CN1058469C - Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating - Google Patents

Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating Download PDF

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CN1058469C
CN1058469C CN95196132A CN95196132A CN1058469C CN 1058469 C CN1058469 C CN 1058469C CN 95196132 A CN95196132 A CN 95196132A CN 95196132 A CN95196132 A CN 95196132A CN 1058469 C CN1058469 C CN 1058469C
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vanadium dioxide
pyrolysis
temperature
particulate
minute
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CN1162949A (en
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P·莱格兰德
J-R·加瓦里
J-C·瓦尔马莱特
G·瓦克奎尔
D·勒菲弗
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Peintures Jefco Les
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Abstract

Vanadium dioxide microparticles having formula V1-xMxO2, wherein 0<= x <= 0.05 and M is a doping metal, and being characterised in that they have a particle size of less than 10 mu m, a method for preparing same, and the use of said microparticles, in particular for surface coating, are disclosed.

Description

Vanadium dioxide particles and method for making thereof and as the purposes of top coat
The objective of the invention is vanadium dioxide particles, make said particulate method, with and use, in particular as the top coat that is added with this particulate.
At first, the present invention relates to general formula V 1-xM xO 2The vanadium dioxide particle, in formula, 0≤x≤0.05 and M are doping metals, the size of said particulate is lower than 10 microns, especially is lower than 5 microns, is preferably the 0.1-0.5 micron.
The optional self energy of doping metals provides the transition element of ionic fluid greater than vanadium ion, as Nb or Ta, maybe can provide the metal of electronics, and as Mo or W, W and Mo are preferred.
Particulate of the present invention is preferably by general formula V 1-xW xO 2Vanadium dioxide form, wherein, x is between 0 and 0.02.
Vanadium dioxide particles of the present invention is used in the technical field that will be the coating composition of veneer with the form of film or paper tinsel especially, but as the coating of paint, varnish and any other layer by layer deposition.
Therefore, the objective of the invention is to utilize above-mentioned vanadium dioxide particles to realize a kind of " intelligence " material, this material can reduce the emission of the solar rays of infrared region automatically when reaching a certain temperature levels.Therefore, can benefit from infrared energy under a certain fixed temperature being lower than, and when being higher than this temperature, remove excessive heating.
One of main application of vanadium dioxide particles of the present invention is attached to the surface that is exposed to the buildings under the atrocious weather as coating.The heat absorption that is exposed to the dark-coloured coating under the sunlight is many more than the coating of light color, thereby can suffer significantly to expand-the contraction cycle variation, thereby coating is degraded too early.Therefore can not guarantee that at present luminous intensity is lower than 35% dead color paint.
Vanadium dioxide pigment can limit this phenomenon in addition in coating (its fixed transition temperature is for example about 25 ℃).
The another kind of application is the protection on transparent or semitransparent surface; these surfaces must allow visible light to pass; for example greenhouse, balcony, dwelling house window, but its internal temperature needs control, and this application also it is contemplated that on the window glass and vehicle body that is used in car and other vehicle.
In summer, enter buildings by reducing incident sunlight, this coating can reduce the needs to conditioner, and in winter, this coating restriction is to the thermal transpiration of open air, thus this coating helps energy-conservation.
In fact, one of order of the present invention is the transfer and the absorption of the heat energy of control wall surface, and need not material is carried out special transformation or processing, but, by depositing a coating, as realizing, concerning the said coating of the present invention with coating with any known method, itself just can be such coating, thereby can implement economically and make.
Now, known have many lewis' acid compounds can change its optical property under influence of temperature change, mainly is to change color, and this is because the variation of electronic structure: these compounds are called " thermochromism " compound.Promote it, have the compound that absorbs and/or reflect dissimilar radiation qualities, also can be called the compound of " thermochromism " owing to variation of temperature causes the change of electronic structure.Vanadium dioxide is through research for many years, in temperature T t=341K or 68 ℃ have a structural transformation; Be lower than T tThe time, crystalline structure is an oblique crystal, and is higher than T tThe time, this compound is a rutile structure.This transformation is because electronic property is undergone mutation: when temperature was lower than Tt, this compound became the insulation attitude, was higher than T and work as temperature tThe time, become metallic state; Optically, this variation makes it near and far absorption and reflectivity properties deep the change be taken place.
At the rest part of this specification sheets, " vanadium dioxide " should comprise and be generally VO 2Or V 2O 4Vanadium dioxide.
Recently, this compound has been carried out various researchs, as the S.M.Babulanam that can select from publication, Mat.Opt.Sol.Light Techn.692 (1986) 8 and J.C.Valmalette, Sol.Energy Mater 33 (1994) 135.Therefore, the vanadium dioxide thin layer that is deposited on the various matrixes is studied: the Development of Materials that they see through the infrared part that only allows sunlight at low temperatures especially shows actual interest.For this reason, its seemingly unique transformation of vanadium dioxide at present is positioned at the compound of the temperature and the wavelength region of the thermal conditioning that is suitable for dwelling house.
And this compound also has another advantage, promptly can carry out chemical replacement with suitable atom, as will further defining, thereby makes temperature T t shift to lower temperature.
Like this, carried out the research of many tests,, especially studied at visible light and near-infrared region optical transmittance with deposition vanadium dioxide thin layer on various matrixes; For this reason, various deposition methods have been imagined, as negative electrode spraying under the vacuum, electron beam evaporation down, vapour phase electroless plating and " colloidal sol " method.
According to " colloidal sol " method, the tetravalence vanadium is dissolved in solvent, through hydrolysis and condensation,, then,, form gel with solvent evaporation progressively to form colloidal sol, then gel is heat-treated under the atmosphere of meticulous control, obtain VO 2
By suitable matrix is immersed in the colloidal sol, can directly on matrix, form VO 2Film.On matrix, directly form gel.In U.S. Pat 4,957, special in 725 this moistening or " dip-coating " method is discussed.
Yet, the quality of restive sedimentary last film, promptly be difficult to uniform method place the method for monoblock or its surface under the high temperature and be difficult to control its carrier and the interaction between the sedimentary gel etc..Like this, on the one hand, in fact these methods that are not applied to the material that has constituted can not be applied on the big surface, and use surface coating composition, are to accomplish as coating.On the other hand, resulting result's is repeated bad, nor reliable.In addition, if big surface, then cost is very high.
Dry method with general then take a long time (about about 15 days), so cost is very high, and this method only can obtain about 30 microns and above molecule particle.This does not change its color with being added in the coating is inconsistent, far can not obtain uniform mixture, also can not bring optics to transmit the variation of character.
Therefore, a problem that is proposed can be contained to mix or the small particle powder of the vanadium dioxide of the tungsten that undopes basically, in order to obtain top coat, it can be added in liquid or the sticking carrier.
Secondly, therefore the present invention relates to by pyrolysis and mixing or plain ammonium hexavanadate obtains general formula V 1-xM xO 2The method of vanadium dioxide particles, M is a doping metals in the formula, 0≤x≤0.02, it is characterized in that, said pyrolysis is to be at least under 100 ℃/minute at temperature about 400 ℃ and 650 ℃ and temperature rise rate to carry out, and keep within the specific limits and direct contact to few 1/2 hour with reaction medium by the gas that pyrolysis produces, be preferably 1 hour.
Industrial, make V as catalyzer 2O 5Use ammonium hexavanadate (NH 4) 2V 6O 16Be well-known, still, the tetravalence vanadium is considered to the impurity of catalytically inactive, need remove.In order to obtain vanadium dioxide separately, from obtaining V 2O 3Rise, the test of making of physical efficiency before this just all can not get anything, and each document is all thought the pure vanadium dioxide that can not obtain.
Implement the characteristic condition of method for pyrolysis of the present invention, promptly
-temperature rise rate is at least 100 ℃/minute, is preferably 200 ℃/minute or 300 ℃/minute, and
Gas, especially NH that the thermolysis of-ammonium hexavanadate salt produces 3Need not find time, but sealing gland ground keeps contacting at least 5 minutes with reaction medium, be preferably 1/2-2 hour, mostly be entire synthesis process most, can obtain complete reaction and do not have the V of any remnants 2O 5Generation, reaction formula is as follows:
In fact, can notice, " hurriedly " reaction can take place under fast pyrogenation speed generate N 2O, H 2O is with excessive N H 3Sluggish is decomposed generation H 2O and N 2
Yet, in today, in the existing Reaktionsofen of great majority, perhaps purge reaction zone, take away the NH of generation 3Thereby, stop only to produce V 6O 13Reduction reaction and can not generate vanadium oxide VO 2, V 2O 4Perhaps opposite, add NH by circulation 3Other method, can produce the reduction reaction of the suitable degree of depth, and cause generating V 2O 3Mixture with several barium oxides.
The gas that the ammonium hexavanadate thermolysis is produced is preferably in minute-pressure, and 0.5 crust is collected in down and is preferably placed at than in the high airbag of reactor according to appointment.
Pyrolysis temperature should be about 400-650 ℃, is preferably 635 ℃.If temperature is higher than 650 ℃, be present in the V in the reaction medium 2O 5Before reaction, have fused danger; In addition, temperature of reaction is lower than 400 ℃ of VO that can cause non-thermochromism 2(B).
Under the situation of the adulterated vanadium dioxide particle of preparation, also must be in this way with the reaction times fixing obtaining adulterated homogeneous body, and prevent to be used for the trade-off optimization of temperature-time and particle increased.
For example, to the doping rate of 5%W:
600 ℃ 650 ℃ 700 ℃ of temperature
6 hours 3 hours 1 hour minimum time
Maximum duration 60 hours 12 hours 6 hours
Prepare the vanadium dioxide particles (being equivalent to the pure zirconia vanadium) that structure transition temperature is different from 68 ℃ if desired, need be higher than 4 replacement product doping with stablizing valency.
In the preferred case, the metal that is selected from Nb, Ta, Mo and W will be as replacing product, and W and Mo are preferred.
Can obtain a kind of finished product with tungsten (W) replacement, this product has sizable temperature rate of change along with replacing the per-cent difference: sizable gradient in fact can cover very large-scale temperature.For example, under above-mentioned x value, the transition temperature of acquisition is:
x＝0％ 1％ 2％ 3％
T t＝68℃ 40℃ 12℃ -16℃
Present method one preferred aspect, therefore employed ammonium hexavanadate is with being selected from a kind of metal-doped of Nb, Ta, Mo and W, W and Mo are preferred.
Narration part below, especially tungsten or molybdenum mix to be meant the compound form that contains this metal with the pure state formula with " with metal-doped " of above-mentioned definition.
The ammonium hexavanadate that is used for the inventive method can be buied in market, also can make from ammonium meta-vanadate with currently known methods.
When hope prepares adulterated vanadium dioxide particles, or mix, or by the synthetic hexavanadate of ammonium meta-vanadate the time, doping metals is added with ammonium hexavanadate.
Also be favourable with tungsten as replacing product so far, because ammonium tungstate is soluble in water.
It should be noted that for being ground paste uniformly, minimum water-content is 20% weight when wishing can easily ammonium tungstate to be placed the solution of water with ammonium hexavanadate when the synthetic ammonium hexavanadate adds tungsten.
According to following reduction and substitution reaction, carry out chemistry replacement or doping by the pyrolysis of ammonium tungstate and ammonium hexavanadate precursor mixture:
For obtaining even result's selection x, be the calculating of exact chemical metering.This temperature desired that can obtain 68 ℃ of relevant vanadium dioxide transition temperatures changes: can point out gradient δ for this reason t/ dx=-2810 2The K/ mole, in fact, x=0.01 or 1%, δ t=-28 ℃.
A favourable aspect according to the inventive method, before pyrolysis, took out at least one minute, for example 15 minutes, make ammonium hexavanadate be lower than the ammonium hexavanadate decomposition temperature in temperature by under vacuum, carrying out first time pump, particularly be lower than approximately 230, be preferably the degassing about 200 ℃.
After pyrolysis, the vanadium dioxide that obtains is preferably under the rare gas element and carried out anneal at least 1 hour at least 600 ℃ in temperature, for example 5 hours.
For example, anneal can be carried out under 600 ℃ 14 hours.Carried out under 800 ℃ 5 hours, then particle growth is greater than 5 microns.
Of the inventive method preferred aspect, and choose wantonly after above-mentioned anneal, vanadium dioxide will be cooled to about 120 ℃ under rare gas element.Rate of cooling can for, for example about 150 ℃/minute-250 ℃/minute.
For example, nitrogen and argon can be used as rare gas element.
When vanadium dioxide entered atmosphere, temperature was necessary for the highest about 100 ℃, with the danger that prevents that it from absorbing water and therefore emitting the surface to reoxidize.
What represent in Fig. 1 is the example that carries out the stove of method of the present invention, movably tube furnace (2) that is contained on the track (3) and the treatment chamber of being made up of quartz (1) are wherein arranged, chamber (1) can obtain temperature desired fast, gas, especially NH that airbag (4) can produce the ammonium hexavanadate thermolysis 3Remain on particulate to be processed top in the chamber 1.This can keep enough ammonia dividing potential drops, makes to be reduced into VO 2Reaction carry out fully.Heavier gas N 2O is with to the bottom in said airbag (4), and this can make the compound purity that is obtained increase and optimization.
Fig. 1 also illustrates and can make the last valve (5) of discharging of gas, for steel cylinder (6) and (7), vacuum pump (8) and the pressure indicator dial (9) of argon gas and nitrogen.
Like this,, can obtain being lower than 10 microns, even be lower than 5 microns, be preferably the vanadium dioxide particles of 0.1-0.5 micron according to method of the present invention.
Some particle is the 2-10 micron after reaction, but can be very easily broken by grinding, in fact, when preparing with method of the present invention, these particles all advantageously are " cutting in advance " sheet form, as represent among Fig. 2 by shown in scanning electronic microscope (SEM) photo.And during with the prior art method, as described above, even obtain pure vanadium dioxide, also mainly be the big grain monocrystalline about 30 particulates, and that this is difficult to is broken.
Like this, aspect present method preferred, the vanadium dioxide that obtains after the pyrolysis is carried out wet lapping.Said pyrolysis then optional in addition anneal and/or cooling process, as described above.Said grinding can, for example rotate in the zirconium ball mill and carry out, the rotating speed of ball mill is for being higher than 3000 rev/mins, milling time for less than or equal 2 hours.
After the milled processed, owing to it will be mixed immediately or later in the vanadium dioxide surface coating composition that the present invention obtains, so making its whole particle diameters is the 0.1-0.5 micron: these basic granuleses can access transparent film, and this then desired just purpose, by with adding any pigment but the coating of not obvious change color mix, or join and can keep satisfying application of the present invention in its transparent varnish.
On the other hand, the present invention relates to utilize vanadium dioxide particles of the present invention to prepare surface coating composition.
Can as mixing or unadulterated vanadium dioxide and its dispersion of help and stable dispersion agent paste producing under agitation, vanadium dioxide be added surface coating composition, particularly in coating or the varnish by any method of knowing.Randomly grind to reduce particle diameter, ground 2 hours as changeing above rotation zirconium ball shredder with per minute 3000, can make vanadium dioxide particles broken fully, finally reach micron greater than 0.1-0.5, said grinding to vanadium dioxide, as mentioned above, be before being added to surface coating composition, to carry out.
Like this, the invention still further relates to the surface coating composition of in the present patent application, mentioning that contains vanadium dioxide particles.
The following examples are used to illustrate the present invention, but limit the present invention anything but.Embodiment 1: the production of the synthetic I. ammonium hexavanadate precursor (AHV) of non-doped vanadium dioxide:
In one 250 milliliters beaker, add 20 gram ammonium meta-vanadate (AMV) (AldrichRef.20,5559; Purity: 99%; Molecular weight: 116.78).Beaker is placed on the hot-plate.Under agitation add several dripping to form the liquid paste and to cause the AMV dissolving.Continuing under the stirring beaker to be heated to 55 ℃ ± 5 ℃.When stirring and keeping homo(io)thermism, also drip (when beginning) 1 normal hydrochloric acid soln.
Inspection pH adds sour speed with adjusting and prevents the unexpected decline of pH.This step, used total length of time was greater than half an hour.
When adding about 110 cubic centimetres of acid (3 moles AHV needs 2 moles acid approximately), pH descends suddenly and can not go up.Exceed this point, pH reaches a limit value, and the product of acquisition is orange paste, and after 120 cubic centimetres, adding 1 normal hydrochloric acid can stop.
The orange-yellow precipitation that water under the vacuum suction filter in the filter crucible of No. 5 porositys (acid a little to prevent dissolve again) rinsing obtains, then in a stove 200 ℃ of following dry airs 24 hours, obtain the AHV of 17 grams.
Weight yield (with respect to initial AMV quality representation)=
Molar yield (with the mole expression of vanadium): greater than the pyrolysis of this precursor of 99%II.
The degassing earlier of a.AHV:
In the aluminium basket in the A district of stove (T=200 ℃), deposit the AHV of 2 grams.First pump was taken out 15 minutes under vacuum.
The thermolysis of b.AHV and VO 2Generation:
Then the aluminium basket is placed directly in temperature and is in second district (B) of stove of 600 ± 5 ℃ (heat-up rate is about 250 ℃/minute).
Directly contacting with reactor and under the minute-pressure of 0.5 crust, be collected in all gas of discharging in the airbag and place the height that is lower than reactor, lasting 1 hour.
C. the cooling and from stove, discharge:
With about 200 ℃/minute speed the C district of stove is cooled to 120 ℃ of temperature under by the atmosphere that decompose to produce.
Black-and-blue powder (the VO that generates 2) quality: 1.6680 ± 0.0005 the gram.
At Fig. 3, represented X-beta ray spectrum, INFRARED SPECTRUM and the scanning electron photomicrograph of the product of embodiment 1 in 4 and 5 separately.In Fig. 4 a, be the infrared spectra that writes down more than 68 ℃ in temperature, in Fig. 4 b, be the infrared spectra that writes down under 68 ℃ the temperature being lower than.Embodiment 2: by the synthetic non-adulterated vanadium dioxide of industrial AHV precursor
The degassing earlier of a.AHV:
The AHV (Treibacher (Austria), Ref.AHV Trocken 99%) of 2 grams are placed in the aluminium indigo plant in A district (T=200 ℃) of stove.First pump was taken out 15 minutes under vacuum.
The thermolysis of b.AHV and VO 2Generation:
Then, the aluminium basket being placed directly in temperature is (heat-up rate is about 250 ℃/minute) in 600 ℃ ± 5 ℃ second district (B) of stove.
directly contact with reactor and minute-pressure under, be collected in all gas of discharging in the airbag and place the height that is lower than reactor, last 1 hour.
C. the annealing of vanadium dioxide:
In the presence of decomposition gas, sample was stayed in 600 ± 5 ℃ the reactor 14 hours.
D. cooling and the discharge from stove:
Be cooled to 120 ℃ of temperature by decomposing in the gas that produces with about 200 ℃/minute speed.
Black-and-blue powder (the VO that generates 2) quality: 1.6689 ± 0.0005 the gram.Embodiment 3: by the synthetic non-doped vanadium dioxide of industrial AHV precursor.
Utilize industrial AHV precursor (Treibacher (Austria) Ref.AHV Troken99%).
The degassing of a and b:AHV and thermolysis are with carrying out as method used among the embodiment 2.
C. the annealing of vanadium dioxide:
Sample taken out and puts back to A district (T=200 ℃) in reactor.Earlier whole samples were placed vacuum 15 minutes then.Sample was moved on in the B district of stove 5 hours, the temperature in this district is 800 ℃ thereupon.
D. cooling and discharge from stove:
In decomposing the gas that produces, stove C district is cooled to 120 ℃ of temperature with about 200 ℃/minute speed.
Black-and-blue powder (the VO that generates 2) quality: 1.6682 ± 0.0005 the gram.Embodiment 4: general formula V 1-xM xO 2The production of the AHV precursor of the synthetic I. band doping agent of (x=0.01 and M=W) doped vanadium dioxide:
As at the preparation AHV precursor described in the embodiment 1, but before adding 1 normal hydrochloric acid, add ammonium tungstate (Aldrich Ref.32,238.5 of 0.459 gram; Purity 99%; Molecular weight=265.88).
Resulting product quality is 19.424 grams (comprising ammonium chloride).Carried out the mensuration of the x-ray diffraction pattern and the Fourier transform infrared spectroscopy of product: owing to except that AHV, also have tungstate, so bands of a spectrum are very weak.II. the pyrolysis of precursor
A. the degassing earlier of adulterated AHV
The doping AHV of the above-mentioned preparation of 2.000 grams is deposited in the aluminium indigo plant of stove A district (T=200 ℃).First pump was taken out 15 minutes under vacuum.
B. the mix thermolysis of AHV and with the tungsten VO that mixes 2Generation.
Then aluminium indigo plant is placed directly in second district (B) of stove, wherein temperature is 600 ± 5 ℃ (temperature rise rate is about 250 ℃/minute).
directly contact with reactor and minute-pressure under, be collected in all gas of discharging in the airbag and place under the height that is lower than reactor.
C. the annealing of vanadium dioxide
With sample rest on 600 ℃ 14 hours.
D. cooling and discharge from stove
In the gas that decompose to produce, the C district of stove is cooled to 120 ℃ of temperature under with about 200 ℃/minute speed.
Black-and-blue powder (the VO that is generated 2) quality: 1.669 ± 0.001 the gram.
Infrared spectra and the scanning electron photomicrograph of in Fig. 6 and 7, representing embodiment 4 products separately.In Fig. 6 a, infrared spectra is higher than 68 ℃ of records in temperature, and in Fig. 6 b, infrared spectra is lower than 68 ℃ of records in temperature.Embodiment 5: by the synthetic general formula of industrial AHV precursor is V 1-xM xO 2(x=0.01, the adding of doped vanadium dioxide I. doping agent M=W)
The AHV that adds 20 grams in 25 ml waters of shredder is sticky to form.Then paste is carried out the first time and grind, purpose is with the dispersion liquid homogenizing of AHV in aqueous medium.
Ammonium tungstate is water-soluble white powder.0.539 gram ammonium tungstate is added in the grinding paste, and continues to disperse several minutes.
In 200 ℃ stove or under vacuum, resulting mixture is carried out drying.II. the mix pyrolysis of AHV precursor
Under with the identical implementation condition among the above-mentioned embodiment 2, carry out pyrolysis, and carried out anneal 5 hours at 800 ℃.
Black-and-blue powder (the VO that is generated 2) quality: 1.670 ± 0.001 the gram.Embodiment 6: general formula V 1-xM xO 2(x=0.02, M=W) adding of the synthetic I. doping agent of doped vanadium dioxide
As restraining AHV (Treibacher, Austria, Ref.AHV Troken 99%) in embodiment 5 pointed addings 20.The ammonium tungstate quality that adds is 1.089 grams.The pyrolysis of II. adulterated AHV precursor
Under the implementation condition identical, carry out pyrolysis with the foregoing description 5.
Black-and-blue powder (the VO that generates 2) quality: 1.671 ± 0.001 the gram.Embodiment 7: the evaluation of film and optical detecting
Contain the adulterated or plain VO of useful 1% tungsten with following method preparation 2Dry film (V 1-xM xO 2, x=0.01 and M=W) and (solvent phase):
1) preparation of varnish
The empirical formula of varnish
Plexigum P675 (HULS, Germany) 34 (acrylic copolymer)
Solvanter S340 (EIf, France) 28 (hydrocarbon solvent 100% aromatic series)
Petroleum solvent 17% (EIf, France) 38 (hydrocarbon solvent 17% aromatic series)
100.00
Selvanter S340 and petroleum solvent 17% are weighed in the beaker, under agitation add Plexigum P675 then, then stir up to complete homogenizing.
2) VO 2Adding
100 gram varnish are weighed into beaker.The VO that under agitation adds 1 gram 2(doping or unadulterated).Continuation is stirred at least 15 minutes until complete homogenizing with 1500 rev/mins speed.Grind by the glass microsphere shredder.
3) use
With a manual coating device coating of making is coated on the sheet glass, this can make sedimentary wet coat-thickness is 50 microns.
Carry out drying at normal temperatures.
These films are identified with following method:
-Fourier transform infrared spectroscopy
-carry out optical detecting with optical measurement (measurement of sunlight flux)
4) result
A. identify conversion by Fourier transform infrared spectroscopy.
By on glassly spread, drying and matrix separately prepare free film.
In transmission and overall attenuation reflection (ATR), identify free film by Fourier transform infrared spectroscopy.In heating and cooling owing to contain unadulterated VO 2Film is at T t=66 ± 2 ℃ and contain with the adulterated VO of 1% tungsten 2The disappearance and the reproduction of the absorption band of film in Tt=± 2 ℃ clearly prove the transformation of the isolator-metal of vanadium dioxide.
Accompanying drawing 8a and 8b represent to contain unadulterated VO 2(Fig. 8 is the three dimensional change of cooling absorption band when (Fig. 8 b) then a) in heating for film.Can see having only the absorption band of polymkeric substance to remain unchanged.
B. scanning electron photomicrograph
Scanning electron photomicrograph can
-one side characterizes VO in the dry film 2The distribution of particle,
-on the other hand, carry out the accurate mensuration of thickness.
C. carry out optical detecting by optical measurement
Being used for measuring the device that Fig. 9 of sunlight flux represents is special the manufacturing, in order to confirm that film changes look in the heat of near infrared band and changes.Its principle discussed in one piece of article (J.C.Valmalette et al., Solar Energy Materials, 1994) in the summary of the world.
Artificial sun light source (11) is to concentrate on 1 micron halogen lamp by 50 watts emission maximum to constitute.Sample is laminated film or the coating (13) that is deposited on 58 millimeters of diameters on the glass basis (16), and sample is towards light source (11) and detector (10), and detector (10) is in order to measure the light stream of wavelength 0.3-2.8 micron.The voltage that comes out with volt ohm-milliammeter (15) detector for measuring (10).Each sample can use the thermopair that is attached to thermometer (14) to come the temperature of MEASUREMENTS OF THIN with an airflow (12) heating or cooling.
The utilization of test-results can obtain directly and film method for making and three kinds of relevant optical scales of transformation quality.
The sign of every kind of film is identified and is comprised:
-light source (no sample) radiating is directly measured,
-carry out stdn by the semitransparent thin film that contains non-thermic blackening pigment by high and low-temperature measurement.
-measurement I ° on sheet glass only
-freezing mask (T＜T t) measurement: I Cold
-hotting mask (T＞T t) measurement: I Heat
Defined three kinds of scales by calculating (in the solar spectrum scope of detector):
-opaqueness
-relative efficiency (I-(the I that represents with % Heat/ I Cold)
-absolute efficiency (the I that represents with standard unit Heat-I Cold): watt/meter 2
The result who obtains is following, and (amount of flux that sees through when cold is expressed as 1000 watts/meter of incident radiations 2Function).
Contain the VO that do not mix in a large number 2The dry film of 10 micron thickness equal M.F.=0.01.
-opaqueness=34 ± 2%
-(T＜T when cold t=66 ℃) flux=662 that see through watt/meter 2
-(T＞T when hot t=66 ℃) flux=606 that see through watt/meter 2
-relative efficiency=8.5%
The increase of-absolute efficiency=56 watt/meter 2
Contain a large amount of unadulterated VO 2The dry film of 10 micron thickness equal M.F.=0.025
-opaqueness=40 ± 2%
-(T＜T when cold t=66 ℃) flux=631 that see through watt/meter 2
-(T＞T when hot t=66 ℃) flux=527 that see through watt/meter 2
-relative efficiency=16.5%
The increase of-absolute efficiency=104 watt/meter 2
Contain a large amount of unadulterated VO 2The dry film of 10 micron thickness equal M.F.=0.05
-opaqueness=63%
-(T＜T when cold t=66 ℃) flux=270 that see through watt/meter 2
-(T＞T when hot t=66 ℃) flux=286 that see through watt/meter 2
-relative efficiency=31.1%
The increase of-absolute efficiency=84 watt/meter 2
Contain the unadulterated VO of 1% tungsten 2The dry film of 100 micron thickness equal M.F.=0.005 ± 0.001.
-opaqueness=68 ± 2%
-(T＜T when cold t=66 ℃) flux=708 that see through watt/meter 2
-(T＞T when hot t=66 ℃) flux=635 that see through watt/meter 2
-relative efficiency=31.1%
The increase of-absolute efficiency=73 watt/meter 2
These results show that the volume fraction of pigment directly has influence on:
-heat gain when changing,
The opaqueness of-varnish plate.Embodiment 8: the research of particle diameter
By unadulterated VO on electron microscope to obtaining according to present embodiment 1 and 2 2Several samples of the film that makes calculate implements this research.Film is that the method according to embodiment 7 makes.
The results are shown in the following table 1 and table 2.
Table 1
The unadulterated VO that contains embodiment 1 2Film
Have standard deviation Ln δ=60 at D *Normal logarithm on=0.3 micron distributes.
Film thickness=10 micron
Volume fraction (pigment volume/film cumulative volume)=0.02
Granule number Size (micron) D Account for the % of total particle number Mean sizes D *(micron)
A ＜0.16 0.158 0.1
B 0.16-0.55 0.684 0.3
C ＞0.55 0.158 1
D=particulate diameter; D *=particulate mean diameter
Table 2 contains the not doping VO of embodiment 2 2Film have standard deviation Ln δ=0.8 at D *Normal logarithm on=1 micron distributes.Film thickness=10 micron volume fraction (pigment volume/film cumulative volume)=0.02
Granule number Size (micron) D Account for the % of total particle number Mean sizes D *(micron)
A ＜0.2 23 0.17
B 0.2-0.45 13.6 0.30
C 0.45-1 34.2 0.67
D 1-2.23 34.2 1.5
E 2.23-5 13.6 3.34
F ＞5 23 5.85
D=particulate diameter; D *=particulate mean diameter

Claims (17)

1. general formula V 1-xM xO 2The particulate of vanadium dioxide, 0≤x in the formula≤0.05, M is a metal, being selected to provide ionic fluid maybe can provide the metal of electronics greater than the transition element of vanadium, it is characterized in that the size of said particulate＜5 micron.
2. the particulate of claim 1, wherein said particulate is of a size of the 0.1-0.5 micron.
3. the general formula V of claim 1 1-xM xO 2Particulate, wherein, M is a kind of Nb of being selected from, Ta, the metal of Mo and W.
4. claim 1 or 3 general formula V 1-xM xO 2Particulate, x is between 0-0.02 in the general formula.
5. one kind is mixed by pyrolysis or unadulterated ammonium hexavanadate prepares the method for each vanadium dioxide particles among the claim 1-4, it is characterized in that, said pyrolysis is at least under 100 ℃/minute at 400 ℃-650 ℃ of temperature and temperature rise rate to be carried out, its feature is that also the gas that is produced by said pyrolysis directs contact to few 1/2 hour by the maintenance of sealing gland ground and with reaction medium.
6. the method for claim 5 wherein contacts at least 1 hour.
7. the method for claim 5, said method are to use by a kind of metal-doped ammonium hexavanadate that is selected from claim 3 definition to be undertaken.
8. claim 5 or 7 method is characterized in that temperature rise rate is at least 200 ℃/minute.
9. the method for claim 8, wherein temperature rise rate is at least 300 ℃/minute.
10. claim 5 or 7 method is characterized in that being at least 5 minutes by the sealing gland hold-time by the gas that pyrolysis produces.
11. the method for claim 10, wherein the hold-time is 1/2-2 hour.
12. the method for claim 5 or 7 is characterized in that, before pyrolysis, be lower than 230 ℃ in temperature ammonium hexavanadate is outgased, first pump is evacuated to few 1 minute under vacuum.
13. the method for claim 5 or 7 is characterized in that, after pyrolysis, the vanadium dioxide that obtains can randomly carry out anneal at least 1 hour under at least 600 ℃ of temperature and rare gas element.
14. the method for claim 5 or 7 is characterized in that, after pyrolysis, after the anneal of randomly carrying out as claim 13 definition, randomly vanadium dioxide is chilled to 120 ℃ of temperature under rare gas element.
15. the method for claim 5 or 7 is characterized in that, after the said pyrolysis randomly in addition as claim 9 and 10 defined annealing and/or cooling process after, the vanadium dioxide of acquisition randomly grinds.
16. each particulate is used to prepare the purposes of surface coating composition among the claim 1-4.
17. contain the surface coating composition of each particulate among the claim 1-4.
CN95196132A 1994-11-09 1995-11-03 Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating Expired - Fee Related CN1058469C (en)

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FR9413445A FR2726545B1 (en) 1994-11-09 1994-11-09 VANADIUM DIOXIDE MICROPARTICLES, PROCESS FOR OBTAINING SUCH MICROPARTICLES AND THEIR USE, IN PARTICULAR FOR SURFACE COATINGS
FR94/13445 1994-11-09

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CN100421844C (en) * 2006-12-11 2008-10-01 武汉大学 Preparing process for vanadium dioxide powder
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CN102120615B (en) * 2011-01-21 2012-10-31 中国科学院上海硅酸盐研究所 Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof
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CN103073942B (en) * 2012-01-19 2014-09-10 中国科学院上海硅酸盐研究所 Vanadium dioxide composite powder and preparation method thereof
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WO2015151355A1 (en) * 2014-03-31 2015-10-08 株式会社村田製作所 Vanadium oxide and manufacturing method therefor
CN104022286B (en) * 2014-06-24 2016-08-24 武汉理工大学 Porous VO2nano wire and its preparation method and application
JP6032686B2 (en) * 2015-01-21 2016-11-30 国立研究開発法人理化学研究所 Heat storage material
RU2602896C1 (en) * 2015-07-28 2016-11-20 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Method of producing vanadium dioxide nanoparticles
RU2610866C1 (en) * 2015-09-28 2017-02-16 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Method for ammonium vanadate preparation
WO2017138264A1 (en) * 2016-02-09 2017-08-17 コニカミノルタ株式会社 Method for producing vanadium dioxide particles
CN112209440A (en) * 2020-10-16 2021-01-12 成都先进金属材料产业技术研究院有限公司 Process for preparing M-phase vanadium dioxide nano powder
CN116119713A (en) * 2022-12-13 2023-05-16 攀钢集团研究院有限公司 Preparation method of porous nano vanadium oxide, porous nano vanadium oxide and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD126414A1 (en) * 1976-06-30 1977-07-13

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0742114B2 (en) * 1986-02-25 1995-05-10 新興化学工業株式会社 Vanadium lower oxide manufacturing method
US4957725A (en) * 1988-07-05 1990-09-18 The Johns Hopkins University Vanadium dioxide formed by the sol-gel process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD126414A1 (en) * 1976-06-30 1977-07-13

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