CN101275035A - Low electric conductivity high heat radiation polymeric composition and molded body - Google Patents
Low electric conductivity high heat radiation polymeric composition and molded body Download PDFInfo
- Publication number
- CN101275035A CN101275035A CNA2008100848212A CN200810084821A CN101275035A CN 101275035 A CN101275035 A CN 101275035A CN A2008100848212 A CNA2008100848212 A CN A2008100848212A CN 200810084821 A CN200810084821 A CN 200810084821A CN 101275035 A CN101275035 A CN 101275035A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- electric conductivity
- low electric
- macromolecular material
- heat radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Battery Mounting, Suspending (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Fuel Cell (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The present invention provides a high polymer material capable of ensuring the low electric conductivity, high heat radiation and the molded body. A low electric conductivity, high heat radiation high polymer material is made from 10 to 35% by volume of a mixed carbon fiber (2), and from 1 to 20% by volume of a mixed ceramics (3) in the high polymer material, and the molded body with low electric conductivity and high heat radiation is molded by the high polymer material with low electric conductivity and high heat radiation. As ceramics, the material is able to exemplify alumina (Al<2>O<3>), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si<3>N<4>), silicon carbide (SiC) and so on.
Description
Technical field
The present invention relates to a kind of macromolecular material and formed body with low electric conductivity and high-cooling property.
Background technology
Owing to cut down CO
2Deng environmental factors, in automobile, also to carry out low burnupization, in recent years, motor vehicle driven by mixed power receives publicity.In addition, also predict popularizing of fuel-cell vehicle from now on etc.Wherein, in the associated member of battery and electric motor, the product that much needs low electric conductivity and high-cooling property is arranged,, material or shape have been carried out various researchs in order to ensure this two specific character.
But, in the monomer of Applied Materials, be difficult to guarantee two specific characters.This is because high-cooling property is to be prerequisite with high thermal conductivity (high heat conductivity), but the Applied Materials of high thermal conductivity all has high conductivity basically.That is,
(1) metal has high thermal conductivity, high-cooling property, but because also have high conductivity, so itself can't guarantee low electric conductivity (preferred electrical insulating property).Therefore, must set the insulcrete that is made of resin etc. separately, and the low heat emission of insulcrete becomes problem, perhaps product weight has also increased the insulcrete part.And the proportion of metal itself is also very big.
(2) macromolecular material (resin, rubber) is low electric conductivity (being electrical insulating property substantially), but because also have low heat conductivity, so itself can't guarantee high-cooling property.Therefore, must on shape of product, try every possible means (air passageways is set), guaranteeing high-cooling property, thereby product increases, and needs the very big space that is provided with.
(3) therefore, studied following matrix material.
In patent documentation 1, put down in writing the material that in macromolecular material, mixes the greying carbonization hydrogen that contains organic boron compound.
In patent documentation 2, put down in writing the material of admixed graphite carbon fiber, electrical insulating property heat conductive filler in silicon rubber.
In patent documentation 3, put down in writing in macromolecular material blending surface is coated the heat conductive filler particle after the processing by ceramic-like materials material.
In patent documentation 4, put down in writing in polymkeric substance such as rubber to mix and had the organic compound of hydroxyl and the material of metal oxide.
In patent documentation 5, put down in writing the material of mixed nitride boron in silicon rubber.
In patent documentation 6, put down in writing the material of the boron nitride that in silicon rubber blending surface coats by amino-modified silicone oil.
In patent documentation 7, put down in writing the material of mixed nitride aluminium powder form, metal-powder in liquid-state silicon etc.
Patent documentation 1: the spy opens the 2002-88249 communique
Patent documentation 2: the spy opens the 2002-3717 communique
Patent documentation 3: the spy opens flat 9-321191 communique
Patent documentation 4: the spy opens flat 7-145270 communique
Patent documentation 5: the spy opens flat 7-111300 communique
Patent documentation 6: the spy opens flat 7-33983 communique
Patent documentation 7: the spy opens the 2004-10880 communique
Summary of the invention
Patent documentation 1～7 all is in having the macromolecular material of low electric conductivity (mother metal), fills the filler that is made of the pottery with high-cooling property etc., thereby wishes to guarantee the matrix material of two specific characters.But, in these materials, also have following problem.
(a) if do not fill the filler of enough volumes (high-density), then can't guarantee high-cooling property.
(b) because will fill filler in a large number, so there is restriction (being defined as lamellar) in shape of product.
(c) in mixing process, might coating be severed and exposed the electroconductibility part of filler, lack reliability.
The objective of the invention is to solve above-mentioned problem, a kind of macromolecular material and formed body are provided, it can guarantee low electric conductivity and this two specific character of high-cooling property.
(A) low electric conductivity high heat radiation polymeric composition of the present invention, be in macromolecular material with 10～35 volume % mixed carbon fibres, and form with 1～20 volume % hybrid ceramic.
For each key element among the present invention, its form of following illustration.
(1) macromolecular material
Be not particularly limited as macromolecular material, can the illustration resin, rubber, thermoplastic elastomer, preferred PE (polyethylene), PP (polypropylene), PPS (polyphenylene sulfide), Resins, epoxy or silicone.
1. resin: can vinyl resins such as illustration PP, PE, thermosetting resin such as PS styrene resins such as (polystyrene), PVC ethenoid resins such as (polyvinyl chloride), PPS, LCP (liquid crystalline polymers), PBT (polybutylene terephthalate), PET (polyethylene terephthalate), PA6 PA such as (polyamide 6s) (polymeric amide), PTFE (tetrafluoroethylene), POM engineering plastic resins such as (polyacetal), Resins, epoxy, phenolic resin, acrylic resin.
2. rubber: can illustration EPDM (ternary ethylene-propylene copolymer), CR (chloroprene rubber), NBR (paracril), silicon rubber etc.
3. thermoplastic elastomer: can the illustration olefines, the thermoplastic elastomer of styrenic, polyvinyl chloride-base, polyester, polyurethanes, polyamide-based, fluorine class.
Be not particularly limited as macromolecular material, but preferred thermal conductivity is lower than the material of 1.0W/mK.In addition, more preferably thermal conductivity is the material of 0.1～0.5W/mK.Specifically, the material shown in the table 1 below can illustration.In addition, the thermal conductivity of carbon fiber and pottery is shown in the table 2.
Table 1
| Title material | Thermal conductivity (W/mK) | Title material | Thermal conductivity (W/mK) |
| PE | 0.22※1 | PVC | 0.16※1 |
| PP | 0.14※2 | PET | 0.25※2 |
| PPS | 0.37※2 | PA6 | 0.25※1 |
| PBT | 0.23※2 | PTFE | 0.44※2 |
| CR | 0.25※1 | Resins, epoxy | 0.4※2 |
| Silicone | 0.2※1 | Phenolic resin | 0.33※2 |
| PS | 0.12※1 |
※ 1: technical intelligence association periodical
" the high heat conductionization of electronic equipment part usefulness heat sink material and the evaluation of measuring technology of heat conductivity " P133
※ 2: Nikkan Kogyo Shimbun's periodical
" material database organic materials " P53
Table 2
| Title material | Thermal conductivity (W/mK) | Title material | Thermal conductivity (W/mK) |
| Pitch-based carbon fiber | 540※3 | Magnesium oxide | 60※6 |
| The PAN based carbon fiber | 10※4 | Aluminium nitride | 170※6 |
| Boron nitride | 210※6 | Silicon nitride | 29※7 |
| Aluminum oxide | 36※6 | Silicon carbide | 56※7 |
| Zirconium white | 2.1※5 | Norbide | 36※7 |
※ 3: Mitsubishi Chemical produces the value of the technical information grade " K223HG " of money society
※ 4: “ East レ societies " the value of technical information grade " MLD30 "
※ 5: the internet
※ 6: technical intelligence association periodical
" the high heat conductionization of electronic equipment part usefulness heat sink material and the evaluation of measuring technology of heat conductivity " P133
※ 7: technical intelligence association periodical
" the high heat conductionization of electronic equipment part usefulness heat sink material and the evaluation of measuring technology of heat conductivity " P99
About the thermal conductivity of the thermal conductivity of in resin etc., filling the material behind (mixing) pottery etc. and pottery etc. and the relation of filling ratio, has the Bruggeman formula shown in following formula 1.Because it is less that the thermal conductivity of resin etc. (shown in the table 1) is compared with the thermal conductivity (shown in the table 2) of pottery and carbon fiber, thus produce by changing resin etc., less to the influence (variation of thermal conductivity) of the thermal conductivity of the material of filling pottery in resin etc. etc.
Formula 1
φ: the volume filling ratio of pottery etc.
λ e: the thermal conductivity of in resin etc., filling the material of pottery etc.
λ d: the thermal conductivity of pottery etc.
λ c: the thermal conductivity of resin etc.
(2) carbon fiber
Be not particularly limited as carbon fiber, can illustration PAN based carbon fiber, pitch-based carbon fiber, preferred pitch-based carbon fiber.
(2-1) PAN based carbon fiber
Usually, the PAN based carbon fiber is with the carbon fiber of PAN (polyacrylonitrile) fiber as raw material, and the PAN fiber is carried out precalcining with 1000 ℃～1500 ℃ in rare gas element, carries out carbonization with 2000～3000 ℃ then and makes.
Owing to, constitute the little and random arrangement of graphite crystallization of carbon fiber, conduct electricity or heat conduction along all directions of fiber easily as the feature of PAN based carbon fiber.In addition, because the PAN based carbon fiber has a lot of defectives in crystallization, so that thermal conductivity is compared with pitch-based carbon fiber is less.
(2-2) pitch-based carbon fiber
Usually, pitch-based carbon fiber is with the tar of the petroleum-type carbon fiber as raw material, mixes various Synergist S-421 95s such as tackifier in tar, under 250～400 ℃, make linear, then, in rare gas element, carry out carbonization, and fire and make with 2500～3000 ℃ with 1000～1500 ℃.
Graphite crystallization in the pitch-based carbon fiber is compared greatly with the PAN based carbon fiber, fitly arranges along the length direction of fiber, and defective is less.Therefore, along staple length direction conduction or heat conduction, with PAN based carbon fiber compare greatly easily by thermal conductivity for pitch-based carbon fiber.In addition, by orientation described later, the thermal conductivity of pitch-based carbon fiber is increased significantly, this is owing to make heat conducting direction also consistent by the length direction that makes fiber is consistent.
(3) pottery
Be not particularly limited as pottery, can the illustration metal oxide, nitride, carbide etc., preferred boron nitride, aluminum oxide or aluminium nitride.In addition, be not particularly limited as the shape of pottery, can the illustration powdery, fibrous, flakey etc., be not particularly limited for size, can the illustration median size be 5～100 μ m.
(3-1) oxide compound
Be not particularly limited as metal oxide, can illustration aluminum oxide (Al
2O
3), zirconium white (ZrO
2), magnesium oxide (MgO) etc.
(3-2) nitride
Be not particularly limited as nitride, can illustration aluminium nitride (AlN), boron nitride (BN), silicon nitride (Si
3N
4) etc.
(3-3) carbide
Be not particularly limited as metallic carbide, can illustration silicon carbide (SiC), norbide (B
4C) etc.
(4) combined amount
The combined amount of (4-1) carbon fiber
The combined amount that is mixed to the carbon fiber in the macromolecular material is 10～35 volume %, preferred 15～30 volume %, more preferably 15～25 volume %.If combined amount is few, then produce the tendency that to guarantee sufficient thermal diffusivity, and if too much, then can produce the tendency of low electric conductivity loss, processibility deterioration.
(4-2) ceramic combined amount
The combined amount that is mixed to the pottery in the macromolecular material is 1～20 volume %, more preferably 5～15 volume %.
(5) orientation of carbon fiber
Can utilize magnetic field etc. will be blended in carbon fiber in the macromolecular material carries out orientation and uses.Produce following advantage by this orientation: if the combined amount of carbon fiber is identical, then can improve heat conductivity,, then can reduce the combined amount of carbon fiber perhaps if identical heat conductivity.So-called orientation is meant in the macromolecular material as mother metal the state that fiber is arranged regularly along specific direction.
The affirmation and the evaluation of (5-1) orientation
Orientation can be confirmed with for example following 2 kinds of methods, especially, can estimate with method 1.
1. measure by the lattice orientation angle intensity distribution of the carbon fiber of X-ray diffraction
For example in carbon fiber, graphite crystallization is arranged regularly along the length direction of fiber, by this graphite crystallization (0.0.2) face being utilized the X-ray diffraction angle intensity distribution (Fig. 5 for example described later) that fixes the position, then can know the alignment direction of carbon fiber self.Under the situation of carrying out orientation, on the intensity distribution of position angle, can produce peak value.Especially, under the good situation of orientation,, define following orientation degree to this peak value measurement halfwidth.More than or equal to 0.7 o'clock, is the degree that can visually catch orientation at the orientation degree, and it is obvious to be evaluated as the action effect of orientation, especially, at 0.9～1 o'clock, can be called good good orientation.
Orientation degree=(180 °-halfwidth)/180 ° ... formula 2
2. utilize range estimation affirmations such as microscopic examination
Formed body is confirmed that along hope the face of orientation cuts, with the direction of observation carbon fibers such as scanning electron microscope.But,, be difficult to determine quantitatively the degree of orientation according to this observation.
The direction of (5-2) orientation
The alignment direction of the carbon fiber in macromolecular material is not particularly limited, but for example contains under the situation of plate-like portion at formed body, can be any one direction along the surface of this plate-like portion, also can be the thickness direction of this plate-like portion.
The method of (5-2) orientation
Be not particularly limited method that can the following use of illustration magnetic field and pass through method for processing as the method that makes the carbon fiber orientation.
1. use the method in magnetic field
This method is to be shaped to formed body or as the formed body of the raw material of this formed body by above-mentioned low electric conductivity high heat radiation polymeric composition, have under the mobile state at the macromolecular material of these formed bodys, utilize magnetic field to make carbon fiber orientation in this macromolecular material.Carbon fiber is with the mode orientation along field direction (direction of magnetic line of force).After orientation, macromolecular material is solidified by cooling etc.The intensity in magnetic field is not particularly limited, and is preferably greater than or equals the high-intensity magnetic field of 1T (tesla).According to this method, its advantage is, as long as make alignment direction consistent with field direction, just can realize comprising the various alignment direction of above illustrative alignment direction.
Here, so-called macromolecular material has mobile state, is not particularly limited, can illustration fused state, the state before the crosslinking polymerization etc.
2. pass through method for processing
This method is to be shaped to formed body or as the formed body of the raw material of this formed body by above-mentioned low electric conductivity high heat radiation polymeric composition, macromolecular material at these formed bodys has under the mobile state, make at least a portion extension strain of formed body by processing, thereby make the carbon fiber orientation in this macromolecular material.Carbon fiber is with the mode orientation along prolonging direction.After orientation, macromolecular material is passed through curing such as cooling.
In addition, in aforesaid method, the formed body of so-called raw material as formed body, for example be meant formed body for the sheet material under the situation of the sheet material vacuum forming being given 3D shape like this, through the formed body of the last stage under the situation of a plurality of stage moulding.
(B) low electric conductivity high-cooling property of the present invention formed body is to utilize above-mentioned low electric conductivity high heat radiation polymeric composition moulding to form.
Specific product as this formed body is not particularly limited, can the following product of illustration.
As shown in Figure 2, make insulating insulcrete 12 or accumulator box 13, busbar modules etc. between the cell device of cell box 11 such as (electricity of motor vehicle driven by mixed power, fuel-cell vehicle etc. drive car)
The motor winding insulated enclosure material of (electricity driving car etc.) electric motor etc.
(electricity drives car, household electrical appliances etc.) umformer box
(household electrical appliances, Personal Computer etc.) radiator element, housing etc.
Exploitation of the present invention is passed through and is acted on as described below.
The heat conductivity of carbon fiber (being thermal diffusivity) height, and have enhancing to macromolecular material, so be applicable to this purpose.But because the electroconductibility of carbon fiber is also high, so in the present invention, target is to have suppressed to mix the electroconductibility of the material of carbon fiber.
And the result of big quantity research by carbon fiber and various potteries with insulativity are made up and be blended in the macromolecular material, thereby obtains guaranteeing the type material of low electric conductivity and high-cooling property.
The effect of invention
According to macromolecular material of the present invention and formed body, can guarantee this two specific character of low electric conductivity and high-cooling property.
Description of drawings
Fig. 1 is a synoptic diagram of implementing the low electric conductivity high heat radiation polymeric composition of enforcement product of the present invention.
Fig. 2 is the oblique drawing of expression by the example of the formed body of macromolecular material moulding of the present invention.
Fig. 3 is that expression is used to utilize magnetic field to make the explanatory view of the device and method of carbon fiber orientation.
Fig. 4 represents to utilize equally magnetic field to make the explanatory view of the method for carbon fiber orientation.
Fig. 5 is the graphic representation that expression utilizes the measuring result of the position angle intensity distribution that X-ray diffraction obtains.
Fig. 6 is the microphotograph of example that does not make the formed body of carbon fiber orientation.
Fig. 7 is the microphotograph of example that makes the formed body of carbon fiber orientation.
Embodiment
The invention provides a kind of low electric conductivity high heat radiation polymeric composition, its be in macromolecular material with 15～30 volume % mixed carbon fibres, and form with 5～15 volume % hybrid ceramics.In addition, also provide a kind of low electric conductivity high-cooling property formed body by this low electric conductivity high heat radiation polymeric composition moulding.
Embodiment
Following table 3 is, macromolecular material 1 as mother metal, use polyethylene (PE) resin (" Sumitomo Chemical society " system, trade name is " ス ミ カ セ Application G807 "), in this polyvinyl resin, with carbon fiber 2 and pottery 3 with specified amount blended embodiment 1～15 and with composition and the physical properties with specified amount blended comparative example 1～5 such as carbon fiber.
Embodiment 1～11st, the material of mixed carbon fibre and boron nitride, and embodiment 12～14th, and the material of mixed carbon fibre and aluminum oxide, embodiment 15 are materials of mixed carbon fibre and aluminium nitride.
On the other hand, comparative example 1 is the material that has only polyvinyl resin, comparative example the 2, the 3rd, the material of mixed carbon fibre only, comparative example the 4, the 5th, the only material of mixed nitride boron.
In addition, following table 4 is the composition and the physical properties of embodiment 16～43 and comparative example 6～8, they are the macromolecular materials 1 as mother metal, replace polyethylene (PE) resin and use polypropylene (PP) resin (" Japanese Port リ プ ロ society " system, trade name is " ノ バ テ Star Network PP "), polyphenylene sulfide (PPS) resin (“ East レ society " system; trade name is " ト レ リ Na A900 "); silicon rubber (" chemistry society of SHIN-ETSU HANTOTAI " system; trade name is " KE106 ") or bisphenol A type epoxy resin (" リ Off ア イ Application テ Star Network society " system, trade name is " エ Port マ ウ Application ト ").
As the macromolecular material of the mother metal that uses in each sample, embodiment 16～24 and comparative example 6 are acrylic resin, and embodiment 25～33 and comparative example 7 are the PPS resin, and embodiment 34～42 and comparative example 8 are silicon rubber, and embodiment 43 is a bisphenol A type epoxy resin.
In addition, embodiment 16～19,25～28,34～37th, with carbon fiber and the mixed material of boron nitride, embodiment the 20～23,29～32,38～41, the 43rd, and with carbon fiber and the mixed material of aluminum oxide, embodiment the 24,33, the 42nd, with carbon fiber and the mixed material of aluminium nitride.
In addition, the carbon fiber that uses in this test is the pitch-based carbon fiber of " Mitsubishi Chemical Chan Capital society " system, trade name is " ダ イ ア リ one De K223HGM " (median size Φ 10 * 50 μ m), boron nitride (BN) is " GE ス ペ シ ヤ リ テ イ one マ テ リ ア Le ズ society " system, trade name is " PT110 " (median size 50 μ m), aluminum oxide (Al
2O
3) be " Electricity mood chemical industry society " system, trade name be " DAW10 " (median size 10 μ m), aluminium nitride (AlN) Wei “ East ocean ア Le ミ society " to make, trade name is " FAN-f80 " (median size 80 μ m).
(moulding and physical property test)
Mixing material with each embodiment or comparative example, utilize “ East Yang Jing Machine System to do society of institute " closed mixing machine (model " KF70V ") that stirs of the test plasticity of system is to mix under the condition of 210 ℃ (polyvinyl resins), 200 ℃ (acrylic resin), 320 ℃ (PPS resin), room temperature (silicon rubber, bisphenol A type epoxy resin), rotating speed 100rpm, 10 minutes time, filling ratio 70% in temperature.With mixed material use hand press, under the pressure of 20MPa, with polyvinyl resin 210 ℃ of following 5 minutes, acrylic resin 200 ℃ of following 5 minutes, PPS resin 320 ℃ of following 5 minutes, silicon rubber 150 ℃ of following 30 minutes, at room temperature 24 hours condition extrusion molding of bisphenol A type epoxy resin, make the test film of 25mm * 25mm * (thickness) 2mm.
For each test film, use following method to measure physical properties.
(1) heat conductivity is measured
As determinator, using the trade name of " NETZSCH society " system is " Xe Off ラ Star シ ユ ア Na ラ イ ザ one LFA447 Nanoflash ", measures under 25 ℃ (room temperatures).The heat conduction direction is the thickness direction of test film.
(2) the volume intrinsic impedance is measured
Be less than or equal to 10 at the volume intrinsic impedance
6Under the situation of Ω cm, using the trade name of " ダ イ ヤ イ Application ス Star Le メ Application ト society " system as determinator is " ロ レ ス GP ", utilizes four-terminal method to measure.Electric current applies the departure direction (sense of current) of terminal, the departure direction (direction of potential difference) of voltage determination terminal is the thickness direction of test film.
At the volume intrinsic impedance more than or equal to 10
6Under the situation of Ω cm, using the trade name of " ダ イ ヤ イ Application ス Star Le メ Application ト society " system as determinator is " Ha イ レ ス UP ", measures with dual around-France (JISK1911 standard).
(physical properties evaluation)
All embodiment guarantee low electric conductivity simultaneously, and (the volume intrinsic impedance is more than or equal to 1 * 10
2Ω cm) and high-cooling property (thermal conductivity is more than or equal to 0.5W/mK).On the other hand, for comparative example 1,6～8, though guarantee low electric conductivity, high-cooling property is relatively poor.For comparative example 2,3, though guarantee high-cooling property, low electric conductivity is very poor.For comparative example 4,5, though guarantee low electric conductivity and high-cooling property simultaneously, because physical strength is low, so and impracticable.
In addition, when the heat conductivity of estimating various mixing materials and electroconductibility, need be with corresponding by the concrete product category of the low electric conductivity high-cooling property formed body of mixing material moulding, consider that the level of desired high-cooling property, low electric conductivity level are all inequality.
(making the pilot study of carbon fiber orientation)
At first be used to confirm to utilize magnetic field to make the pilot study of carbon fiber orientation.Will be in polyvinyl resin with pitch-based carbon fiber with 15 volume %, 25 volume %, 30 volume %, or the mixed material of 35 volume %, with be these five kinds of materials of the mixed material of aluminum oxide 5 volume % of 10 μ m with asphalt-based carbon fiber 15 volume % and median size, the test film that mixes and be shaped to 25mm * 25mm * 2mm with condition same as described above, then for carbon fiber with 15 volume %, 25 volume %, 35 volume % and carbon fiber and aluminum oxide are carried out the blended example apply magnetic field (also exist carbon fiber not apply magnetic field in the 30 volume % blended examples, carbon fiber is carried out not applying in the blended example situation in magnetic field with 25 volume %).Specifically, as shown in Figures 3 and 4, carry out orientation with following apparatus and order.
As the magnetic field generation unit, use the cooling type superconducting magnet apparatus (HF10-100VHT) of " lives in You Chong Machine tool industry society " system.
Bottom in the space 22 of the magnetic field center portion that is positioned at this device 21 (boring) is provided with electricradiator 23, and above this electricradiator 23, above-mentioned test film 24 is placed on each 1 ground, and making the test film thickness direction is field direction (magnetic line of force direction).
Test film in this space 24 is used electricradiator 23 heating in polyvinyl resin fused temperature province (enforcement be 220 ℃), make the mother metal polyvinyl resin fusion of test film.At this moment, keep test film to make it keep aforementioned dimensions.
When keeping this heating and temperature, make this device work, apply magnetic field (enforcement be 8T (tesla)), test film 24 was placed 1 hour in this magnetic field to test film.
Then, stop aforementioned heating, test film 24 is placed 0.5 hour naturally cooling, the mother metal polyvinyl resin of test film is solidified.
From the space 22 of this device 21, take out test film 24, confirm the orientation of carbon fiber.
The orientation of carbon fiber is confirmed with following 2 kinds of methods.
1. measure by the position angle intensity distribution of the carbon fiber lattice of X-ray diffraction
For not applying magnetic field carbon fiber is carried out the blended example, applies magnetic field carbon fiber is carried out the blended example, mixes the example of 35 volume % and with carbon fiber and aluminum oxide blended example with 15 volume % with 30 volume %, use the X-ray diffraction device, as previously mentioned graphite crystallization (0.0.2) face of carbon fiber is utilized the X-ray diffraction angle intensity distribution that fixes the position.Its measurement result shown in Figure 5.Carbon fiber is applying magnetic field carbon fiber is carried out the blended example, mixes the example of 35 volume % and carbon fiber and aluminum oxide are carried out in the blended example with 15 volume %, orientation is good on the thickness direction of test film 24, produces peak value in the intensity distribution of position angle.To this peak value measurement halfwidth, calculate the result of orientation degree according to the formula 2 of aforementioned proposition, it is 0.98 that carbon fiber is carried out the blended example with 15 volume %, the example that mixes 35 volume % is 0.97.
2. carrying out naked eyes by the microscopic examination of sample confirms
For do not apply magnetic field with carbon fiber with 25 volume % carry out the blended example, applied magnetic field carbon fiber is carried out the blended example with 25 volume %, test film is cut off on thickness direction, and the thickness direction that uses scanning electron microscope to observe carbon fiber has or not orientation.At this microphotograph shown in Fig. 6 and Fig. 7.Dark grey partly is a polyvinyl resin, and light grey part is a carbon fiber.Fig. 6 is the example that does not apply magnetic field, and the carbon fiber direction is at random.Fig. 7 is the example that has applied magnetic field, and carbon fiber can think that regularly towards thickness direction orientation is good.In addition, applying magnetic field carbon fiber is carried out in the blended example with 25 volume %, the orientation degree of trying to achieve according to the formula 2 of aforementioned proposition is 0.98.
(make carbon fiber orientation after embodiment)
(a) mother metal of polyvinyl resin
Because can in this pilot study, confirm to make the situation of carbon fiber orientation well, so, below at embodiment 1,2,3,5,6,12,13,14,15 and comparative example 1,2,3,4,5, make material separately form identical with forming method, only, obtain embodiment 1a, 2a, 3a, 5a, 6a, 12a, 13a, 14a, 15a and comparative example 1a, 2a, 3a, 4a, 5a in that to utilize magnetic field to make on the carbon fiber orientation this point in the macromolecular material (polyvinyl resin) of mother metal different.In addition, their carbon fibers of containing are by orientation especially well (the orientation degree of trying to achieve according to the formula 2 of aforementioned proposition is 0.9～1).
The orientation that utilizes magnetic field to carry out utilizes device shown in Fig. 3 and Fig. 4 and order, carries out in the same manner with aforementioned pilot study.And the test film that will take out from install 21 space 22 is used for aforesaid physical property test.Its result is shown in the table 5.In addition, for embodiment 1a, to also measuring with the thermal conductivity of the orthogonal direction of carbon fiber alignment direction, its value is 1.1W/mK.
In addition, the mensuration of the melt flow rate (MFR) of each sample (MFR), be to be standard with JISK7210-1999, use “ East Yang Jing Machine System to do institute " trade name of system is " メ Le ト イ Application デ Network サ one P-001 type "; and in test temperature: carry out under 220 ℃, the test conditions of test load: 2.16kgf (21.18N), its result is shown in the following table 6.
Table 6
| The sample title | Comparative example 1a | Comparative example 2a | Comparative example 3a | Comparative example 4a | Comparative example 5a |
| MFR(g/10min、2.16kg、220℃) | 115.0 | 34.0 | 16.0 | 20 | 6.5 |
| The sample title | Embodiment 1a | Embodiment 2a | Embodiment 3a | Embodiment 5a | Embodiment 6a |
| MFR(g/10min、2.16kg、220℃) | 64.4 | 47.4 | 39.9 | 39.7 | 26.5 |
| The sample title | Embodiment 12a | Embodiment 13a | Embodiment 14a | Embodiment 15a | |
| MFR(g/10min、2.16kg、220℃) | 26.3 | 19.8 | 20.6 | 65.8 |
(B) mother metal of resin outside the polyvinyl resin etc.
For the macromolecular material of mother metal is embodiment 16～43 and comparative example 6～8 outside the polyvinyl resin, with the sample of aforementioned polyvinyl resin in the same manner, it is identical with forming method that each material is formed, only, obtain embodiment 16a～42a and comparative example 6a～8a utilizing magnetic field to make carbon fiber orientation this point difference in the macromolecular material of mother metal.In order to make the carbon fiber orientation, respectively the sample of acrylic resin is heated to 220 ℃, the sample of PPS resin is heated to 320 ℃, make it become molten state and carry out the orientation of carbon fiber, silicon rubber and bisphenol A type epoxy resin be heating and melting not, but carries out the carbon fiber orientation to carry out states before such as polymerization.Its result is shown in Figure 7.
In addition, alignment method and physical property test are identical when being polyvinyl resin with the macromolecular material of above-mentioned mother metal.
In addition, the mensuration of the melt flow rate (MFR) (MFR) of the various samples of embodiment 16a～24a, comparative example 6a (macromolecular material of mother metal is an acrylic resin), identical condition is carried out when being polyvinyl resin with the macromolecular material of above-mentioned mother metal, the mensuration of the melt flow rate (MFR) (MFR) of each sample of embodiment 25a～33a, comparative example 7a (macromolecular material of mother metal is the PPS resin), with test temperature: 320 ℃, the test conditions (other condition is identical with poly situation) of test load: 5kgf (49.03N) carry out.And, use E type viscometer (" メ ト Star Network society " system) to measure each sample (macromolecular material of mother metal is silicon rubber) of embodiment 34a～42a, comparative example 8a and embodiment 43a (macromolecular material of mother metal the is bisphenol A type epoxy resin) viscosity under the state before polymerization etc.Its result is shown in the table 7.
(physical properties evaluation)
In the macromolecular material of mother metal, use the various samples of polyvinyl resin, obtain following result by making the carbon fiber orientation.
All embodiment guarantee low electric conductivity simultaneously, and (the volume intrinsic impedance is more than or equal to 1 * 10
2Ω cm) and high-cooling property (thermal conductivity is more than or equal to 0.5W/mK).
Embodiment increases substantially high-cooling property (thermal conductivity), though low electric conductivity (volume intrinsic impedance) worsens slightly, can guarantee desired performance.On the other hand, for comparative example 2a, high-cooling property improves bigger, but low electric conductivity further worsens.For comparative example 3a, low electric conductivity further worsens.
The various samples of the resin in the macromolecular material of mother metal outside the use polyvinyl resin etc. have following effect by making the carbon fiber orientation.
All embodiment guarantee low electric conductivity simultaneously, and (the volume intrinsic impedance is more than or equal to 1 * 10
2Ω cm) and high-cooling property (thermal conductivity is more than or equal to 0.5W/mK).
The combined amount of carbon fiber is the embodiment of 15～30 volume %, and its high-cooling property improves, and especially, the combined amount of carbon fiber is the material of 15～20 volume %, and high-cooling property improves significantly.
The combined amount of carbon fiber is the embodiment of 15～20 volume %, and except that a part (examples of implementation 38,39), its low electric conductivity improves.
The present invention is not limited to previous embodiment, can be in the scope that does not break away from inventive concept, and suitably change and specialize.
Claims (8)
1. a low electric conductivity high heat radiation polymeric composition is characterized in that,
In macromolecular material,, and form with 1～20 volume % hybrid ceramic with 10～35 volume % mixed carbon fibres.
2. the macromolecular material of low electric conductivity high-cooling property as claimed in claim 1 is characterized in that,
The thermal conductivity of aforementioned macromolecular material is lower than 1.0W/mK.
3. the macromolecular material of low electric conductivity high-cooling property as claimed in claim 1 is characterized in that,
Aforementioned macromolecular material is polyethylene, polypropylene, polyphenylene sulfide, silicone or Resins, epoxy.
4. low electric conductivity high heat radiation polymeric composition as claimed in claim 1 is characterized in that,
Aforementioned pottery is boron nitride, aluminum oxide or aluminium nitride.
5. low electric conductivity high heat radiation polymeric composition as claimed in claim 1 is characterized in that,
Aforementioned carbon fiber is a pitch-based carbon fiber.
6. a low electric conductivity high-cooling property formed body is characterized in that,
By any described low electric conductivity high heat radiation polymeric composition moulding in the claim 1 to 5.
7. low electric conductivity high-cooling property formed body as claimed in claim 6 is characterized in that,
Carbon fiber carries out orientation in macromolecular material.
8. the manufacture method of a low electric conductivity high-cooling property formed body is characterized in that,
Be shaped to formed body or as the formed body of the raw material of this formed body by any described low electric conductivity high heat radiation polymeric composition in the claim 1 to 5, have under the mobile state at the macromolecular material of these formed bodys, utilize magnetic field to make carbon fiber orientation in this macromolecular material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007080490 | 2007-03-27 | ||
| JP2007-080490 | 2007-03-27 | ||
| JP2008-055563 | 2008-03-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101275035A true CN101275035A (en) | 2008-10-01 |
Family
ID=39994910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100848212A Pending CN101275035A (en) | 2007-03-27 | 2008-03-27 | Low electric conductivity high heat radiation polymeric composition and molded body |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2008266586A (en) |
| CN (1) | CN101275035A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565524B (en) * | 2009-04-28 | 2011-04-27 | 华南理工大学 | HDPE-carbon fiber-zinc oxide crystal whisker conductive composite material and preparation method thereof |
| CN102433049A (en) * | 2011-12-19 | 2012-05-02 | 奇瑞汽车股份有限公司 | Insulating heat conduction coating, preparation method and application of insulating heat conduction coating to battery shell |
| CN103421225A (en) * | 2012-05-21 | 2013-12-04 | 特茂热导工业股份有限公司 | Electrical insulation heat-conductive fireproof material |
| CN103435895A (en) * | 2013-09-11 | 2013-12-11 | 四川大学 | Method for preparing insulating high-thermal-conductivity composite material |
| CN103687910A (en) * | 2011-07-15 | 2014-03-26 | 普立万公司 | Polyamide compounds containing pitch carbon fiber |
| CN103975429A (en) * | 2011-12-20 | 2014-08-06 | 迪睿合电子材料有限公司 | Thermally conductive sheet and method for manufacturing thermally conductive sheet |
| CN104194286A (en) * | 2014-08-13 | 2014-12-10 | 上海交通大学 | Carbon fiber reinforced thermoplastic resin composite material and preparation method of carbon fiber reinforced thermoplastic resin composite material |
| CN104841860A (en) * | 2015-05-07 | 2015-08-19 | 马鞍山市恒毅机械制造有限公司 | Excellent-combination-property precoated sand for hot method and preparation method thereof |
| CN106190051A (en) * | 2015-05-05 | 2016-12-07 | 赖中平 | The Graphene stack membrane of tool thermal conductance |
| CN107325383A (en) * | 2017-08-29 | 2017-11-07 | 德阳力久云智知识产权运营有限公司 | A kind of cable composite shielding material and preparation method thereof |
| CN107383553A (en) * | 2017-08-29 | 2017-11-24 | 德阳力久云智知识产权运营有限公司 | A kind of conductive polymer composite and preparation method thereof |
| CN108463882A (en) * | 2016-01-26 | 2018-08-28 | 迪睿合株式会社 | Thermally conductive sheet, the manufacturing method of thermally conductive sheet, radiating component and semiconductor device |
| CN109294032A (en) * | 2018-09-14 | 2019-02-01 | 江苏理工学院 | A kind of modified thermally conductive PE composite material and preparation method of multiple elements design particle filled composite |
| CN112635889A (en) * | 2020-12-10 | 2021-04-09 | 东风汽车集团有限公司 | Explosion-proof battery |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013390A (en) * | 2007-06-04 | 2009-01-22 | Teijin Ltd | Thermally conductive sheet |
| WO2010068326A1 (en) * | 2008-12-10 | 2010-06-17 | Uop Llc | Adsorbent media |
| KR101104650B1 (en) | 2009-03-24 | 2012-01-13 | 에스케이이노베이션 주식회사 | A Vehicle Battery Pack equipped wit h Exterior Member |
| JPWO2011013840A1 (en) * | 2009-07-28 | 2013-01-10 | 帝人株式会社 | Insulated pitch-based graphitized short fiber |
| JP2012243446A (en) * | 2011-05-17 | 2012-12-10 | Kojima Press Industry Co Ltd | Battery pack |
| JP2013175423A (en) * | 2012-01-26 | 2013-09-05 | Toyota Industries Corp | Terminal connection member and battery pack |
| JP6397180B2 (en) * | 2013-11-14 | 2018-09-26 | 国立研究開発法人産業技術総合研究所 | Fiber-reinforced resin composition and fiber-reinforced molded body |
| JP6165603B2 (en) * | 2013-11-28 | 2017-07-19 | 住友理工株式会社 | Elastomer molded body and method for producing the same |
| FR3014442B1 (en) * | 2013-12-10 | 2016-01-01 | Michelin & Cie | TIRE COMPRISING A ROLLER BAND BASED ON A RUBBER COMPOSITION COMPRISING EX BRAI CARBON FIBERS |
| KR101994948B1 (en) * | 2015-06-16 | 2019-09-30 | 주식회사 엘지화학 | Stack and folding-type electrode assembly and method for fabricating the same |
| US10862078B2 (en) * | 2017-01-24 | 2020-12-08 | Ticona Llc | Battery module for an electric vehicle |
| CN110998905A (en) * | 2017-08-08 | 2020-04-10 | 株式会社杰士汤浅国际 | Power storage module and power storage element |
| WO2019111488A1 (en) * | 2017-12-08 | 2019-06-13 | 住友電気工業株式会社 | Coolant and power storage pack using same |
| US20230411633A1 (en) * | 2020-12-31 | 2023-12-21 | Kolon Industries, Inc. | Catalyst layer for fuel cell, manufacturing method therefor, and membrane-electrode assembly and fuel cell which comprise same |
-
2008
- 2008-03-05 JP JP2008055563A patent/JP2008266586A/en not_active Withdrawn
- 2008-03-27 CN CNA2008100848212A patent/CN101275035A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565524B (en) * | 2009-04-28 | 2011-04-27 | 华南理工大学 | HDPE-carbon fiber-zinc oxide crystal whisker conductive composite material and preparation method thereof |
| CN103687910A (en) * | 2011-07-15 | 2014-03-26 | 普立万公司 | Polyamide compounds containing pitch carbon fiber |
| CN102433049A (en) * | 2011-12-19 | 2012-05-02 | 奇瑞汽车股份有限公司 | Insulating heat conduction coating, preparation method and application of insulating heat conduction coating to battery shell |
| CN103975429B (en) * | 2011-12-20 | 2018-03-30 | 迪睿合电子材料有限公司 | The manufacture method of thermal conductivity piece and thermal conductivity piece |
| CN103975429A (en) * | 2011-12-20 | 2014-08-06 | 迪睿合电子材料有限公司 | Thermally conductive sheet and method for manufacturing thermally conductive sheet |
| CN108384248B (en) * | 2011-12-20 | 2021-10-19 | 迪睿合电子材料有限公司 | Thermally conductive sheet and method for producing thermally conductive sheet |
| CN108384248A (en) * | 2011-12-20 | 2018-08-10 | 迪睿合电子材料有限公司 | The manufacturing method of thermal conductivity piece and thermal conductivity piece |
| CN103421225A (en) * | 2012-05-21 | 2013-12-04 | 特茂热导工业股份有限公司 | Electrical insulation heat-conductive fireproof material |
| CN103435895A (en) * | 2013-09-11 | 2013-12-11 | 四川大学 | Method for preparing insulating high-thermal-conductivity composite material |
| CN103435895B (en) * | 2013-09-11 | 2016-02-10 | 四川大学 | A kind of method preparing insulation high-heat-conductive composite material |
| CN104194286A (en) * | 2014-08-13 | 2014-12-10 | 上海交通大学 | Carbon fiber reinforced thermoplastic resin composite material and preparation method of carbon fiber reinforced thermoplastic resin composite material |
| CN104194286B (en) * | 2014-08-13 | 2016-05-25 | 上海交通大学 | Carbon fiber strengthens thermoplas tic resin composite and preparation method thereof |
| CN106190051A (en) * | 2015-05-05 | 2016-12-07 | 赖中平 | The Graphene stack membrane of tool thermal conductance |
| CN104841860A (en) * | 2015-05-07 | 2015-08-19 | 马鞍山市恒毅机械制造有限公司 | Excellent-combination-property precoated sand for hot method and preparation method thereof |
| CN108463882A (en) * | 2016-01-26 | 2018-08-28 | 迪睿合株式会社 | Thermally conductive sheet, the manufacturing method of thermally conductive sheet, radiating component and semiconductor device |
| CN108463882B (en) * | 2016-01-26 | 2022-05-13 | 迪睿合株式会社 | Thermally conductive sheet, method for manufacturing thermally conductive sheet, heat dissipating member, and semiconductor device |
| CN107383553A (en) * | 2017-08-29 | 2017-11-24 | 德阳力久云智知识产权运营有限公司 | A kind of conductive polymer composite and preparation method thereof |
| CN107325383A (en) * | 2017-08-29 | 2017-11-07 | 德阳力久云智知识产权运营有限公司 | A kind of cable composite shielding material and preparation method thereof |
| CN109294032A (en) * | 2018-09-14 | 2019-02-01 | 江苏理工学院 | A kind of modified thermally conductive PE composite material and preparation method of multiple elements design particle filled composite |
| CN112635889A (en) * | 2020-12-10 | 2021-04-09 | 东风汽车集团有限公司 | Explosion-proof battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008266586A (en) | 2008-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101275035A (en) | Low electric conductivity high heat radiation polymeric composition and molded body | |
| US10851277B2 (en) | Highly filled high thermal conductive material, method for manufacturing same, composition, coating liquid and molded article | |
| Yang et al. | A review on thermally conductive polymeric composites: classification, measurement, model and equations, mechanism and fabrication methods | |
| CN101045822B (en) | Low electric conductivity high heat radiation polymeric composition and molded body | |
| Chen et al. | Thermal conductivity of polymer-based composites: Fundamentals and applications | |
| Hu et al. | Thermally conductive PP/AlN composites with a 3-D segregated structure | |
| Zhou et al. | Significant enhancement of thermal conductivity in polymer composite via constructing macroscopic segregated filler networks | |
| KR101432995B1 (en) | Formation of high electrical conductive polymer composites with multiple fillers | |
| Ebadi-Dehaghani et al. | Thermal conductivity of nanoparticles filled polymers | |
| Kim et al. | Improvement of electric conductivity of LLDPE based nanocomposite by paraffin coating on exfoliated graphite nanoplatelets | |
| Alva et al. | Thermal and electrical characterization of polymer/ceramic composites with polyvinyl butyral matrix | |
| US20080242772A1 (en) | Low electric conductivity high heat radiation polymeric composition and molded body | |
| TWI336655B (en) | Injection/compression molding method for conductive thermoplastic resin composition | |
| Liu et al. | Tailored pyroresistive performance and flexibility by introducing a secondary thermoplastic elastomeric phase into graphene nanoplatelet (GNP) filled polymer composites for self-regulating heating devices | |
| Moon et al. | 3D Printable concentrated liquid metal composite with high thermal conductivity | |
| Baek et al. | Thermal transfer, interfacial, and mechanical properties of carbon fiber/polycarbonate-CNT composites using infrared thermography | |
| Luo et al. | Thermal, electrical and rheological behavior of high-density polyethylene/graphite composites | |
| Bai et al. | Effect of PLA crystallization on the thermal conductivity and breakdown strength of PLA/BN composites | |
| Kim et al. | Melt-processable aggregated boron nitride particle via polysilazane coating for thermal conductive composite | |
| Elahee et al. | Acrylic sealants as practicable direct ink writing (DIW) 3D-printable materials | |
| Nanda et al. | Thermal behavior and dielectric response of epoxy–boron nitride composites reinforced with short human hair fiber | |
| Kim et al. | Determination of the glass transition temperature of polymer/layered silicate nanocomposites from positron annihilation lifetime measurements | |
| CN106046362A (en) | Graphene foam-nylon 6 high-thermal-conductivity nanocomposite and preparation method thereof | |
| Brostow et al. | Strong thermoplastic elastomers created using nickel nanopowder | |
| US20190131207A1 (en) | A heat sink, a filler for a heat sink and methods thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081001 |