CN102109584A - 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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- CN102109584A CN102109584A CN 201010589426 CN201010589426A CN102109584A CN 102109584 A CN102109584 A CN 102109584A CN 201010589426 CN201010589426 CN 201010589426 CN 201010589426 A CN201010589426 A CN 201010589426A CN 102109584 A CN102109584 A CN 102109584A
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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 the mangneto variable color 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), common measurement instruments 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 measuring the electromotive force of 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 field-free region fast, measure magnetic flux density by the ballistic method principle with magnetic test coil upset suddenly.
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 the action of a magnetic fields simultaneously, because magnetization curve is non-linear, and the asymmetric district that is operated in curve unshakable in one's determination, make to be wrapped in the voltage that the magnetic test coil on the iron core inducts and contain even-order harmonic component, particularly second harmonic.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.Two AC excitation coils series connection back is by the oscillator power supply, and the magnetic field intensity that produces in two iron cores is Δ H, but direction is opposite.Like this, first-harmonic of inducting in the magnetic test coil and odd harmonic voltage are cancelled out each other.When probe is in intensity is H
0Tested stationary magnetic field in the time, two iron cores are subjected to H respectively
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 resolving power reaches 100 skin spies.Be mainly used in the measurement low-intensity magnetic field.Be widely used in geology, ocean and the space technology.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 10 respectively
-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 pass to DC current I between the opposite end surface of thin slice, then produces electromotive force E (being Hall effect) between the respective point of other both ends of the surface.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 the magnetosensitive characteristic again.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 do Bao Erxiao, can stretch in the close clearance and measure, also can be in order to measure non-uniform magnetic-field.The device that the magnetosensitive characteristic is arranged also has bismuth spiral, magnetodiode etc. except that 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 a 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 magnetic flux density or magnetic field intensity exactly 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 power supply or magnetizing coil, and volume is bigger, and it is convenient inadequately 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.It is short that solid phase method has technological process, the product quality height, and characteristics such as particle is ultra-fine, even, good dispersion, but its technical difficulty is big, and high to the structure and the material requirement of equipment, application surface is narrower.
Liquid phase method prepares magnetic Nano material and has that reaction conditions gentleness, raw material cheaply are easy to get, easy and simple to handle, characteristics such as particle diameter is controlled, is super paramagnetic 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 magnetic ferric oxide nano particle, also is the main production method of the super paramagnetic contrast medium of commercialization.In non-oxidizing atmosphere, excessive precipitator 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),, formed the magnetic Fe 3O4 nano particle of black when the pH of solution value precipitation reaction has taken place during for 8-14.The chemical equation of coprecipitation reaction is as follows:
2Fe
3++Fe
2++8OH
-→Fe
3O
4+4H
2O
The factor that influences 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,, follow crystal growing process slowly after the fulminant nucleation, make nucleation and crystallization process be difficult to separate, cause poor, the out-of-shape of particle monodispersity, and be difficult to Fe because reaction velocity is very fast
3O
4Particle grain size is regulated and control.In order to satisfy the needs of using in the magnetic resonance imaging body, obtain particle diameter Fe uniformly
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 the aqueous solution and be reflected at, 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 to the influence 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 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.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 being adsorbed on the surface of nano particle easily, has influenced Fe
3O
4The biocompatibility of nano particle has limited its application in imaging in vivo.
3. solvent thermal 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 thermal decomposition method single Fe3O4 of dispersion nano particle of preparing high magnetic intensity has received researcher's concern in recent years.The solvent thermal 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 being decomposed rapidly, form a large amount of nucleus (explosive forming core) in the 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 helps the crystallization of product, and Fe
3O
4Nucleation process separate with crystal growing process, therefore the growth time of crystal grain can be prepared crystallinity and the good Fe of monodispersity much at one
3O
4Particle.In addition, can regulate and control the particle size of product accurately, the nano particle of preparation particle diameter from several nanometers to tens nanometers by crystal seed mediating growth mode.Also can be by changing means such as surfactant structure and consumption to Fe
3O
4The pattern of nano particle is regulated and control, the Fe of preparation class ball-type, cube type, different-shape such as star-like
3O
4Nano particle.
But employed solvent of this method and surfactant are hydrophobic molecule, the magnetic Fe that makes preparation
3O
4Nano grain surface is a 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 modify once more 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 the magnetic Fe of surface hydrophilicity by single step reaction
3O
4Nano particle is that solvent has prepared Fe with the stronger 2-pyrrolinone of polarity
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 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 non-polar solvents such as diphenyl ether, the magnetic Fe that makes preparation
3O
4Nano grain surface has certain water wettability, but poor in the still more traditional coprecipitation of 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 is meant 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, make common 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, still transmits the media of pressure at liquid state or gaseous state, thus simultaneously since under high pressure most reactants all can be partially dissolved in water and impel to be reflected in liquid phase or the gas phase and carry out.Hydro-thermal method has been widely used in the preparation of nano material in recent years, compares with other preparation method, and the purity height of hydrothermal preparation nano material, crystal grain are grown, and have 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 as mixed solvent, oleic acid/sodium oleate, under 180 ℃, airtight condition of high voltage, prepared all better Fe of monodispersity and crystallinity with water and ethanol
3O
4Nano particle.
But because synthetic particle surface combines organic dispersing agents such as oleic acid, Fe
3O
4Particle surface is a 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.This method utilizes the higher polyvalent alcohol of boiling point (mainly being dibasic alcohol) as solvent and reductive agent, under stirring, slaine is dissolved in polyol solvent, as ethylene glycol (EG), diethylene glycol or polyglycol (PEG) etc., polyvalent alcohol directly reduces the generation metal simple-substance with metallic ion under hot conditions, or alcoholysis forms metal oxide.The nano particle diameter narrow distribution of polyol reduction method preparation, and,, help improving the degree of crystallization of nano particle for preparation feedback provides higher temperature of reaction because the polyvalent alcohol boiling point is higher.Because polyvalent alcohol has stronger polarity, make product have water wettability preferably after being adsorbed on the nano grain surface that reaction forms.Another advantage of this 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, magnetization height, Fe that monodispersity is good very much
3O
4Nano particle has very big potentiality in the preparation of super paramagnetic 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 constitute by particle diameter 10nm left and right sides magnetic-particle and propping material, such magnetic microsphere has magnetic responsiveness preferably, and can avoid the remanent magnetism effect to cause reunion between microballoon.Wherein the magnetic-particle of Cai Yonging 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 wherein the inorganic material of normal employing is a silicon dioxide, and macromolecular material is a polystyrene etc.The preparation method front of magnetic nanoparticle is mentioned, mainly introduces the magnetic microsphere preparation method of different clads here.
Generally by the sol-gel process preparation, it is that the magnetic nanoparticle that will prepare earlier 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 the enhancement effect of magnetic microsphere, be difficult to satisfy the needs of magnetic resonance Enhanced Imaging proton relaxation.If the concentration of magnetic nanoparticle in the increase reactant makes coated pellet number increase 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 at the deficiency that existing steady magnetic field ionization meter technology exists, to provide a kind of reagent and method thereof of utilizing the mangneto variable color to measure magnetic field intensity.Comprise and provide a kind of easy to use, need not the power supply power supply, need not magnetizing coil, Miniaturized, but large tracts of landization, and the reagent of the lower measurement magnetic field intensity of cost of manufacture, and utilize this reagent to measure the method for magnetic field intensity, promptly 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 the mangneto variable color to measure magnetic field intensity, it is characterized in that, the three-phase material system that it is made up of super paramagnetic 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 is formed, 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 thermal 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 super paramagnetic nano colloid cluster (CNCs).
During enforcement, utilize colourless transparent material that described three-phase material system sealed package is formed a kind of test paper of measuring magnetic field intensity such as plastic sheeting.
The present invention also provides a kind of method of utilizing the described reagent of claim 1 to measure magnetic field intensity, it is characterized in that, comprises the steps:
Step 1: described reagent is placed the external magnetic field, CNCs is under the action of a magnetic field, magnetic attraction that is caused by super paramagnetic 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 color of the grating constant decision diffraction light of described photonic crystal, the color of described reagent shows different colors because of 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 analytical calculation (or computing machine comparison) to reflectance spectrum.
During enforcement, described " color-magnetic field intensity table of comparisons " writes down corresponding reagent color under the 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 the power supply power supply, environmental protection and energy saving, safe in utilization, big I freely design, can ultra-thin microminiaturization or large tracts of landization, observe intuitively, cost of manufacture is relatively low, each instrument and equipment that it is relevant in magnetic field, engineering use and 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 synoptic 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 the mangneto variable color to measure magnetic field intensity, promptly a kind of three-phase material system of forming by super paramagnetic 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 is formed.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, the test paper of making through above-mentioned processing is convenient to preserve and carry, and it is convenient more and quick to make 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, as all industrial transparent plastic films such as PE film, PET film, PVC film, BOPP films.
In the present invention, the super paramagnetic single domain Fe for preparing with the polyvalent alcohol method
3O
4Nano particle is a 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 super paramagnetic single domain Fe for preparing earlier
3O
4Nano particle (the Fe that promptly 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, be coated on Fe by acid/salt catalytic reaction
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 super paramagnetic single domain Fe
3O
4The raw material of nano particle also can be by routine method such as coprecipitation, microemulsion method, solvent thermal 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, i.e. the liquid resin that 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, 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 the action of a magnetic field, and the magnetic attraction that is caused by super paramagnetic 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, the color of chain spacing decision diffraction light, and this can be by the Bragg diffraction theoretical explanation.Therefore, the color of this three phase material can obtain by the chain spacing of using the external magnetic field to change the CNCs11 particle adjusting.This three-phase material system of being made up 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 synoptic 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), the observation angle difference, 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 to measure magnetic field, directly observe the color except that 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 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.Promptly 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 the comparison of standard diffraction peak collection of illustrative plates, thereby 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 calculating such as liquid resin coefficient of viscosity provide; Or under the 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,, from above-mentioned table, can find corresponding magnetic field intensity according to the color that reagent place shows.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 |
More than shown in only be the preferred embodiments of the present invention, only be 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 limited, revise, even the change of equivalence, but all will fall within the scope of protection of the present invention.
Claims (9)
1. reagent that utilizes the mangneto variable color to measure magnetic field intensity, it is characterized in that, the three-phase material system that it is made up of super paramagnetic nano colloid cluster, liquid flux and liquid resin, each super paramagnetic nano colloid cluster is by a plurality of single domain Fe of coated with silica
3O
4Magnetic nanoparticle is formed.
2. the reagent that utilizes the mangneto variable color to measure magnetic field intensity as claimed in claim 1 is characterized in that described Fe
3O
4The single domain magnetic nanoparticle is to utilize a kind of method in coprecipitation, microemulsion method, solvent thermal decomposition method, hydro-thermal method and the polyvalent alcohol method to be prepared from.
3. the reagent that utilizes the mangneto variable color to measure magnetic field intensity as claimed in claim 1 is characterized in that described super paramagnetic nano colloid cluster is with Fe
3O
4The single domain magnetic nanoparticle is dispersed in the teos solution, makes teos hydrolysis form monox by acid/salt catalytic reaction, is coated on Fe
3O
4Magnetic nanoparticle surface and making.
4. the reagent that utilizes the mangneto variable color to measure magnetic field intensity as claimed in claim 1 is characterized in that, is to 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.
5. the reagent that utilizes the mangneto variable color to measure magnetic field intensity as claimed in claim 1 is characterized in that, the liquid resin that liquid resin adopts UV light-cured resin or heat reactive resin etc. to solidify; Liquid resin also can adopt the common liq resin, and test paper must be in the magnetic field all the time when still measuring magnetic field, and after breaking away from magnetic field, reagent recovers original sepia.
6. the reagent that utilizes the mangneto variable color to measure magnetic field intensity as claimed in claim 1 is characterized in that liquid flux is such as organic solvents such as ethanol.
7. a method of utilizing each described reagent of claim 1-6 to measure magnetic field intensity is characterized in that, comprises the steps:
Step 1: described reagent is placed the external magnetic field, super paramagnetic nano colloid cluster is under the action of a magnetic field, magnetic attraction that is caused by super paramagnetic nano colloid cluster and electrostatic repulsion and solvation power reach balance, formation is along the chain structure of the magnetic line of force, a large amount of chain structures formation photonic crystal that evenly distributes;
Step 2: the color of the grating constant decision diffraction light of described photonic crystal, the color of described reagent shows different colors because of 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.
8. the method for utilizing the described reagent of claim 1 to measure magnetic field intensity as claimed in claim 7 is characterized in that, also can utilize spectrometer accurately to measure the reflectance spectrum of reagent, obtains magnetic field intensity by analytical calculation or computing machine comparison to reflectance spectrum.
9. the method for utilizing the described reagent of claim 1 to measure magnetic field intensity as claimed in claim 7, described " color-magnetic field intensity table of comparisons " is under the known standard magnetic field intensity, write down corresponding reagent color, thereby draw " color-magnetic field intensity table of comparisons ".
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