structure along the magnetic line of force, in a large number the chain structures formation photon crystal structure that evenly distributes.The size of making a concerted effort of attractive force and repulsive force has determined the chain spacing of CNCs11 particle, and the chain spacing of this CNCs11 particle is exactly the grating constant of formed photonic crystal, and the chain spacing determines the color of diffraction light, and this can be by the Bragg diffraction theoretical explanation.Therefore, the color of this three phase material can be adjusted by the chain spacing of using the external magnetic field to change the CNCs11 particle.This three-phase material system that is comprised of CNCs11, liquid flux 12 and liquid resin 13 can successfully be stablized the CNCs11 particle, and can show different colours because of the difference in magnetic field.According to the corresponding relation of color and magnetic field intensity, search " color-magnetic field intensity table of comparisons " and can draw corresponding magnetic field intensity.Fig. 2 measures magnetic field intensity process schematic diagram, the color that reagent induced magnetism place produces is a kind of schemochrome (relies on the interaction of light and body surface periodic nano-structure and produce color), observation angle is different, its color has certain deviation, therefore, during measurement, the observer should be in the level observation of test paper dead ahead.
Alternatively, when utilizing this reagent measuring magnetic field, directly observe the color except adopting naked eyes, also can utilize spectrometer accurately to measure the reflectance spectrum of reagent, obtain magnetic field size (as shown in Figure 2) by the analytical calculation (or computing machine comparison) to reflectance spectrum, but concrete list of references " Structural colourprinting using a magnetically tunable and lithographically fixable photoniccrystal ", Hyohi Kim, Jiangping Ge, Junhoi Kim, Sung-eun Choi, Hosuk Lee, Wook Park, Yadong Yin and Sunghoon Kwon*, NATURE PHOTONICS, vol3, September 2009, and the diffraction peak collection of illustrative plates among the 534-540. among the Figure 2d figure is judged corresponding magnetic field according to diffraction peak.Namely obtain standard diffraction peak collection of illustrative plates by standard Magnetic Field, during measurement, the diffraction peak collection of illustrative plates in the unknown magnetic field that obtains and standard diffraction peak collection of illustrative plates are compared, thus the magnetic field intensity of obtaining.
Fig. 3 shows one " color-magnetic field intensity table of comparisons ".Being somebody's turn to do " color-magnetic field intensity table of comparisons " can be according to the CNCs11 grain size, and the calculating such as liquid resin coefficient of viscosity provide; Or under known standard Magnetic Field intensity, record test paper color, thus draw " color-magnetic field intensity table of comparisons ".In the process of measuring magnetic field intensity, according to the color that reagent place shows, from above-mentioned table, can find corresponding magnetic field intensity.Color-magnetic field intensity table of comparisons is as shown in table 2.
Table 2
| Test paper (or reagent) color | Brown | Red | Orange | Yellow | Green | Blue or green | Blue | Purple |
| Corresponding magnetic field intensity | 0 | B 1 | B2 | B3 | B4 | B5 | B6 | B7 |
Only being the preferred embodiments of the present invention shown in above, only is illustrative for the purpose of the present invention, and nonrestrictive.Common knowledge personnel understand at this professional skill field tool, can carry out many changes to it in the spirit and scope that claim of the present invention limits, revise, even the change of equivalence, but all will fall within the scope of protection of the present invention.
Claims (4)
1. a method of utilizing magneto discoloration reagent measuring magnetic field intensity is characterized in that, comprises the steps:
Step 1: described magneto discoloration reagent is placed the external magnetic field, and the superparamagnetic nano-colloid cluster (CNCs) in the magneto discoloration reagent forms photonic crystal under magnetic fields, and under the different magnetic field strength condition, magneto discoloration reagent is different colours;
Step 2:, according to the corresponding relation of color and magnetic field intensity, search " color-magnetic field intensity table of comparisons " according to the color that magneto discoloration reagent place presents and obtain institute's measuring magnetic field intensity; Or adopt spectrometer accurately to measure the reflectance spectrum of magneto discoloration reagent, obtain institute's measuring magnetic field intensity by analytical calculation or computing machine comparison to reflectance spectrum;
Wherein, the three-phase material system that described magneto discoloration reagent is comprised of superparamagnetic nano-colloid cluster (CNCs), liquid flux and liquid resin, wherein superparamagnetic nano-colloid cluster (CNCs) is by a plurality of Fe of coated with silica
3O
4The single domain magnetic nanoparticle forms;
Described Fe
3O
4The single domain magnetic nanoparticle is to utilize a kind of method in coprecipitation, microemulsion method, solvent heat decomposition method, hydro-thermal method and the polyvalent alcohol method to be prepared from;
Described superparamagnetic nano-colloid cluster is with Fe
3O
4The single domain magnetic nanoparticle is dispersed in the teos solution, makes teos hydrolysis form silicon dioxide by acid/salt catalytic reaction, is coated on Fe
3O
4Single domain magnetic nanoparticle surface and making;
Described liquid resin adopts the liquid resin that can solidify; Liquid resin also can adopt the common liq resin, but test paper must be in the magnetic field all the time when measuring magnetic field, and after breaking away from magnetic field, magneto discoloration reagent recovers original sepia;
Described liquid flux is alcohol organic solvent;
Described magneto discoloration reagent is to utilize plastic sheeting that described three-phase material system sealed package is formed a kind of test paper of measuring magnetic field intensity.
2. the method for claim 1, described " color-magnetic field intensity table of comparisons " is under known standard Magnetic Field intensity, records the color of corresponding magneto discoloration reagent, thereby draws " color-magnetic field intensity table of comparisons ".
3. the method for claim 1, the described liquid resin that can solidify is UV light-cured resin or heat reactive resin.
4. the method for claim 1, described alcohol organic solvent is ethanol.
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