CN100451052C - Composite material - Google Patents
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- CN100451052C CN100451052C CNB2006100866993A CN200610086699A CN100451052C CN 100451052 C CN100451052 C CN 100451052C CN B2006100866993 A CNB2006100866993 A CN B2006100866993A CN 200610086699 A CN200610086699 A CN 200610086699A CN 100451052 C CN100451052 C CN 100451052C
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Abstract
A composite material, including: an elastomer; carbon nanofibers having an average diameter of 0.7 to 15 nm and an average length of 0.5 to 100 micrometers; and carbon black having an average particle diameter of 10 to 100 nm and a DBP absorption of 100 ml/100g or more, the carbon nanofibers and the carbon black being dispersed in the elastomer. The elastomer includes an unsaturated bond or a group exhibiting affinity to the carbon nanofibers. The composite material includes the carbon nanofibers in an amount of 1 to 30 vol% and the carbon black in an amount of 10 to 40 vol%. The composite material has an average coefficient of linear expansion of 100 ppm (1/K) or less and a differential coefficient of linear expansion of 120 ppm (1/K) or less at -80 to 300 DEG C.
Description
Technical field
The present invention relates to contain the matrix material of carbon black and carbon nanofiber.
Background technology
Usually,, be with body material and fortifying fibre or strengthen particle and make up, give physical properties according to purposes as matrix material.Particularly in fields such as semiconductor manufacturing facility, optical device, ultra tiny processing units, need to reduce the influence that the parts thermal expansion is caused, therefore, various fortifying fibres have been proposed to adopt, the scheme of the matrix material of carbon fiber (referring to, for example international text that discloses No. 00/64668) for example.
But, to compare with the matrix material that uses particle, the matrix material of use fiber is difficult to obtain the isotropy of thermal expansion.Therefore, its purposes is restricted to sheet and tabular, but also need make fiber form the operation of three-dimensional arrangements such as two dimension, three dimensional fabric etc.In addition, elastomerics under different temperature condition linear expansivity great changes have taken place, particularly will be under lower temperature because of thermal ageing take place in molecular rupture, therefore linear expansivity can sharply raise (the following temperature that will begin to take place this thermal ageing is called heat resisting temperature) near this temperature.Therefore, with regard to using elastomerics, also there not be proposition in the temperature range of broadness, to have the matrix material of stable low linear expansion coefficient as with regard to the matrix material of matrix.
In addition, as the previous matrix material that proposes such as the inventor, have carbon nanofiber is dispersed in the elastomerics and the matrix material that forms (referring to, for example the spy opens the 2005-68386 communique).As this matrix material, by elastomerics and carbon nanofiber are carried out mixing, improved the dispersiveness of the strong carbon nanofiber of concentration.
Summary of the invention
Therefore, the purpose of this invention is to provide to contain and be dispersed with carbon black and carbon nanofiber, the particularly little matrix material of thermal expansion in the temperature range of broadness equably.
Matrix material of the present invention contains elastomerics, the mean diameter that is dispersed in this elastomerics is that 0.7～15nm and mean length are the carbon nanofiber of 0.5～100 μ m, with median size be 10～100nm and DBP absorbed dose carbon black more than or equal to 100ml/100g, above-mentioned elastomerics possesses unsaturated link(age) or the group that affinity is arranged with above-mentioned carbon nanofiber, the content of above-mentioned carbon nanofiber is 1～30 volume %, the content of above-mentioned carbon black is 10～40 volume %, under-80～300 ℃, average coefficient of linear expansion smaller or equal to the differential value of 100ppm (1/K) and linear expansivity smaller or equal to 120ppm (1/K).
According to matrix material of the present invention, by carbon black and the very thin carbon nanofiber that contains the structure prosperity, thereby in the temperature range of broadness, have low linear expansion coefficient, reached stabilization.Therefore, can be with this matrix material and the low material of linear expansivity, for example metal or pottery etc. are used in combination.Particularly owing to can in the broader temperature range of general elastomerics, use, thereby can get up, carry out the goods design easily with the low combination of materials of linear expansivity.
Assemble flourishing high structural carbon black by this use elastomerics integral body is carried out reinforcement, even a spot of carbon nanofiber also can reach the thermal expansion that suppresses matrix material, the effect that reduces linear expansivity.
In addition, by the active part of elastomeric unsaturated link(age) or group and carbon nanofiber, particularly the free radical of carbon nanofiber end carries out bonding, can weaken carbon nanofiber aggregation force, improve its dispersiveness.As a result, matrix material is dispersed in as in the elastomerics of base material and the material that obtains carbon nanofiber with regard to becoming.
Matrix material of the present invention contains elastomerics, be dispersed in mean diameter in this elastomerics is that 0.7～15nm and mean length are that the carbon nanofiber of 0.5～100 μ m and median size are 10～100nm and the DBP absorbed dose carbon black more than or equal to 100ml/100g,
Above-mentioned elastomerics possesses unsaturated link(age) or the group that affinity is arranged with above-mentioned carbon nanofiber,
The content of above-mentioned carbon nanofiber is 1～30 volume %,
The content of above-mentioned carbon black is 10～40 volume %,
Under-80～300 ℃, the linear expansivity of any direction X and with the ratio of linear expansivity on the vertical direction Y of this direction X be 0.7～1.3 times.
According to matrix material of the present invention,, there is not the anisotropy of linear expansivity by containing homodisperse carbon black and carbon nanofiber.Therefore, matrix material of the present invention is not limited to sheet, platy morphology in the past, can adopt variform.
In matrix material of the present invention, the length-to-diameter ratio that can make above-mentioned carbon nanofiber is more than or equal to 50.
As matrix material of the present invention, can make its heat resisting temperature more than or equal to 300 ℃.Because heat resisting temperature is the high temperature more than or equal to 300 ℃, thereby also can be as the parts that use in the hot environment.
Elastomerics among the present invention can be any in rubber-like elastomerics or the thermoplastic elastomer.In addition, when it was the rubber-like elastomerics, elastomerics can be any in crosslinked body or the non-crosslinked body, but preferably used the non-crosslinked body.
Description of drawings
Describe in the present embodiment to adopt Fig. 1 model utility and open the refining method elastomerics and carbon nanofiber are carried out mixing method figure.
Fig. 2 is the graphic representation of differential value of the temperature-linear expansivity of embodiment 1,2 and comparative example 1.
Embodiment
Below, with reference to accompanying drawing embodiments of the invention are elaborated.
Matrix material described in the present embodiment contains elastomerics, the mean diameter that is dispersed in this elastomerics is that 0.7～15nm and mean length are the carbon nanofiber of 0.5～100 μ m, with median size be 10～100nm and DBP absorbed dose carbon black more than or equal to 100ml/100g, above-mentioned elastomerics possesses unsaturated link(age) or the group that affinity is arranged with above-mentioned carbon nanofiber, the content of above-mentioned carbon nanofiber is 1～30 volume %, the content of above-mentioned carbon black is 10～40 volume %, under-80～300 ℃, average coefficient of linear expansion smaller or equal to the differential value of 100ppm (1/K) and linear expansivity smaller or equal to 120ppm (1K).
In addition, as the matrix material described in the present embodiment, under-80～300 ℃, the linear expansivity on any direction X and with the ratio of linear expansivity on the vertical direction Y of this direction X be 0.7～1.3 times.
The manufacture method of the matrix material described in the present embodiment comprises the carbon black of agglomerated prosperity and carbon nanofiber has the unsaturated link(age) of affinity or the elastomerics of group to mix to above-mentioned carbon nanofiber with possessing, and utilizes shearing force to make its dispersive operation.
As elastomerics, for example, except with the affinity height of carbon nanofiber, preferably also possess following feature, promptly molecular length for to a certain degree long, have a flexibility etc.In addition, as utilizing shearing force to make carbon nanofiber be dispersed in operation in the elastomerics, preferably adopt high as far as possible shearing force to carry out mixing.
(I) at first, elastomerics is described.Elastomeric molecular weight is preferably 5000 to 5,000,000, and more preferably 20,000 to 3,000,000.If elastomeric molecular weight is in this scope, then elastomer molecules twine mutually, interconnection, so elastomerics has the carbon nanofiber of making and carries out the dispersive favorable elasticity.Because elastomerics has viscosity, be easy to interpenetrate with the accumulative carbon nanofiber, and the elasticity that it had makes carbon nanofiber to be separated from each other.If elastomeric molecular weight is less than 5000, then elastomer molecules can not be tangled each other fully, even apply shearing force in subsequent handling, its elastic force is still little, thereby it is little to make carbon nanofiber carry out the dispersive effect.In addition, if elastomeric molecular weight surpasses 5,000,000, then elastomerics is really up to the mark, processing difficulties.
As elastomerics, when adopting pulsed NMR to utilize rare grace echo method to measure under 30 ℃, the spin spin relaxation time of the network component in its non-crosslinked body (T2n/30 ℃) was preferably for 100 to 3000 μ seconds, more preferably 200 to 1000 μ seconds.By spin spin relaxation time (T2n/30 ℃) with above-mentioned scope, can make the promptly soft transport properties of molecules that has height again of elastomerics, that is, have the carbon nanofiber of making and carry out dispersive appropriateness elasticity.In addition, because elastomerics has viscosity, when elastomerics mixed with carbon nanofiber, elastomerics can immerse carbon nanofiber space each other easily by the molecular motion of height.If spin spin relaxation time (T2n/30 ℃) is less than 100 μ seconds, then elastomerics can not have competent transport properties of molecules.In addition, if spin spin relaxation time (T2n/30 ℃) greater than 3000 μ seconds, then elastomerics is easy to resemble the liquid mobile, elasticity is little, thereby is difficult to make carbon nanofiber to disperse.
In addition, as elastomerics, when adopting pulsed NMR to utilize rare grace echo method to measure under 30 ℃, the spin spin relaxation time (T2n) of network component was 100 to 2000 μ seconds in its crosslinked body.Its reason is identical with above-mentioned non-crosslinked body.That is, if it is crosslinked that the non-crosslinked body with above-mentioned condition is carried out, then the T2n of the crosslinked body that is obtained roughly is comprised in the above-mentioned scope.
The spin spin relaxation time that adopts pulsed NMR to utilize rare grace echo method to obtain is the yardstick that characterizes the transport properties of molecules of material.Specifically, if adopt pulsed NMR to utilize rare grace echo method to measure elastomeric spin spin relaxation time, then can detect the 1st composition with short the 1st spin spin relaxation time (T2n) and the 2nd composition with long the 2nd spin spin relaxation time (T2nn).The 1st composition is equivalent to high molecular network component (molecule of the skeleton), and the 2nd composition is equivalent to high molecular non-network component (tip composition such as terminal chain).Therefore, the 1st spin spin relaxation time is short more, and transport properties of molecules is low more, and so-called elastomerics is hard more.In addition, the 1st spin spin relaxation time is long more, and transport properties of molecules is high more, and so-called elastomerics is soft more.
As the assay method of pulsed NMR, be not only rare grace echo method, solid echo method (solid echo method), CPMG method (Carr-Purcell-Meiboom-Gill method) or 90 ° of impulse methods also suit.But because elastomerics of the present invention has medium spin spin relaxation time (T2), therefore rare grace echo method is optimum.Usually, solid echo method and 90 ° of impulse methods are suitable for the mensuration of short T2, and rare grace echo method is suitable for the mensuration of medium T2, and the CPMG method is suitable for the mensuration of long T2.
Possess unsaturated link(age) or the group that the terminal free radical of carbon nanofiber is had affinity at least a chain in elastomeric main chain, side chain and the terminal chain, or have the character that is easy to generate this free radical or group.As above-mentioned unsaturated link(age) or group, can be to be selected from least a in the functional groups such as two keys, triple bond, α hydrogen, carbonyl, carboxyl, hydroxyl, amino, itrile group, ketone group, amide group, epoxy group(ing), ester group, vinyl, halogen, urethane ester group, biuret groups, allophanate group and urea groups.
As carbon nanofiber, usually the side is made of the carbon atom six-ring, and the top is introduced five-ring and formed the structure of sealing, but owing to there is exception on the structure, in fact is easy to produce defective, is easy to generate free radical or functional group in this part.In the present embodiment, owing to possess high unsaturated link(age) or the group of affinity (reactivity or polarity) with the free radical of carbon nanofiber at least a chain in elastomeric main chain, side chain and the terminal chain, make elastomerics and carbon nanofiber can carry out bonding.Thus, overcome gathering power and can easily disperseing of carbon nanofiber.Therefore can infer that when elastomerics and carbon nanofiber carry out when mixing, elastomeric molecular chain is cut off the defective that free radical that the back forms can be attacked carbon nanofiber, at the surface of carbon nanofiber generation free radical.
As elastomerics, can use natural rubber (NR), epoxy natural rubber (ENR), styrene butadiene rubbers (SBR), paracril (NBR), chloroprene rubber (CR), ethylene-propylene rubber(EPR) (EPR, EPDM), isoprene-isobutylene rubber (IIR), chlorinated butyl rubber (CIIR), acrylic elastomer (ACM), organo-silicone rubber (Q), viton (FKM), divinyl rubber (BR), epoxidation divinyl rubber (EBR), epichloro hydrin rubber (CO, CEO), urethanes (U), thiorubber elastomerics classes such as (T); Olefines (TPO), polyvinyl chloride (TPVC), polyester (TPEE), polyurethanes (TPU), polyamide-based (TPEA), styrenic thermoplastic elastomers such as (SBS); And their mixture.Be easy to generate free radical and the high elastomerics of polarity, for example natural rubber (NR), paracril (NBR) etc. when mixing particularly preferably in elastomerics.In addition, even the low elastomerics of polarity, ethylene-propylene rubber(EPR) (EPDM) for example, owing to can generate free radical when making melting temperature be comparatively high temps (for example being 50～150 ℃ when for EPDM), thereby also can be used for the present invention.
Elastomerics in the present embodiment can be any one in rubber-like elastomerics or the thermoplastic elastomer.In addition, under the elastomeric situation of rubber-like, elastomerics can be any one in crosslinked body or the non-crosslinked body, but preferably uses the non-crosslinked body.
(II) below, carbon black and carbon nanofiber are described.As the carbon black described in the present embodiment, can use the carbon black of the various grades that adopt various raw materials formation.As carbon black, preferred basic comprising particle (so-called primary particle) fusion connects formed aggregate (so-called secondary aggregate) prosperity and has higher structural kind.
As the carbon black described in the present embodiment, the median size of its basic comprising particle is 10～100nm, and the DBP absorbed dose is more than or equal to 100ml/100g, and more preferably median size is 10～40nm, and the DBP absorbed dose is 110～500ml/100g.If the not enough 10nm of the median size of carbon black, processing (mixing) difficulty then, if median size greater than 100nm, then reinforcing effect is poor.Because the reinforcing effect of carbon black is subjected to the influence of the structural height of congeries prosperity, therefore, if the DBP absorbed dose more than or equal to 100ml/100g, then reinforcing effect is big.
As this carbon black, for example can use kitchen range to deceive carbon blacks such as (kitchen black), SAF, SAF-HS, ISAF, ISAF-HS, HAF, HAF-HS, FEF, FEF-HS, SRF-HS.
The mean diameter of carbon nanofiber is 0.7～15nm, and mean length is 0.5～100 μ m.If the mean diameter of carbon nanofiber is less than 0.7nm, subject to damage when then mixing, if mean diameter greater than 15nm, then can not obtain the sealing effect of carbon nanofiber and carbon black, reinforcing effect is poor.If the mean length of carbon nanofiber is less than 0.5 μ m, then reinforcing effect is poor, if mean length greater than 100 μ m, is then processed (mixing) difficulty.
In addition, the length-to-diameter ratio of carbon nanofiber is preferably greater than and equals 50, and more preferably length-to-diameter ratio is 100～20,000.If length-to-diameter ratio less than 50 then can not obtain the effect of sealed elastic body, matrix material for example can take place to flow and thermal ageing under 300 ℃ sometimes.
Matrix material contains 1～30 volume %, the carbon nanofiber of preferred 1～15 volume %, and preferably contain the carbon black of 10～40 volume %.Contain the carbon black of this volume ratio and the matrix material of carbon nanofiber, average coefficient of linear expansion under-80～300 ℃ is smaller or equal to 100ppm (1/K), and the differential value of linear expansivity promptly has stable low linear expansion coefficient smaller or equal to 120ppm (1/K).If carbon nanofiber less than 1 volume %, then can not retrain elastomerics, thereby can not reduce linear expansivity, if surpass 15 volume %, though can reduce linear expansivity,, when particularly surpassing 30 volume %, will use expensive carbon nanofiber in a large number, be not preferred in practice.During carbon black less than 10 volume %, just can not reduce linear expansivity if do not contain carbon nanofiber in a large number, if surpass 40 volume %, then processing (mixing) difficulty is not preferred.
As carbon nanofiber, for example can illustration so-called carbon nanotube etc.Carbon nanotube has by carbon hexagon wire side graphite flake layer closure for single layer structure cylindraceous or have by these cylinder-like structures and carry out the nested multilayered structure that constitutes.That is to say that carbon nanotube not only can be made of single layer structure, also can only be made of multilayered structure, can also be that single layer structure and multilayered structure exist simultaneously.In addition, can also use carbon material with part carbon nanotube structure.Also have, except the title of carbon nanotube, also be referred to as the graphite filaments nanotube sometimes.
Single-layer carbon nano-tube or multilayer carbon nanotube are to make desirable shape by arc discharge method, laser ablation method, vapor growth method etc.
The arc discharge method is under the argon gas or hydrogen environment lower slightly than normal atmosphere, carries out arc-over between the electrode materials that carbon-point is made, thereby obtains to be deposited in the method for the multilayer carbon nanotube on the negative electrode.In addition, single-layer carbon nano-tube is to sneak into catalyzer such as nickel/cobalt and carry out arc-over in above-mentioned carbon-point, and the flue dust that adheres to from the processing vessel medial surface obtains again.
Laser ablation method is in rare gas element (for example argon gas), by with the intense pulse laser of YAG laser to as sneaking into of target the carbon surface of catalyzer such as nickel/cobalt shine, make carbon surface fusion evaporation and form the method for single-layer carbon nano-tube.
Vapor growth method is to decompose hydrocarbon such as benzene or toluene in gas phase, thereby the method for synthesizing carbon nanotubes specifically, can be enumerated flowing catalyst method, zeolite supported catalyst method etc.
Carbon nanofiber can be in advance by surface treatment before mixing with elastomerics, and for example ion implantation processing, sputter etching processing, Cement Composite Treated by Plasma etc. are improved and elastomeric cohesiveness or wetting property.
(III) then, sneak in the elastomerics, and carry out the dispersive operation by shearing force and describe making above-mentioned carbon black and above-mentioned carbon nanofiber.This operation can adopt out refining method, banburying method, multiaxis to extrude mixing method etc. and implement.
In the present embodiment, as making carbon nanofiber be distributed to operation in the elastomerics by shearing force, be that example describes smaller or equal to the refining method of opening of 0.5mm with the roller gap.
Fig. 1 be model utility describe to use the figure that opens the refining method of two rollers.In Fig. 1, symbol 10 expressions the 1st roller, symbol 20 expressions the 2nd roller.The 1st roller 10 and the 2nd roller 20 have predetermined gap d, for example gap of 1.5mm for being provided with.The the 1st and the 2nd roller can be in the same way or reverse rotation.In illustrated embodiment, the 1st roller 10 and the 2nd roller 20 rotate in a direction indicated by the arrow.
At first, under the state that the 1st, the 2nd roller 10,20 is rotated, elastomerics takes place and accumulates in the elastomerics 30 of reeling on the 2nd roller 20,10,20 on roller, has formed so-called accumulation 32.Add above-mentioned carbon black 50 and carbon nanofiber 40 in this is piled up, if make 10,20 rotations of the 1st, the 2nd roller, then carbon black and carbon nanofiber are sneaked in the elastomerics, thereby obtain mixture.From mill, take out this mixture.Gap d with the 1st roller 10 and the 2nd roller 20 is preferably set to smaller or equal to 0.5mm again, and more preferably 0.1～0.5mm carries out the thin-pass operation in the mixture input mill with resulting elastomerics and carbon nanofiber.Thin-pass is preferably carried out for example about 10 times.If as V1, as V2, both surface velocities are preferably 1.05～3.00 than (V1/V2) when then carrying out thin-pass with the surface velocity of the 2nd roller 20 with the surface velocity of the 1st roller 10, more preferably 1.05～1.2.By adopting such surface velocity ratio, the shearing force that can obtain to expect.
In addition, as the order of throwing in carbon black and carbon nanofiber in elastomerics, the preferred carbon black that drops into earlier drops into carbon nanofiber again.
By thus obtained shearing force, elastomerics 30 is applied high shear force, the carbon nanofiber 40 that gathers is dispersed in the elastomerics 30 to be separated from each other by the mode of one one ground of elastomer molecules tractive.
In addition, in this operation, in order to obtain high as far as possible shearing force, mixing preferably at 0～50 ℃ of elastomerics and carbon nanofiber more preferably carried out under 5～30 ℃ lesser temps.Also have, when using EPDM, preferably adopt mixing operation of two steps, in the first mixing operation,, EPDM is mixed under first temperature than low 50～100 ℃ of the second mixing operation with carbon nanofiber in order to obtain high as far as possible shearing force as elastomerics.First temperature is preferably 0～50 ℃, more preferably 5～30 ℃.Second temperature of mixing roller is set at 50～150 ℃ comparatively high temps, thereby can improves the dispersiveness of carbon nanofiber.
In addition, in this operation, generated free radical in the elastomerics by the shearing force shearing,, made the surface of carbon nanofiber obtain activation by the attack on this radical pair carbon nanofiber surface.For example, when using natural rubber (NR) as elastomerics, each natural rubber (NR) molecule is cut off through roller mixing the time, has formed small molecular weight before being put to mill.Owing to generated free radical in natural rubber (NR) molecule that is so cut off, mixing during the radical pair carbon nanofiber attack, therefore with regard to activated carbon nanofiber surface.
At this moment, owing to make the elastomerics described in the present embodiment have above-mentioned feature, promptly have by elastomer molecules form (molecular length) or elasticity that molecular motion showed, viscosity and particularly with the features such as chemical interaction of carbon nanofiber, make the dispersion of carbon nanofiber easy, so that can obtain the dispersiveness of carbon nanofiber and the excellent matrix material of dispersion stabilization (an end dispersive carbon nanofiber is difficult to gather again).More particularly, if elastomerics mixes with carbon nanofiber, the elastomerics and the carbon nanofiber that then have viscosity immerse mutually, and elastomeric specific part carries out bonding by chemical interaction and the active high part of carbon nanofiber.Under this state, if have the elastomerics of suitable length, transport properties of molecules height (having elasticity) and the mixture of carbon nanofiber to impose strong shearing force to molecule, then be accompanied by elastomeric distortion, carbon nanofiber also is moved, and by the elastomerics restoring force that elasticity caused after cutting off, the accumulative carbon nanofiber is separated, thereby be dispersed in the elastomerics.According to present embodiment, can infer when mixture when extrude in narrow roller gap, by the restoring force that elastomeric elasticity caused, mixture is deformed into thicker than the gap of mixing roller.This distortion makes the mixture that has applied strong shearing force that complex flow further take place, and carbon nanofiber is dispersed in the elastomerics.Thereby in a single day carbon nanofiber has obtained dispersion, just can have good dispersion stabilization by preventing that with elastomeric interaction it from reassociating.
This operation is not limited to the above-mentioned refining method of opening, and also can use banburying method or the multiaxis addressed to extrude mixing method.In a word, as long as in this operation, the accumulative carbon nanofiber is separated and can apply the shearing force that to cut off elastomer molecules and generate free radical to get final product to elastomerics.
After the last operation that carbon nanofiber is dispersed in the elastomerics, can adopt known method to implement to extrude operation, molding procedure, crosslinked operation etc.
Carbon nanofiber is distributed in the operation in the elastomerics, or, can adding employed Synergist S-421 95 in the elastomeric processing such as rubber usually in the front and back of this operation.Synergist S-421 95 can use known material.As Synergist S-421 95, for example can enumerate carbon black as tinting material, as the lime carbonate of extender, as strengthening agent silicon-dioxide, talcum, clay, as superoxide of linking agent etc., and vulcanizing agent, vulcanization accelerator, vulcanization retarder, tenderizer, softening agent, solidifying agent, filler, antiaging agent etc.
(IV) below, the matrix material that the operation by above-mentioned (III) is obtained is described.
Matrix material described in the present embodiment contains elastomerics, is dispersed in carbon black in this elastomerics and the carbon nanofiber of 1～30 volume % with 10～40 volume %, under-80～300 ℃, average coefficient of linear expansion smaller or equal to the differential value of 100ppm (1/K) and linear expansivity smaller or equal to 120ppm (1/K).
The average coefficient of linear expansion of matrix material changes with the volume ratio of carbon black and carbon nanofiber, and average coefficient of linear expansion was low when the volume ratio of carbon black and carbon nanofiber was high, average coefficient of linear expansion height when the volume ratio of carbon black and carbon nanofiber is low.That is to say, can control the average coefficient of linear expansion of matrix material by the volume ratio of carbon black and carbon nanofiber.If carbon nanofiber less than 1 volume % then can not retrain elastomerics, thereby can not reduce linear expansivity, just can reduce linear expansivity if surpass 15 volume %, but when particularly surpassing 30 volume %, use carbon nanofiber in a large number, be not preferred in practicality.If carbon black less than 10 volume %, then if do not contain carbon nanofiber in a large number and just can not reduce linear expansivity, and when surpassing 40 volume %, it is difficult that processing (mixing) becomes, and is undesirable.
The volume ratio of carbon nanofiber and carbon black is relevant, when the volume ratio of carbon nanofiber hangs down, improve the volume ratio of carbon black, when the volume ratio of carbon black hangs down, improve the volume ratio of carbon nanofiber, thereby linear expansivity is controlled at low-level.
The differential value of the linear expansivity of matrix material is low to moderate under-80～300 ℃ smaller or equal to 120ppm (1/K), and is stable in the temperature range of broadness, can not produce transient heat and expand.The maximum value of the differential value of matrix material linear expansivity changes with the volume ratio of carbon black and carbon nanofiber, and its value diminished when the proportioning of carbon black and carbon nanofiber was high, and its value uprised when the volume ratio of carbon black and carbon nanofiber was low.That is to say, can control the maximum value of the linear expansivity differential value of matrix material by the volume ratio of carbon black and carbon nanofiber.In addition, if carbon carbon nanofiber less than 1 volume %, the linear expansivity instability under then-80～300 ℃, heat resisting temperature also is lower than 300 ℃.And, when the volume ratio less than 10 volume % of the volume ratio less than 15 volume % of carbon nanofiber, carbon black, the maximum value of linear expansivity differential value can surpass 120ppm (1/K), big change takes place in linear expansivity in-80～300 ℃ temperature range, and it is unstable that thermal expansion becomes in specific temperature province.
Matrix material described in the present embodiment is under-80～300 ℃, and the linear expansivity on any direction X is 0.7～1.3 times with ratio perpendicular to the linear expansivity on the direction Y of this direction X.
If for example the sense of rotation with mill is any direction X, then using under the straight stiff fibre enhanced situation usually, it is orientated and is minimum with the linear expansivity on the vertical direction Y of direction X, demonstrate anisotropy, but the linear expansivity of the described matrix material of present embodiment has isotropy.
In the described in the present embodiment matrix material, surrounded by carbon black and carbon nanofiber, formed the constraint as the elastomerics of matrix.This constraint limitation and restriction elastomeric motion.The mean diameter that contains 1～30 volume % is the matrix material of the carbon black of the thin carbon nanofiber of 0.7～15nm and 10～40 volume %, and the constraint on arbitrary face is very little, so elastomerics suffers restraints in the mode of physical crosslinking.And the constraint that is formed by carbon nanofiber can be in the temperature range of broadness, gives heat stable linear expansivity under for example-80～300 ℃.
Matrix material can be the non-crosslinked body, also can be crosslinked body, can select aptly according to purposes.If matrix material is the non-crosslinked body, then can carries out recirculation and use.
The heat resisting temperature of the described matrix material of present embodiment is more than or equal to 300 ℃.
Heat resisting temperature can begin to rupture by the elastomeric molecular linkage that the constitutes matrix material rapid rising of the linear expansivity that caused is judged.
In the described matrix material of present embodiment, carbon black and carbon nanofiber are dispersed in the elastomerics as matrix.This situation also can be called elastomerics because of carbon black and the bound state of carbon nanofiber.Under this state, owing to be subjected to the constraint of carbon black and carbon nanofiber, the mobility of elastomer molecules is little when not retrained by carbon black and carbon nanofiber.It is short when therefore, first spin spin relaxation time (T2n) of the described matrix material of present embodiment, second spin spin relaxation time (T2nn) and spin-lattice relaxation time (T1) are than the elastomerics monomer that adopts not carbon black and carbon nanofiber.
In addition, elastomerics is considered to owing to following reason usually because of carbon black and the bound state of carbon nanofiber, that is, non-network component (non-netted chain composition) reduces to some extent.That is to say, it has been generally acknowledged that if the mobility of elastomer molecules reduces because of carbon black and carbon nanofiber are whole, then the motion parts that is difficult for of non-network component increases, be easy to produce the behavior identical with network component, in addition, because non-network component (terminal chain) is easy to activity, thereby be easy to be adsorbed on the active site of carbon black and carbon nanofiber, because with first-class reason, non-network component reduces to some extent.
Owing to above-mentioned reason, the use pulsed NMR of the described matrix material of present embodiment utilizes rare grace echo (hahn echo) measured value that method obtained to be expected to be in the following scope.
Promptly, in the non-crosslinked matrix material, 150 ℃ of first spin spin relaxation times (T2n) of measuring down were 100 to 3000 μ seconds, second spin spin relaxation time (T2nn) was 1000 to 10000 μ seconds, and the composition branch rate (fnn) that preferably has a composition of second spin spin relaxation time is a less than 0.2.
In addition, in crosslinked matrix material, 150 ℃ of first spin spin relaxation times (T2n) of measuring down were 100 to 2000 μ seconds, second spin spin relaxation time (T2nn) does not exist or was 1000 to 5000 μ seconds, and preferred above-mentioned composition branch rate (fnn) with composition of second spin spin relaxation time is a less than 0.2.
The spin-lattice relaxation time (T1) that adopts pulsed NMR (pulsed nuclear magnetic resonance analyser) to utilize counter-rotating answer method to measure is the same with spin spin relaxation time (T2) to be the yardstick that characterizes the transport properties of molecules of material.Specifically, elastomeric spin-lattice relaxation time is short more, and transport properties of molecules is low more, and promptly elastomerics is hard more, and elastomeric spin-lattice relaxation time is long more, and transport properties of molecules is high more, and promptly elastomerics is soft more.Therefore, the transport properties of molecules that carbon black and carbon nanofiber obtain homodisperse matrix material reduces, and its T2n, T2nn, fnn are in the above-mentioned scope.
In the temperature dependency of dynamic viscoelastic was measured, the yield temperature of the described matrix material of present embodiment was preferably high 20 ℃ than the monomeric yield temperature of raw material elastomerics.In the described matrix material of present embodiment, carbon black and carbon nanofiber are scattered in the elastomerics well.As mentioned above, this situation also can be described as elastomerics because of carbon black and the bound state of carbon nanofiber.Under this state, the mobility of elastomer molecules is little during than carbon black not and carbon nanofiber, result, the mobile reduction.By having this yield temperature characteristic, the temperature dependency of the dynamic viscoelastic of the matrix material of present embodiment is little, and the result just has excellent thermotolerance.
As mentioned above, the thermal expansion character of the described matrix material of present embodiment is stable in the temperature range of broadness.And the average coefficient of linear expansion of matrix material is low, thereby thermal expansion is little in the temperature range of broadness.In addition, because the maximum value of the differential value of the linear expansivity of matrix material is little, thereby stable in the temperature range of broadness, transient heat can not take place expand change greatly.
Below, embodiments of the invention are described, but the present invention is not limited thereto.(embodiment 1～7, comparative example 1～4)
(1) making of sample
The refining method is opened in employing, and the carbon black of mixing predetermined amount and carbon nanofiber obtain sample in the elastomerics shown in the table 1.Prepare non-crosslinked sample and crosslinked sample by the following method.
(a) making of non-crosslinked sample
1) in 6 inches mills (10～20 ℃ of mixing roll temperatures), drops into elastomerics, be wound on the mixing roller.
2) in elastomerics, drop into carbon black and carbon nanofiber (being designated as " CNT1 ", " CNT2 " in the table 1).At this moment, the gap of mixing roller is 1.5mm.
3) if the input of carbon black and carbon nanofiber is finished, then from mixing roller, take out the mixture of elastomerics and carbon black and carbon nanofiber.
4) gap with mixing roller is reduced to 0.3mm from 1.5mm, drops into mixture and carries out thin-pass.At this moment, making the ratio of two roller surface velocities is 1.1.Carry out 10 thin-pass operations repeatedly.
5) mixing roller is set at predetermined gap (1.1mm), drops into mixture, carry out compressing tablet through thin-pass.
According to said method, obtain the non-crosslinked sample of embodiment 1～7 and comparative example 1～4.In table 1, as the raw material elastomerics, " NR " is natural rubber, and " EPDM " is ethylene-propylene rubber(EPR), and " SBR " is styrene butadiene rubbers.In addition, in table 1, " CNT1 " is that the about 1nm of median size, mean length are the single-layer carbon nano-tube of 1～10 μ m, and " CNT13 " is that the about 13nm of median size, mean length are the multilayer carbon nanotube of 1～25 μ m.In table 1, the median size of " kitchen range is black " is that 34nm, DBP absorbed dose are 500ml/100g, and the median size of " HAF-HS " is that 27nm, DBP absorbed dose are 127ml/100g, and the median size of " HAF-LS " is that 28nm, DBP absorbed dose are 86ml/100g.In embodiment 1,3～7 and comparative example 1～4, before dropping into carbon black and carbon nanofiber, with respect to the elastomerics input of 100phr superoxide (PO) 2phr as linking agent.Also have, embodiment 2 implements 1 non-crosslinked sample.
(b) making of crosslinked sample
The non-crosslinked sample of embodiment 1,3～7 and comparative example 1～4 is cut into the mould size, is placed in the mould, at 175 ℃, 100kgf/cm
2Condition under, pressurizeed crosslinked 20 minutes.
The volume ratio of each compounding substances is shown in Table 1 in the matrix material of embodiment 1,3～7 and comparative example 1～4.
(2) observe by electron microscope
For each non-crosslinked sample and crosslinked sample, (SEM) observes the dispersion state of carbon nanofiber and carbon black with electron microscope.Can be observed in whole samples, carbon nanofiber and carbon black are dispersed in the situation in the elastomerics.
(3) mensuration of linear expansivity and heat resisting temperature
For the crosslinked sample of non-crosslinked sample, embodiment 1,3～7 and the comparative example 1～4 of embodiment 2, measure linear expansivity and heat resisting temperature.It the results are shown in table 1.Determinator is the TMASS that SII company makes, and that measures sample is shaped as 1.5mm * 1.0mm * 10mm, and the long load of side is 25KPa, and measuring temperature is-80～350 ℃, and heat-up rate is 2 ℃/minute.Fig. 2 be embodiment 1 (A among the figure), embodiment 2 (B among the figure) and comparative example (C among the figure) temperature (℃)-differential line coefficient of expansion ppm (1/K) curve line chart.
(4) low tensile stress test
With the speed of 10mm/min the stretch embodiment 1～7 of wide 5mm * long 50mm * thick 1mm and the crosslinked sample and the non-crosslinked sample of comparative example 1～4, the stress when obtaining 10% distortion.Measure direction and be the direction (L) parallel with the grain direction of each sample and with the rectangular direction of L (T).Low tensile stress ratio calculates by the stress of the stress/T direction of L direction.The results are shown in table 1.
Then Fig. 2 compares with comparative example 1 as can be known, and the linear expansivity of embodiment 1 and 2 in measuring temperature range is little, is stable.In a plurality of temperature ranges, the differential value of the linear expansivity of comparative example 1 changes greatly.Relative with it, the differential value of the linear expansivity of embodiments of the invention 1 and 2 in measuring temperature range changes little, is stable.And, can find out with comparative example 1 and compare that the differential value of embodiment 1 and 2 linear expansivity is little.In addition, the differential value of the linear expansivity of embodiment 1 and embodiment 2 indifference almost.
In addition, as known from Table 1,, can confirm following situation according to embodiments of the invention 1～7.That is, under-80～300 ℃, the average coefficient of linear expansion of the matrix material of embodiment 1～7 smaller or equal to the differential value of 100ppm (1/K) and linear expansivity smaller or equal to 120ppm (1/K).In addition, the heat resisting temperature of the matrix material of embodiment 1～7 and comparative example 1 is more than or equal to 300 ℃.Also have, the average coefficient of linear expansion of the matrix material of comparative example 1 is that the maximum value of the differential value of 62ppm (1/K), linear expansivity is 107ppm (1/K).In addition, under-80～300 ℃, comparative example 2 and 4 linear expansivity instability, thereby can not calculate the maximum value of the differential value of average coefficient of linear expansion and linear expansivity, comparative example 2 and 4 heat resisting temperature are respectively 260 ℃ and 270 ℃.Because comparative example 3 can not carry out mixing processing, thereby do not measure linear expansivity, heat resisting temperature and low elongation stress ratio.In addition, the low elongation stress ratio of the matrix material of embodiments of the invention 1～7 shows, when containing this fiber of carbon nanofiber, has carried out isotropically reinforcement.
The non-crosslinked sample of embodiment 2 has also obtained the result roughly the same with the crosslinked sample of embodiment 1.
From the above, matrix material of the present invention thermal expansion in the temperature range of broadness is little, is stable.
Symbol description
10 the 1st rollers 20 the 2nd roller, 30 elastomers
40 carbon nano-fibers, 50 carbon blacks
Claims (9)
1. matrix material, wherein, described matrix material contains elastomerics, be dispersed in mean diameter in this elastomerics is that 0.7～15nm and mean length are that the carbon nanofiber of 0.5～100 μ m and median size are 10～100nm and the DBP absorbed dose carbon black more than or equal to 100ml/100g
Described elastomerics comprises unsaturated link(age) or the group that has affinity with described carbon nanofiber,
The length-to-diameter ratio of described carbon nanofiber is more than or equal to 50,
The content of described carbon nanofiber is 1～30 volume %,
The content of described carbon black is 10～40 volume %,
Under-80～300 ℃, the average coefficient of linear expansion of described matrix material smaller or equal to the differential value of 100ppm (1/K) and linear expansivity smaller or equal to 120ppm (1/K).
2. matrix material according to claim 1,
Under-80～300 ℃, the linear expansivity on the described matrix material any direction X and with the ratio of linear expansivity on the vertical direction Y of this direction X be 0.7～1.3 times.
3. matrix material according to claim 1 and 2, wherein, described matrix material is the non-crosslinked body.
4. matrix material according to claim 1 and 2, wherein, described matrix material is crosslinked body.
5. matrix material according to claim 1 and 2, wherein, described elastomeric molecular weight is 5000～5,000,000.
6. matrix material according to claim 1 and 2 wherein, has at least a chain in described elastomeric main chain, side chain and the terminal chain to be selected from described carbon nanofiber and has at least a in two keys, triple bond and the functional group of affinity.
7. matrix material according to claim 1 and 2, wherein, as described elastomerics, when adopting pulsed NMR to utilize rare grace echo method to measure under 30 ℃, the spin spin relaxation time of network component (T2n) was 100 to 3000 μ seconds in the non-crosslinked body.
8. matrix material according to claim 1 and 2, wherein, as described elastomerics, when adopting pulsed NMR to utilize rare grace echo method to measure under 30 ℃, the spin spin relaxation time of network component (T2n) was 100 to 2000 μ seconds in the crosslinked body.
9. matrix material according to claim 1 and 2, wherein, described matrix material heat resisting temperature is more than or equal to 300 ℃.
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| EP2493967A1 (en) * | 2009-10-27 | 2012-09-05 | E. I. du Pont de Nemours and Company | Compositions and articles for high-temperature wear use |
| CN102390119B (en) * | 2011-09-08 | 2013-10-02 | 洛阳轴研科技股份有限公司 | Method for manufacturing carbon-metlbond lamination retaining frame materials for rolling bearings |
| CN104619760B (en) * | 2012-08-02 | 2016-10-26 | 阿米利尔股份公司 | Natural rubber containing nano-sized carbon |
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| US4833305A (en) * | 1986-08-12 | 1989-05-23 | Mitsuboshi Belting Limited | Thermally self-regulating elastomeric composition and heating element utilizing such composition |
| US20040144963A1 (en) * | 2002-12-19 | 2004-07-29 | Thomas Braig | Conductive thermoplastics with carbon black and carbon nanofibrils |
| CN1535999A (en) * | 2003-04-09 | 2004-10-13 | �źӵ�����ҵ��ʽ���� | Carbon fibre composite material and mfg. method thereof |
| CN1575964A (en) * | 2003-07-23 | 2005-02-09 | 日信工业株式会社 | Carbon fiber composite material and its forming products,carbon fiber-metal composite material and its forming products, and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4833305A (en) * | 1986-08-12 | 1989-05-23 | Mitsuboshi Belting Limited | Thermally self-regulating elastomeric composition and heating element utilizing such composition |
| US20040144963A1 (en) * | 2002-12-19 | 2004-07-29 | Thomas Braig | Conductive thermoplastics with carbon black and carbon nanofibrils |
| CN1535999A (en) * | 2003-04-09 | 2004-10-13 | �źӵ�����ҵ��ʽ���� | Carbon fibre composite material and mfg. method thereof |
| CN1575964A (en) * | 2003-07-23 | 2005-02-09 | 日信工业株式会社 | Carbon fiber composite material and its forming products,carbon fiber-metal composite material and its forming products, and method of producing the same |
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