CN106241755A - A kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials and preparation method thereof - Google Patents
A kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials and preparation method thereof Download PDFInfo
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Abstract
The invention provides the preparation method of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, the method first passes through electrospinning process and obtains titanium nitride/silicon nitride composite nano materials, then carbon nitrogen source is added, titanium nitride/silicon nitride/carbonitride composite nano materials is i.e. prepared by simple roasting, material of the present invention has the most excellent combination property, and material presents uniform threadiness, a diameter of tens nanometers of fiber, a length of 12 um, pore volume is 0.33～0.44cm3/ g, specific surface area is up to 163.2～183.0m2/ g, vickers hardness hv 20.1 22.5Gpa, bending strength 953 980Mpa, fracture toughness 9.6 10.5Mpa m½, relative density 98.9%, electrical conductivity is 6～9S/cm；It addition, composite nano materials of the present invention is applied in fuel cell, photosensitized solar cell and ultracapacitor be respectively provided with the most excellent performance, it it is the most wide nano composite material of a kind of prospect.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related 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, is also whole world many scientists
The focus of research.The aspect in place of the mystery of nano material and the most do not known by people causes the extensive concern of people especially；
The research that is prepared nano material and apply the most current focus and difficult point, is also to develop high-tech emphasis.
Titanium nitride is a kind of broad-spectrum superhard material, and the block TiN of ideal stoichiometric ratio belongs to cubic system, in
Golden yellow, and there is metallic luster, density is 5.22g/cm3, fusing point 29～30 DEG C, microhardness is about 21GPa, elastic modelling quantity
Being about 590GPa, linear expansion coefficient is 9.35 × 10-6/ DEG C (20～1000/ DEG C), thermal conductivity is 19.3W/ (m K) (20
DEG C), resistivity is 25.0 Ω cm, water insoluble, sour, is slightly soluble in hot chloroazotic acid and hydrofluoric acid mixed solution.Because it has high-strength
The series of advantages such as degree, high rigidity, high temperature resistant, acid resistance corrodes, wear-resistant and good electric conductivity, heat conductivity, at machinery
Process tool, cutlery, various material mould and the wear-resistant coating of wear parts and various metal parts have widely
Application.
Nano-silicon nitride is a kind of important structural material, and it is a kind of superhard material, itself has lubricity, and resistance to
Abrasion；Outside dehydrogenation fluoric acid, it not with other inorganic acid reaction, resistance to corrosion is strong, antioxidation during high temperature.And it can also be resisted
Thermal shock, is heated to more than l000 DEG C in atmosphere, and quick refrigeration the most drastically heats, also will not fragmentation.Specific to physical property
Can aspect, silicon nitride material has that hardness is high, wear-resistant, elastic modelling quantity is big, intensity is high, high temperature resistant, thermal coefficient of expansion is little, heat conduction
The features such as coefficient is big, good thermal shock, density are low, skin-friction coefficient is little, electrical insulation capability is good；And chemical property aspect, it
The advantages such as the most corrosion-resistant, antioxidation.In Electronic Packaging, silicone adds the Double-protection of silicon nitride film can significantly improve electricity
The water resistance of submodule.Silicon nitride, as one passivation and insulating film material, is widely used in semiconductor device and partly leads
Body integrated circuit.But itself dielectric constant is higher, hinder its application at encapsulation field insulant.
Carbonitride is a class organic semiconductor catalysis material, and carbonitride is considered as the organic polymer of room-temperature stable
Semi-conducting material.The fundamental structural unit of class graphitic nitralloy carbon is formed piperazine ring (C6N7) by the sp2 hydridization of CN, between ring and ring
Being linked by the atom N of end, define 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, in advantages such as visible-range responses, make it have wide application in much fields such as photocatalysis, electronics, optics, biology
Prospect.
At present, although titanium nitride in prior art, silicon nitride, carbon nitride material report more, although they have good
Good electric conductivity and mechanical stability, but its combination property or not ideal enough, need to improve further；Therefore tool is developed
The composite nano materials tool having excellent comprehensive performance is of great significance.
Summary of the invention
It is an object of the invention to provide the tri compound nano material of a kind of excellent combination property, be specifically related to threadiness nitrogen
Change titanium/silicon nitride/carbonitride composite nano materials and preparation method thereof.
For solving the problems referred to above, the technical solution used in the present invention is:
The preparation method of a kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, comprises the steps:
(1) preparation of titanium nitride/silicon nitride composite nano materials: under being stirred continuously successively by 15～20g Titanium Citrates, 20～
The Ludox of 30g is added sequentially to polyvinylpyrrolidone and the 70～90 anhydrous second of mL of 2～3g, 0.005～0.008mol/L
In the mixed solution of alcohol/DMF, and at 30～40 DEG C, stir 4～8h hour, mixed precursor solution uniformly, then
Being inserted by precursor solution in the syringe with spinning head, carry out spinning, the condition of spinning is: sample rate is 0.3-1m1/
H, between plate, voltage is 1-2kv/cm, obtains precursor fibre；By precursor fibre in atmosphere 600-800 DEG C carry out heat treatment,
Time is 3-5 hour, then naturally cools to room temperature, obtains amorphous ti silica composite nano fiber；Afterwards by above-mentioned Nanowire
Dimension is placed in tube furnace, leads to high pure nitrogen with the flow velocity of 100～130mL/min in intensification forward direction stove, then leads at this flow velocity
In the case of nitrogen, at the uniform velocity heat up, furnace temperature is raised to 1100～1200 DEG C, keep this temperature 6～8 hours, then at logical nitrogen
Under the conditions of, reduce the temperature to room temperature, obtain titanium nitride/silicon nitride composite nano materials；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 6～10g carbon nitrogen sources are dissolved in 40～50mL dehydrated alcohol
In, and add the titanium nitride/silicon nitride composite nano materials that step (1) obtains, then the mixture obtained is placed in 40～60
At a temperature of DEG C, lower being evaporated by dehydrated alcohol being stirred continuously, the product after being finally evaporated is at 450～550 DEG C of nitrogen gas
Roasting 3～5h in atmosphere, obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Wherein, described composite nano materials is filamentary structure, a diameter of tens nanometers of fiber, a length of 1-2
Um, pore volume is 0.33～0.44cm3/ g, specific surface area is 163.2～183.0m2/g。
The mechanical property of described tri compound nano material is: vickers hardness hv 20.1-22.5Gpa, bending strength 953-
980Mpa, fracture toughness 9.6-10.5Mpa m½, relative density 98.9%.
Described carbon nitrogen source is tripolycyanamide or cyanamide.
Described inserting in syringe by precursor solution, syringe leading portion connection diameter is the spinning head of 0.5-1.6mm, note
Emitter is placed in medical micro-injection pump.
In the mixed solution of described dehydrated alcohol/DMF, dehydrated alcohol is 2:1 with the volume ratio of DMF.
It addition, composite nano materials of the present invention can enter in fuel cell, photosensitized solar cell and ultracapacitor
Row application.
The technique effect of the present invention is: relative to prior art, and gained titanium nitride/silicon nitride/carbonitride of the present invention is combined
Nano material, preparation method is simple, and production cost is low, and the technique using electrostatic spinning, the material obtained presents uniform fiber
Shape, a diameter of tens nanometers of fiber, a length of 1-2 um, pore volume is 0.33～0.44cm3/ g, specific surface area is up to
163.2～183.0m2/ g, it addition, material of the present invention also has the most excellent combination property, vickers hardness hv 20.1-
22.5Gpa, bending strength 953-980Mpa, fracture toughness 9.6-10.5Mpa m½, relative density 98.9%, electrical conductivity be 6～
9S/cm；It addition, composite nano materials of the present invention is applied in fuel cell, photosensitized solar cell and ultracapacitor all to have
There is the most excellent performance, be the most wide material of a kind of prospect.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 composite nano materials.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is further elaborated:
Embodiment 1
The preparation method of a kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, comprises the steps:
(1) preparation of titanium nitride/silicon nitride composite nano materials: successively by 15g Titanium Citrate, the silicon of 20g under being stirred continuously
Colloidal sol is added sequentially in the polyvinylpyrrolidone of 2g, 0.006mol/L and the mixed solution of 70 mL dehydrated alcohol/DMF, and
Stir 8h hour at 30 DEG C, mixed precursor solution uniformly, then precursor solution is inserted and there is spinning head
In syringe, carrying out spinning, the condition of spinning is: sample rate is 0.6m1/h, and between plate, voltage is 1kv/cm, obtains presoma
Fiber；By precursor fibre in atmosphere 700 DEG C carry out heat treatment, the time is 4 hours, then naturally cools to room temperature, obtains
Amorphous ti silica composite nano fiber；Afterwards above-mentioned nanofiber is placed in tube furnace, with 120mL/ in intensification forward direction stove
The flow velocity of min leads to high pure nitrogen, then in the case of this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1100 DEG C, keeps
This temperature 7 hours, then under logical condition of nitrogen gas, reduces the temperature to room temperature, obtains titanium nitride/silicon nitride composite nano materials；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 6g tripolycyanamide is dissolved in 40mL dehydrated alcohol, and adds
Enter the titanium nitride/silicon nitride composite nano materials that step (1) obtains, then the mixture obtained be placed at a temperature of 50 DEG C,
Lower being evaporated by dehydrated alcohol being stirred continuously, the product after being finally evaporated is roasting 4h in 550 DEG C of nitrogen atmospheres, obtains nitrogen
Change titanium/silicon nitride/carbonitride tri compound nano material.
Embodiment 2
The preparation method of a kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, comprises the steps:
(1) preparation of titanium nitride/silicon nitride composite nano materials: successively by 20g Titanium Citrate, the silicon of 30g under being stirred continuously
Colloidal sol is added sequentially in the polyvinylpyrrolidone of 3g, 0.007mol/L and the mixed solution of 90 mL dehydrated alcohol/DMF, and
Stir 4h hour at 40 DEG C, mixed precursor solution uniformly, then precursor solution is inserted and there is spinning head
In syringe, carrying out spinning, the condition of spinning is: sample rate is 0.6m1/h, and between plate, voltage is 2kv/cm, obtains presoma
Fiber；By precursor fibre in atmosphere 800 DEG C carry out heat treatment, the time is 3 hours, then naturally cools to room temperature, obtains
Amorphous ti silica composite nano fiber；Afterwards above-mentioned nanofiber is placed in tube furnace, with 130mL/ in intensification forward direction stove
The flow velocity of min leads to high pure nitrogen, then in the case of this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1100 DEG C, keeps
This temperature 6 hours, then under logical condition of nitrogen gas, reduces the temperature to room temperature, obtains titanium nitride/silicon nitride composite nano materials；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 10g cyanamide is dissolved in 50mL dehydrated alcohol, and adds
Enter the titanium nitride/silicon nitride composite nano materials that step (1) obtains, then the mixture obtained be placed at a temperature of 60 DEG C,
Lower being evaporated by dehydrated alcohol being stirred continuously, the product after being finally evaporated is roasting 5h in 550 DEG C of nitrogen atmospheres, obtains nitrogen
Change titanium/silicon nitride/carbonitride tri compound nano material.
Embodiment 3
The preparation method of a kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, comprises the steps:
(1) preparation of titanium nitride/silicon nitride composite nano materials: successively by 18g Titanium Citrate, the silicon of 25g under being stirred continuously
Colloidal sol is added sequentially in the polyvinylpyrrolidone of 2.5g, 0.006mol/L and the mixed solution of 80 mL dehydrated alcohol/DMF,
And stir 6h hour at 35 DEG C, mixed precursor solution uniformly, then precursor solution is inserted and there is spinning head
Syringe in, carry out spinning, the condition of spinning is: sample rate is 0.6m1/h, and between plate, voltage is 1.5kv/cm, before obtaining
Drive body fiber；By precursor fibre in atmosphere 700 DEG C carry out heat treatment, the time is 5 hours, then naturally cools to room temperature,
Obtain amorphous ti silica composite nano fiber；Afterwards above-mentioned nanofiber is placed in tube furnace, in intensification forward direction stove with
The flow velocity of 110mL/min leads to high pure nitrogen, then in the case of this flow velocity leads to nitrogen, at the uniform velocity heats up, furnace temperature is raised to 1150
DEG C, keep this temperature 6 hours, then under logical condition of nitrogen gas, reduce the temperature to room temperature, obtain that titanium nitride/silicon nitride is compound to be received
Rice material；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 9g tripolycyanamide is dissolved in 45mL dehydrated alcohol, and adds
Enter the titanium nitride/silicon nitride composite nano materials that step (1) obtains, then the mixture obtained be placed at a temperature of 45 DEG C,
Lower being evaporated by dehydrated alcohol being stirred continuously, the product after being finally evaporated is roasting 4h in 500 DEG C of nitrogen atmospheres, obtains nitrogen
Change titanium/silicon nitride/carbonitride tri compound nano material.
Embodiment 4
The preparation method of a kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, comprises the steps:
(1) preparation of titanium nitride/silicon nitride composite nano materials: successively by 19g Titanium Citrate, the silicon of 26g under being stirred continuously
Colloidal sol is added sequentially in the polyvinylpyrrolidone of 2.8g, 0.007mol/L and the mixed solution of 78mL dehydrated alcohol/DMF,
And stir 6h hour at 36 DEG C, mixed precursor solution uniformly, then precursor solution is inserted and there is spinning head
Syringe in, carry out spinning, the condition of spinning is: sample rate is 0.6m1/h, and between plate, voltage is 1.6kv/cm, before obtaining
Drive body fiber；By precursor fibre in atmosphere 700 DEG C carry out heat treatment, the time is 4 hours, then naturally cools to room temperature,
Obtain amorphous ti silica composite nano fiber；Afterwards above-mentioned nanofiber is placed in tube furnace, in intensification forward direction stove with
The flow velocity of 120mL/min leads to high pure nitrogen, then in the case of this flow velocity leads to nitrogen, at the uniform velocity heats up, furnace temperature is raised to 1100
DEG C, keep this temperature 6 hours, then under logical condition of nitrogen gas, reduce the temperature to room temperature, obtain that titanium nitride/silicon nitride is compound to be received
Rice material；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 7g cyanamide is dissolved in 46mL dehydrated alcohol, and adds
The titanium nitride/silicon nitride composite nano materials that step (1) obtains, is then placed at a temperature of 50 DEG C by the mixture obtained,
Being stirred continuously and lower be evaporated by dehydrated alcohol, the product after being finally evaporated is roasting 4h in 500 DEG C of nitrogen atmospheres, obtains nitridation
Titanium/silicon nitride/carbonitride tri compound nano material.
Embodiment 5
The preparation method of a kind of threadiness titanium nitride/silicon nitride/carbonitride composite nano materials, comprises the steps:
(1) preparation of titanium nitride/silicon nitride composite nano materials: successively by 20g Titanium Citrate, the silicon of 27g under being stirred continuously
Colloidal sol is added sequentially in the polyvinylpyrrolidone of 3g, 0.008mol/L and the mixed solution of 80 mL dehydrated alcohol/DMF, and
Stir 7h hour at 37 DEG C, mixed precursor solution uniformly, then precursor solution is inserted and there is spinning head
In syringe, carrying out spinning, the condition of spinning is: sample rate is 1m1/h, and between plate, voltage is 1.2kv/cm, obtains presoma
Fiber；By precursor fibre in atmosphere 800 DEG C carry out heat treatment, the time is 4 hours, then naturally cools to room temperature, obtains
Amorphous ti silica composite nano fiber；Afterwards above-mentioned nanofiber is placed in tube furnace, with 130mL/ in intensification forward direction stove
The flow velocity of min leads to high pure nitrogen, then in the case of this flow velocity leads to nitrogen, at the uniform velocity heats up, and furnace temperature is raised to 1200 DEG C, keeps
This temperature 6 hours, then under logical condition of nitrogen gas, reduces the temperature to room temperature, obtains titanium nitride/silicon nitride composite nano materials；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 6g cyanamide is dissolved in 43mL dehydrated alcohol, and adds
The titanium nitride/silicon nitride composite nano materials that step (1) obtains, is then placed at a temperature of 52 DEG C by the mixture obtained,
Being stirred continuously and lower be evaporated by dehydrated alcohol, the product after being finally evaporated is roasting 5h in 500 DEG C of nitrogen atmospheres, obtains nitridation
Titanium/silicon nitride/carbonitride tri compound nano material.
Embodiment 6
Performance test to material prepared by embodiment 1-5, result is as follows:
| Specific surface area m2/g | Electrical conductivity S/cm | Vickers hardness Gpa | Bending strength Mpa | Fracture toughness Mpa m½ | |
| 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/carbonitride composite nano materials that prepared by the present invention has good combining
Close performance, be the most wide composite nano materials of a kind of application prospect.
Finally it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although
Being described in detail the present invention with reference to previous embodiment, for a person skilled in the art, it still can be right
Technical scheme described in foregoing embodiments is modified, or wherein portion of techniques feature is carried out equivalent.All
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included in the protection of the present invention
Within the scope of.
Claims (7)
1. the preparation method of fibrous titanium nitride/silicon nitride/carbonitride composite nano materials, it is characterised in that include as
Lower step:
(1) preparation of titanium nitride/silicon nitride composite nano materials: under being stirred continuously successively by 15～20g Titanium Citrates, 20～
The Ludox of 30g is added sequentially to polyvinylpyrrolidone and the 70～90 anhydrous second of mL of 2～3g, 0.005～0.008mol/L
In the mixed solution of alcohol/DMF, and at 30～40 DEG C, stir 4～8h hour, mixed precursor solution uniformly, then
Being inserted by precursor solution in the syringe with spinning head, carry out spinning, the condition of spinning is: sample rate is 0.3-1m1/
H, between plate, voltage is 1-2kv/cm, obtains precursor fibre；Again by precursor fibre in atmosphere 600-800 DEG C carry out at heat
Reason, the time is 3-5 hour, then naturally cools 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 with the flow velocity of 100～130mL/min, then at this flow velocity in intensification forward direction stove
In the case of logical nitrogen, at the uniform velocity heat up, furnace temperature is raised to 1100～1200 DEG C, keep this temperature 6～8 hours, finally at logical nitrogen
Under the conditions of gas, reduce the temperature to room temperature, obtain titanium nitride/silicon nitride composite nano materials；
(2) titanium nitride/silicon nitride/carbonitride composite nano materials: 6～10g carbon nitrogen sources are dissolved in 40～50mL dehydrated alcohol
In, and add the titanium nitride/silicon nitride composite nano materials that step (1) obtains, then the mixture obtained is placed in 40～60
At a temperature of DEG C, lower being evaporated by dehydrated alcohol being stirred continuously, the product after being finally evaporated is at 450～550 DEG C of nitrogen gas
Roasting 3～5h in atmosphere, obtain titanium nitride/silicon nitride/carbonitride tri compound nano material.
Composite nano materials the most according to claim 1, it is characterised in that described composite nano materials is threadiness knot
Structure, a diameter of tens nanometers of fiber, a length of 1-2 um, pore volume is 0.33～0.44cm3/ g, specific surface area is
163.2～183.0m2/g。
Composite nano materials the most according to claim 1, it is characterised in that the mechanical property of described tri compound nano material
Can be: vickers hardness hv 20.1-22.5Gpa, bending strength 953-980Mpa, fracture toughness 9.6-10.5Mpa m½, the closeest
Degree 98.9%.
Composite nano materials the most according to claim 1, it is characterised in that described carbon nitrogen source is tripolycyanamide or single cyanogen
Amine.
Composite nano materials the most according to claim 1, it is characterised in that precursor solution is inserted in syringe, note
Emitter leading portion connection diameter is the spinning head of 0.5-1.6mm, and syringe is placed in medical micro-injection pump.
Composite nano materials the most according to claim 1, it is characterised in that anhydrous in the mixed solution of dehydrated alcohol/DMF
Ethanol is 2:1 with the volume ratio of DMF.
7. composite nano materials described in an any one of claim 1-6 is at fuel cell, photosensitized solar cell and super electricity
Application in container.
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