CN104003409B - A kind of preparation method of controlled monodisperse spherical Large stone nano silicon - Google Patents
A kind of preparation method of controlled monodisperse spherical Large stone nano silicon Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of controlled monodisperse spherical Large stone nano silicon, with
Description
Technical field:
The present invention relates to a kind of preparation method of controlled monodisperse spherical Large stone nano silicon, utilize
the method that sol-gel method is combined with intermittent injecting reactant, the spherical SiO that controlledly synthesis monodispersity is excellent
2particle, belongs to nano material synthesis field.
Background technology:
In recent years, nano-silicon dioxide particle has in scientific research and industrial circle and studies more widely.Wherein, nano silicon can be used for the preparation of shear thickening liquid, for the research of soft bullet-resistant garment.Shear thickening fluid is generally disperseed to obtain in a liquid by certain density solids.Shear thickening fluid is generally made up of two-phase dispersion system, and one is made up of nanoparticle mutually, such as silicon-dioxide, calcium carbonate, PMMA particle etc., and another is carrier fluid mutually, such as water, polyoxyethylene glycol etc., and dispersed phase particles dispersion wherein.Shear thickening fluid is a kind of non-Newtonian fluid, and shear thickening behavior is the behavior that certain density dispersion system shows, and when higher than critical shear rate, its viscosity sharply rises, and macroscopic view is the transformation of liquid dispersion system to solid-phase.
The particle diameter of nano-silicon dioxide particle and the performance of monodispersity to shear thickening system have a great impact.Wherein, along with nano particle diameter reduces, shear thickening system critical shear rate increases.The monodispersity of nano-silicon dioxide particle declines, and causes the critical thickening starting point of system to move to high shear rate direction.This is disadvantageous for the application of STF in soft protective material.Therefore, the requirement preparing the nano-silicon dioxide particle of excellent, the Large stone of monodispersity is very urgent.
For the synthesis technique of nano-silicon dioxide particle, mainly contain three kinds of methods at present.The Pileni size that utilized micro-emulsion process to prepare can reach the silicon dioxide granule of thousands of nanometer.This method with
synthetic method is compared, and be more suitable for the silicon dioxide granule of compound particle size at 30-60nm, and particle has good monodispersity.But this preparation process needs a large amount of tensio-active agent (in general large than the massfraction of silicon dioxide granule) formation to stablize micelle.Therefore, product pellet needs process further, to eliminate the tensio-active agent of particle surface.In addition, in soft sensitivity, middle maintenance stable homogeneous micella composition is also very difficult mutually.
BalthisandMendenhall (J.H.Balthis.P.Wendenhall.Preprationofsolsfromfinelydivid edsilicon, USP2614994.1952) report a kind of method for hydrolysis utilizing pre-treatment elemental silicon, prepare single dispersing small particle size nano silicon.Reaction is by ammonia-catalyzed, and temperature of reaction controls at 20-90 DEG C.Meanwhile, the clear superiority of this method is before the reaction, and reactant is through acid solution, deionized water, and ethanol, ether process successively, and the oxide containing silicon of particle surface can be removed, outside the silicon face of cleaning is exposed to.Prepared the good nano-silicon dioxide particle of 8-15nm regularity in patent, the particle diameter that this patent provides is less, can not meet size of particles requirement needed for preparation shear thickening liquid.
The present invention with
based on sol-gel method, the processing condition affecting particle synthesis are probed into, optimizes catalyst concn, TEOS and water and react the factors such as mol ratio.Control reaction conditions, under less dropping number of times, obtain dispersed excellent, Large stone nano-silicon dioxide particle.Reaction system is simple, aftertreatment is easy, is the method for controlledly synthesis Large stone nano silicon.
Summary of the invention:
The object of this invention is to provide a kind of preparation method of controlled monodisperse spherical Large stone nano silicon, with
based on sol-gel method, tetraethoxy obtains orthosilicic acid through hydrolysis, by the method for intermittent injecting tetraethoxy, dehydrating condensation obtains silicon-dioxide, and the method technical process is simple, mild condition, post processing mode is easy, and production efficiency is high, is applicable to suitability for industrialized production.By intermittent injecting reactant, controlledly synthesis Large stone nano-silicon dioxide particle.The nano-silicon dioxide particle product that this preparation method obtains has spherical regular, the feature such as monodispersity is excellent.
The present invention with
based on sol-gel method, tetraethoxy (TEOS) obtains orthosilicic acid through hydrolysis, dehydrating condensation obtains silicon-dioxide, adopts weak base catalysis, and the method that interval substep adds tetraethoxy obtains excellent, the spherical Large stone nano silicon of monodispersity.
The preparation method of controlled monodisperse spherical Large stone nano silicon provided by the invention, concrete steps and condition are:
(1) be scattered in by ammoniacal liquor in dehydrated alcohol or ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 8 ~ 40:1, preferably 10 ~ 20:1, and dispersed with stirring is even; Added by tetraethoxy in mixing solutions, control rate of addition is 10 ~ 60ml/min, preferably 20 ~ 40ml/min, tetraethoxy and H
2o mol ratio is 1:2 ~ 20, preferred 1:3 ~ 6;
(2), under normal temperature, control stirring velocity 200 ~ 750r/min, preferred 500-750r/min, reaction times 2 ~ 8h, preferably 4 ~ 6h, obtain silicon dioxide gel;
(3) drip tetraethoxy in the silicon dioxide gel obtained in step (2), adding the mol ratio adding tetraethoxy in the amount of tetraethoxy and step (1) is 1:10 ~ 4:1; Preferred 1:2 ~ 4:1.Adding of preferred tetraethoxy point is carried out for 2 ~ 4 times, after being added dropwise to complete at every turn, and stirring reaction 2 ~ 4h, then drip next time.
(4) reactant that obtains of step (3) is through centrifugation, removing supernatant liquor, product is scattered in solvent again, through dispersion, centrifugation again repeatedly, until supernatant liquor is neutral, the preferred ultrasonic disperse of dispersing mode, solvent is selected from dehydrated alcohol, acetone or deionized water, finally by vacuum-drying, dry obtained target product, bake out temperature is preferably 60-90 DEG C.
Reaction equation prepared by silicon-dioxide is:
Si(OC
2H
5)
4+2H
2O→SiO
2+4C
2H
5OH
Wherein, the hydrolysis of tetraethoxy: Si (OC
2h
5)
4+ 4H
2o → Si (OH)
4+ 4C
2h
5oH is main reaction, and this reaction is Si (OC
2h
5)
4nucleophilic substitution reaction, the Siliciumatom positively charged in TEOS, in reaction process, the Siliciumatom of the hydroxyl radical attacks positively charged of water, oxyethyl group is left away, and obtains orthosilicic acid.Base catalysis is conducive to the carrying out of nucleophilic substitution reaction, and in this reaction system, ammoniacal liquor is catalyzer, and along with the increase of catalyst concn, particle diameter increases, but size distribution broadens, and monodispersity declines.Therefore, in order to take into account particle diameter, particle spherical with monodispersity etc. problem, need to select suitable ammonia concn, this is also key problem in technology of the present invention.
In the dispersion process of step (1), add the process of tetraethoxy, not only need to control tetraethoxy add-on, control is also needed to add speed, the mol ratio of preferred tetraethoxy and water is 1:3 ~ 1:6, rate of addition is 20 ~ 40ml/min preferably, and especially when ammonia concn is higher, the rate of addition of TEOS has larger impact to balling-up regularity and particle diameter.
In the reaction process of step (2), stirring velocity is preferably 500-750r/min.In reaction process, stirring velocity is constant, avoids the nanoparticle generated to reunite.Reaction times is preferably 4-6h.Treat that the particle diameter of nano-silicon dioxide particle no longer changes, reactant reacts completely, and particle is formed stable spherical.
In order to obtain Large stone nano-silicon dioxide particle in step (3), adopt " interval drips growth method ", in the nano-silicon dioxide particle colloidal sol formed, add tetraethoxy, with the silicon-dioxide generated for core, by the further reaction of tetraethoxy, particle diameter is increased.Add the mol ratio adding tetraethoxy in the amount of tetraethoxy and step (1) and be preferably 1:2 ~ 4:1.In reaction process, interval sampling characterizes, to obtain the silicon dioxide granule of required particle diameter.
The present invention compared with prior art, has the following advantages:
Under existing reaction system, determine in sol-gel method the processing parameter affecting particle diameter and regularity.Adopt substep to add the method for reactant, achieve controlledly synthesis Large stone nano-silicon dioxide particle, and particle monodispersity is excellent.The method technical process is simple, mild condition, and post processing mode is easy, and production efficiency is high, is applicable to suitability for industrialized production.In addition, the Large stone nano-silicon dioxide particle of patent supplying method synthesis, in shear thickening liquid field, has potential using value.
The present invention characterizes the testing tool used: German BRUKERTENSOR27 type Fourier infrared spectrograph, Hitachi S4800 scanning electronic microscope (sweep voltage 5KV), FEI Hong Kong company limited TecnaiG
220 transmission electron microscopes, Japanese Shimadzu XRD-6000, MCR301 rheometer.
The major experimental medicine that the present invention is used: ammoniacal liquor, analytical pure, Beijing Chemical Plant; Tetraethoxy, analytical pure, Beijing Yili Fine Chemicals Co., Ltd.; Ethanol, analytical pure, Beijing Chemical Plant; Acetone, analytical pure, Beijing Chemical Plant.
Accompanying drawing illustrates:
Fig. 1. the particle diameter that embodiment 1 obtains is about 290nmSiO
2sEM picture
Fig. 2. the SiO that embodiment 1 is obtained
2infrared spectrum
Fig. 3. the particle diameter that embodiment 2 obtains is about 340nmSiO
2sEM picture
Fig. 4. embodiment 2 obtains SiO
2xRD spectra
Fig. 5. the particle diameter that embodiment 3 obtains is about 410nmSiO
2sEM picture
Fig. 6. the particle diameter that embodiment 3 obtains is about 410nmSiO
2tEM picture
Fig. 7. the SEM picture (1) of the MP4540M silicon-dioxide that Japanese Nissan chemical company produces
Fig. 8. the SEM picture (2) of the MP4540M silicon-dioxide that Japanese Nissan chemical company produces
Fig. 9. the particle diameter that embodiment 4 obtains is about 500nmSiO
2sEM picture
Figure 10. the particle diameter that embodiment 5 obtains is about 600nmSiO
2sEM picture
Figure 11. the STF viscosity of massfraction 53.5% is with the change curve of shearing rate
Figure 12. the STF viscosity of massfraction 53.5% is with the change curve of shear-stress
From the stereoscan photograph of Fig. 1, Fig. 3, Fig. 5, Fig. 9, Figure 10 silicon dioxide granule, by controlling the processing condition of embodiment 1-5, preparing particle diameter and being about spherical regular, the particle that monodispersity is excellent of 300-600nm.From Fig. 2, Fig. 4 and Fig. 6 to infrared, the XRD of product pellet and TEM (transmission electron microscope) analysis, the particle of known preparation is noncrystal solid spherical silicon dioxide granule.From Fig. 5, Fig. 6, the obtained 410nm particle of embodiment 3 contrasts with the MP4540M particle produced from Japanese Nissan chemical company, the product pellet that method provided by the invention obtains spherical regular, monodispersity is excellent.
Figure 11, Figure 12 are that the silicon dioxide granule utilizing particle diameter in embodiment 5 to be about 600nm prepares STF, massfraction is 53.5%, by its rheology testing, system critical thickening starting point is lower, can show shear thickening behavior at low shear rate, the product prepared by explanation has using value.
Embodiment:
Below in conjunction with comparative example and embodiment, the present invention is described further.
Embodiment 1
(1) be scattered in ethanolic soln by a certain amount of ammoniacal liquor, the mol ratio of ethanol and ammoniacal liquor is 16:1, and electric stirring is uniformly dispersed, and is added by tetraethoxy in mixing solutions, and controlling rate of addition is 25ml/min, TEOS and H
2o mol ratio is 1:5.
(2) normal temperature, controls stirring velocity 650r/min, and reaction 5h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtained in step (2), substep adds TEOS, control 650r/min constant speed stirs, constant pressure funnel drips TEOS, control rate of addition is 25ml/min, be 1:2 with the mol ratio of the TEOS added in step (1), once add, after dropwising, control 650r/min constant speed stirs, reaction 4h.
(4) reactant that obtains of step (3) is through centrifugation, and removing supernatant liquor, is scattered in acetone again by centrifugal thing.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in vacuum drying oven, in 80 DEG C, dries 20h.
Sample respectively after step (1) and step (3) add TEOS, by SEM and laser particle size analysis test, the particle diameter that step (1) obtains is about 170nm, and obtaining particle diameter after step (3) reaction terminates is 290nm.In addition, from infrared test result, the method has successfully prepared nano-silicon dioxide particle, and post-treating method is feasible, and product purity is high.
Analyze from product infrared spectrum, 1103cm
-1the absorption band of Qiang Erkuan is Si-O-Si antisymmetric stretching vibration peak, 800cm
-1, 470cm
-1the peak at place is Si-O key symmetrical stretching vibration peak, 3442cm
-1the broad peak at place is water of constitution-OH antisymmetric stretching vibration peak, 1633cm
-1neighbouring peak is the H-O-H flexural vibration peak of water, 950cm
-1the peak at place belongs to the flexural vibration absorption peak of Si-OH.
Without the assorted peak of other groups in spectrogram, illustrate that preparation and last handling process are feasible.
Embodiment 2
(1) be scattered in ethanolic soln by a certain amount of ammoniacal liquor, the mol ratio of ethanol and ammoniacal liquor is 13:1, and electric stirring is uniformly dispersed, and is added by tetraethoxy in mixing solutions, and controlling rate of addition is 20ml/min, TEOS and H
2o mol ratio is 1:4.
(2) normal temperature, controls stirring velocity 600r/min, and reaction 5h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtained in step (2), substep adds TEOS, control stirring velocity 600r/min, constant pressure funnel drips TEOS, control rate of addition is 20ml/min, be 1:1 with the mol ratio of the TEOS added in step (1), add at twice, after dropwising at every turn, control stirring velocity 600r/min constant speed to stir, reaction 3h.
(4) reactant that obtains of step (3) is through centrifugation, and removing supernatant liquor, is scattered in dehydrated alcohol again by centrifugal thing.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in vacuum drying oven, in 70 DEG C, dries 22h.
Sample respectively after step (1) and step (3) add TEOS, by SEM and laser particle size analysis test, the particle diameter that step (1) obtains is about 210nm, step adds TEOS twice in (3), finally obtains the silicon dioxide granule that particle diameter is 340nm.Illustrate that silicon-dioxide particle diameter can be made to increase gradually, and reaction conditions is gentle, reaction process is controlled through adding TEOS step by step.
In addition, compose from the XRD figure of particle, be about 23 ° at 2 θ and occur wide diffraction peak, the nanoparticle that reaction obtains is non-crystalline material.
Embodiment 3
(1) be scattered in ethanolic soln by a certain amount of ammoniacal liquor, the mol ratio of ethanol and ammoniacal liquor is 11:1, and electric stirring is uniformly dispersed, and is added by tetraethoxy in mixing solutions, and controlling rate of addition is 40ml/min, TEOS and H
2o mol ratio is 1:6.
(2) normal temperature, controls stirring velocity 700r/min, and reaction 6h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtained in step (2), substep adds TEOS, control stirring velocity 700r/min, constant pressure funnel drips TEOS, control rate of addition is 40ml/min, be 2:1 with the mol ratio of the TEOS added in step (1), point add, after dropwising for three times at every turn, control stirring velocity 700r/min constant speed to stir, reaction 2h.
(4) reactant that obtains of step (3) is through centrifugation, and removing supernatant liquor, is scattered in dehydrated alcohol again by centrifugal thing.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in vacuum drying oven, in 90 DEG C, dries 16h.
After step (1) and step (3) have been reacted, sample and characterized by SEM and laser particle size analysis test, the particle diameter that step (1) obtains is about 260nm, after step (3) reacts completely, particle diameter is 410nm (as Fig. 8 shows), Fig. 9 and Figure 10 is the scanning electron microscopic picture of the MP4540M (Large stone particle is 450nm) that Japanese Nissan chemical company produces, contrast known, the product pellet that embodiment 4 obtains is spherical regular, and monodispersity is excellent.
Embodiment 4
(1) be scattered in ethanolic soln by a certain amount of ammoniacal liquor, the mol ratio of ethanol and ammoniacal liquor is 10:1, and electric stirring is uniformly dispersed, and is added by tetraethoxy in mixing solutions, and controlling rate of addition is 30ml/min, TEOS and H
2o mol ratio is 1:1.
(2) normal temperature, controls stirring velocity 750r/min, and reaction 6h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtained in step (2), substep adds TEOS, control stirring velocity 750r/min, constant pressure funnel drips TEOS, be 1:3 with the mol ratio of the TEOS added in step (1), divide and add for three times, after dropwising, control stirring velocity 750r/min constant speed and stir, reaction 2h.
(4) reactant that obtains of step (3) is through centrifugation, and removing supernatant liquor, is scattered in deionized water again by centrifugal thing.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in vacuum drying oven, in 90 DEG C, dries 16h.
After step (3) has been reacted, sample and characterized by SEM and laser particle size analysis test, the particle diameter obtained has been about 500nm, and can be observed product pellet from the scanning electron microscopic picture of product pellet spherical regular, monodispersity is excellent.
Embodiment 5
(1) be scattered in ethanolic soln by a certain amount of ammoniacal liquor, the mol ratio of ethanol and ammoniacal liquor is 10:1, and electric stirring is uniformly dispersed, and is added by tetraethoxy in mixing solutions, and controlling rate of addition is 30ml/min, TEOS and H
2o mol ratio is 1:1.
(2) normal temperature, controls stirring velocity 750r/min, and reaction 6h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtained in step (2), substep adds TEOS, control stirring velocity 750r/min, constant pressure funnel drips TEOS, control rate of addition is 30ml/min, be 1:4 with the mol ratio of the TEOS added in step (1), point add, after dropwising for 4 times at every turn, control stirring velocity 750r/min constant speed to stir, reaction 2h.
(4) reactant that obtains of step (3) is through centrifugation, and removing supernatant liquor, is scattered in deionized water again by centrifugal thing.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in vacuum drying oven, in 90 DEG C, dries 16h.
After step (3) has been reacted, sample and characterized by SEM and laser particle size analysis test, the particle diameter obtained has been about 600nm, and can be observed product pellet from the scanning electron microscopic picture of product pellet spherical regular, monodispersity is excellent.
Silicon dioxide granule particle diameter obtained for embodiment 5 being about 600nm is used for the preparation of shear thickening liquid, is scattered in by 4.6g product pellet in 4gPEG400 (polyoxyethylene glycol), and adding dehydrated alcohol 40ml increases system dispersiveness.Room temperature magnetic agitation dispersion 6h, obtains uniform dispersion system.By system in 80 DEG C of water-bath distillation process, removing small-molecule substance ethanol, obtains the STF of massfraction 53.5%.After system is cooled to room temperature, vacuumize, with the bubble in removing system.
The shear thickening liquid prepared utilizes MCR301 rheometer to carry out rheometer test, and test procedure is:
1,0.1-1000pa carries out stress scans 180s
Creep 60s under the shearing rate of 2,1s-1
3, shear zero, zero stress replys 60s
4, from 0.1-1000pa stress scans
As the change curve of viscosity with shearing rate and shear-stress that Figure 11, Figure 12 are shear thickening fluid, shear thickening system as can be seen from Figure 11 presents shear shinning characteristic at low shear rate, 0.2s
-1for critical thickening point, when shearing rate increases further, system viscosity has a larger change, shows the performance of shear thickening.Compare with domestic literature, critical thickening starting point is lower, namely at low shear rates, can show the performance of shear thickening.(Xu Yulei, Gong Xinglong, Jiang Wanquan, etc. the preparation of STF and performance characterization [J] thereof. functional materials, 2007,38 (10): 3904-3906.)
Claims (8)
1. the preparation method of a controlled monodisperse spherical Large stone nano silicon, based on sol-gel method, orthosilicic acid is obtained by teos hydrolysis, dehydrating condensation obtains silicon-dioxide, adopt weak base catalysis, interval substep adds the method for tetraethoxy, obtained monodisperse spherical Large stone nano silicon, and concrete steps and condition are:
(1) be scattered in by ammoniacal liquor in dehydrated alcohol or ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 8 ~ 40:1, and dispersed with stirring is even; Added by tetraethoxy in mixing solutions, control rate of addition is 10 ~ 60ml/min, tetraethoxy and H
2o mol ratio is 1:2 ~ 20;
(2), under normal temperature, stirring reaction 2 ~ 8h, obtains silicon dioxide gel;
(3) tetraethoxy is dripped in the silicon dioxide gel obtained in step (2), adding of tetraethoxy point is carried out for 2 ~ 4 times, after being added dropwise to complete at every turn, stirring reaction 2 ~ 4h, drip, adding the mol ratio adding tetraethoxy in the amount of tetraethoxy and step (1) is 1:10 ~ 4:1 next time again;
(4) reactant that obtains of step (3) is through being separated, removing supernatant liquor, product through washing, dry, dry and obtain target product.
2. preparation method according to claim 1, is characterized in that: in step (1), the mol ratio of ethanol and ammoniacal liquor is 10 ~ 20:1, tetraethoxy and H
2the mol ratio of O is 1:3 ~ 6, and control rate of addition is 20 ~ 40ml/min.
3. preparation method according to claim 1, is characterized in that: adding the mol ratio adding tetraethoxy in the amount of tetraethoxy and step (1) in step (3) is 1:2 ~ 4:1.
4. preparation method according to claim 1, is characterized in that: controlling stirring velocity in the reaction of step (2) is 200 ~ 750r/min.
5. preparation method according to claim 1, is characterized in that: the reaction times of step (2) is 4 ~ 6h.
6. preparation method according to claim 1, it is characterized in that: the product in step (4) after removing supernatant liquor is scattered in solvent again, through dispersion, centrifugation again repeatedly, until supernatant liquor is neutral, solvent is selected from dehydrated alcohol, acetone or deionized water, finally by vacuum-drying, dries obtained target product.
7. preparation method according to claim 6, is characterized in that: in step (4), and dispersing mode is ultrasonic disperse.
8. preparation method according to claim 6, is characterized in that: in step (4), and bake out temperature is 60-90 DEG C.
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| 光子晶体用SiO2/Ag/SiO2核壳结构亚微米微球制备与性能研究及其自组装;祝名伟;《中国优秀博硕士学位论文全文数据库 (博士) 工程科技Ⅰ辑》;20050515;第53页倒数1-2段，第58页第1段，第59页第1段，第61页第2段，第68页第3-4段 * |
| 单分散二氧化硅胶体颗粒的制备及其应用研究;刘汉银;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120315;第15页第2.2.2.2节至第16页第2.2.2.3节，第17-18页第2.3.1.2节，第35页第2.3.5节 * |
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