CN102099288B - Carbon nanoprecursor, method for producing the same, carbon nanocomposite and method for producing the same - Google Patents
Carbon nanoprecursor, method for producing the same, carbon nanocomposite and method for producing the same Download PDFInfo
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- CN102099288B CN102099288B CN2009801282322A CN200980128232A CN102099288B CN 102099288 B CN102099288 B CN 102099288B CN 2009801282322 A CN2009801282322 A CN 2009801282322A CN 200980128232 A CN200980128232 A CN 200980128232A CN 102099288 B CN102099288 B CN 102099288B
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Abstract
Disclosed is a carbon nanoprecursor (11), a method for producing the same, a carbon nanocomposite and a method for producing the same, wherein the carbon nanoprecursor (11) contains monodispersed carbon nanotubes (12) and a carbon black (13) in the form of primary particles adhering to the surfaces of the carbon nanotubes (12). Since the carbon black (13) in the form of primary particles adheres to the surfaces of the monodispersed carbon nanotubes (12), the carbon nanoprecursor (11) has a relatively large particle size and good handleability. In addition, due to the carbon black (13) in the form of primary particles adhering to the surfaces of the monodispersed carbon nanotubes (12), the carbon nanoprecursor (11) can provide a base material with high electrical conductivity and high strength when mixed with the base material.
Description
Technical field
The present invention relates to a kind of carbon nanometer precursor, its manufacture method, silver/carbon nano composite body and manufacture method thereof.
Background technology
As the high performance material of nano-scale, known nano-carbon material just like carbon nanotube and so on.Nano-carbon material take carbon nanotube as representative is added, be used in and require high performance various material.
At this, Japanese Unexamined Patent Application Publication 2007-507562 communique (patent documentation 1) and TOHKEMY 2006-83249 communique (patent documentation 2) disclose the technology that relates to the composition that comprises carbon nanotube.Patent documentation 1 discloses a kind of organic polymer precursor, monolayer nanotube composition and electroconductibility precursor composition of the electroconductibility packing material of nano-scale arbitrarily of containing.In addition, according to patent documentation 2, as the manufacture method of the rubber combination that is combined with nano-sized carbon, in rubber after mixing cooperation toughener and/or packing material Synergist S-421 95, mixing cooperation nano-sized carbon.
In addition, TOHKEMY 2006-45034 communique (patent documentation 3) discloses the matrix material that relates to the carbon nanotube that the carbon material by carbon nanotube and other consists of and the technology of its manufacture method.According to patent documentation 3, disperse in order to make the carbon nanotube disintegration that is condensed into piece, the matrix material of Formed nanotube, carbon nanotube and temperature of combustion is lower than carbon nanotube, as to have adsorptivity carbon material mixes in solvent, disperses and generates mixture, this mixture is carried out drying, obtain required mixture.
In addition, No. 2005/110594 communique of WO (patent documentation 4) discloses the technology that relates to small carbon dispersion.
The background technology document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2007-507562 communique
Patent documentation 2: TOHKEMY 2006-83249 communique
Patent documentation 3: TOHKEMY 2006-45034 communique
No. 2005/110594 communique of patent documentation 4:WO
Summary of the invention
The problem that invention will solve
In the prior art shown in patent documentation 1 or patent documentation 2, owing to by the mixing grade of simple mechanicalness, nano-sized carbon being matched with in the base materials such as rubber or plastics, the degree of scatter of the nano-sized carbon in base material may be insufficient.That is, in base material, nano-sized carbon is the state of partial agglomeration sometimes.Such state can not be given full play to the characteristic of nano-sized carbon, and its result can cause resulting physical property insufficient.Particularly, for the base material that is combined with nano-sized carbon, be difficult to give high conductivity or high strength.In addition, very little as nano-sized carbon, the particularly size of nano-sized carbon simple substance, its difficult treatment need to improve operability in the time of in being mixed in base material.
In addition, according to patent documentation 3, although the degree of scatter of the state that carbon nanotube form to be disperseed, the particle of the gac carbon nanotube in large and mixture than carbon nanotube is also insufficient, the physical property of the mixture that obtains still can not be satisfactory.
The object of the invention is to, provide a kind of treatability good, can give base material high conductivity and high-intensity carbon nanometer precursor.
Another object of the present invention is, a kind of have high conductivity and high-intensity silver/carbon nano composite body are provided.
Other purpose of the present invention is, a kind of carbon nanometer precursor manufacture method is provided, and it can easily be made and can give base material high conductivity and high-intensity carbon nanometer precursor.
Other purpose of the present invention is, a kind of manufacture method of silver/carbon nano composite body is provided, and it can easily be made has high conductivity and high-intensity silver/carbon nano composite body.
Solve the method for problem
Carbon nanometer precursor of the present invention contain monodisperse status carbon nanotube, be attached to the carbon black of the primary particle state of carbon nano tube surface.For such carbon nanometer precursor, be attached to the carbon nano tube surface of monodisperse status due to the carbon black of primary particle state, therefore, its shape matching is large, and treatability is good.In addition, utilize the carbon black of the primary particle state of the carbon nano tube surface that is attached to monodisperse status, in the situation that in being mixed in base material, can give high conductivity and high strength to base material.At this, monodisperse status refers to that carbon nanotube exists with independent state respectively, also comprises the network-like state that is separated into.In addition, the primary particle state refers to that carbon black is further disperseed the state of the primary particle that forms by the level of the secondary aggregation body of several microns left and right.Need to prove, at the such state of this so-called coating of adhering to the whole surface that refers to the coated carbon nanotube or with the state that the mode on the part surface of exposing carbon nanotube covers, in addition, comprise that also carbon nanotube and carbon black are wound around mutually such state.
In addition, for the carbon black of primary particle state, use to have wetting ability and hydrophobic tensio-active agent, be attached to carbon nano tube surface.
Carbon nanometer precursor of the present invention is made by following method, after adding in advance carbon nanotube make monodisperse status in comprising the solution with wetting ability and hydrophobic tensio-active agent, the aggregate of carbon black made an addition in solution and make the carbon black of primary particle state, making the carbon black of primary particle state be attached to carbon nano tube surface.Need to prove to have the solution of wetting ability and hydrophobic tensio-active agent for above-mentioned containing, at length be recorded in patent documentation 4.
Preferably remove the solution composition of tensio-active agent in carbon nanometer precursor.At this, can utilize such as heating or freeze-dried, filtration etc. to remove.
In addition, carbon nanotube comprises compound wall (multiwall) carbon nanotube.
In other side of the present invention, silver/carbon nano composite body possesses base material and network-like the carbon nanometer precursor that is included in base material.At this, carbon nanometer precursor comprises the carbon nanotube of monodisperse status and is attached to the carbon black of the primary particle state of carbon nano tube surface.Therefore such silver/carbon nano composite body, has high conductivity and high strength owing to comprising by the carbon nanotube of monodisperse status and being attached to the carbon nanometer precursor that the carbon black of this surperficial primary particle state consists of network-likely.
As a preferred embodiment, base material comprises rubber.
In another other side of the present invention, the manufacture method of carbon nanometer precursor comprises: the operation of preparing to comprise the solution with wetting ability and hydrophobic tensio-active agent; Add carbon nanotube in solution, make carbon nanotube be the operation of monodisperse status in solution; And making carbon nanotube add the carbon black of aggregate and form the primary particle state in being the solution of monodisperse status, make carbon nano tube surface adhere to the operation of the carbon black of primary particle state.Utilize the manufacture method of such carbon nanometer precursor, can make under solution state, therefore, can easily make carbon nanometer precursor.
The preferred operation of removing solution composition after the carbon black that makes carbon nano tube surface adhere to the primary particle state that also is included in.
In another other side of the present invention, the manufacture method of silver/carbon nano composite body comprises: the operation of preparing to comprise the solution with wetting ability and hydrophobic tensio-active agent; Add carbon nanotube in solution, make carbon nanotube be the operation of monodisperse status in solution; Add the carbon black of aggregate and form the primary particle state in the solution that carbon nanotube is monodisperse status, making carbon nano tube surface adhere to the operation of the carbon black of primary particle state; Remove solution composition and obtain the operation of carbon nanometer precursor after making carbon nano tube surface adhere to the carbon black of primary particle state; And the carbon nanometer precursor that is mixed to get and the operation of base material.Utilize the manufacture method of such silver/carbon nano composite body, owing to using the carbon nanometer precursor of making under solution state, therefore, can easily make silver/carbon nano composite body.
The invention effect
Utilize carbon nanometer precursor of the present invention, be attached to the carbon nano tube surface of monodisperse status due to the carbon black of primary particle state, thereby its shape matching is large, treatability is good.In addition, utilize the carbon black of the primary particle state of the carbon nano tube surface that is attached to monodisperse status, in the situation that be mixed in base material, can give high conductivity and high strength to base material.
In addition, for such silver/carbon nano composite body, owing to comprising by the carbon nanotube of monodisperse status and being attached to the carbon nanometer precursor that the carbon black of this surperficial primary particle state consists of network-likely, therefore, have high conductivity and high strength.
In addition, utilize the manufacture method of such carbon nanometer precursor, can make under solution state, therefore, can easily make carbon nanometer precursor.
In addition, utilize the manufacture method of such silver/carbon nano composite body, owing to using the carbon nanometer precursor of making under solution state, therefore, can easily make silver/carbon nano composite body.
Description of drawings
Fig. 1 means the schema of representational operation of manufacture method of the carbon nanometer precursor of an embodiment of the invention.
Fig. 2 means the electron micrograph of a part of the carbon nanometer precursor of an embodiment of the invention, for amplifying the photo of 5000 times.
Fig. 3 means a part of electron micrograph of the carbon nanometer precursor of an embodiment of the invention, for amplifying the photo of 10000 times.
Fig. 4 is the basis with electron micrograph shown in Figure 3, schematically shows the schematic diagram of the carbon nanometer precursor of an embodiment of the invention.
Fig. 5 means the electron micrograph of other parts of the carbon nanometer precursor of an embodiment of the invention, for amplifying the photo of 5000 times.
Fig. 6 means the electron micrograph of other parts of the carbon nanometer precursor of an embodiment of the invention, for amplifying the photo of 10000 times.
Fig. 7 means the electron micrograph of other parts of the carbon nanometer precursor of an embodiment of the invention, for amplifying the photo of 10000 times.
Fig. 8 means the electron micrograph of other parts of the carbon nanometer precursor of an embodiment of the invention, for amplifying the photo of 30000 times.
Fig. 9 means the electron micrograph of the part of existing carbon nano tube compound material, for amplifying the photo of 10000 times.
Figure 10 means the photo of the filtration condition of the solution that comprises carbon nanometer precursor.
Figure 11 means the photo of the filtration condition of the solution that comprises carbon nanometer precursor.
Figure 12 means the photo of the filtration condition of the solution that comprises carbon nanometer precursor.
Figure 13 means the photo of the filtration condition of the talcose CNT dispersion liquid of bag.
Figure 14 means the photo of the state before the filtration that adds the liquid that entry forms in the CNT powder.
Figure 15 means the photo of the filtrate after the filtration that adds the liquid that entry forms in the CNT powder.
Figure 16 means the photo of the filter paper after the filtration that adds the liquid that entry forms in the CNT powder.
Figure 17 means the photo of the state before the filtration that adds the liquid that entry forms in CB.
Figure 18 means the photo of the filtrate after the filtration that adds the liquid that entry forms in CB.
Figure 19 means the photo of the filter paper after the filtration that adds the liquid that entry forms in CB.
Figure 20 means the photo of the state that the filtration of CNT dispersion liquid is front.
Figure 21 means the photo of the filtrate after the filtration of CNT dispersion liquid.
Figure 22 means the photo of the filter paper after the filtration of CNT dispersion liquid.
Figure 23 means the outside drawing of the test film of the cooperation shown in embodiment 2.
Figure 24 means the outside drawing of the test film of the cooperation shown in comparative example 4.
The figure of the measuring point in the test film when Figure 25 means the mensuration volume specific resistance.
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are described.At first, the manufacture method of the carbon nanometer precursor of an embodiment of the invention described.Fig. 1 means the schema of representational operation of manufacture method of the carbon nanometer precursor of an embodiment of the invention.
With reference to Fig. 1, at first, prepare to comprise have wetting ability and hydrophobic tensio-active agent, be the solution (Fig. 1 (A)) of zwitterionics.Then, add carbon nanotube in solution, make carbon nanotube dispersed in solution, make carbon nanotube be monodisperse status (Fig. 1 (B)).Then, be at carbon nanotube the carbon black that adds aggregate in the solution of monodisperse status and form the primary particle state, make carbon nano tube surface adhere to the carbon black of primary particle state (Fig. 1 (C)).At this moment, the mode with the whole surface of coating carbon nanotube is adhered to the carbon black of primary particle state.Then, remove solution composition (Fig. 1 (D)).So, the carbon nano tube surface that is manufactured on monodisperse status is attached with the carbon nanometer precursor of the carbon black of primary particle state.Need to prove, in operation afterwards, in the situation that utilize solution composition etc., also can not remove solution.That is, can omit the operation of removing solution composition.
As the concrete example of above-mentioned manufacturing process, at first, be added with in the scope with mass concentration 0.01～0.4% carbon nanotube (CNT) that adds 3 quality % in the aqueous solution of zwitterionics, make the CNT dispersion liquid.At this moment, by such as vibration or control pH, electrolytical concentration etc., make carbon nanotube be monodisperse status.Then, the carbon black of 70g is made an addition in this 3 quality %CNT dispersion liquid of 60ml, via migration, cleaning, the drying process of the carbon black of primary particle state, make the nano-sized carbon precursor.
need to prove, for the above-mentioned solution that comprises zwitterionics, particularly, for example can pass through to mix " 3-(N, N-dimethylmyristylammonio)-propanesulfonate " (3-(N, N-dimethyl myristyl is amino)-propane sulfonic acid, zwitterionics, Fluka makes) 2.0g, polyoxyethylene toluylene phenyl ether (Japanese Kao Co., Ltd. system) 2.0g, alkyl (14-18) dimethyl betaine (Japanese Kao Co., Ltd. system) 1.0g and deionized water 400ml and obtain.
In addition, for making the CNT dispersion liquid, for example, can followingly operate.(diameter is 20nm to add the carbon nanotube of 20.2～20.5g in the solution that comprises zwitterionics that obtains take aforesaid method, length is 2～10 μ m), with deionized water with solution is integrally-regulated be 500ml after, devote ball mill body (round shape, internal volume=1800ml, the diameter of zirconium pearl=50～150mm, the loading level of pearl=1200g), the ball mill body is equipped on rotation pallet (Japanese morning sun physics and chemistry institute make " AS ONE ") slowly to be stirred about 8 hours, making contains a dispersion liquid (thick dispersion liquid) of carbon nanotube.Then, the carbon nanotube that comprises that obtains is thus all taken out from the ball mill body, use ball mill (" DYNO-MILL ", the tubular that WAB company makes, internal volume=2000ml, fill the zirconium oxide bead 1800g that diameter is 1.0mm), flow with 1000ml/ minute, carried out dispersion treatment 30～60 minutes, the twice dispersing liquid of preparation carbon nanotube (being more than 96% one by one of carbon nanotube disperses, and is isolated monodisperse status) obtains the CNT dispersion liquid thus.
In addition, as carbon nanotube, particularly, can use Baytubes that the Nanocyl-7000 that makes such as Nanocyl company or Bayer Material Science company make etc.
Then, the structure of the carbon nanometer precursor of the manufacture method manufacturing that utilizes above-mentioned carbon nanometer precursor described.Fig. 2 and Fig. 3 mean the electron micrograph of a part of the carbon nanometer precursor of an embodiment of the invention.Fig. 2 amplifies the photo of 5000 times, and Fig. 3 amplifies the photo of 10000 times.In addition, Fig. 4 is the basis with electron micrograph shown in Figure 3, schematically shows the schematic diagram of the carbon nanometer precursor of an embodiment of the invention.
With reference to Fig. 2～Fig. 4, carbon nanometer precursor 11 comprises the carbon nanotube 12 of monodisperse status and is attached to the carbon black 13 of the primary particle state on carbon nanotube 12 surfaces.Carbon nanotube 12 is the compound wall carbon nanotube.Need to prove, as carbon nanotube 13, for example can use diameter is that 60 nanometers, length are the carbon nanotube of tens of microns.In addition, also can use diameter to be the carbon nanotube of several nanometers or the diameter carbon nanotube as tens nanometer.
At this, if carbon black exists with the form of secondary aggregation body, in the situation that amplify 5000 times or 10000 times, can not the form of photo as shown in Figures 2 and 3, but should be able to see the carbon black of very large secondary aggregation body and the carbon nanotube of monodisperse status.But, do not see carbon black and the carbon nanotube of such form, but see carbon nanotube and the carbon black of Fig. 2 and form shown in Figure 3.Can think the state that the carbon nanotube of such form and carbon black that carbon black is the primary particle state adhere in the mode of the carbon nano tube surface of coating monodisperse status.Need to prove, at this moment, can think that the carbon black of primary particle state is to spread all over multilayer to carry out the state that the mode of coating is adhered to.
Explanation in further detail.Fig. 5, Fig. 6, Fig. 7 and Fig. 8 mean the electron micrograph of other parts of the carbon nanometer precursor of an embodiment of the invention.Fig. 5 is for amplifying the photo of 5000 times, and Fig. 6 and Fig. 7 are for amplifying the photo of 10000 times, and Fig. 8 amplifies the photo of 30000 times.Fig. 6 is equivalent to amplify the regional photo of a part of photo shown in Figure 5, and Fig. 8 is equivalent to amplify the regional photo of a part of photo shown in Figure 7.In addition, in Fig. 5～Fig. 8, represent yardstick, be the standard of length.At this, object as a comparison is shown in Fig. 9 with the electron micrograph of the carbon nano tube compound material shown in Fig. 5 (b-3) of patent documentation 3.Fig. 9 illustrates length standard for the photo of 10000 times of amplifications outside the frame of electron micrograph.
With reference to Fig. 5～Fig. 8, although some gaps are arranged, the carbon black that can be used as the primary particle state is attached to the state of carbon nano tube surface with stratiform.In addition, comparison diagram 5～Fig. 8 and Fig. 9, in Fig. 9, carbon nanotube disperses in the many gac modes on every side that are attached to bulk.For the size of gac, the gac that its diameter is large is several microns left and right.That is, many carbon nanotubes are to expose its surperficial mode, to disperse with the state on the activated carbon particles that is attached to about several microns sizes.On the other hand, in Fig. 5～Fig. 8, carbon black becomes the carbon black of stratiform with the primary particle state, at least with around the carbon nanotube of one one that is attached to monodisperse status than 1 micron little particle state.The carbon black of primary particle state described herein reaches 100 nanometers at most, is approximately 20 nanometers to 40 about nanometers.
For such carbon nanometer precursor 11, owing to being that therefore, its shape is larger than the carbon nanotube simple substance of monodisperse status at the surface attachment of the carbon nanotube of the monodisperse status as above state of the carbon black of particle state once.This can prove by experiment shown below.
Figure 10, Figure 11 and Figure 12 mean the photo of the filtration condition of the above-mentioned solution that comprises carbon nanometer precursor.Figure 10 represents the situation with respect to carbon nanotube (following simple be " CNT ") dispersion liquid 30ml interpolation 10g carbon black (following simple be " CB ") (FEF (fast extruding furnace black)), Figure 11 represents with respect to CNT dispersion liquid 30ml, add the situation of 10gCB (HAF (high abrasion furnace black(HAF))), Figure 12 represents to add with respect to CNT dispersion liquid 60ml the situation of 10gCB (HAF).Need to prove, dispersion liquid refers to comprise the solution with wetting ability and hydrophobic tensio-active agent.
With reference to Figure 10～Figure 12, in the beaker shown in each figure, the filtrate after saving bit by bit respectively solution to above-mentioned carbon nanometer precursor and filtering.The color of filtrate is all water white transparency.Can think that this expression because of the carbon nanometer precursor of above-mentioned formation, namely comprise the CNT of monodisperse status and to be attached to the carbon nanometer precursor of CB of primary particle state on CNT surface larger by filter paper filtering than CNT simple substance, does not exist CNT and CB in filtrate.Need to prove, for filtration, the material of filter paper is set as paper pulp, thickness setting is 0.15mm, bulk density is set as 0.03g/cm
3, Gas permeability (Ge Erlaishi, 4 overlapping) is set as 1.4 seconds.
Need to prove, as a reference, (Tal c: situation talcum) is shown in Figure 13 with adding the 10g talcum with respect to CNT dispersion liquid 30ml.With reference to Figure 13, the filtrate in beaker is black.Can think that the CNT simple substance of this expression monodisperse status is not filtered, and is present in filtrate.
In addition, will be shown in Figure 14, Figure 15 and Figure 16 to add the situation that solution that entry forms filters in the CNT powder.Figure 14 is illustrated in and adds the front state of solution filter that entry forms, the filtrate after Figure 15 represents to filter, the filter paper after Figure 16 represents to filter in the CNT powder.With reference to Figure 14～Figure 16, when adding entry in the CNT powder, CNT is waterborne state, and CNT is not scattered in solution, but directly cohesion.That is, CNT is not that form with monodisperse status is present in liquid.At this moment, filtrate is water white transparency, has CNT on filter paper, can think that this is only not disperse the water constituent of CNT to pass through filter paper.Need to prove, because such CNT powder is so-called gossamer state, therefore, even when mixing in rubber constituent, also for being very difficult to mixing state.
Then, will be shown in Figure 17, Figure 18 and Figure 19 to add the situation that solution that entry forms filters in CB simple substance.Figure 17 is illustrated in and adds the front state of solution filter that entry forms, the filtrate after Figure 18 represents to filter, the filter paper after Figure 19 represents to filter in CB simple substance.With reference to Figure 17～Figure 19, when adding entry in CB simple substance, CB simple substance is scattered in water, disperses with the form of so-called secondary aggregation body.At this moment, filtrate is water white transparency, has CB on filter paper, can think,, CB secondary aggregation body large as the particle diameter of the CB of secondary aggregation body has been filtered.
Then, the situation of filtering the CNT dispersion liquid is shown in Figure 20, Figure 21 and Figure 22.Figure 20 represents the state before the CNT dispersion liquid filters, the filtrate after Figure 21 represents to filter, the filter paper after Figure 22 represents to filter.At this, the CNT dispersion liquid refers to only add the dispersion liquid that CNT simple substance forms in comprising the solution of zwitterionics.With reference to Figure 20～Figure 22, in the CNT dispersion liquid, CNT is monodisperse status.At this moment, filtrate is black, has CNT on filter paper.Can think that the CNT that is present in dispersion liquid with monodisperse status is not filtered and has passed through filter paper, is present in filtrate.In addition, can think that a part of CNT is filtered and is present on filter paper.
That is, in dispersion liquid, because CNT is monodisperse status, therefore, exist with one by one little state, be not filtered.But, if be the state that the CB of primary particle state adheres to, because becoming, its shape is filtered greatly, separate with dispersion liquid.Residue thing on this filter paper is so-called carbon nanometer precursor of the present invention.
Then, the above-mentioned silver/carbon nano composite body that comprises carbon nanometer precursor is described.At this, describe as the situation of the base material of silver/carbon nano composite body using rubber.At first, the manufacture method of silver/carbon nano composite body of the present invention is described, utilize above-mentioned operation to make carbon nanometer precursor.Then, mix carbon nanometer precursor and the rubber made, make silver/carbon nano composite body.At this moment, can make silver/carbon nano composite body by utilizing the mixing of rubber compositions such as hot-rolling and carbon nanometer precursor.At this, for the carbon nanometer precursor that obtains, because solution composition is removed, therefore, material become easily on the roller sticking around, can easily carry out mixing.
Particularly, for example, the raw material that obtains nano-sized carbon precursor and rubber is mixing with the ratio of 200: 20 after, via a series of techniques such as sulfidizing, make the rubber combination as silver/carbon nano composite body.
The silver/carbon nano composite body of making thus possesses rubber and network-like the carbon nanometer precursor that is included in rubber.For such silver/carbon nano composite body, because above-mentioned carbon nanometer precursor is contained in rubber network-likely, therefore, have high conductivity and high strength.
Need to prove, the not raw material of nano-sized carbon, CB and the rubber of dispersion is used in experiment in contrast, makes rubbery sample with the same terms.Measure electroconductibility, the rubber combination that comprises the nano-sized carbon precursor that result is made with present technique demonstrates high conductivity.On the other hand, the rubber combination of dispersing nanometer carbon, CB and rubber does not almost demonstrate electroconductibility.
At this, the characteristic of above-mentioned silver/carbon nano composite body is specifically estimated, for evaluation, as a comparative example 1, use the rubber combination that does not add CNT.Need to prove, coordinating example is shown in table 1.
[table 1]
With reference to table 1, for comparative example 1, take EPDM (ethylene propylene diene monomer) as base material, with respect to the EPDM200 weight part, add CB (HAF) 80 weight parts and stearic acid 1 weight part, zinc oxide 5 weight parts etc.For this cooperation, the rubber combination take EPDM as base material is common composition.On the other hand, for embodiment 1, with respect to the CB80 weight part of comparative example 1, coordinate CB73.4 weight part, CNT6.6 weight part, other title complex and ratio thereof are identical with comparative example 1.At this, for CB and the CNT of embodiment 1, coordinate as the carbon nanometer precursor that obtains with above-mentioned manufacture method.
[table 2]
| Physical property | Comparative example 1 | Embodiment 1 |
| Tensile strength (MPa) | 20.2 | 21.3 |
| Elongation (%) | 570 | 640 |
| Hardness (HA) | 54 | 56 |
| Volume conduction | 1×10 6Above | 1×10 2The order of magnitude |
Table 2 is the table of the characteristic of the above-mentioned comparative example 1 of expression and embodiment 1.With reference to table 2, for tensile strength, comparative example 1 is 20.2MPa, and on the other hand, embodiment 1 is 21.3MPa, improves 5% with respect to comparative example 1.In addition, for elongation, comparative example 1 is 570%, and on the other hand, embodiment 1 is 640%, improves 10% left and right.For hardness, comparative example 1 is 54H
A, on the other hand, embodiment 1 is 56H
A, slightly be improved.Like this, with respect to comparative example 1, the mechanical characteristics of the tensile strength of embodiment 1, elongation, hardness and so on improves, and is high strength.In addition, for electrical characteristic, comparative example 1 is 1 * 10
6More than Ω cm, on the other hand, embodiment 1 is 1 * 10
2The order of magnitude.That is, embodiment 1 has high conductivity.
Then, to embodiment 1 and as a comparative example 3 examples that are added with powder CNT compare.Embodiment 1 is different with the addition means of the CNT that comparative example 3 only adds.For embodiment 1, as mentioned above, for having used the addition means of CNT dispersion liquid.On the other hand, for comparative example 3, although total use level of CNT is identical with embodiment 1, it is only CNT to be carried out that mechanicalness is disperseed and with other additives in the pulverulence of cohesion to a certain degree and EPDM mixing forming together.
[table 3]
[table 4]
| Physical property | Comparative example 3 | Embodiment 1 |
| Tensile strength (MPa) | 18.1 | 21.8 |
| Elongation (%) | 600 | 640 |
| Hardness (HA) | 55 | 56 |
| Volume conduction | 1×10 3The order of magnitude | 1×10 2The order of magnitude |
Table 3 means the table of the coordinating example of comparative example 3 and embodiment 1, and is corresponding with table 1.Table 4 means the table of the characteristic of comparative example 3 and embodiment 1, and is corresponding with table 2.With reference to table 3 and table 4, for tensile strength, comparative example 3 is 18.1MPa, and on the other hand, embodiment 1 is 21.3MPa, improves 17.7% with respect to comparative example 1.In addition, for elongation, comparative example 3 is 600%, and on the other hand, embodiment 1 is 640%, improves 7% left and right.For hardness, comparative example 3 is 55H
A, on the other hand, embodiment 1 is 56H
A, slightly be improved.Like this, with respect to comparative example 3, the mechanical characteristics of the tensile strength of embodiment 1, elongation, hardness and so on improves, and compares with comparative example 3 also to be high strength.In addition, for electrical characteristic, comparative example 1 is 1 * 10
3More than Ω cm, on the other hand, embodiment 1 is 1 * 10
2The order of magnitude.That is, compare with comparative example 3, embodiment 1 also has high conductivity.
In addition, use other rubber, the characteristic of silver/carbon nano composite body is specifically estimated.Table 5 means the table of the coordinating example of comparative example 2 and embodiment 2, and is corresponding with table 1.At this, use SBR (styrene butadiene ribber) as base material, change the cooperation ratio of carbon.Table 6 means the table of the characteristic of comparative example 2 and embodiment 2, and is corresponding with table 2.
[table 5]
[table 6]
| Physical property | Comparative example 2 | |
| Tensile strength (MPa) | 15.5 | 17.1 |
| Elongation (%) | 450 | 530 |
| Hardness (HA) | 52 | 52 |
| Volume conduction | 1×10 6Above | 1×10 2The order of magnitude |
With reference to table 5 and table 6, at this moment, with respect to comparative example 2, the tensile strength of embodiment 2 and elongation improve.Although hardness is identical, can say that mechanical characteristics improves, and is high strength.In addition, identical with the relation of comparative example 1 and embodiment 1 for electrical characteristic, embodiment 2 has high conductivity.
Then, to embodiment 2 and as a comparative example the example of 4 interpolation powder CNT compare.Embodiment 2 is identical with the situation of the above embodiments 1 and comparative example 3 with comparative example 4, and the addition means of the CNT that only adds is different.For embodiment 2, as mentioned above, for having used the addition means of CNT dispersion liquid.On the other hand, for comparative example 4, although total use level of CNT is identical with embodiment 2, it is only CNT to be carried out that mechanicalness is disperseed and form in the mixing SBR of entering together with other additive with the pulverulence of cohesion to a certain degree.
[table 7]
Table 7 means the table of the coordinating example of comparative example 4 and embodiment 2, and is corresponding with table 1.In the cooperation shown in comparative example 4, produce cob webbing, can not obtain the test film of so-called normal molding.Figure 23 is the outside drawing of the test film of the cooperation shown in above-described embodiment 2.Figure 24 is the outside drawing of the test film of the cooperation shown in comparative example 4.The longitudinal length of each test film is that 12cm, lateral length are 12cm.With reference to Figure 23 and Figure 24, for the outward appearance of test film shown in Figure 23, can't see the aggregate of CNT fully.On the other hand, for the outward appearance of test film shown in Figure 24, the aggregate of CNT can be seen in 46 positions that fence up with white circle youngster in Figure 24.In addition, for the tensile strength in embodiment 2, obtain although the mean value of 8 test films is calculated, its standard deviation is 1.52.On the other hand, if the tensile strength in mensuration comparative example 4, the standard deviation of 8 test films is 2.25.According to these results as can be known, for the cooperation in comparative example 4, can not normally be shaped.
Need to prove, for above-mentioned electrical characteristic, particularly, measure volume specific resistance shown below and it is estimated.The figure of the measuring point in the test film when Figure 25 means the mensuration volume specific resistance.With reference to Figure 25, measure test film in Figure 25 with 24 positions shown in sequence number.Use the low-resistivity meter to measure.Need to prove, test film is made into the lamellar of rectangle, and it is estimated.Evaluation result is shown in table 8～table 11.Table 8 and table 9 are the test film that only uses CB to make as a comparative example.Table 8 is the situation of face of the table side of determination test sheet, and table 9 is the situation of face of the dorsal part of determination test sheet.In addition, table 10 and table 11 are the test film of making as the above-mentioned carbon nanometer of the use of embodiment precursor.Equally, table 10 is the situation of face of the table side of determination test sheet, and table 11 is the situation of face of the dorsal part of determination test sheet.Need to prove, "-" expression in table 8～table 11 can't be measured, and the unit of numerical value is Ω cm.At this, can't be determined as the volume resistance value is 1 * 10
6The test film that Ω cm is above.
[table 8]
| - | - | 0.906×10 3 | - |
| - | 0.272×10 3 | 1.360×10 2 | - |
| 0.317×10 3 | - | - | - |
| - | - | - | - |
| - | - | - | - |
| - | - | - | - |
[table 9]
| - | - | - | - |
| 0.227×10 3 | - | - | - |
| - | - | - | - |
| - | - | - | - |
| - | - | - | - |
| - | - | - | - |
[table 10]
| 1.360×10 1 | 1.360×10 1 | 0.227×10 2 | 0.906×10 2 |
| 0.453×10 2 | 0.453×10 2 | 0.227×10 2 | 0.453×10 2 |
| - | 0.906×10 2 | 0.499×10 2 | 0.453×10 2 |
| 0.453×10 2 | 0.453×10 2 | 0.589×10 2 | 0.453×10 2 |
| 1.360×10 2 | 1.813×10 1 | 0.317×10 2 | 1.813×10 1 |
| 0.453×10 2 | 0.453×10 2 | 1.360×10 1 | 1.813×10 1 |
[table 11]
| 0.906×10 2 | 0.272×10 2 | 1.813×10 1 | 0.906×10 1 |
| 0.453×10 2 | 0.227×10 2 | 0.363×10 2 | 1.360×10 1 |
| 0.906×10 2 | 0.906×10 2 | 0.906×10 2 | 0.453×10 2 |
| 0.453×10 2 | 0.634×10 2 | 0.906×10 2 | 0.906×10 2 |
| 0.227×10 2 | 0.272×10 2 | 0.453×10 2 | 0.453×10 2 |
| 1.813×10 1 | 1.360×10 1 | 1.360×10 1 | 0.453×10 2 |
With reference to table 8～table 11, for the test film of comparative example, nearly all measuring point is all to measure.On the other hand, for the test film of embodiment, nearly all measuring point can be measured its volume specific resistance, and resistance value is 1 * 10
1～1 * 10
2, 1 * 10
3Ω cm level.Therefore, the test film of embodiment has high conductivity.
Then, other embodiment described.Table 12 means the table of the coordinating example of comparative example 5 and embodiment 3, and is corresponding with table 1.At this, use SBR as base material, change the cooperation ratio of carbon.Table 13 means the table of the characteristic of comparative example 5 and embodiment 3, and is corresponding with table 2.
[table 12]
[table 13]
With reference to table 12 and table 13, for tensile strength, comparative example 5 is 3.1MPa, and on the other hand, embodiment 3 is 3.6MPa, improves 16% with respect to comparative example 5.In addition, for elongation, comparative example 5 is 530%, and on the other hand, embodiment 3 is 540%, improves 1.9% left and right.For hardness, comparative example 5 is 31H
A, on the other hand, embodiment 3 is 35H
A, improve 13%.Like this, with respect to comparative example 1, the mechanical characteristics of the tensile strength of embodiment 1, elongation, hardness and so on improves, and is high strength.On the other hand, for electrical characteristic, comparative example 5 and embodiment 3 are 1 * 10
6More than Ω cm, do not change.
Then, further other embodiment is described.Table 14 means the table of the coordinating example of embodiment 4 and embodiment 5, and is corresponding with table 1.At this, use SBR as base material.Table 15 means the table of the characteristic of embodiment 4 and embodiment 5, and is corresponding with table 2.
[table 14]
[table 15]
| Physical property | Embodiment 4 | |
| Tensile strength (MPa) | 19.1 | 18 |
| Elongation (%) | 390 | 370 |
| Hardness (HA) | 71 | 73 |
| Volume conduction | 1×10 0The order of magnitude | 1×10 0The order of magnitude |
With reference to table 14 and table 15, for tensile strength, embodiment 4 is 19.1MPa, and embodiment 5 is 18MPa.For elongation, embodiment 4 is that 390%, embodiment 5 is 370%.For hardness, embodiment 4 is 71H
A, embodiment 5 is 73H
AAt this, with above-mentioned comparative example 1, namely compare with the cooperation of not adding CNT, in mechanical characteristics, tensile strength, elongation rate variance, but hardness improves.On the other hand, for electrical characteristic, embodiment 4 and embodiment 5 all improve widely, are 1 * 10
0Ω cm.That is, in the situation that require volume conduction significantly to improve, can be set as the cooperation as embodiment 4 and embodiment 5.
And then, other embodiment is described.Table 16 means the table of the characteristic of embodiment 6 and embodiment 7.Embodiment 6 further appends wax and mixing the forming again of 1.5 parts according to the cooperation in embodiment 4.Embodiment 7 further appends wax and mixing the forming again of 1.5 parts according to the cooperation in embodiment 5.
[table 16]
| Physical property | Embodiment 6 | Embodiment 7 |
| Tensile strength (MPa) | 21.7 | 21.8 |
| Elongation (%) | 480 | 480 |
| Hardness (HA) | 69 | 70 |
With reference to table 16, for tensile strength, embodiment 6 is 21.7MPa, and embodiment 7 is 21.8MPa.For elongation, embodiment 6 is that 480%, embodiment 7 is 480%.For hardness, embodiment 6 is 69H
A, embodiment 7 is 70H
AAt this, to compare with comparative example 1, the value of tensile strength improves greatly.Therefore, in the situation that require the characteristic of tensile strength, can be set as such coordinating example.
At this, the embodiment 6 shown in his-and-hers watches 16 and embodiment 7 carry out the ozone ageing test.For the ozone ageing test, the test film under the state of elongation 20% is estimated its Degree of Ageing in being exposed to the environment of 40 ℃ of temperature, ozone concn 50pphm (parts per hundred million(pphm)).In embodiment 6, even after through 72 hours, also produce be full of cracks.In embodiment 7, even through after 336 hours, also produce be full of cracks.Therefore, such coordinating example can be effectively applied to require the situation of good ozone ageing characteristic.
According to above-mentioned situation, because such silver/carbon nano composite body comprises by the carbon nanotube of monodisperse status and is attached to the carbon nanometer precursor that the carbon black of this surperficial primary particle state consists of network-likely, therefore, have high conductivity and high strength.
Need to prove, in the above-described embodiment, use rubber as base material, but be not limited thereto, can also use plastics as base material, also can use pottery as base material.
In addition, in the above-described embodiment, carbon nanotube uses the compound wall carbon nanotube, but is not limited thereto, and can use single-layer carbon nano-tube, also can use the two.
Need to prove, in the above-described embodiment, use the solution that comprises zwitterionics to make the carbon nanometer precursor of an embodiment of the invention, but be not limited thereto, also can utilize other method to make the carbon nanometer precursor of above-mentioned formation.
Abovely with reference to accompanying drawing, embodiments of the present invention are illustrated, but the present invention is not limited to illustrated embodiment.With respect to illustrated embodiment, in the scope identical with the present invention, or in the scope of equalization, various revisions or distortion in addition.
Industrial utilizability
When such carbon nanometer precursor is blended in base material, can be effectively applied to require high conductivity and high-intensity situation.
Such silver/carbon nano composite body can be effectively applied to require high conductivity and high-intensity situation.
When can being effectively applied to require to be blended in base material, the manufacture method of such carbon nanometer precursor easily makes the situation of giving high conductivity and high-intensity carbon nanometer precursor.
The manufacture method of such silver/carbon nano composite body can effectively utilize in requiring easily to make the situation with high conductivity and high-intensity silver/carbon nano composite body.
Nomenclature
11 carbon nanometer precursors
12 carbon nanotubes
13 carbon blacks.
Claims (10)
1. carbon nanometer precursor, the carbon black that it comprises the carbon nanotube of monodisperse status and is attached to the primary particle state of described carbon nano tube surface.
2. carbon nanometer precursor as claimed in claim 1, wherein, the carbon black of described primary particle state uses has wetting ability and hydrophobic tensio-active agent is attached to described carbon nano tube surface.
3. carbon nanometer precursor as claimed in claim 1, it is by following method manufacturing: after adding in advance described carbon nanotube form monodisperse status in comprising the solution with wetting ability and hydrophobic tensio-active agent, the aggregate of carbon black is made an addition to the carbon black that forms the primary particle state in described solution, make the carbon black of described primary particle state be attached to described carbon nano tube surface.
4. carbon nanometer precursor as claimed in claim 2, wherein, in described carbon nanometer precursor, remove the solution composition of described tensio-active agent.
5. carbon nanometer precursor as claimed in claim 1, wherein, described carbon nanotube comprises the compound wall carbon nanotube.
6. silver/carbon nano composite body, it possesses base material and network-like the carbon nanometer precursor that is contained in described base material, and described carbon nanometer precursor comprises the carbon nanotube of monodisperse status and is attached to the carbon black of the primary particle state of described carbon nano tube surface.
7. silver/carbon nano composite body as claimed in claim 6, wherein, described base material comprises rubber.
8. the manufacture method of a carbon nanometer precursor, it comprises following operation:
Preparation comprises the operation of the solution with wetting ability and hydrophobic tensio-active agent;
Add carbon nanotube in described solution, make described carbon nanotube be the operation of monodisperse status in described solution; And
Form the primary particle state making described carbon nanotube add the carbon black of aggregate in being the described solution of monodisperse status, make described carbon nano tube surface adhere to the operation of the carbon black of described primary particle state.
9. the manufacture method of carbon nanometer precursor as claimed in claim 8, after it also is included in the carbon black that makes the described primary particle state of described carbon nano tube surface coating, the operation of removing solution composition.
10. the manufacture method of a silver/carbon nano composite body, it comprises following operation:
Preparation comprises the operation of the solution with wetting ability and hydrophobic tensio-active agent;
Add carbon nanotube in described solution, make described carbon nanotube be the operation of monodisperse status in described solution;
Form the primary particle state making described carbon nanotube add the carbon black of aggregate in being the described solution of monodisperse status, make described carbon nano tube surface adhere to the operation of the carbon black of described primary particle state;
After making described carbon nano tube surface adhere to the carbon black of described primary particle state, remove solution composition and obtain the operation of carbon nanometer precursor; And
The operation of mixing resulting described carbon nanometer precursor and base material.
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| PCT/JP2009/062790 WO2010008014A1 (en) | 2008-07-18 | 2009-07-15 | Carbon nanoprecursor, method for producing the same, carbon nanocomposite and method for producing the same |
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| US9550907B2 (en) | 2015-02-27 | 2017-01-24 | Gates Corporation | Carbon nanostructure preblends and their applications |
| CN107206389B (en) * | 2015-03-10 | 2021-09-17 | 海佩里恩催化国际公司 | Method for co-processing nanocarbon in carbon black and products obtained thereby |
| JP6630905B2 (en) * | 2016-04-28 | 2020-01-15 | 株式会社ＤＲ．ｇｏｏ | Method for granulating carbon having different bulk densities and method for producing granulated carbon |
| JP6984269B2 (en) * | 2017-09-19 | 2021-12-17 | 三菱ケミカル株式会社 | Carbon nanotube / carbon black / rubber complex and its manufacturing method |
| WO2019058911A1 (en) * | 2017-09-22 | 2019-03-28 | 日本ゼオン株式会社 | Rubber composition |
| CN114621621A (en) * | 2020-12-14 | 2022-06-14 | 清华大学 | Light absorber prefabricated liquid and preparation method thereof |
| CN114624798B (en) * | 2020-12-14 | 2023-05-16 | 清华大学 | Light absorber and method for producing the same |
| CN114623605B (en) | 2020-12-14 | 2023-08-22 | 清华大学 | Solar heat collector and solar water heater |
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| CN1770515A (en) * | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
| CN1891740A (en) * | 2005-06-30 | 2007-01-10 | 日信工业株式会社 | Composite material |
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| EP2113302A4 (en) * | 2004-05-13 | 2009-12-23 | Univ Hokkaido Nat Univ Corp | Fine carbon dispersion |
| JP4872112B2 (en) * | 2004-05-13 | 2012-02-08 | 国立大学法人北海道大学 | Fine carbon dispersion |
| JP4930873B2 (en) * | 2005-03-24 | 2012-05-16 | 国立大学法人北海道大学 | Fine carbon dispersion |
| JP2007039649A (en) * | 2005-06-30 | 2007-02-15 | Nissin Kogyo Co Ltd | Composite material |
| JP2008056765A (en) * | 2006-08-30 | 2008-03-13 | Mitsubishi Rayon Co Ltd | Carbon nanotube-containing structure and its manufacturing method |
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