CN104387089A - Synthetic method for nanotube polymer function material - Google Patents
Synthetic method for nanotube polymer function material Download PDFInfo
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- CN104387089A CN104387089A CN201410562446.3A CN201410562446A CN104387089A CN 104387089 A CN104387089 A CN 104387089A CN 201410562446 A CN201410562446 A CN 201410562446A CN 104387089 A CN104387089 A CN 104387089A
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Abstract
The invention relates to a synthetic method for a nanotube polymer function material. The synthetic method specifically comprises the steps of (1) putting high-purity nanotubes as precursor raw materials in a mould under the protective atmosphere, pressing the nanotubes to form prepressed blanks by using a tablet press, and then packing the prepressed blanks in a high-pressure mould; (2) putting the high-pressure mould on a high-pressure device, and preserving the temperature for 5-300 minutes under the pressure of 1-50 GPa within the temperature range of 20-2500 DEG C; (3) cooling down at 1-100 DEG C/min and releasing the pressure at 0.1-100 MPa/min, taking out the products and performing the surface treatment to obtain the nanotube polymer materials. Compared with the prior art, the synthetic method for the nanotube polymer function material has the advantages that the process is simple, the repeatability is strong, the industrial production and application are performable, and the realistic value and research significance are important.
Description
Technical field
The invention belongs to materialogy and physics crossing domain, be specifically related to a kind of synthetic method of nanotube polymer functional materials.
Background technology
Since Japanese Scientists Iijima was in Late Cambrian carbon nanotube (CNTs) in 1991, this quasi-one-dimensional material demonstrates important theoretical investigation and actual application value with the electricity of its uniqueness, chemistry and mechanical property, thus caused its research boom facilitate develop rapidly (the Michael F.L.De Volder et al.Science of nanosecond science and technology widely at world wide, 2013,339,535-539).Research shows, carbon nanotube intensity is in the axial direction about 100 times of steel, but being the structure of similar graphite linings and easily sliding of being formed radially due to it, cause intensity radially not high, significantly limit the application of CNTs as ultrastrength material.For this shortcoming, researchist adopts high temperature and high pressure method to be polymerized carbon nano-tube bundle, and in temperature lower than 1500 DEG C, pressure is less than 20GPa just to make in carbon nanotube carbon atom by full sp
2hybrid form is partly or entirely transformed into sp
3hybrid form, forms the three dimensional carbon nanotubes polymkeric substance of known carbon phase or novelty (as Popov et al.Phys.Rev.B 2002,65,33408; Khabashesku et al.Phys.Chem.B 2002,106,11155; Kumar et al.Diam.Relat.Mater.2007,16,1250; Wang et al.PNAS.2004,101,13699).In addition, the carbon nanotube polymer of experiment synthesis also has some unusual character, as high consistency and elasticity modulus, and peculiar conductivity etc.
High temperature and high pressure method is a kind of method of effective synthesizing new carbon nanotube polymer.At present, many structural similitudies and having successfully are prepared compared with the nano-tube material of Large Diameter Pipeline size range, as unitary Si, Ge nanotube, and polynary SiC, BN, ZnO, MoS
2, CdS, CdTe, SiO
2, TiO
2with BCN nanotube etc.And there is great difference in their physics, chemical property and corresponding block materials.Although do not launch the research widely of these nanotube polymers, high temperature and high pressure method is adopted to prepare the method with the material of the performances such as special power, heat, electricity, light, magnetic that nanotube polymer is current beyond doubt and a kind of practicable synthesis in future is new.Gained nanotube polymer can be used as the materials such as potential novel photoelectric, thermoelectricity, magnetoelectricity, has broad application prospects.
The present invention is intended to by two important thermodynamical coordinates in regulation and control synthesis technique, and temperature and pressure, explores the top condition of synthesis of nano pipe polymkeric substance.Current industrial press equipment can reach the condition of synthesis of nano pipe polymer materials, is expected to realize suitability for industrialized production, and has important references value to the synthesis of follow-up new function material and application.So far, there is not yet the Patents report of synthesis of nano pipe Functionally structure.
Summary of the invention
Object of the present invention is exactly the synthetic method providing simple, the effective nanotube polymer of a kind of method in order to overcome weak point that above-mentioned existing synthetic method exists.
The object of the invention can be achieved through the following technical solutions: a kind of synthetic method of nanotube polymer functional materials, and it is characterized in that, the method specifically comprises the following steps:
(1) with high-purity nm pipe for precursor raw material, it is loaded in mould under protective gas atmosphere, and adopts tabletting machine to be pressed into preformed compact, subsequently preformed compact is encapsulated in Belt-type tools;
(2) being placed on high-tension apparatus by Belt-type tools, is 1 ~ 50GPa at pressure, and temperature is under 20 ~ 2500 DEG C of conditions, insulation 5 ~ 300min;
(3) cool release, rate of temperature fall is 1 ~ 100 DEG C/min, and decompression rate is 0.1 ~ 100MPa/min, is taken out by product and carries out surface treatment, obtains nanotube polymer material.
Nanotube described in step (1) can be powder, particle or block; The material of nanotube is the purity > 95.0% of unitary nano-tube material or polynary nanometer tube material, nanotube, and nanotube caliber is
average particle size particle size is 400 ~ 100 orders.
Described unitary nano-tube material comprises Si or Ge nanotube, and described polynary nanometer tube material comprises SiC, BN, ZnO, MoS
2, CdS, CdTe, SiO
2, TiO
2, BCN or other known nanotube, the purity > 99.9% of nanotube, preferred > 99.99%.
Protection gas described in step (1) is vacuum or rare gas element, and air pressure is less than 0.1MPa, and temperature is 20 ~ 40 DEG C, can reduce in operation because of impact that precursor material water suction, oxidation etc. bring as far as possible.
Be provided with one deck protective sleeve liner in mould described in step (1), ensure that the powder of nanotube or particle can be pressed into bulk, tabletting machine pressure is 5 ~ 1000MPa.
The module that step (1) or the Belt-type tools described in step (2) are made up of transmission medium, heating member, muff and protective sleeve.
The material of described transmission medium is pyrophyllite or MgO, and the material of described heating member is graphite, Re or LaCrO
3, the material of described muff is ZrO
2, the material of described protective sleeve is BN, Ta or graphite.
The character of nano-tube material and the requirement of annealing process are depended in the selection of the rate of temperature fall described in step (3), decompression rate.
Sample preparation described in step (3) can comprise the various physics of employing, chemical process is removed the dirt of sample surfaces or carries out finishing, and nanotube polymer can grind to form powder after surface treatment, depends on service requirements.
The technique of synthesis of nano pipe Functionally structure of the present invention has the following advantages:
(1) utilization of high pressure tactics, can obtain the material being difficult at ambient pressure synthesize;
(2) preformed compact is suppressed in protective gas atmosphere, and impurity can be avoided to introduce;
(3) synthesis technologic parameter can accuracy controlling, repeatable strong;
(4) industrial press can be less than 2500 DEG C by satisfied temperature, and pressure, lower than the condition of 10GPa, is expected to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of unitary nanotube;
Fig. 2 is a kind of structural representation of unitary nanotube polymer;
Fig. 3 is a kind of structural representation of bielement nano pipe;
Fig. 4 is a kind of structural representation of bielement nano pipe polymkeric substance.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, and the present invention will provide following examples, but should point out, enforcement of the present invention is not limited to following embodiment.
Material
High-purity nm pipe raw material used in following embodiment is all purchased from Alfa Aesar company.
Embodiment 1:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% Si nanotube powder (structural representation is see Fig. 1) be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into by pyrophyllite, graphite, ZrO
2coordinate in the Belt-type tools of composition with BN crucible, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be first forced into 1GPa, then heat to 1000 DEG C, temperature of reaction, generally lower than the fusing point of material, is incubated 60min.Next be cooled to normal temperature with the speed of 10 DEG C/min, then unload with the speed of 5MPa/min and be depressed into normal pressure.Sample is taken out and the dirt on pickling, dry removing surface, obtain Si nanotube polymer material (structural representation is see Fig. 2).
Embodiment 2:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% Si nanotube powder be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into and coordinate by pyrophyllite, graphite and BN crucible the Belt-type tools formed, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be first forced into 4GPa, then heat to 600 DEG C, temperature of reaction, generally lower than the fusing point of material, is incubated 30min.Next be cooled to normal temperature with the speed of 10 DEG C/min, then unload with the speed of 5MPa/min and be depressed into normal pressure.Sample is taken out also pickling, dry removing surface contaminants, obtain Si nanotube polymer material.
Embodiment 3:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% Si nanotube powder be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into and coordinate by pyrophyllite and BN crucible the Belt-type tools formed, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be at room temperature forced into 6GPa, the time is 100min.Next unload with the speed of 5MPa/min and be depressed into normal pressure.Sample is taken out also pickling, dry removing surface contaminants, obtain Si nanotube polymer material.
Embodiment 4:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% SiC nanotube powder (structural representation is see Fig. 3) be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into by pyrophyllite, graphite, ZrO
2coordinate in the Belt-type tools of composition with BN crucible, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be first forced into 3GPa, then heat to 1500 DEG C, temperature of reaction, generally lower than the fusing point of material, is incubated 100min.Next be cooled to normal temperature with the speed of 50 DEG C/min, then unload with the speed of 10MPa/min and be depressed into normal pressure.Sample is taken out also pickling, dry removing surface contaminants, obtain SiC nanotube polymer material (structural representation is see Fig. 4).
Embodiment 5:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% SiC nanotube powder be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into and coordinate by pyrophyllite and BN crucible the Belt-type tools formed, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be at room temperature forced into 6GPa, time 150min.Next unload with the speed of 10MPa/min and be depressed into normal pressure.Sample is taken out also pickling, dry removing surface contaminants, obtain SiC nanotube polymer material.
Embodiment 6:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% SiC nanotube powder be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into by pyrophyllite, Re, LaCrO
3, MgO, ZrO
2coordinate in the Belt-type tools of composition with BN crucible, more than operate in glove box and carry out.Belt-type tools is placed in octahedral top swaging machine and carries out high-pressure synthesis, be first forced into 20GPa, then heat to 1000 DEG C, all the other describe identical with embodiment 4.
Embodiment 7:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 98.0% ZnO nanotube/powder be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into by pyrophyllite, graphite, ZrO
2coordinate in the Belt-type tools of composition with BN crucible, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be first forced into 3GPa, then heat to 1200 DEG C, all the other describe identical with embodiment 4.
Embodiment 8:
A synthetic method for nanotube polymer functional materials, the method detailed step is as follows:
By purity be 99.9% BCN nanotube powder be loaded in mould under argon atmosphere protection, air pressure is less than 0.1MPa, and temperature range is 20 ~ 40 DEG C, and adopts tabletting machine to be pressed into preformed compact being less than under 1000MPa.Subsequently preformed compact is put into by pyrophyllite, Re, LaCrO
3, MgO, ZrO
2coordinate in the Belt-type tools of composition with BN crucible, more than operate in glove box and carry out.Belt-type tools is placed in cubic apparatus swaging machine and carries out high-pressure synthesis, be first forced into 50GPa, then heat to 2500 DEG C, insulation 5min, is next cooled to normal temperature with the speed of 100 DEG C/min, then unloads with the speed of 100MPa/min and be depressed into normal pressure.Sample is taken out and the dirt on pickling, dry removing surface, obtain BCN nanotube polymer material.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.Such as, the present invention obviously can adopt the tabletting machine of various model, and can produce the press apparatus of pressure.Various heating method can be adopted to heat to sample.
In addition, the scope of each parameter that the present invention mentions comprises the arbitrary combination of any upper and lower bound, any number scope that the occurrence also comprising this parameter in each specific embodiment is formed as the upper limit or lower values; All these scopes all contain within the scope of the invention, just for saving space, do not enumerate in the description.Any value of two end points is comprised therebetween for representing that the symbol " ~ " of numerical range represents in this specification sheets.
In addition, each preferred aspect of the present invention is separately independently.Such as, the preferable range of a parameter can combine with the preferable range of other parameter, and all these technical schemes combined, equally in protection scope of the present invention, just for saving space, do not enumerate in the description.The technical scheme that can not combine because of these or numerical range are not illustrated book and clearly mention and be regarded as and exceed outside the scope of the invention.
Claims (9)
1. a synthetic method for nanotube polymer functional materials, is characterized in that, the method specifically comprises the following steps:
(1) with high-purity nm pipe for precursor raw material, it is loaded in mould under protective gas atmosphere, and adopts tabletting machine to be pressed into preformed compact, subsequently preformed compact is encapsulated in Belt-type tools;
(2) being placed on high-tension apparatus by Belt-type tools, is 1 ~ 50GPa at pressure, and temperature is under 20 ~ 2500 DEG C of conditions, insulation 5 ~ 300min;
(3) cool release, rate of temperature fall is 1 ~ 100 DEG C/min, and decompression rate is 0.1 ~ 100MPa/min, is taken out by product and carries out surface treatment, obtains nanotube polymer material.
2. the synthetic method of nanotube polymer functional materials according to claim 1, is characterized in that, the nanotube described in step (1) can be powder, particle or block; The material of nanotube is the purity > 95.0% of unitary nano-tube material or polynary nanometer tube material, nanotube, and nanotube caliber is
average particle size particle size is 400 ~ 100 orders.
3. the synthetic method of nanotube polymer functional materials according to claim 2, is characterized in that, described unitary nano-tube material comprises Si or Ge nanotube, and described polynary nanometer tube material comprises SiC, BN, ZnO, MoS
2, CdS, CdTe, SiO
2, TiO
2, BCN or other known nanotube, the purity > 99.9% of nanotube, preferred > 99.99%.
4. the synthetic method of nanotube polymer functional materials according to claim 1; it is characterized in that; protection gas described in step (1) is vacuum or rare gas element; air pressure is less than 0.1MPa; temperature is 20 ~ 40 DEG C, can reduce in operation because of impact that precursor material water suction, oxidation etc. bring as far as possible.
5. the synthetic method of nanotube polymer functional materials according to claim 1; it is characterized in that; be provided with one deck protective sleeve liner in mould described in step (1), ensure that the powder of nanotube or particle can be pressed into bulk, tabletting machine pressure is 5 ~ 1000MPa.
6. the synthetic method of nanotube polymer functional materials according to claim 1; it is characterized in that, the module that step (1) or the Belt-type tools described in step (2) are made up of transmission medium, heating member, muff and protective sleeve.
7. the synthetic method of nanotube polymer functional materials according to claim 6, is characterized in that, the material of described transmission medium is pyrophyllite or MgO, and the material of described heating member is graphite, Re or LaCrO
3, the material of described muff is ZrO
2, the material of described protective sleeve is BN, Ta or graphite.
8. the synthetic method of nanotube polymer functional materials according to claim 1, is characterized in that, the character of nano-tube material and the requirement of annealing process are depended in the selection of the rate of temperature fall described in step (3), decompression rate.
9. the synthetic method of nanotube polymer functional materials according to claim 1, it is characterized in that, sample preparation described in step (3) comprises the various physics of employing, chemical process is removed the dirt of sample surfaces or carries out finishing, nanotube polymer can grind to form powder after surface treatment, depends on service requirements.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574665A (en) * | 2018-12-05 | 2019-04-05 | 青海大学 | A kind of synthetic method of buik silicon functional material |
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2014
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Non-Patent Citations (2)
| Title |
|---|
| VALERY N. KHABASHESKU ET AL: "Polymerization of Single-Wall Carbon Nanotubes under High Pressures and High Temperatures", 《J. PHYS. CHEM. B 》 * |
| ZHONGWU WANG ET AL: "A quenchable superhard carbon phase synthesized by cold compression of carbon nanotubes", 《PNAS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574665A (en) * | 2018-12-05 | 2019-04-05 | 青海大学 | A kind of synthetic method of buik silicon functional material |
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