CN106241755B - A kind of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material and preparation method thereof - Google Patents
A kind of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides the preparation method of fibrous titanium nitride/silicon nitride/nitridation carbon composite nano-material, this method obtains titanium nitride/silicon nitride composite nano materials by electrospinning process first, then carbon nitrogen source is added, titanium nitride/silicon nitride/nitridation carbon composite nano-material is made by simply roasting, material of the present invention has very excellent comprehensive performance, and uniform threadiness, a diameter of tens nanometers of fiber is presented in material, length is 12 um, and pore volume is 0.33~0.44cm3/ g, specific surface area are up to 163.2~183.0m2/ g, 20.1 22.5Gpa of vickers hardness hv, 953 980Mpa of bending strength, 9.6 10.5Mpam of fracture toughness½, relative density 98.9%, electrical conductivity is 6~9S/cm；In addition, composite nano materials of the present invention are applied to be respectively provided with very excellent performance in fuel cell, photosensitized solar cell and ultracapacitor, it is a kind of very wide nanocomposite of prospect.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, and in particular to a kind of threadiness titanium nitride/silicon nitride/carbonitride
Composite nano materials and preparation method thereof.
Background technology
Research to nano material is a Disciplinary Frontiers in current scientific research, and many scientific workers in the whole world
The hot spot of research.The magical part of nano material and the extensive concern for not causing people even more by the aspect that people know also；
The research and application prepared to nano material is even more current hot and difficult issue, and develops high-tech emphasis.
Titanium nitride is a kind of widely used superhard material, ideal stoichiometric than block TiN belong to cubic system, be in
Golden yellow, and there is metallic luster, density 5.22g/cm3, 29~30 DEG C of fusing point, microhardness is about 21GPa, elasticity modulus
About 590GPa, linear expansion coefficient are 9.35 × 10-6/ DEG C (20~1000/ DEG C), thermal conductivity are 19.3W/ (mK) (20
DEG C), resistivity is 25.0 μ Ω cm, not soluble in water, sour, is slightly soluble in hot chloroazotic acid and hydrofluoric acid mixed solution.Because it is with high-strength
The series of advantages such as degree, high rigidity, high temperature resistant, acid resistance corrode, wear-resistant and good electric conductivity, thermal conductivity, in machinery
Process tool, cutlery, a variety of materials molding die and the wear-resistant coating of wear parts and various metal parts have widely
Using.
Nano-silicon nitride is a kind of important structural material, it is a kind of superhard material, itself has lubricity, and resistance to
Abrasion；In addition to hydrofluoric acid, not with other inorganic acid reactions, resistance to corrosion is strong for it, and when high temperature is anti-oxidant.And it can also be resisted
Thermal shock, is heated to more than l000 DEG C in atmosphere, and quick refrigeration drastically heats again, will not fragmentation.Specific to physical
Can aspect, silicon nitride material has that hardness is high, wear-resistant, elasticity modulus is big, intensity is high, high temperature resistant, thermal coefficient of expansion are small, heat conduction
Coefficient is big, good thermal shock, the features such as density is low, skin-friction coefficient is small, electrical insulation capability is good；And in terms of chemical property, it
The advantages that also corrosion-resistant, anti-oxidant.In Electronic Packaging, silicone adds the Double-protection of silicon nitride film to significantly improve electricity
The water resistance of submodule.Silicon nitride is widely used in semiconductor devices and partly leads as a kind of passivation and insulating film material
Body integrated circuit.But itself dielectric constant is higher, its application in encapsulation field insulating materials is hindered.
Carbonitride is a kind of organic semiconductor catalysis material, and carbonitride is considered as organic polymer stable at room temperature
Semi-conducting material.The fundamental structural unit of class graphitic nitralloy carbon forms piperazine ring by the sp2 hydridization of CN（C6N7）, between ring and ring
Linked by the N atoms of end, form pi-conjugated plane, therefore, this special chemical structure makes it energy gap and is
The narrow bandgap semiconductor material of 2.67eV, Carrier recombination speed is higher, has stable chemical property, easily prepares, and nothing
Poison, visible-range respond the advantages that, it is much there is in fields wide application in photocatalysis, electronics, optics, biology etc.
Prospect.
At present, although titanium nitride, silicon nitride, the report of carbon nitride material are more in the prior art, although they are with good
Good electric conductivity and mechanical stability, but its comprehensive performance or not ideal enough, need to be further improved；Therefore exploitation tool
The composite nano materials tool for having excellent comprehensive performance is of great significance.
The content of the invention
The object of the present invention is to provide a kind of tri compound nano material of excellent combination property, and in particular to fibrous nitrogen
Change titanium/silicon nitride/nitridation carbon composite nano-material and preparation method thereof.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, includes the following steps：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 15~20g Titanium Citrates,
The Ludox of 20~30g be added sequentially to 2~3g, the polyvinylpyrrolidone of 0.005~0.008mol/L and 70~90 mL without
In the mixed solution of water-ethanol/DMF, and at 30~40 DEG C stir 4~8h it is small when, obtain uniformly mixing precursor solution,
Then precursor solution is inserted in the syringe with spinning head, carries out spinning, the condition of spinning is：Sample rate is 0.3-
1m1/h, voltage is 1-2kv/cm between plate, obtains precursor fibre；Precursor fibre is subjected to hot place for 600-800 DEG C in atmosphere
Reason, when the time is 3-5 small, then cooled to room temperature, obtains amorphous ti silica composite nano fiber；Afterwards by above-mentioned nanometer
Fiber is placed in tube furnace, leads to high pure nitrogen into stove with the flow velocity of 100~130mL/min before heating, then in this flow velocity
In the case of logical nitrogen, at the uniform velocity heat up, furnace temperature is raised to 1100~1200 DEG C, when keeping this temperature 6~8 small, then in logical nitrogen
Under the conditions of gas, room temperature is reduced the temperature to, obtains titanium nitride/silicon nitride composite nano materials；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：It is anhydrous that 6~10g carbon nitrogen sources are dissolved in 40~50mL
In ethanol, and add step（1）Obtained titanium nitride/silicon nitride composite nano materials, are then placed in 40 by obtained mixture
At a temperature of~60 DEG C, be stirred continuously it is lower absolute ethyl alcohol is evaporated, finally by the product after being evaporated in 450~550 DEG C of nitrogen
3~5h is roasted in gas atmosphere, up to titanium nitride/silicon nitride/carbonitride tri compound nano material.
Wherein, the composite nano materials are filamentary structure, a diameter of tens nanometers of fiber, length 1-2
Um, pore volume are 0.33~0.44cm3/ g, specific surface area are 163.2~183.0m2/g。
The mechanical property of the tri compound nano material is：Vickers hardness hv 20.1-22.5Gpa, bending strength 953-
980Mpa, fracture toughness 9.6-10.5Mpam½, relative density 98.9%.
The carbon nitrogen source is melamine or cyanamide.
Described to insert precursor solution in syringe, syringe leading portion connection diameter is the spinning head of 0.5-1.6mm, is noted
Emitter is placed in medical micro-injection pump.
The volume ratio of absolute ethyl alcohol and DMF are 2 in the mixed solution of the absolute ethyl alcohol/DMF：1.
In addition, composite nano materials of the present invention can in fuel cell, photosensitized solar cell and ultracapacitor into
Row application.
The present invention technique effect be：Relative to the prior art, present invention gained titanium nitride/silicon nitride/carbonitride is compound
Nano material, preparation method is simple, and production cost is low, and using the technique of electrostatic spinning, uniform fiber is presented in obtained material
Shape, a diameter of tens nanometers of fiber, length are 1-2 um, and pore volume is 0.33~0.44cm3/ g, specific surface area are up to
163.2~183.0m2/ g, in addition, material of the present invention also has very excellent comprehensive performance, vickers hardness hv 20.1-
22.5Gpa, bending strength 953-980Mpa, fracture toughness 9.6-10.5Mpam½, relative density 98.9%, electrical conductivity for 6~
9S/cm；In addition, composite nano materials of the present invention are applied to have in fuel cell, photosensitized solar cell and ultracapacitor
There is very excellent performance, be a kind of very wide material of prospect.
Brief description of the drawings
Fig. 1 is that the SEM of 1 composite nano materials of the embodiment of the present invention schemes.
Embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
A kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, includes the following steps：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 15g Titanium Citrates, 20g
Ludox be added sequentially to the polyvinylpyrrolidone of 2g, 0.006mol/L and the mixed solution of 70 mL absolute ethyl alcohols/DMF
In, and at 30 DEG C stir 8h it is small when, obtain uniformly mixing precursor solution, then insert precursor solution with spinneret
In the syringe of head, spinning is carried out, the condition of spinning is：Sample rate is 0.6m1/h, and voltage is 1kv/cm between plate, before obtaining
Drive body fiber；Precursor fibre is heat-treated for 700 DEG C in atmosphere, the time for 4 it is small when, then cooled to room temperature,
Obtain amorphous ti silica composite nano fiber；Above-mentioned nanofiber is placed in tube furnace afterwards, before heating into stove with
The flow velocity of 120mL/min leads to high pure nitrogen, then in the case where this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1100
DEG C, when keeping this temperature 7 small, then under logical condition of nitrogen gas, room temperature is reduced the temperature to, obtains that titanium nitride/silicon nitride is compound to be received
Rice material；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：6g melamines are dissolved in 40mL absolute ethyl alcohols,
And add step（1）Obtained mixture, is then placed in 50 DEG C of temperature by obtained titanium nitride/silicon nitride composite nano materials
Under, be stirred continuously it is lower absolute ethyl alcohol is evaporated, the product after being evaporated finally is roasted into 4h in 550 DEG C of nitrogen atmospheres, i.e.,
Obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Embodiment 2
A kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, includes the following steps：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 20g Titanium Citrates, 30g
Ludox be added sequentially to the polyvinylpyrrolidone of 3g, 0.007mol/L and the mixed solution of 90 mL absolute ethyl alcohols/DMF
In, and at 40 DEG C stir 4h it is small when, obtain uniformly mixing precursor solution, then insert precursor solution with spinneret
In the syringe of head, spinning is carried out, the condition of spinning is：Sample rate is 0.6m1/h, and voltage is 2kv/cm between plate, before obtaining
Drive body fiber；Precursor fibre is heat-treated for 800 DEG C in atmosphere, the time for 3 it is small when, then cooled to room temperature,
Obtain amorphous ti silica composite nano fiber；Above-mentioned nanofiber is placed in tube furnace afterwards, before heating into stove with
The flow velocity of 130mL/min leads to high pure nitrogen, then in the case where this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1100
DEG C, when keeping this temperature 6 small, then under logical condition of nitrogen gas, room temperature is reduced the temperature to, obtains that titanium nitride/silicon nitride is compound to be received
Rice material；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：10g cyanamides are dissolved in 50mL absolute ethyl alcohols,
And add step（1）Obtained mixture, is then placed in 60 DEG C of temperature by obtained titanium nitride/silicon nitride composite nano materials
Under, be stirred continuously it is lower absolute ethyl alcohol is evaporated, the product after being evaporated finally is roasted into 5h in 550 DEG C of nitrogen atmospheres, i.e.,
Obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Embodiment 3
A kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, includes the following steps：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 18g Titanium Citrates, 25g
The Ludox polyvinylpyrrolidone and 80 mL absolute ethyl alcohols/DMF that are added sequentially to 2.5g, 0.006mol/L mixing it is molten
In liquid, and at 35 DEG C stir 6h it is small when, obtain uniformly mix precursor solution, then by precursor solution insert have spray
In the syringe of silk head, spinning is carried out, the condition of spinning is：Sample rate is 0.6m1/h, and voltage is 1.5kv/cm between plate, is obtained
To precursor fibre；Precursor fibre is heat-treated for 700 DEG C in atmosphere, when the time is 5 small, then naturally cools to room
Temperature, obtains amorphous ti silica composite nano fiber；Above-mentioned nanofiber is placed in tube furnace afterwards, before heating into stove with
The flow velocity of 110mL/min leads to high pure nitrogen, then in the case where this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1150
DEG C, when keeping this temperature 6 small, then under logical condition of nitrogen gas, room temperature is reduced the temperature to, obtains that titanium nitride/silicon nitride is compound to be received
Rice material；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：9g melamines are dissolved in 45mL absolute ethyl alcohols,
And add step（1）Obtained mixture, is then placed in 45 DEG C of temperature by obtained titanium nitride/silicon nitride composite nano materials
Under, be stirred continuously it is lower absolute ethyl alcohol is evaporated, the product after being evaporated finally is roasted into 4h in 500 DEG C of nitrogen atmospheres, i.e.,
Obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Embodiment 4
A kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, includes the following steps：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 19g Titanium Citrates, 26g
Ludox be added sequentially to the polyvinylpyrrolidone of 2.8g, 0.007mol/L and the mixed solution of 78mL absolute ethyl alcohols/DMF
In, and at 36 DEG C stir 6h it is small when, obtain uniformly mixing precursor solution, then insert precursor solution with spinneret
In the syringe of head, spinning is carried out, the condition of spinning is：Sample rate is 0.6m1/h, and voltage is 1.6kv/cm between plate, is obtained
Precursor fibre；Precursor fibre is heat-treated for 700 DEG C in atmosphere, when the time is 4 small, then naturally cools to room
Temperature, obtains amorphous ti silica composite nano fiber；Above-mentioned nanofiber is placed in tube furnace afterwards, before heating into stove with
The flow velocity of 120mL/min leads to high pure nitrogen, then in the case where this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1100
DEG C, when keeping this temperature 6 small, then under logical condition of nitrogen gas, room temperature is reduced the temperature to, obtains that titanium nitride/silicon nitride is compound to be received
Rice material；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：7g cyanamides are dissolved in 46mL absolute ethyl alcohols, and
Add step（1）Obtained mixture, is then placed in 50 DEG C of temperature by obtained titanium nitride/silicon nitride composite nano materials
Under, be stirred continuously it is lower absolute ethyl alcohol is evaporated, the product after being evaporated finally is roasted into 4h in 500 DEG C of nitrogen atmospheres, i.e.,
Obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Embodiment 5
A kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, includes the following steps：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 20g Titanium Citrates, 27g
Ludox be added sequentially to the polyvinylpyrrolidone of 3g, 0.008mol/L and the mixed solution of 80 mL absolute ethyl alcohols/DMF
In, and at 37 DEG C stir 7h it is small when, obtain uniformly mixing precursor solution, then insert precursor solution with spinneret
In the syringe of head, spinning is carried out, the condition of spinning is：Sample rate is 1m1/h, and voltage is 1.2kv/cm between plate, before obtaining
Drive body fiber；Precursor fibre is heat-treated for 800 DEG C in atmosphere, the time for 4 it is small when, then cooled to room temperature,
Obtain amorphous ti silica composite nano fiber；Above-mentioned nanofiber is placed in tube furnace afterwards, before heating into stove with
The flow velocity of 130mL/min leads to high pure nitrogen, then in the case where this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1200
DEG C, when keeping this temperature 6 small, then under logical condition of nitrogen gas, room temperature is reduced the temperature to, obtains that titanium nitride/silicon nitride is compound to be received
Rice material；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：6g cyanamides are dissolved in 43mL absolute ethyl alcohols, and
Add step（1）Obtained mixture, is then placed in 52 DEG C of temperature by obtained titanium nitride/silicon nitride composite nano materials
Under, be stirred continuously it is lower absolute ethyl alcohol is evaporated, the product after being evaporated finally is roasted into 5h in 500 DEG C of nitrogen atmospheres, i.e.,
Obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Embodiment 6
Performance test to embodiment 1-5 material prepared, it is as a result as follows：
| Specific surface area m2/g | Electrical conductivity S/cm | Vickers hardness Gpa | Bending strength Mpa | Fracture toughness Mpam½ | |
| Embodiment 1 | 173.4 | 9 | 21.5 | 970 | 9.9 |
| Embodiment 2 | 169.3 | 7 | 22.5 | 968 | 10.2 |
| Embodiment 3 | 175.3 | 6 | 20.1 | 953 | 9.6 |
| Embodiment 4 | 183.0 | 8 | 20.8 | 980 | 10.5 |
| Embodiment 5 | 163.2 | 7 | 21.7 | 961 | 9.7 |
As can be seen from Table 1, titanium nitride/silicon nitride/nitridation carbon composite nano-material that prepared by the present invention has good
Comprehensive performance, be a kind of very wide composite nano materials of application prospect.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To modify to the technical solution described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent replacement, improvement and so on, should be included in the present invention's
Within protection domain.
Claims (6)
1. a kind of preparation method of threadiness titanium nitride/silicon nitride/nitridation carbon composite nano-material, it is characterised in that including such as
Lower step：
（1）The preparation of titanium nitride/silicon nitride composite nano materials：In the case where being stirred continuously successively by 15~20g Titanium Citrates, 20~
The Ludox of 30g is added sequentially to 2~3g, the polyvinylpyrrolidone of 0.005~0.008mol/L and the anhydrous second of 70~90 mL
In the mixed solution of alcohol/DMF, and at 30~40 DEG C stir 4~8h it is small when, obtain uniformly mixing precursor solution, then
Precursor solution is inserted in the syringe with spinning head, carries out spinning, the condition of spinning is：Sample rate is 0.3-1m1/
H, voltage is 1-2kv/cm between plate, obtains precursor fibre；Precursor fibre is subjected to hot place for 600-800 DEG C in atmosphere again
Reason, when the time is 3-5 small, then cooled to room temperature, obtains amorphous ti silica composite nano fiber；Afterwards by above-mentioned nanometer
Fiber is placed in tube furnace, leads to high pure nitrogen into stove with the flow velocity of 100~130mL/min before heating, then in this flow velocity
In the case of logical nitrogen, at the uniform velocity heat up, furnace temperature is raised to 1100~1200 DEG C, when keeping this temperature 6~8 small, finally in logical nitrogen
Under the conditions of gas, room temperature is reduced the temperature to, obtains titanium nitride/silicon nitride composite nano materials；
（2）Titanium nitride/silicon nitride/nitridation carbon composite nano-material：6~10g carbon nitrogen sources are dissolved in 40~50mL absolute ethyl alcohols
In, and add step（1）Obtained titanium nitride/silicon nitride composite nano materials, are then placed in 40~60 by obtained mixture
At a temperature of DEG C, be stirred continuously it is lower absolute ethyl alcohol is evaporated, finally by the product after being evaporated in 450~550 DEG C of nitrogen atmospheres
3~5h of middle roasting, up to titanium nitride/silicon nitride/carbonitride tri compound nano material.
2. the preparation method of composite nano materials according to claim 1, it is characterised in that the titanium nitride/silicon nitride/
Carbonitride tri compound nano material is filamentary structure, and a diameter of tens nanometers of fiber, length is 1-2 μm, pore volume
For 0.33~0.44cm3/ g, specific surface area are 163.2~183.0m2/g。
3. the preparation method of composite nano materials according to claim 1, it is characterised in that the tri compound nanometer material
The mechanical property of material is：Vickers hardness hv 20.1-22.5GPa, bending strength 953-980MPa, fracture toughness 9.6-
10.5MPa·m½, relative density 98.9%.
4. the preparation method of composite nano materials according to claim 1, it is characterised in that the carbon nitrogen source is trimerization
Cyanamide or cyanamide.
5. the preparation method of composite nano materials according to claim 1, it is characterised in that precursor solution is inserted into note
In emitter, syringe leading portion connection diameter is the spinning head of 0.5-1.6mm, and syringe is placed in medical micro-injection pump.
6. the preparation method of composite nano materials according to claim 1, it is characterised in that the mixing of absolute ethyl alcohol/DMF
The volume ratio of absolute ethyl alcohol and DMF are 2 in solution：1.
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