CN101372338A - Nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder and preparation thereof - Google Patents
Nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder and preparation thereof Download PDFInfo
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- CN101372338A CN101372338A CNA2008101414564A CN200810141456A CN101372338A CN 101372338 A CN101372338 A CN 101372338A CN A2008101414564 A CNA2008101414564 A CN A2008101414564A CN 200810141456 A CN200810141456 A CN 200810141456A CN 101372338 A CN101372338 A CN 101372338A
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Abstract
The invention pertains to the field of nano composite materials, in particular discloses a halloysite nanotube composite powder filled with tin dioxide nano-particles in situ and a preparation thereof. The method adopts hydrothermal method to prepare the nano filled halloysite nanotube composite powder, and comprises the following steps: first tin salt or stannate is dissolved into water, added with alkali to regulate the pH value of the water solution until the pH value is 7-14; then added with the halloysite nanotube, evenly mixed, and hydrothermally reacted at 120-180 DEG C to obtain the powder. The preparation method has the advantages of simple and easily controlled preparation course, and no pollution.
Description
Technical field
The invention belongs to field of nanocomposite materials, be specifically related to nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder and preparation method.
Background technology
Halloysite is a kind of nanotube-shaped natural mineral of hollow of both ends open of complete form, even size distribution, about 0.5～3 μ m of pipe range, the about 30-80nm of external diameter of pipe, the about 6-40nm of bore, belong to monodimension nanometer material, the internal surface of halloysite nanotubes has stronger polarity, and positively charged ion, polar molecule etc. is had stronger adsorptive power.The chemical constitution of halloysite is Al
4[Si
4O
10] (OH)
8, chemical property is stable; The tubular structure of halloysite uniqueness, higher specific surface area, internal surface polarity, better adsorption capability make halloysite nanotubes can be used as the enhancing body and the material carrier of matrix material, as drug delivery carrier, and hydrogen storage carrier and support of the catalyst etc.Patent CN101070163A discloses halloysite hydrogen storage property and preparation method thereof, and patent CN101096665A discloses halloysite as the application of a kind of enzyme biocatalyst solid support material in enzyme immobilization carrier.And tindioxide (SnO
2) be one of important semiconductor material with wide forbidden band, energy gap is 3.6eV, except that having at aspects such as transparency electrode, solar cell, function ceramics, information material, sensitive material and catalytic materials important use is worth, also bringing into play important effect aspect fire-retardant at macromolecular material; SnO
2Be a kind of stable compound, nontoxic, non-volatile, do not produce corrosive gases, do not produce secondary pollution, be a kind of safe fire retardant, R.G.Baggaley[Fire Materials, 1997,21:179～184] use SnO
2PVC is carried out fire-retardant research obtained good effect; People such as Jiang Hai [Chinese plastics, 2005,19 (6): 87-90] find SnO
2/ SiO
2Composite flame-retardant agent is having good synergistic effect aspect the flame retardancy and smoke suppression of halogen containing polymers, can improve the surplus charcoal rate of system, improves oxygen index, reduces smoke density.Halloysite is a kind of alumino-silicate materials, its SiO
2Content is 46.54%, and therefore, tindioxide/halloysite nanotubes matrix material will have the potential using value aspect the macromolecular material flame retardancy and smoke suppression.
Patent CN100371243C discloses the preparation method of nano-stannic oxide parcel carbon nanotube, but tindioxide/halloysite nanotubes composite study report is not arranged as yet, and preparation stannic oxide particle/halloysite nanotubes matrix material all has actual application value to the expansion application of halloysite and the exploitation of tindioxide matrix material with application.
Summary of the invention
The object of the present invention is to provide a kind of nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder novel material, another purpose is to provide its preparation method.
For realizing the object of the invention, technical scheme is as follows: use the hydro-thermal reaction method to be raw material with pink salt or stannate, carry out original position and fill halloysite nanotubes under 120-200 ℃ of hydrothermal condition.Can be full of the pink salt or the stannate aqueous solution in the halloysite pipe because of both ends open, under hydrothermal condition, the presoma of tin is nucleation in the halloysite pipe, and then original position generates tin oxide nano particles, and because environment is limited in the nanotube, avoided further growing up of tin oxide nano particles, formed nano-stannic oxide particle and fill the halloysite nanotubes matrix material, wherein stannic oxide particle is of a size of 2-8nm.
Concrete preparation process is as follows:
(1) the preparation mass percent is 0.5%～10% the pink salt or the stannate aqueous solution, and the pH value that adds the alkali regulator solution is in the 9-14 scope;
(2) halloysite that will purify adds in the above-mentioned solution, and ultrasonic 5-30 minute, halloysite feedstock purification method was referring to patent CN101070163A;
(3) with step 2) mixing solutions that obtains transfers in the hydrothermal reaction kettle, at 120-200 ℃ of reaction 2-20h;
(4) product water is washed till neutrality, can obtains the nano-stannic oxide filling type galapectite nano-tube composite powder behind the centrifugal drying.
Said pink salt or stannate are stannic chloride pentahydrate or sodium stannate trihydrate among the present invention; Alkali is sodium hydroxide or ammoniacal liquor.
Nano-stannic oxide provided by the invention is filled halloysite nanotubes method advantage:
(1) utilizes the halloysite both ends open, solution energy completely filled is soaked full and its internal surface adsorbs polarity ionic character easily, in hydrothermal reaction process, contain tin ion in the inner nucleation of halloysite nanotubes, and then original position generates tindioxide/halloysite nanotubes matrix material;
(2) adjust the matrix material that the mass ratio of tindioxide and halloysite nanotubes can obtain the tindioxide/halloysite nanotubes of diverse microcosmic appearance by changing pink salt or stannate concentration;
(3) simple, the safety of production technique, cost are low, pollution-free.
(4) make nano-stannic oxide filling type galapectite nano-tube composite powder novel material, filled up blank, expanded the Application Areas of fire retardant material.
Description of drawings
Fig. 1 is the powder crystal diffractogram that the nano-stannic oxide of embodiment 1 preparation is filled the halloysite nanotubes mixture, adopts Philips X ' Pert pro type X ray polycrystalline diffractometer (Cu target).HNTs is the abbreviation of halloysite (Halloysites) among the figure.
Fig. 2 is the transmission electron microscope photo that the nano-stannic oxide of embodiment 1 preparation is filled the halloysite nanotubes mixture, adopts FEI Tecnai G
220 type transmission electron microscopes (200KV).
Embodiment
For the present invention is better illustrated, as follows for embodiment:
Embodiment 1
Adopt the described method purification of patent CN101070163A halloysite raw material;
The 0.5g stannic chloride pentahydrate is dissolved in the 80g water, adding sodium hydrate regulator solution PH is 9, add the halloysite nanotubes that 0.5g purified then, behind ultrasonic 5 minutes of the 100Hz, it is joined in the hydrothermal reaction kettle, and 150 ℃ were reacted 8 hours, and naturally cooled to room temperature, to neutral, centrifugal drying promptly obtains tindioxide and fills halloysite nanotubes product through water washing.
Embodiment 2
Adopt the described method purification of patent CN101070163A halloysite raw material;
The 2g stannic chloride pentahydrate is dissolved in the 80g water, adding sodium hydrate regulator solution PH is 9, add the halloysite nanotubes that 0.5g purified then, behind ultrasonic 5 minutes of the 100Hz, it is joined in the hydrothermal reaction kettle, and 120 ℃ were reacted 20 hours, and naturally cooled to room temperature, to neutral, centrifugal drying promptly obtains tindioxide and fills halloysite nanotubes product through water washing.
Embodiment 3
Adopt the described method purification of patent CN101070163A halloysite raw material;
The 4g sodium stannate trihydrate is dissolved in the 80g water, adding ammoniacal liquor regulator solution PH is 12, add the halloysite nanotubes that 2g purified then, behind ultrasonic 15 minutes of the 100Hz, it is joined in the hydrothermal reaction kettle, and 180 ℃ were reacted 5 hours, and naturally cooled to room temperature, to neutral, centrifugal drying promptly obtains tindioxide and fills halloysite nanotubes product through water washing.
Embodiment 4
Adopt the described method purification of patent CN101070163A halloysite raw material;
The 6g sodium stannate trihydrate is dissolved in the 80g water, adding ammoniacal liquor regulator solution PH is 14, add the halloysite nanotubes that 4g purified then, behind ultrasonic 30 minutes of the 100Hz, it is joined in the hydrothermal reaction kettle, and 200 ℃ were reacted 2 hours, and naturally cooled to room temperature, to neutral, centrifugal drying promptly obtains tindioxide and fills halloysite nanotubes product through water washing.
Claims (5)
1. the nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder is characterized in that, nano-stannic oxide particle in situ is filled in the halloysite nanotubes, and stannic oxide particle is of a size of 2-8nm.
2. the preparation method of a nano-stannic oxide particle in situ filling halloysite nanotubes is characterized in that, synthesize with hydrothermal method, its processing step is as follows:
(1) the preparation mass percent is 0.5%～10% the pink salt or the stannate aqueous solution, and the pH value that adds the alkali regulator solution is in the 9-14 scope;
(2) halloysite is added in the above-mentioned solution ultrasonic 5-30 minute;
(3) with step 2) mixing solutions that obtains transfers in the hydrothermal reaction kettle, at 120-200 ℃ of reaction 2-20h;
(4) product water is washed till neutrality, gets final product behind the centrifugal drying.
3. fill the preparation method of halloysite nanotubes by the described nano-stannic oxide particle in situ of claim 2, it is characterized in that described pink salt or stannate are stannic chloride pentahydrate or sodium stannate trihydrate.
4. fill the preparation method of halloysite nanotubes by the described nano-stannic oxide particle in situ of claim 2, it is characterized in that described alkali is sodium hydroxide or ammoniacal liquor.
5. fill the preparation method of halloysite nanotubes by the described nano-stannic oxide particle in situ of claim 2, it is characterized in that, halloysite is through purifying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101414564A CN101372338B (en) | 2008-09-25 | 2008-09-25 | Nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder and preparation thereof |
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|---|---|---|---|
| CN2008101414564A CN101372338B (en) | 2008-09-25 | 2008-09-25 | Nano-stannic oxide particle in situ filling type galapectite nano-tube composite powder and preparation thereof |
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| CN101372338A true CN101372338A (en) | 2009-02-25 |
| CN101372338B CN101372338B (en) | 2010-09-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167346A (en) * | 2011-01-30 | 2011-08-31 | 福州大学 | Kaolin nanotube and preparation method thereof |
| CN103990429A (en) * | 2014-05-29 | 2014-08-20 | 苏州科技学院 | Halloysite nanotube-ammonium phosphate composite material and preparation method and application thereof |
| CN108751212A (en) * | 2018-06-14 | 2018-11-06 | 中南大学 | A kind of halloysite nanotubes material and preparation method thereof as siRNA protections |
| CN113829461A (en) * | 2021-10-14 | 2021-12-24 | 中南大学 | Flame-retardant transparent wood and preparation method thereof |
| CN116063865A (en) * | 2023-01-18 | 2023-05-05 | 浙江理工大学 | Self-cleaning antistatic heat-insulating functional filler and preparation method and application thereof |
-
2008
- 2008-09-25 CN CN2008101414564A patent/CN101372338B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167346A (en) * | 2011-01-30 | 2011-08-31 | 福州大学 | Kaolin nanotube and preparation method thereof |
| CN102167346B (en) * | 2011-01-30 | 2012-08-22 | 福州大学 | Kaolin nanotube and preparation method thereof |
| CN103990429A (en) * | 2014-05-29 | 2014-08-20 | 苏州科技学院 | Halloysite nanotube-ammonium phosphate composite material and preparation method and application thereof |
| CN103990429B (en) * | 2014-05-29 | 2016-04-13 | 苏州科技学院 | A kind of halloysite nanotubes-ammonium phosphate salt composite and its production and use |
| CN108751212A (en) * | 2018-06-14 | 2018-11-06 | 中南大学 | A kind of halloysite nanotubes material and preparation method thereof as siRNA protections |
| CN113829461A (en) * | 2021-10-14 | 2021-12-24 | 中南大学 | Flame-retardant transparent wood and preparation method thereof |
| CN116063865A (en) * | 2023-01-18 | 2023-05-05 | 浙江理工大学 | Self-cleaning antistatic heat-insulating functional filler and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN101372338B (en) | 2010-09-08 |
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