CN105060324B - The ultrasonic synthetic method of nano aluminium oxide and its application - Google Patents
The ultrasonic synthetic method of nano aluminium oxide and its application Download PDFInfo
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- CN105060324B CN105060324B CN201510459161.1A CN201510459161A CN105060324B CN 105060324 B CN105060324 B CN 105060324B CN 201510459161 A CN201510459161 A CN 201510459161A CN 105060324 B CN105060324 B CN 105060324B
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Abstract
The invention discloses a kind of ultrasonic synthetic method of nano aluminium oxide, with Al (NO3)3For raw material, NH4HCO3For precipitating reagent, calcined after supersound process, prepare presoma, obtain nano aluminium oxide.The ultrasonic synthetic method of the nano aluminium oxide of the present invention, the features such as the nano aluminium oxide pattern of synthesis, performance are influenceed by the control on ultrasound parameter, the further development that sonochemical method will be promoted to prepare nano material, inject new vitality for nanosecond science and technology.
Description
Technical field
The invention belongs to chemical material field, and in particular to a kind of ultrasonic synthetic method of nano aluminium oxide and its application.
Background technology
At present, the technology of preparing of domestic and international nano aluminium oxide can be divided into solid phase method, vapor phase method and liquid phase method three major types.Solid phase
Method is simple to operate, but the particle diameter for generating particle is difficult to control；Vapor phase method equipment investment is big, complex operation, thus liquid phase method should
With more extensive.In liquid phase method, the precipitation method use inorganic raw material more, and cost is low, and production equipment and technique are simple, and particle
Purity is high, and granularity is small, and particle diameter distribution is narrow, therefore is that one kind has emulative method.
In recent years, research of the ultrasonic technique in terms of new material synthesis is very active, acoustic cavitation (acoustic
Cavitation) processing is a kind of highly effective technology for preparing nano material, special physics that acoustic cavitation is triggered, is changed
Learn environment and provide important approach for people's preparation nano material.
Pei little Miao etc. have studied sol-gal process under ultrasonic field and prepare nanometer Al using hexamethylenetetramine as precipitating reagent2O3Powder
The technique of body, ESEM (SEM), X-ray diffraction (XRD) analysis and grain size analysis are carried out to product.Test result indicates that
The introducing of ultrasonic wave is remarkably improved the performance of powder.In 1100 DEG C of calcinings group has been made in 2 hours in the presoma being ultrasonically treated
It is poly- few, α-Al of the average grain diameter in 30nm or so2O3Powder.
Wang Yajuan etc. is using aluminum nitrate and ammonium carbonate as raw material, the method that is combined using ultrasonic wave with precipitated phase, has been made flat
The alumina ultrafine powder that equal particle diameter is (12 ± 2) nm.Precipitation knows that its chemical composition is through XRD, TG and DTA experimental analysis
NH4Al(OH)2CO3, this is deposited in 475K and starts to decompose into aluminum oxide, and θ-Al are almost completely converted into 1273K2O3。
Ultrasonic cavitation can be greatly enhanced the speed of heterogeneous reaction, and it is equal to realize that Jie between heterogeneous reaction thing sees
Even mixing, accelerate the diffusion process of reactant and product, promote the generation of solid cenotype, control size and the distribution of particle.It is super
Sound wave is compared in terms of the mass transfer between strengthening heterogeneous interface with traditional method has obvious advantage and distinctive feature.It is logical
The efficient couplings of different technologies is crossed to strengthen chemical reaction or transmittance process is that one of chemistry and chemical field in recent years newly becomes
Gesture.Such as laser technology, high-gravity technology, plasma technique, microwave technology etc. have phase in terms of the preparation of nano material
The research report of pass, designs the optimum organization between these technologies the characteristics of for specific system, it is possible to less cost
Reach the purpose of anticipation.At present, in the market has had plant-scale ultrasonic wave generating apparatus, and this is to be used to surpass by ultrasonic technique
Thin and nano-powder material prepare with scale lays the foundation, and ultrasonic technique has vast potential for future development in this respect.
Nano aluminium oxide crystalline phase is stable, hardness is high, good stability of the dimension, can be widely applied in various paint, plays resistance to
Mill, the effect of hardening.The hardness of paint typically increases with the increase of nano aluminium oxide addition, and wearability is nano oxidized
Optimum value can be reached during the certain addition of aluminium, mechanical performance using common aluminum oxide than strengthening 8-10 times.
In recent years, research of the ultrasonic technique in terms of new material synthesis is very active, is a kind of to prepare having for nano material
Effect technology.Special physics that acoustic cavitation is triggered, chemical environment provide important channel for the preparation of nano material.Ultrasonic wave
The generation of solid cenotype can be effectively facilitated, controls size and the distribution of particle, particle size is small and is evenly distributed.Ultrasonic cavitation is produced
Raw localized hyperthermia high pressure, its caused shock wave and microjet have pulverization, can prevent the formation of hydrogen bond, reach the group of preventing
Poly- purpose.
Under ultrasonic field action, a certain amount of dispersant is added, certain pattern, size tunable are prepared using chemical precipitation method
Nano aluminium oxide, be added into paint, for produce function admirable paint new thinking is provided.
The content of the invention
An object of the present invention is for overcome the deficiencies in the prior art, there is provided a kind of ultrasound synthesis of nano aluminium oxide
Method.
The present invention provides a kind of ultrasonic synthetic method of nano aluminium oxide, with Al (NO3)3For raw material, NH4HCO3For precipitation
Agent, calcined after supersound process, prepare presoma, obtain nano aluminium oxide.
Further, Al (NO are taken3)3Solution, PEG300 is added, be well mixed, obtain mixed solution；It is molten to the mixing
NH is added in liquid4HCO3Solution, pH value is determined, is ultrasonically treated, is filtered after ageing, discarded filtrate, washing precipitation, calcined after drying,
With stove natural cooling, nano aluminium oxide is obtained.
Further, Al (NO are taken3)3Solution, PEG300 is added, is stirred vigorously, be well mixed, obtain mixed solution；Separately take
Isometric NH with the mixed solution4HCO3Solution, by the mixed solution and the NH4HCO3Solution is respectively placed in 40 DEG C
Constant temperature 15min in water-bath, then rapidly by the NH4HCO3Solution is added in the mixed solution and mixed, and determines pH value, ultrasound
Processing, filtered after being aged 24h, discard filtrate, washing precipitation, calcined after drying, with stove natural cooling, obtain nano aluminium oxide.
Further, the Al (NO3)3With NH4HCO3Mol ratio be 1:3.
Further, the supersound process parameter is frequency 20kHz, power 100w, 30-90 minutes ultrasonication time.
Further, the pH ＜ 9.10.
Further, the method for the washing precipitation is that respectively washed once with absolute ethyl alcohol and ammoniacal liquor respectively.
Further, the condition of the drying is 100 DEG C of drying 1h.
Further, the temperature of the calcining is 500-900 DEG C, and the time of calcining is 1.5h.
Further, the nano aluminium oxide is bar-shaped γ-Al2O3。
The present invention also provides a kind of application of above-mentioned nano aluminium oxide in paint is prepared.
The beneficial effects of the present invention are：The ultrasonic synthetic method of the nano aluminium oxide of the present invention, by ultrasound parameter
Control influence the nano aluminium oxide pattern of synthesis, the feature such as performance, will promote what sonochemical method prepared nano material to enter one
Step development, inject new vitality for nanosecond science and technology.The nano aluminium oxide of the present invention is added in paint, is the paint of function admirable
Production new thinking is provided.
Brief description of the drawings
Fig. 1 show the infrared spectrum of three embodiments of ultrasonic synthetic method of nano aluminium oxide of the present invention；
Fig. 2 show the XRD of three embodiments of ultrasonic synthetic method of nano aluminium oxide of the present invention；
Fig. 3 show the SEM figures of the embodiment of the present invention 3.
Embodiment
The specific embodiment of the invention is described in detail below in conjunction with specific accompanying drawing.It should be noted that in following embodiments
The combination of the technical characteristic or technical characteristic of description is not construed as isolated, and they can be mutually combined so as to reach
To superior technique effect.
Embodiment one
Prepare 0.1mol/L Al (NO3)3The NH of solution and 0.3mol/L4HCO3Solution.Take the 0.1mol/L's for preparing
Al(NO3)3Solution, a small amount of PEG300 is added, is stirred vigorously, be well mixed, obtain mixed solution；It is another to take and the body such as mixed solution
Long-pending 0.3mol/L NH4HCO3Solution, by mixed solution and NH4HCO3Solution is respectively placed in constant temperature 15min in 40 DEG C of water-baths,
Then rapidly by NH4HCO3Solution is added in mixed solution and mixed, and determines pH=8.08, and in frequency 20kHz, power 100w's is super
Ultrasound 30 minutes in sound field.After ultrasound terminates, remove sample, filtered after being aged 24h, discard filtrate, respectively with absolute ethyl alcohol and
Ammoniacal liquor respectively washs precipitation once, 100 DEG C of drying 1h, is put into crucible, and design temperature is 500 DEG C, calcines 1.5h, naturally cold with stove
But, bar-shaped γ-Al are obtained2O3And aggregate.
Embodiment two
Prepare 0.1mol/L Al (NO3)3The NH of solution and 0.3mol/L4HCO3Solution.Take the 0.1mol/L's for preparing
Al(NO3)3Solution, a small amount of PEG300 is added, is stirred vigorously, be well mixed, obtain mixed solution；It is another to take and the body such as mixed solution
Long-pending 0.3mol/L NH4HCO3Solution, by mixed solution and NH4HCO3Solution is respectively placed in constant temperature 15min in 40 DEG C of water-baths,
Then rapidly by NH4HCO3Solution is added in mixed solution and mixed, and determines pH=8.08, and in frequency 20kHz, power 100w's is super
Ultrasound 30 minutes in sound field.After ultrasound terminates, remove sample, filtered after being aged 24h, discard filtrate, respectively with absolute ethyl alcohol and
Ammoniacal liquor respectively washs precipitation once, 100 DEG C of drying 1h, is put into crucible, and design temperature is 700 DEG C, calcines 1.5h, naturally cold with stove
But, bar-shaped γ-Al are obtained2O3And aggregate.
Embodiment three
Prepare 0.1mol/L Al (NO3)3The NH of solution and 0.3mol/L4HCO3Solution.Take the 0.1mol/L's for preparing
Al(NO3)3Solution, a small amount of PEG300 is added, is stirred vigorously, be well mixed, obtain mixed solution；It is another to take and the body such as mixed solution
Long-pending 0.3mol/L NH4HCO3Solution, by mixed solution and NH4HCO3Solution is respectively placed in constant temperature 15min in 40 DEG C of water-baths,
Then rapidly by NH4HCO3Solution is added in mixed solution and mixed, and determines pH=8.08, and in frequency 20kHz, power 100w's is super
Ultrasound 30 minutes in sound field.After ultrasound terminates, remove sample, filtered after being aged 24h, discard filtrate, respectively with absolute ethyl alcohol and
Ammoniacal liquor respectively washs precipitation once, 100 DEG C of drying 1h, is put into crucible, and design temperature is 900 DEG C, calcines 1.5h, naturally cold with stove
But, bar-shaped γ-Al are obtained2O3。
Design temperature is 900 DEG C, calcines 1.5h, with stove natural cooling, obtains bar-shaped γ-Al2O3；And 500 DEG C and 700 DEG C
It is bar-shaped except having, also aggregate, from XRD it is also seen that only 900 DEG C for γ-Al2O3；And 500 DEG C and 700 DEG C
Crystal formation it is more complicated, guess is the rise with calcining heat, Al2O3Crystal formation is converted, 900 DEG C be changed into γ-
Al2O3。
As shown in figure 1, in 400-1000cm-1There is a wide absorption band in wave-number range, this is the feature of nano aluminium oxide
Absorption band.500 DEG C, 700 DEG C are calcined as seen from the figure, are produced characteristic absorption here with 900 DEG C, are relatively not difficult to find out with document
Low temperature can prepare nano aluminium oxide under ultrasonic field.In 1600-1000cm-1Three stronger absworption peaks in section, respectively
Positioned at 1394cm-1、1516cm-1、1635cm-1Left and right.The sample absorption peak strength of different temperatures calcination processing is different.Due to adopting
With ultrasonic technique, the less nano aluminium oxide crystal of particle diameter is prepared for.Nano alumina surface atom occupies sizable ratio
Example, and the dangling bond vertical telescopic vibration perpendicular to surface becomes active, the bands of a spectrum relevant with longitudinal acoustical mode are strengthened.Together
When, control sintering temperature can obtain the nanometer Al of different crystal forms2O3.700 DEG C of sample 1390cm in Fig. 1-1And 1520cm-1Absorption
Intensity substantially weakens, and illustrates mainly to obtain nanocluster, and the dangling bond vibration of only nano aluminium oxide could effectively produce absorption spectra
Band, also, the dangling bond of surface atom is more, and band intensity is bigger.500 DEG C of contrast and 900 DEG C of samples are it can be found that when calcining temperature
When degree is respectively 500 DEG C and 900 DEG C, absorption peak strength increase, illustrates that the composition of nanocluster is reduced, inferred with this, aluminum oxide
The transformation of pattern is experienced at 700 DEG C, degree of crystallization is increased slightly.
As shown in Fig. 2 500 DEG C are calcined 1.5 hours, precursor has been converted into amorphous γ-Al2O3, it is three most strong in figure
67.037 ° of diffraction maximum, 45.679 °, d values are respectively corresponding to 37.016 °：0.13949,0.19345 and 0.24255 with standard
γ-Al in PDF cards2O3Card (29-63) goodness of fit it is preferable.37.016 ° of diffraction maximum is more obvious at 700 DEG C,
Diffraction maximum at 67.037 ° and 45.679 ° is more sharp, illustrates that calcining heat raises, crystallization degree increases.Obtained at 900 DEG C
Crystal formation is more single and particle diameter less γ-Al2O3, it is consistent with results of IR.
As shown in figure 3, it is 1 in aluminium salt and the amount of precipitant material ratio:Presoma is prepared under conditions of 3, pH ＜ 9.10,
900 DEG C of calcining precursor 1.5h, effect 30min can be made more homogeneous and bar-shaped receive in the ultrasonic field that frequency is 20kHz
Rice aluminum oxide.
Take a small amount of nano aluminium oxide to add silane coupler and carry out surface modification, ultrasonic disperse is into emulsion monomer, in advance
Emulsify 30min.1/6 pre-emulsion is taken, initiator and pre-emulsion are added dropwise under the conditions of 65 DEG C -70 DEG C of water-bath, 3h is reacted, is warming up to
95 DEG C, constant temperature 30min, regulation pH is 8-9, discharging.Emulsion is milky white band blue phase stiff fluid, uniformly not stratified.
Spices is added into deionized water, wetting agent, surfactant, coalescents are in high speed homogenization agitator high speed
It is uniformly dispersed.It is uniform to add a certain proportion of talcum powder, titanium dioxide, calcium carbonate high-speed stirred, proper quantity of defoaming agent is added dropwise, stirring is equal
Stirring at low speed is changed to after even, adds emulsion, mould inhibitor, thickener, is dispersed with stirring uniformly, filtering and discharging.Coating appearance is white
Stiff fluid, measure viscosity are 120-200s, solid content>40%, surface drying time 7min, actual drying time 24h, 25 DEG C water-fast
Property test>96h, without caking after placing 2 months, does not influence to use after stirring, detected again, indices close without whiting
Lattice.
The ultrasonic synthetic method of the nano aluminium oxide of the present invention, the nano oxygen of synthesis is influenceed by the control on ultrasound parameter
Change the features such as aluminium pattern, performance, the further development that sonochemical method will be promoted to prepare nano material is new for nanosecond science and technology injection
Vigor.The nano aluminium oxide of the present invention is added in paint, the production for the paint of function admirable provides new thinking.
Although having been presented for some embodiments of the present invention herein, it will be appreciated by those of skill in the art that
Without departing from the spirit of the invention, the embodiments herein can be changed.Above-described embodiment be it is exemplary, no
Restriction that should be using the embodiments herein as interest field of the present invention.
Claims (3)
1. the ultrasonic synthetic method of nano aluminium oxide, it is characterised in that take Al (NO3)3Solution, PEG300 is added, is stirred vigorously,
It is well mixed, obtain mixed solution；Separately take the NH isometric with the mixed solution4HCO3Solution, the Al (NO3)3With
NH4HCO3Mol ratio be 1:3, by the mixed solution and the NH4HCO3Solution is respectively placed in constant temperature in 40 DEG C of water-baths
15min, then rapidly by the NH4HCO3Solution is added in the mixed solution and mixed, and measure pH ＜ 9.10, is ultrasonically treated, institute
It is frequency 20kHz to state and be ultrasonically treated parameter, power 100W, 30-90 minutes ultrasonication time, is filtered after being aged 24h, discards filter
Liquid, washing precipitation, is calcined after drying, and the temperature of the calcining is 500-900 DEG C, and the time of the calcining is 1.5h, with stove certainly
So cooling, obtains nano aluminium oxide, the nano aluminium oxide is bar-shaped γ-Al2O3。
2. the ultrasonic synthetic method of nano aluminium oxide as claimed in claim 1, it is characterised in that the method for the washing precipitation
Respectively to washed once with absolute ethyl alcohol and ammoniacal liquor respectively.
3. the ultrasonic synthetic method of nano aluminium oxide as claimed in claim 2, it is characterised in that the condition of the drying is
100 DEG C of drying 1h.
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| CN106799500B (en) * | 2017-01-05 | 2019-03-29 | 天津大学 | The preparation method of ultrafine tungsten powder |
| CN107176617B (en) * | 2017-06-08 | 2019-07-05 | 南京工业大学 | A kind of preparation method of ball-aluminium oxide |
| CN108558373A (en) * | 2018-06-13 | 2018-09-21 | 宣城晶瑞新材料有限公司 | A kind of preparation and application of novel nano alumina ceramic material |
| CN117843020A (en) * | 2024-01-04 | 2024-04-09 | 兰州兰石中科纳米科技有限公司 | Preparation method of nano alumina powder |
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| CN101182018A (en) * | 2007-12-17 | 2008-05-21 | 中国铝业股份有限公司 | Method for preparing thermostable activated alumina |
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