CN110804325A - Boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler and preparation method and application thereof - Google Patents

Boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler and preparation method and application thereof Download PDF

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CN110804325A
CN110804325A CN201910997974.4A CN201910997974A CN110804325A CN 110804325 A CN110804325 A CN 110804325A CN 201910997974 A CN201910997974 A CN 201910997974A CN 110804325 A CN110804325 A CN 110804325A
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boron nitride
titanium dioxide
nano titanium
nitride nanosheet
coated nano
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CN110804325B (en
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李忠磊
范铭升
杜伯学
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Tianjin University
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Abstract

The invention discloses a preparation method and application of a boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler for polymer dielectrics. The polypropylene matrix shows higher electrical performance after being doped with the high-performance composite filling particles with the core-shell structure, and has important application value.

Description

Boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler and preparation method and application thereof
Technical Field
The invention relates to the field of composite materials with a core-shell structure, in particular to a boron nitride nanosheet coated nano titanium dioxide core-shell structure filler and a preparation method and application thereof.
Background
The composite material with the core-shell structure is a hybrid formed by coating one material with another material through chemical bonds or other actions, and the structure can combine the advantages of various nano materials to realize the multifunction of the material.
The boron nitride nanosheet with the material of the two-dimensional lamellar structure has an important effect in the fields of optics, electronics, sensors, energy storage materials and the like due to the high specific surface area, high temperature resistance, wide band gap, excellent thermal conductivity and unique electrical properties.
In order to respond to the development of the high voltage direct current transmission technology and avoid the generation of the environmental problem, it is one of the major key problems to be solved urgently at present to develop an environment-friendly dielectric with excellent insulating property. Polymer-based nanocomposite dielectrics can effectively improve the performance of electrical insulation materials. At present, no attempt for improving the performance of the polymer by using a particle with a core-shell structure formed by the interaction of a boron nitride nanosheet and nano titanium dioxide as a filler has been reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler, and a preparation method and application thereof.
The invention provides a preparation method of a core-shell structure filler of nanometer titanium dioxide coated by boron nitride nanosheets, wherein the boron nitride nanosheets can react with oxygen in the air to form boron oxide in the high-temperature calcination process, and then the boron oxide and the nanometer titanium dioxide form a core-shell structure under the action of continuous high temperature.
The invention specifically comprises the following steps:
1) placing the boron nitride nanosheet and the nano titanium dioxide in a drying oven at 90 ℃ for drying for 12 hours;
2) weighing 1g of boron nitride nanosheets, placing the boron nitride nanosheets into a beaker, adding 200ml of absolute ethyl alcohol into the beaker to enable the content of the boron nitride nanosheets in the suspension to be 5mg/ml, and stirring the suspension for five minutes by using an electric stirrer at the rotating speed of 2000 rpm;
3) adding 0.2g of nano titanium dioxide into the turbid liquid obtained in the step 2), keeping the rotating speed of the electric stirring machine unchanged, and starting an ultrasonic cleaning machine to fully disperse the boron nitride nanosheets and the nano titanium dioxide in ethanol;
4) after 120min, evaporating ethanol to dryness in an environment of 90 ℃, and drying the boron nitride nanosheets and the nano titanium dioxide to obtain uniformly dispersed nano composite particles of the boron nitride nanosheets and the titanium dioxide;
5) putting the uniformly dispersed nano particles into a corundum crucible, putting the whole corundum crucible into a muffle furnace, raising the temperature to the calcining temperature, and keeping the temperature for calcining;
6) after cooling, grinding by using an agate mortar, and sieving by using a 200-mesh plastic nylon mesh screen after fully grinding to obtain composite particles of the boron nitride nanosheet coated nano titanium dioxide;
7) and (3) carrying out surface treatment on the composite particles of the boron nitride nanosheet coated nano titanium dioxide by using a coupling agent.
According to the mass ratio, the boron nitride nanosheet: nano titanium dioxide ═ (4-7): 1, preferably 5: 1.
the invention controls the calcination temperature at 850-950 ℃ and preferably 900 ℃ at the heating rate of 3.65 ℃/min.
The calcination time in the present invention is controlled to 17 to 25 hours, preferably 20 hours.
The coupling agent is a silane coupling agent and is selected from one of KH550, KH560 and KH 570.
The second technical scheme of the invention is that the boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler obtained by the preparation method comprises isotactic polypropylene, the boron nitride nanosheet and nano titanium dioxide;
the boron nitride nanosheet-coated nano titanium dioxide core-shell structure particles account for 1% by mass;
the thickness of the boron nitride nanosheet is 50nm, and the diameter of the boron nitride nanosheet is 0.5-5 um.
The particle size of the nano titanium dioxide is 40nm, and the crystal form is rutile type.
The third technical scheme of the invention is the application of the boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler obtained by the preparation method, and the boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler is applied to the dielectric insulating material.
The fourth technical scheme of the invention is a composite particle surface modification treatment method, which comprises the following steps:
1) placing 2gKH550 coupling agent, 7.2g absolute ethyl alcohol and 0.8g deionized water in a beaker, and stirring for 15 minutes at the rotating speed of 2000rpm and the environment of 80 ℃ by an electric stirrer to fully hydrolyze KH 550;
2) mixing 1g of the hydrolyzed solution with 4g of fired composite particles of boron nitride nanosheet-coated nano titanium dioxide, stirring at the rotating speed of 2000rpm for 2 hours in the environment of 80 ℃, and finishing surface modification;
3) and taking out the modified solution, putting the modified solution into a drying oven, and drying the solution for 8 hours at the temperature of 90 ℃ to finally obtain the boron nitride nanosheet-coated nano titanium dioxide composite particles subjected to surface modification by the coupling agent with the mass fraction of 5%.
The invention has the advantages and beneficial effects that: the boron nitride-coated nano titanium dioxide composite particles with the core-shell structure combine the two-dimensional characteristics of boron nitride nanosheets and the high dielectric constant characteristics of nano titanium dioxide, and the boron nitride-coated nano titanium dioxide composite particles can be used as a filler to be doped into a polymer, so that current carriers can be easily attracted by the highly polar nano titanium dioxide, and can be blocked by the two-dimensional boron nitride nanosheets, further the average free path of the current carriers is reduced, collision ionization is not easy to occur in the polymer under the action of an external electric field, electrons in a conduction band are not easy to accumulate enough energy to form 'hot electrons', and therefore the electrical performance of the polymer can be improved.
Drawings
FIG. 1 is a scanning electron microscope image of a mixed particle of boron nitride nanosheets and nano titanium dioxide.
FIG. 2 is a scanning electron microscope image of the boron nitride nanosheet-coated nano titanium dioxide composite microparticle.
FIG. 3 shows the distribution of energy spectrum elements of the boron nitride nanosheet-coated nano titanium dioxide composite microparticle.
FIG. 4 is an X-ray diffraction spectrum of the boron nitride nanosheet coated nano titanium dioxide composite microparticle.
FIG. 5 is a Weibull distribution diagram of the direct-current breakdown field strength of the nanometer titanium dioxide composite particles coated by the polypropylene-based boron nitride nanosheets.
Detailed Description
The invention is further described below with reference to the following figures and specific examples.
Example 1
A preparation method of a boron nitride nanosheet coated nano titanium dioxide core-shell structure filler comprises the following steps:
1) mixing boron nitride nanosheets and nano titanium dioxide according to the weight ratio of 5: 1 proportion is put in a drying box at 90 ℃ to be dried for 12 hours;
2) weighing 1g of boron nitride nanosheets, placing the boron nitride nanosheets into a beaker, adding 200ml of absolute ethyl alcohol into the beaker to enable the content of the boron nitride nanosheets in the suspension to be 5mg/ml, and stirring the suspension for five minutes by using an electric stirrer at the rotating speed of 2000 rpm;
3) adding 0.2g of nano titanium dioxide into the turbid liquid obtained in the step 2), keeping the rotating speed of the electric stirring machine unchanged, and starting an ultrasonic cleaning machine to fully disperse the boron nitride nanosheets and the nano titanium dioxide in ethanol;
4) after 120min, evaporating ethanol to dryness in an environment of 90 ℃, and drying the boron nitride nanosheet and the nano titanium dioxide to obtain the boron nitride nanosheet and the nano titanium dioxide with the mass ratio of 5: 1, uniformly dispersed nanocomposite particles;
5) putting the uniformly dispersed nano particles into a corundum crucible, putting the whole corundum crucible into a muffle furnace, heating to 900 ℃ at the heating rate of 3.65 ℃/min, and keeping the temperature for calcining for 20 hours;
6) after cooling, grinding by using an agate mortar, and sieving by using a 200-mesh plastic nylon mesh screen after fully grinding to obtain composite particles of the boron nitride nanosheet coated nano titanium dioxide;
7) and (3) performing surface treatment on the composite particles of the boron nitride nanosheet coated nano titanium dioxide by using a KH550 coupling agent.
Example 2
A preparation method of a boron nitride nanosheet coated nano titanium dioxide core-shell structure filler comprises the following steps:
1) b, mixing boron nitride nanosheets and nano titanium dioxide according to a ratio of 4: 1 proportion is put in a drying box at 90 ℃ to be dried for 12 hours;
2) weighing 1g of boron nitride nanosheets, placing the boron nitride nanosheets into a beaker, adding 200ml of absolute ethyl alcohol into the beaker to enable the content of the boron nitride nanosheets in the suspension to be 5mg/ml, and stirring the suspension for five minutes by using an electric stirrer at the rotating speed of 2000 rpm;
3) adding 0.25g of nano titanium dioxide into the turbid liquid obtained in the step 2), keeping the rotating speed of the electric stirring machine unchanged, and starting an ultrasonic cleaning machine to fully disperse the boron nitride nanosheets and the nano titanium dioxide in ethanol;
4) after 120min, evaporating ethanol to dryness in an environment of 90 ℃, and drying the boron nitride nanosheet and the nano titanium dioxide to obtain the boron nitride nanosheet and the nano titanium dioxide with the mass ratio of 4: 1, uniformly dispersed nanocomposite particles;
5) putting the uniformly dispersed nano particles into a corundum crucible, putting the whole corundum crucible into a muffle furnace, heating to 850 ℃ at the heating rate of 3.65 ℃/min, and keeping the temperature for calcining for 17 hours;
6) after cooling, grinding by using an agate mortar, and sieving by using a 200-mesh plastic nylon mesh screen after fully grinding to obtain composite particles of the boron nitride nanosheet coated nano titanium dioxide;
7) KH570 coupling agent is adopted to carry out surface treatment on the composite particles of the boron nitride nanosheet coated nano titanium dioxide.
Example 3
A preparation method of a boron nitride nanosheet coated nano titanium dioxide core-shell structure filler comprises the following steps:
1) b, mixing the boron nitride nanosheet and the nano titanium dioxide according to the weight ratio of 7: 1 proportion is put in a drying box at 90 ℃ to be dried for 12 hours;
2) weighing 1g of boron nitride nanosheets, placing the boron nitride nanosheets into a beaker, adding 200ml of absolute ethyl alcohol into the beaker to enable the content of the boron nitride nanosheets in the suspension to be 5mg/ml, and stirring the suspension for five minutes by using an electric stirrer at the rotating speed of 2000 rpm;
3) adding 0.14g of nano titanium dioxide into the turbid liquid obtained in the step 2), keeping the rotating speed of the electric stirring machine unchanged, and starting an ultrasonic cleaning machine to fully disperse the boron nitride nanosheets and the nano titanium dioxide in ethanol;
4) after 120min, evaporating ethanol to dryness in an environment of 90 ℃, and drying the boron nitride nanosheet and the nano titanium dioxide to obtain a mixture of the boron nitride nanosheet and the nano titanium dioxide with a mass ratio of 7: 1, uniformly dispersed nanocomposite particles;
5) putting the uniformly dispersed nano particles into a corundum crucible, putting the whole corundum crucible into a muffle furnace, heating to 950 ℃ at the heating rate of 3.65 ℃/min, and keeping the temperature for calcining for 25 hours;
6) after cooling, grinding by using an agate mortar, and sieving by using a 200-mesh plastic nylon mesh screen after fully grinding to obtain composite particles of the boron nitride nanosheet coated nano titanium dioxide;
7) and (3) performing surface treatment on the composite particles of the boron nitride nanosheet coated nano titanium dioxide by using a KH560 coupling agent. Example 4
The preparation method of the composite particle/polymer composite material of the boron nitride nanosheet coated nano titanium dioxide after surface treatment comprises the following steps:
1) the composite particles of BNNS coated with nano TiO2 are dried in a drying oven at 90 ℃ for 12 hours.
2) The roller was heated to maintain the roller temperature at 205 ℃. A certain amount of polypropylene is placed on a roller, mixed for 4-5 min and then taken out, thus achieving the purpose of cleaning the double rollers.
3) 100phr (parts per hubs of rubber) of polypropylene was weighed into a twin roll and kneaded for 4 min.
4) Weighing 1phr of TiO2@ BNNS, adding the TiO2@ BNNS into 100phr of polypropylene matrix, and mixing for 10min to uniformly mix the rubber material to obtain the polypropylene nano composite material with the TiO2@ BNNS mass fraction of 1 wt%.
5) An appropriate amount of sizing material is weighed and covered by an upper PET film and a lower PET film. And (3) putting the rubber material into a mold of a hot-press forming machine, keeping the temperature at 205 ℃ for 10min under the condition of 10MPa, and then cooling and taking out a sample.
As shown in FIG. 1, the mixed particle of the boron nitride nanosheet and the nano titanium dioxide is mostly dissociated in the boron nitride nanosheet or adsorbed on the surface of BNNS, and has a relatively obvious agglomeration phenomenon.
As shown in fig. 2, after the boron nitride nanosheets and the nano titanium dioxide are subjected to a calcination process at a temperature of 900 ℃, the nano titanium dioxide is partially or completely coated by the boron nitride nanosheets, and a stable core-shell structure is formed.
From the results of the energy spectral element distribution of fig. 3, the kind and content of the elements contained in the box can be determined.
The boron nitride nano-sheet and the nano titanium dioxide can be obtained by analyzing the X-ray diffraction spectra before and after calcination of the 4-boron nitride nano-sheet and the nano titanium dioxide: a new diffraction peak appears at the position of the pentagram after calcination, the diffraction peak corresponds to a new substance, and the chemical formula of the new substance is TiB0.024O2I.e., boron-doped rutile titanium dioxide, corresponds to PDF # 87-0921. The result also shows that the boron nitride nanosheet and the nano titanium dioxide are combined together under the action of chemical bonds to form a stable core-shell structure.
As shown in FIG. 5, the electric field strength of the polypropylene-based boron nitride nanosheet-coated nano titanium dioxide composite material at 63.2% breakdown probability is 336.2kV/mm, which is 18.2% higher than that of polypropylene with the breakdown field strength of 284.4 kV/mm.

Claims (10)

1. A preparation method of a boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler is characterized in that the boron nitride nanosheet can react with oxygen in the air to form boron oxide in a high-temperature calcination process, and then the boron oxide and the nano titanium dioxide form a core-shell structure under the action of continuous high temperature.
2. The preparation method of the boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler according to claim 1, comprising the following steps:
1) placing the boron nitride nanosheets and the nano titanium dioxide in a drying box for drying;
2) weighing boron nitride nanosheets, putting the boron nitride nanosheets into a beaker, adding absolute ethyl alcohol into the beaker to enable the content of the boron nitride nanosheets in the suspension to be 5mg/ml, and stirring the suspension;
3) adding nano titanium dioxide into the turbid liquid obtained in the step 2), keeping the stirring rotating speed unchanged, and starting an ultrasonic cleaning machine to fully disperse the boron nitride nanosheets and the nano titanium dioxide in ethanol;
4) evaporating ethanol, and drying the boron nitride nanosheets and the nano titanium dioxide to obtain uniformly dispersed nano composite particles of the boron nitride nanosheets and the titanium dioxide;
5) putting the uniformly dispersed nano particles into a corundum crucible, putting the whole corundum crucible into a muffle furnace, raising the temperature to the calcining temperature, and keeping the temperature for calcining;
6) after cooling, grinding by using an agate mortar, and sieving after fully grinding to obtain composite particles of the boron nitride nanosheet coated nano titanium dioxide;
7) and (3) carrying out surface treatment on the composite particles of the boron nitride nanosheet coated nano titanium dioxide by using a coupling agent.
3. The preparation method of the boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler according to claim 2, characterized in that: according to the mass ratio, the boron nitride nanosheet: nano titanium dioxide ═ (4-7): 1, preferably 5: 1.
4. the preparation method of the boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler according to claim 2, characterized in that: the calcination temperature is controlled at 850-.
5. The preparation method of the boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler according to claim 2, characterized in that: the calcination time is controlled to 17 to 25 hours, preferably 20 hours.
6. The preparation method of the boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler according to claim 2, characterized in that: the coupling agent is a silane coupling agent and is selected from one of KH550, KH560 and KH 570.
7. The boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler obtained by the preparation method according to any one of claims 1 to 6, wherein: the composite material comprises isotactic polypropylene, boron nitride nanosheets and nano titanium dioxide;
the boron nitride nanosheet-coated nano titanium dioxide core-shell structure particles account for 1% by mass;
the thickness of the boron nitride nanosheet is 50nm, and the diameter of the boron nitride nanosheet is 0.5-5 um.
8. The boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler according to claim 7, wherein: the particle size of the nano titanium dioxide is 40nm, and the crystal form is rutile type.
9. The use of the boron nitride nanosheet-coated nano titanium dioxide core-shell structured filler obtained by the preparation method according to any one of claims 1 to 6, wherein: the boron nitride nanosheet-coated nano titanium dioxide core-shell structure filler is applied to a dielectric insulating material.
10. A surface modification treatment method for composite particles is characterized in that: the method comprises the following steps:
1) placing 2gKH550 coupling agent, 7.2g absolute ethyl alcohol and 0.8g deionized water in a beaker, and stirring for 15 minutes at the rotating speed of 2000rpm and the environment of 80 ℃ by an electric stirrer to fully hydrolyze KH 550;
2) mixing 1g of the hydrolyzed solution with 4g of fired composite particles of boron nitride nanosheet-coated nano titanium dioxide, stirring at the rotating speed of 2000rpm for 2 hours in the environment of 80 ℃, and finishing surface modification;
3) and taking out the modified solution, putting the modified solution into a drying oven, and drying the solution for 8 hours at the temperature of 90 ℃ to finally obtain the boron nitride nanosheet-coated nano titanium dioxide composite particles subjected to surface modification by the coupling agent with the mass fraction of 5%.
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