CN1750994A - Nanocomposites: products, process for obtaining them and uses thereof - Google Patents
Nanocomposites: products, process for obtaining them and uses thereof Download PDFInfo
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Abstract
The present invention is related to nanocomposites comprising polymers, carbon nanotubes and layered silicate nanoparticles. The present invention also concerns methods for obtaining said nanocomposites as well as their uses.
Description
Invention field
The present invention relates to comprise the field of compound material of polymkeric substance and carbon nanotube.
The state of the art
Carbon nanotube be at first by Iijima observed in 1991 (S.Iijima, Nature, 354 (1991), 56-58).This pipe is made up of the carbon atom of arranging with sexangle and pentagon, and pentagon is enriched in the zone such as pipe end.Usually, carbon nanotube is made up of single-walled pipe (hereinafter being referred to as SWNT) and multi-walled pipes (hereinafter being referred to as MWNT).
Carbon nanotube has snappiness, anti-applied stress.They are in various field, such as all having the potential industrial use in field emission apparatus, electricity and thermal conductor, storage hydrogen body and the molecular sieve.
Carbon nanotube can, for example make by arc-over, laser ablation or the catalytic decomposition of hydrocarbon.
Comprise carbon nanotube some polymer matrix composite preparation referring to document (people such as C.Pirlot, Adv.Eng.Mater., 4, N ° 3, (2002), 109-114; People such as B.McCarthy, J.Phys.Chem.B, 106 (2002), 2210-2216; People such as V.K.Gupta, World Patent Information, 22 (2000), 185-189).However, in industrial discovery, it is very difficult obtaining the homogeneous dispersion of nanotube in polymer matrix, and this only causes some interesting performance to be transferred in the matrix material by carbon nanotube.
Goal of the invention
The present invention aims to provide the nano composite material that comprises polymkeric substance and carbon nanotube, and there is not the defective of prior art nano composite material in this nano composite material.
Or rather, the present invention aims to provide has the enhanced physical performance with respect to the matrix material of prior art, i.e. the nano composite material of enhanced machinery and electrical property, this industrial may be interesting.
Another object of the present invention provide industrial can be relatively easily and the nano composite material made of cost relatively cheaply.
Summary of the invention
The present invention relates to comprise polymkeric substance, carbon nanotube and phyllosilicate nano particle nano composite material as component.
Preferably, described nano composite material component homodisperse.
Preferably, polymkeric substance is selected from thermoplastic polymer, polyolefine, ethylene-based polymer, acrylonitrile polymer, polyacrylic ester, elastomerics, fluoropolymer, thermoplastic condensed polymer (polycondensate), rigid plastics (duroplastic) polycondensate, silicon resin, thermoplastic elastomer, multipolymer and ter-polymers, graftomer and composition thereof.
Preferably, carbon nanotube is selected from SWNT and MWNT, and described carbon nanotube is pure, and is partial-purified, thick or functionalized carbon nanotube.
Preferably, the phyllosilicate nano particle is organically-modified phyllosilicate nano particle.
Preferably, the phyllosilicate nano particle is the organically-modified layered silicate that comes from other insertion of chemical level (intercalated) of 2:1 phyllosilicate (phyllosilicate) and montmorillonite.
Advantageously, the total content scope of layered silicate and carbon nanotube is 0.01-50 weight %, preferred 0.5-25 weight %, most preferably 1-10 weight %.
Advantageously, carbon nanotube and phyllosilicate nano particulate weight ratio scope are 0.01-100, preferred 0.1-10.
Preferably, nano composite material of the present invention also comprises at least a little weighting agent, and preferably its content range is 1-70 weight %.
The present invention also relates to the purposes of described nano composite material.
Particularly, the present invention relates to different purposes according to nano composite material of the present invention:
The purposes of ■ in the flameproof protection structure,
■ is as the purposes of fire retardant,
■ is as the purposes of antistatic material,
■ is as the purposes of luminescent material,
■ is as the purposes of lead,
■ is as the purposes of wire protective device shell,
■ is as the purposes of the anticracking agent in the surface protection coating,
■ is as the purposes of the anticracking agent in the reinforcement material,
■ is as the purposes of surface protection coating,
■ is as the purposes of reinforcement material.
Another object of the present invention relates to the purposes of nano composite material of the present invention as fire retardant.
The invention still further relates to the method that obtains nano composite material of the present invention, described method comprises provides different components, be polymkeric substance, carbon nanotube, phyllosilicate nano particle, provide the step of little weighting agent in case of necessity, with the step of described different component being mixed with the acquisition homogeneous dispersion under appropriate condition.
Preferably, in described method, provide the step of carbon nanotube to be included in the step that generates described carbon nanotube on the M/MgO catalyzer, wherein M is selected from Co, Fe, Ni, Mo or its mixture, and M accounts for the 0.1-50 weight % of catalyzer, and MgO is prepared on the spot by MAGNESIUM METAL.
Preferably, in described method, provide the step of carbon nanotube also to comprise, before dissolving spent catalyst (spent catalyst), while nanotube are dispersed on the catalyzer well, by under 250-500 ℃, in the oxygen of pure or dilution, to thick given for some time of nanotube oxidation, with the step of the thick carbon nanotube that generated in purifying such as the claim 14.
In a preferred embodiment of described method, provide the step of carbon nanotube also to comprise, comprise the nanotube/water " wet cake " of preferred 80-95 weight % water and the carbon nanotube that generates is carried out dry by lyophilize to obtain the step of very thin powder.
In another preferred embodiment of described method, provide the step of carbon nanotube also to comprise, by component distillation comprise the nanotube/water " wet cake " of preferred 80-95 weight % water and the dry carbon nanotube that generates to obtain the step of very thin powder, wherein benzene, toluene or dimethylbenzene are used to form azeotrope.
Definition
What should be noted that is, in this manual, wording " ... based nano composite material " and " contains ... nano composite material " be of equal value.
Term " weighting agent " and " little weighting agent " are meant the composition of any other except that polymkeric substance in the nano composite material.
" dispersion " means component, i.e. the dispersion of carbon nanotube in polymer matrix.
The accompanying drawing summary
Fig. 1 a and 1b provide, and comprise EVA (EVA=ethylene-vinyl acetate copolymer; Escorene UL 00328) as polymkeric substance and the pure MWNT of 4.8 weight % (Fig. 1 a: sample 2) or organic clay (Fig. 1 b: nano composite material sample 6) is at 35kW/m
2Carry out the cone calorimetry analysis image of resistates afterwards down.Fig. 1 c: sample 7 also represents to comprise simultaneously the cone calorimetry analytical results of resistates of the EVA based nano composite material of pure MWNT of 2.4 weight % and 2.4 weight % organic claies.
Detailed Description Of The Invention
I. raw material explanation
The I.A.-polymkeric substance
Operable polymkeric substance can be selected from thermoplastic polymer (as polystyrene etc.), polyolefine (as polyethylene, polypropylene etc.), ethylene-based polymer (as PVC or PVDF), acrylonitrile polymer, polyacrylic ester, elastomerics, fluoropolymer, thermoplastic condensed polymer (as PA, PC, PETP), rigid plastics polycondensate, silicon resin, thermoplastic elastomer, multipolymer (as EVA), ter-polymers, graftomer with and blend.
The general introduction of suitable polymkeric substance can be referring to " the DieKunststoffe und ihre Eigenschaften " of Hans Dominghaus, 2 Auflage, and VDI-Verlag is from VII to XI.
The I.B.-nanotube
Nanotube is SWNT, MWNT or its mixture.Nanotube is pure, partial-purified, thick or functionalized.Thick nanotube comprises spent catalyst and other forms of carbon, and they are the by products during nanotube synthesizes.By product is a decolorizing carbon, RESEARCH OF PYROCARBON, and carbon nano-particle, carbon (carbon onion), soccerballene wraps in the metal nanoparticle in the carbon, carbon fiber.Partial-purified nanotube comprises the by product that can not eliminate in purge process.Spent catalyst is an oxide compound, mixed oxide, and aluminosilicate, zeolite, oxycarbide mixes oxycarbide, carbonate, metal hydroxides, metal nanoparticle etc.
Thick and pure nanotube sample is used for preparing nano composite material.Thick MWNT is at CATALYST Co-Fe/Al (OH) by acetylene
3On, carry out under 700 ℃ that catalytic decomposition forms, thick SWNT be by methane under 950 ℃, at Co/MgO catalyzer or M/MgO
*Catalyzer (M=Co, Fe, Ni, Mo or its mixture; The 0.1-50 weight % of M=catalyzer) carries out on that catalytic decomposition forms.The Co/MgO catalyzer is to prepare by the alcoholic solution dipping commodity MgO with cobalt salt, and M/MgO
*Catalyzer then is to prepare according to following method: at first, 10 gram MAGNESIUM METAL are imported in the 200 milliliters of alcohol (that is, MeOH, EtOH etc.) that are included in 1 liter of flask, wherein flask equipped has reflux exchanger and mechanical stirrer.After about 5 minutes, following reaction takes place with magnesium in the alcohol beginning:
If the alcohol boiling too, control speed of reaction by the cooling flask.Secondly, by supersound process metal-salt (for example 13.727 is restrained Fe (NO
3)
39H
2O) be dissolved in 50 milliliters of alcohol, under vigorous stirring, join in the alcoholic solution of magnesium then.The very fast generation gelling of solution homogenizes gel but prolong to stir.Afterwards, under agitation 300 ml waters are joined in the gel, form incomplete white gels as described below:
Whole alcohol (250 milliliters) is distilled by component distillation, pack 50 ml waters into to keep the constant volume of gel by per 50 milliliters of overhead products again.At last,, make gel standing over night at room temperature in order to carry out slaking, and with it under super critical condition or preferably by the freeze-drying drying.Dried residue further is heated to 370 ℃ by the speed with 3 ℃/minute under air-flow from room temperature, and keeps 2 hours down and dewater at 370 ℃, afterwards with 6 ℃/minute speed cool to room temperature.The dehydration of back is carried out as described below:
Collect the powder after dewatering, be referred to as M/MgO
*Catalyzer, and find, it prepares SWNT for the catalytic decomposition by methane in the presence of hydrogen and has very high activity.
When carrier is dissolved in the ebullient concentrated sodium hydroxide, catalyst dissolution in concentrated hydrochloric acid after, obtain pure MWNT.
Catalyzer and carrier are dissolved in the concentrated hydrochloric acid, and subsequent filtration also washs pH value=5-7, obtains comprising the nanotube/water " wet cake " of about 80-95 weight % water, and it is obtained pure SWNT 120 ℃ of following dried overnight.In order to reduce the metal content among the SWNT behind the purifying, we find, before catalyst-solvent and carrier, with thick SWNT under 250-500 ℃ in air the one given period of oxidation (preferably 300 ℃ of following oxidations 1 hour) be very effective because nanotube can be dispersed on the spent catalyst well.For pure SWNT is dispersed in the polymer matrix better, find that also it is more more convenient 120 ℃ of following dried overnight than it that nanotube/water " wet cake " is carried out lyophilize.In fact, can obtain stone SWNT " stone " 120 ℃ of dryings, and cryodesiccated SWNT is very thin powder.
The catalyzer and the vector contg of nanotube sample are shown in table 1.
Table 1: the characteristic of nanotube sample and catalyzer thereof and vector contg
| Sample (a) | Nanotube | Catalyzer | Carrier | |||
| Length (μ m) | Diameter (nm) | Co (wt.％) | Fe (wt.％) | Al 2O 3 (wt.％) | MgO (wt.％) | |
| Thick MWNT | ca.50 | 5-15 | 0.3 | 0.3 | 19 | - |
| Pure MWNT | ca.50 | 5-15 | 0.2 | 0.3 | 0.2 | - |
| Thick SWNT-1 | ca.10 | 1-2 | 2.5 | - | - | 92.5 |
| Pure SWNT-1 | ca.10 | 1-2 | 15 | - | - | 0 |
| Oxidation, purifying and cryodesiccated SWNT-1 | ca.10 | 1-2 | 0.3 | - | - | 0 |
| Thick SWNT-2 | ca.10 | 1-2 | 12 | - | - | 79 |
| Pure SWNT-2 | ca.10 | 1-2 | 14 | - | - | 0 |
| Oxidation, purifying and cryodesiccated SWNT-2 | ca.10 | 1-2 | 0.5 | - | - | 0 |
| Thick SWNT-3 | ca.10 | 1-2 | - | 12 | - | 79 |
| Pure SWNT-3 | ca.10 | 1-2 | - | 15.5 | - | 0 |
| Oxidation, purifying and cryodesiccated SWNT-3 | ca.10 | 1-2 | - | 0.8 | - | 0 |
(a): SWNT-1 generates on Co/MgO; SWNT-2 is at Co/MgO
*Last generation; SWNT-3 is at Fe/MgO
*Last generation.
I.C.-phyllosilicate nano particle
The silicate nano particle is from 2:1 phyllosilicate or montmorillonite, such as the organically-modified layered silicate of other insertions of chemical level such as polynite, hectorite, saponite.
Polynite is the most normally used layered silicate (clay).It is crystalloid 2:1 layered clay mineral matter, and the alumina octahedral sheet of central authorities is clipped between two silicon tetrahedrallayer.When these nanoparticulate dispersed are in polymkeric substance, they or insert or leafing by " macromole " form.Therefore, insert structure shows alternative layered silicate and polymer chain regularly, and in contrast, in the middle of the leafing structure, independently clay seam delaminates and is dispersed in the polymer matrix.
Usually, observed performance is best concerning the leafing nano composite material.But, in identical materials, can and deposit this two kinds of extreme situations.
The ion exchange reaction of the silicate interlayer sodium cation by organic clay hereinafter referred to as and alkyl ammonium cation etc. can promote the consistency (G.Beyer, Polymer News, November calendar year 2001) of polymkeric substance-silicate.
The organic clay that is used to study, Nanofil
The 15th, provide by S ü d-Chemie (Germany).It is a kind of sodium cation by distearyl Dimethyl Ammonium cationic exchange na montmorillonite.This organic clay comprises the organic cation of about 30 weight % in its structure, it is characterized in that the interlayer distance is 2.8 nanometers.
II. comprise the preparation of the matrix material of carbon nanotube
When preparation is the nano composite material of polymer based with carbon nanotube and silicate nano particle, preferably use a kind of in the different methods hereinafter described.These methods can be called " mechanical process " and " solution method " according to being to disperse each component or disperse each component to be divided into two types by mechanical means in solution.
The II.A.-mechanical process
Extrusion molding:
In the method, forcing machine is used for molten polymer and carbon nanotube and organic clay are mixed.Organic clay preferably mixes or and mixed with polymers before extruding or with carbon nanotube.
Polymkeric substance, carbon nanotube and organic clay also can mix before extruding together or not together.
Form, length and the rotating speed of regulating extruder screw obtain suitable mixing time.Blended efficient depends on screw rod parameter (type, length-to-diameter ratio and rotating speed), and the extrusion temperature of adjusting polymer viscosity.According to the nano composite material of hope, temperature or homogeneous, perhaps change along screw rod.
Reactive extrusion molding:
Extrude parameter with " extrusion molding ", difference is the chemical reaction outside the amount in the extrusion step process (as crosslinked etc.).
Interrupter method:
In the method, molten polymer and carbon nanotube and organic clay mix in reactor (internal mixer or roller mill) under given temperature or temperature cycle.Nano composite material component or importing or importing together one by one.Chemical reaction also can carry out between component.
It is the internal mixer preparation of Brabender that the sample 1-12b of table 2 is to use model, and described internal mixer has one 72 milliliters the mixing section that wherein is equipped with the roller sheet.The rotating speed that uses is 45 or 120rpm (table 2).The mixing time of using is 10 minutes, and mixing temperature is 130 or 140 ℃ (table 2).In preferred embodiments, polymer EVA (50g) is imported in the mixing section of 125 ℃ of following preheatings, when polymer melt, adds weighting agent, mixes and delays 10 minutes again.Afterwards, open mixing section, reclaim nano composite material.
The II.B.-solution method
Solution method a:
In the method, the nano composite material component under suitable temperature by dispersed with stirring in solvent.Dispersion depends on the mixing order of various nano composite material compositions.Stirring produces by mechanical means or is formed by ultrasonic wave.Afterwards, perhaps by filtering or desolvating by under suitable temperature, evaporating to remove.They are also can be before mixing independent or non-ly be dispersed in the solvent independently.
Preferred solvent is to be characterised in that solubility parameter approaches those solvents of the polymer matrix solubility parameter of studying.Solvent mixture also is effective.
Tensio-active agent, tensio-active agent also can join in the nano composite material composition and be used for making dispersion to be enhanced as known in the art.Non-solvent (being solubility parameter those solvents away from research polymer matrix solubility parameter) also can join in the nano composite material component disperser before filtering.
Solution method b:
In the method, carbon nanotube and polymkeric substance be as in " solution method a ", under suitable temperature by dispersed with stirring in solvent.Afterwards, perhaps by filtering or desolvating by under suitable temperature, evaporating to remove.Organic clay and extra nano composite material component import by a kind of " mechanical process ".
Solution method c:
In the method, organic clay and polymkeric substance be as in " solution method a ", under suitable temperature by dispersed with stirring in solvent.Afterwards, perhaps by filtering or desolvating by under suitable temperature, evaporating to remove.Carbon nanotube and extra nano composite material component import by a kind of " mechanical process ".
Solution method d:
In the method, use the polymer precursor replace polymeric.Then, as at " solution method a ", under suitable temperature, the nano composite material component is dispersed in the solvent by stirring.After this, after the nano composite material component reaches sufficient dispersion, carry out polymerization.By filtering or desolvating by under suitable temperature, evaporating to remove.
Solution method e:
In the method, as in " solution method a ", with carbon nanotube under suitable temperature by dispersed with stirring at solvent, still, use the polymer precursor replace polymeric.Afterwards, after reaching sufficient dispersion, carry out polymerization.By filtering or desolvating by under suitable temperature, evaporating to remove.Organic clay and extra nano composite material component import by a kind of " mechanical process ".
Solution method f:
In the method, as in " solution method a ", with organic clay under suitable temperature by dispersed with stirring at solvent, still, use the polymer precursor replace polymeric.Afterwards, after reaching sufficient dispersion, carry out polymerization.By filtering or desolvating by under suitable temperature, evaporating to remove.Carbon nanotube and extra nano composite material component import by a kind of " mechanical process ".
III. the mensuration of composite property
III.A-transmission electron microscope (TEM) is analyzed
Study the dispersion of nanotube in polymer matrix with Philips Tecna ǐ T10 by transmission electron microscopy spectrogram (TEM).In order to analyze, composite sample is cut into extremely thin sheet (about 80nm) with ultramicrotome.Then, section is left on the common transmission electron microscope screen.
All there be the dispersion (table 2 and 3 of nanotube in polymer matrix relatively uniformly in all samples; Disperse to reduce order: +++＞++＞+＞-＞--＞---).However, when using MWNT, add organic clay and the weight % that uses thick nanotube and increase nanotube will cause forming more uniform dispersion.When using SWNT, use " oxidation, purifying and cryodesiccated " sample can obtain best dispersion (table 3).Add organic clay and also help the dispersion of SWNT in polymer matrix.
III.B.-TGA analyzes
Carrying out TGA with 20K/ minute speed on polymer EVA (Escorene UL 00328) and EVA based nano composite material in air analyzes.The result is summarized in table 2.
As can be seen from Table 2, for the EVA based nano composite material, its T
MaxThan polymer EVA height.According to G.Beyer at Polymer News, described in November calendar year 2001, T
MaxBeing second top temperature under the oxidizing condition, therefore is the main degradation peak of EVA degraded.
Relate to the TGA result of the nano composite material that comprises pure MWNT of 2.4 weight % (sample 1) or organic clay (sample 5) from table 2, the aerial heat stabilization of polymkeric substance weighting agent is as follows: organic clay＞pure MWNT.
Relate to the TGA result of the nano composite material that comprises the pure MWNT of 4.8 weight % (sample 2), thick MWNT (sample 8a) or organic clay (sample 6) from table 2, the aerial heat stabilization of polymkeric substance weighting agent is as follows: thick MWNT＞organic clay＞pure MWNT.
Organic clay content is increased to 4.8 weight % from 2.4 weight % and causes T
MaxReduce by (table 2).
Different with the effect that increases organic clay content, the content that increases pure MWNT causes T
MaxVery little increase (table 2) is arranged.
However, when using the thick MWNT (sample 8a) of 5 weight %, observe aerial maximum heat stabilization.Surprisingly, thermally-stabilised for polymkeric substance, thick MWNT is than the more effective weighting agent of pure MWNT.This improvement may be that to have MWNT, support of the catalyst and catalyzer by the companion caused.
From comprising pure MWNT of 2.4 weight % and 2.4 weight % organic clay (samples 7; The TGA analytical results of nano composite material table 2) is by T
MaxClearly as seen, follow the collaborative improved action that uses pure MWNT and organic clay can not cause producing thermally-stabilised aspect as the polymkeric substance weighting agent simultaneously.
The III.C.-cone calorimetry is analyzed
G.Beyer reports in the Polymer in November calendar year 2001 News from engineering viewpoint, importantly know in burning to prevent which type of danger, only in this way could propose to be used for to measure and improved strategy.
At NIST (National Institute for Standards and Technology, USA) broad research draws so important conclusion, this conclusion makes the problem of danger of combustion be able to tangible simplification: rate of heat release, particularly the peak value rate of heat release is unique topmost parameter in the burning, and it can be counted as incendiary " impellent ".
Therefore, current, the selection that is common to the flame retardant polymer engineering test is a cone calorimetry.Its measuring principle is the relation between oxygen depletion and aerial oxygen depletion amount and the thermal discharge.
The standard of cone calorimetry is ASTM E 1354 and ISO 5660.
At polymer EVA (Escorene UL 00328), polymer P E (BP 8063), EVA based nano composite material and the enterprising enforcement 35kW/m of PE based nano composite material
2The cone calorimetry analysis.The result is summarized in table 2 and 3.In these tables, following important parameters is used for characterizing the fire retardation of different polymkeric substance weighting agents.These parameters are:
■ PHRR (rate of heat release peak value), the maximum heatrelease rate in its expression combustion processes.
The ■ fracture density, from the resistates of cone calorimetry analysis estimate (the reduction order of fracture density: +++＞++＞+＞-＞--＞---).
The ■ surface quality, from estimate with the resistates of cone calorimetry analysis (the reduction order of surface quality: +++＞++＞+＞-＞--＞---).
III.C.a.-PHRR result
From the PHRR angle, high-visible by the result of table 2, all filled polymers of use all have improved fire retardation.
For EVA that comprises 2.4 weight % weighting agents and EVA based nano composite material, PHRR reduces in the following order: EVA＞organic clay～pure nanotube.
Surprisingly, pure nanotube is the same with the organic clay based nano composite material effective aspect the reduction of PHRR.
For EVA that comprises 4.8 weight % weighting agents and EVA based nano composite material, PHRR reduces in the following order: EVA＞organic clay＞pure nanotube=thick nanotube.
Surprisingly, thick nanotube is the same with pure nanotube effective aspect the PHRR reduction.
Filler content is increased to 4.8 weight % from 2.4 weight %, if weighting agent is an organic clay, then produces the fire retardation that increases, when using pure or thick MWNT, it is extremely important that the fire retardation of this increase will become.
For the nano composite material (sample 7) that comprises pure MWNT of 2.4 weight % and 2.4 weight % organic claies, observe, between MWNT and organic clay, there is surprising cooperative flame retardant effect.Back one sample is found to be best anti-flaming nano composite material.
From the PHRR angle, when screw speed becomes 120rpm (sample 8b) by 45rpm (sample 8a),, can not cause its flame retardant properties to change for the nano composite material that comprises the thick MWNT of 4.8 weight %.
For PE that comprises 4.8 weight % weighting agents and PE based nano composite material (table 3), PHRR reduces in the following order: pure SWNT＞thick SWNT＞PE＞pure MWNT＞thick MWNT.Order is identical concerning the nano composite material that comprises 9.1 weight % weighting agents.
From PHRR with draw such conclusion (table 3) ignitor firing time, MWNT plays the effect of fire retardant in PE, do not reduce ignitor firing time, and SWNT does not play fire retardant in PE.
III.C.b.-fracture density result and surface quality result
For the fire-retardant EVA based nano composite material (table 2) that comprises 2.4 weight % weighting agents, fracture density increases with following order: pure MWNT＜organic clay.Again, when nano composite material comprises the pure MWNT of 2.4 weight % and the organic clay of 2.4 weight % (figure Ic), observe fracture density astoundingly and be reduced to zero very important synergistic effect.
The combination of the weighting agent of nanotube and organic clay is used to improve the surprising synergistic effect of flame retardant resistance and can explains by the close-knit surface that improves.This enhanced coke plays isolates and the effect of incombustible material, has reduced volatile products (fuel) and has been dispersed into chance in the flame region.The crack that exists is few more, reduces to distribute and to reduce the effect of PHRR just good more.Filler plays a positive role in the forming process of coke, but clearly, it also makes coke strengthen and make it more anti-machinery and ftractures.
For the fire-retardant EVA based nano composite material (table 2 that comprises 4.8 weight % weighting agents; Fig. 1 a-b), fracture density increases by following order: thick MWNT＜pure MWNT＜organic clay.
The filler content of EVA based nano composite material is increased to 4.8 weight % (table 2), fracture density reduction when causing using pure MWNT or organic clay from 2.4.
Observe similar flame retardant properties with listed dissimilar thick or pure SWNT in the table 1.In the middle of the nano composite material that comprises thick or pure SWNT, observe preferable performance with SWNT-2 and-3.SWNT-2 and-3 better performances may be since the nanotube content in the sample higher due to.For " oxidation, purifying and cryodesiccated " SWNT-1 ,-2 and-3 samples, the performance of observation even better.Improve back one may be because SWNT disperses sufficient result in nano composite material.
The III.D.-conductivity measurement
Description of test:
Use four-wire method to measure resistivity.Sample is cut into is of a size of 60 millimeters * 20 millimeters * 2.8 millimeters small pieces.
Form point of contact by copper wire (2 millimeters of diameters) and silver paste.Along coiling fixedly V and I electrode: be I-V-V-I.V-V and V-I distance between electrodes are respectively 35 millimeters and 12 millimeters.Use 4 line microohm meters (Burnster, model is P133/0020) to measure the resistance between the V electrode.Use Pouillet rule calculated resistance rate.
The result:
Along with the increase of nanotube concentration in matrix material, resistivity reduces.When with the pure MWNT of 2.4 weight %, resistivity is higher than 2 * 10
3Ohmcm, but when with the pure MWNT of 4.8 weight %, resistivity but is reduced to and is lower than 10 ohmcms.
Surprisingly, in the matrix material that contains 2.4 weight %MWNT, add the organic clay of 2.4 weight %, can make resistivity from being higher than 2 * 10
3Ohmcm is reduced to about 8 * 10
1Ohmcm.The reduction of back one resistivity is because nanotube is dispersed in the polymeric matrix that the synergy by organic clay and carbon nanotube obtains causes.
According to concentration and blending means, resistivity value is found and is in 8 ohmcms and 8 * 10
12Between the ohmcm.
In general, show that the resistivity of nano composite material of the present invention is 10
-4Ohmcm-8 * 10
12Between the ohmcm, preferred 1 ohmcm-10
3Ohmcm.
Conclusion
As a conclusion, in nano composite material disclosed by the invention, each component good dispersion.Show that by adding binder component, such as the phyllosilicate nano particle, can improve the physicals of the nano composite material that finally obtains, this returns approximately should be in described uniform dispersed texture.Therefore, these nano composite materials are by having uniform dispersion and having obtained important industrial progress from the performance that carbon nanotube is transferred to the increase of matrix material.The homodisperse of described nanotube in nano composite material and the performance of transferring to the improvement on the matrix material that is obtained are that the synergy by organic clay and carbon nanotube realizes.
In addition, the advantage of nano composite material of the present invention is can be according to very method manufacturing widely, and has optimum manufacturing handiness.
Can be according to their the different application scenario of the described nano composite material of functional design.For example, they can be used as fire retardant, as the antistatic material in the lead; as wire protective device shell, as the anticracking agent in the surface protection coating, as the anticracking agent in the reinforcement material; as surface protection coating, as reinforcement material and as or be used for light-emitting device.
Table 2: come from the nanotube dispersion of tem observation, come from the flame retardance results of TGA and cone calorimetry analysis and the electrical resistivity results of EVA based nano composite material
| Sample | EVA (wt.％) | MWNT (wt.％) | SWNTs1 (wt.％) | Organic clay (wt.%) | Nanotube dispersion (TEM) | TGA analyzes T max℃) | Cone calorimetry is analyzed | Resistivity (Ω cm) | ||||
| Pure | Slightly | Pure | Slightly | PHRR (kW/m 2) | Fracture density | Surface quality | ||||||
| Esco- rene | 100 | - | - | - | - | - | 477 | 580 | * | |||
| 1 a | 97.6 | 2.4 | - | - | - | - | + | 501 | 530 | + | + | * |
| 2 a | 95.2 | 4.8 | - | - | - | - | ++ | 503 | 400 | - | + | 8.33 |
| 3 a | 95.2 | - | 2.4 | - | - | 2.4 | + | |||||
| 4 a | 95.2 | - | - | - | 2.4 | 2.4 | + | |||||
| 5 a | 97.6 | - | - | - | - | 2.4 | 511 | 530 | +++ | * | ||
| 6 a | 95.2 | - | - | - | - | 4.8 | 505 | 470 | ++ | - | * | |
| 7 a，b | 95.2 | 2.4 | - | - | - | 2.4 | +++ | 503 | 370 | --- | +++ | 83.98 |
| 8a a | 95.2 | - | 4.8 | - | - | - | +++ | 513 | 400 | -- | ++ | 18.24 |
| 8b c | 95.2 | - | 4.8 | - | - | - | +++ | 400 | -- | ++ | 128.01 | |
| 9 a | 97.6 | - | - | 2.4 | - | - | -- | 470 | + | + | ||
| 10 a | 95.2 | - | - | 4.8 | - | - | - | 420 | - | + | ||
| 11 a，b | 95.2 | - | - | 2.4 | - | 2.4 | + | 380 | --- | +++ | ||
| 12a a | 95.2 | - | - | - | 4.8 | - | + | |||||
| 12b c | 95.2 | - | - | - | 4.8 | - | ++ | |||||
A: screw speed is 45rpm, and mixing temperature is 130 ℃.
B: nanotube and nano-filled dose were pre-mixed before their adding.
C: screw speed is 120rpm, and mixing temperature is 140 ℃.
*: the too high not energy measurement of resistivity.
Table 3: come from TEM and Tork nanotube dispersion of observing and the flame retardance results that comes from the analysis of PE based nano composite material cone calorimetry
| Sample | PE C(wt.％) | MWNTs (wt.％) | SWNTs-1 (wt％) | Tork d (a.u.) | Nanotube dispersion (TEM) | Cone calorimetry is analyzed | |||||
| Pure | Slightly | Pure | Slightly | Ignitor firing time (s) | PHRR (kW/m 2) | Fracture density | Surface quality | ||||
| PE | 100 | - | - | - | - | 90 | 454 | ||||
| 13 a | 95.2 | 4.8 | - | - | - | 400 | +++ | 100 | 289 | -- | + |
| 14 a | 90.9 | 9.1 | - | - | - | 820 | +++ | 114 | 359 | -- | + |
| 15 a | 95.2 | - | 4.8 | - | - | 320 | +++ | 91 | 326 | -- | + |
| 16 a | 90.9 | - | 9.1 | - | - | 620 | +++ | 100 | 374 | -- | + |
| 17 a，b | 95.2 | - | - | 4.8 | - | 180 | ++ | 68 | 673 | ++ | - |
| 18 a，b | 90.9 | - | - | 9.1 | - | 340 | ++ | 63 | 615 | ++ | - |
| 19 a | 95.2 | - | - | - | 4.8 | 160 | ++ | 103 | 634 | ++ | - |
| 20 a | 90.9 | - | - | - | 9.1 | 240 | ++ | 104 | 476 | ++ | - |
A: screw speed is 45rpm, and mixing time is 10 minutes, and mixing temperature is 180 ℃.
B:SWNT is oxidized, purifying and lyophilize.
C:PE represents polyethylene BP 8063.
D:Tork mixes the relative power that nano composite material needs.It is illustrated in the relative viscosity of mixing nano composite material when finishing in 10 minutes.
Claims (24)
1. nano composite material, it comprises that polymkeric substance, carbon nanotube and phyllosilicate nano particle are as component.
2. according to the nano composite material of claim 1, wherein component is uniform dispersion form.
3. according to the nano composite material of claim 1 or 2, it is characterized in that polymkeric substance is selected from thermoplastic polymer, polyolefine, ethylene-based polymer, acrylonitrile polymer, polyacrylic ester, elastomerics, fluoropolymer, thermoplastic condensed polymer, rigid plastics polycondensate, silicon resin, thermoplastic elastomer, multipolymer and ter-polymers, graftomer and its mixture.
4. according in any one nano composite material of preceding claim, it is characterized in that carbon nanotube is selected from SWNT and MWNT, described carbon nanotube is pure, and is partial-purified, thick or functionalized.
5. according in any one nano composite material of preceding claim, it is characterized in that the phyllosilicate nano particle is organically-modified phyllosilicate nano particle.
6. according to the nano composite material of claim 5, it is characterized in that the phyllosilicate nano particle is the organically-modified layered silicate from other insertion of chemical level of 2: 1 phyllosilicate and montmorillonite.
7. according in any one nano composite material of preceding claim, the total content scope that it is characterized in that layered silicate and carbon nanotube is 0.01-50 weight %, preferred 0.5-25 weight %, most preferably 1-10 weight %.
8. according in any one nano composite material of preceding claim, carbon nanotube and phyllosilicate nano particulate weight ratio scope are 0.01-100, preferred 0.1-10.
9. according in any one nano composite material of preceding claim, it is characterized in that it also comprises at least a little weighting agent, preferably its amount is 1-70 weight %.
10. according in any one the purposes of nano composite material in the flameproof protection structure of preceding claim.
11. according in any one nano composite material of preceding claim as the purposes of fire retardant.
12. according in any one nano composite material of preceding claim as the purposes of twinkler.
13. according in any one nano composite material of preceding claim as the purposes of antistatic material.
14. according in any one nano composite material of preceding claim as the purposes of lead.
15. according in any one nano composite material of preceding claim as the purposes of wire protective device shell.
16. according to any one nano composite material of preceding claim as surface protection coating in the purposes of anticracking agent.
17. according to any one nano composite material of preceding claim as reinforcement material in the purposes of anticracking agent.
18. according in any one nano composite material of preceding claim as the purposes of surface protection coating.
19. according in any one nano composite material of preceding claim as the purposes of reinforcement material.
20. be used to obtain according in any one the method for nano composite material of preceding claim, it is characterized in that it comprises provides different components, be polymkeric substance, carbon nanotube, phyllosilicate nano particle, provide the step of little weighting agent in case of necessity, with the step of described different component being mixed with the acquisition homogeneous dispersion under appropriate condition.
21. method according to claim 20, it is characterized in that providing the step of carbon nanotube to be included in the step that generates described carbon nanotube on the M/MgO catalyzer, wherein M is selected from Co, Fe, Ni, Mo or its mixture, and M accounts for the 0.1-50 weight % of catalyzer, and MgO is prepared on the spot by MAGNESIUM METAL.
22. method according to claim 20 or 21, wherein provide the step of carbon nanotube also to comprise, before dissolving spent catalyst, while nanotube are dispersed on the catalyzer well, by under 250-500 ℃, in the oxygen of pure or dilution, to thick given for some time of nanotube oxidation, with the step of the thick carbon nanotube that generated in purifying such as the claim 14.
23. according to any one method of claim 20-22, wherein provide the step of carbon nanotube also comprise by lyophilize comprise preferred 80-95 weight % water nanotube/water " wet cake " and the carbon nanotube drying that generates to obtain the step of very thin powder.
24. according to any one method of claim 20-22, wherein provide the step of carbon nanotube also comprise by component distillation comprise the nanotube/water " wet cake " of preferred 80-95 weight % water and the dry carbon nanotube that is generated to obtain the step of very thin powder, wherein benzene, toluene or dimethylbenzene are used for forming azeotrope.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087513A (en) * | 2011-11-02 | 2013-05-08 | 青岛泰瑞自动化技术有限公司 | Spherical filler modifying material formula |
| CN101568582B (en) * | 2006-12-26 | 2013-07-03 | 第一毛织株式会社 | Electroconductive thermoplastic resin composition and plastic article |
| CN108002365A (en) * | 2018-02-01 | 2018-05-08 | 广东工业大学 | A kind of method of dispersing Nano carbon tubes |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101568582B (en) * | 2006-12-26 | 2013-07-03 | 第一毛织株式会社 | Electroconductive thermoplastic resin composition and plastic article |
| CN103087513A (en) * | 2011-11-02 | 2013-05-08 | 青岛泰瑞自动化技术有限公司 | Spherical filler modifying material formula |
| CN108002365A (en) * | 2018-02-01 | 2018-05-08 | 广东工业大学 | A kind of method of dispersing Nano carbon tubes |
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