GRAPHITE MATERIAL AND PRODUCTION METHOD THEREOF
20170275515 · 2017-09-28
Inventors
- Atsushi TANAKA (Osaka, JP)
- Naomi Nishiki (Kyoto, JP)
- Hidetoshi Kitaura (Osaka, JP)
- Kimiaki Nakaya (Osaka, JP)
Cpc classification
B32B5/142
PERFORMING OPERATIONS; TRANSPORTING
B32B2264/108
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
A graphite material has a flexible part and can be utilized as a heat-conveying material in a narrow space. The graphite material, includes: at least one heat-conveying part; and a flexible part. A method for producing a graphite material, includes: (i) subjecting at least one film serving as a material to a heat treatment to obtain at least one carbonaceous film; (ii) providing a monolayer or multilayer structure including the at least one carbonaceous film; and (iii) applying heat and pressure to at least one part of the monolayer or multilayer structure in an inert atmosphere.
Claims
1. A graphite material, comprising: at least one heat-conveying part; and a flexible part.
2. The graphite material according to claim 1, wherein the at least one heat-conveying part has a porosity of 1% to 30%, and the flexible part has a porosity of more than 30% to 50%.
3. The graphite material according to claim 1, wherein the at least one heat-conveying part and the flexible part are formed in a continuous manner, and basal planes of graphite in the heat-conveying part and the flexible part are continuous with each other.
4. The graphite material according to claim 1, wherein the at least one heat-conveying part includes multiple heat-conveying parts, and the flexible part is placed between two of the multiple heat-conveying: parts.
5. The graphite material according to claim 1, wherein the flexible part has a length, of I mm or more.
6. The graphite material according to claim 1, wherein a content of oxygen is 3.1 at % or less, and a content of nitrogen is 4.1 at % or less.
7. The graphite material according to claim 1, therein a gap between layers with six-membered carbon ring structures is 3.73 angstroms or less.
8. The graphite material according to claim 1, wherein said graphite material includes pores, and a part of the graphite material other than the pores consists essentially of carbon.
9. A method for producing a graphite material, comprising: (i) subjecting at least one film serving as a material to a heat treatment to obtain at least one carbonaceous film; (ii) providing a monolayer or multilayer structure including the at least one carbonaceous film; and (iii) applying heat and pressure to at least one part of the monolayer or multilayer structure in an inert atmosphere.
10. The method according to claim 9, wherein, no pressure is applied to a part of the monolayer or the multilayer structure in Step (iii).
11. The method according to claim 10, wherein, in Step (iii), the part to which no pressure is applied is a flexible part of the monolayer or the multilayer structure, and the at least one part to which the pressure is applied is an inflexible part of the monolayer or the multilayer structure.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0010]
[0011]
[0012]
DESCRIPTION OF EMBODIMENTS
[0013]
<Heat-Conveying Part 1>
[0014] The heat-conveying parts 1 convey and release: heat to secure heat radiation. The heat-conveying parts 1 include graphite, and have a graphite-layer structure as shown in
[0015] On the other hand, in cases where the heat-conveying parts 1 each have a thickness of more than 500 μm, the heat-conveying parts 1 have inferior bendability (flexibility), and, consequently, it may become difficult to insert the produced graphite device into a device. Therefore, the thicknesses of the heat-conveying parts 1 are preferably 500 μm or less.
[0016]
[0017] Each of the heat-conveying parts 1 preferably has a porosity of 1% to 30%, If the porosity is smaller than 1%, the graphite produced therein would be monocrystalline, and the heat-conveying parts 1 may become very hard. Therefore, the resulting graphite material would be unsuitable as a thermal countermeasure that is attached on an object. On the other hand, if the porosity exceeds 30%, the degree of heat conveyance would be decreased, and therefore, the resulting graphite material may be unsuitable as a thermal countermeasure.
<Flexible Part 2>
[0018] The flexible part 2 has a certain degree of flexibility or bendability. A length L of the flexible part 2 is preferably 1 mm or more. A height of a component that the graphite material 10, serving as a thermal countermeasure component, needs to cross aver may generally be 300 μm or more. In other words, in cases where the graphite material 10 is used inside an electronic device, the graphite material 10 needs to cross over an electronic component inside the electronic device. In order for the graphite material 10 to cross over an electronic component, the length L may need to be 300 μm or more since most, of electronic components have a height of about 300 μm or more. An upper limit of the length L may be 3 mm. This is because the length L is preferably 3 mm or less in order to secure sufficient thermal conveyance.
[0019] When the length L of the flexible part 2 is smaller than 1 mm, there may be cases in which the graphite material 10 cannot tolerate a difference in heights of electronic components, or the like, and thus, is possibly cracked.
[0020] Preferably, a porosity of the flexible part 2 is more than 30%, and is 50% or less. If the porosity is 30% or less, then, the flexible part 2 may not have sufficient bendability (flexibility) and thus, cracks may be caused in the flexible part 2. On the other hand, if the porosity exceeds 50%, then, heat conveyance properties may significantly be deteriorated, and thus, conveyance of heat may be impaired.
[0021] The terms “flexible”, “flexibility”, “bendable” and “bendability” used herein means that the flexible part 2 is bendable at an angle of 45°. Also, these terms mean that the flexible part 2 is bendable at least once. This is because if is only required that the graphite material 10 may foe bent once, in order to place it in various devices. However, in cases in which the flexible part 2 has flexibility that makes it possible to bend the flexible part 2 two or three times, the graphite material 10 would be used again and again in various devices. Therefore, a graphite material 10 having such flexibility over the flexible part 10 is preferable.
<Method for Producing a Graphite Material 10>
[0022] A graphite material 10 according to the disclosure can be produced based on (i) a carbonaceous film-producing step, (ii) a preparatory step for molding; and (iii) a molding step.
[0023] In the carbonaceous film-producing step (i.e., step (i)) at least one film serving as a material is subjected to a heat treatment at 400° C. to 2000° C. to obtain at least one carbonaceous film. A rate of temperature increase therefor may be from 1 to 5° C./minute.
[0024] In the preparatory step for molding (i.e., step (ii)), a monolayer or multilayer structure including the at least one carbonaceous film obtained in the carbonaceous film-producing step is provided. Multiple films may be subjected to the heat treatment to produce multiple carbonaceous films in Step (i), and the produced multiple carbonaceous films may be layered to provide the multilayer structure in Step (ii).
[0025] In the molding step (i.e., step (iii)), heat and pressure are applied to at least one part of the monolayer or multilayer structure obtained in Step (ii) inside a molding die in an inert atmosphere. The monolayer or multilayer structure say partially be molded by a pressure of 5 MPs to 20 MPa while being maintained at 2200° C. or higher.
[0026] In step (i), the heat treatment temperature for producing carbonaceous films: say ranges from 400° C. to 2000° C. The heat treatment may be carried out at a temperature higher than 2000° C. However, in cases in which the at least one film is subjected to the heat treatment within the above temperature range, and, the resulting at least one carbonaceous film is molded by hot pressing into isotropic graphite including a curved surface processed into a part of the structure, followed, the resulting graphite material 10 will have excellent quality.
[0027] The term “carbonaceous film(s) refers to film(s) made of glass-like and amorphous carbon.
[0028] After the at least one: carbonaceous film is produced in Step (i), the at least one carbonaceous film may be provided as the monolayer structure, or multiple carbonaceous films produced in Step (i) say be layered to provide the multilayer structure in Step (ii). Then, in Step (iii), the monolayer or multilayer structure may be subjected to a molding process that is a substantial press-bonding step under heating conditions after a temperature-increasing step, or may be subjected directly to the molding process, to progress graphitization of carbonaceous materials in the monolayer or multilayer structure. In this way, a graphite material 10 in which graphite crystals are oriented parallel to surfaces of the resulting graphite films is produced.
[0029] In Step (iii), i.e. the molding step, at least one part of the monolayer or multilayer structure may be molded at a pressure of 5 MPa or higher while being maintained at 2200° C. or higher. In that case, the at least one part will serve as a heat-conveying part 1 in the resulting graphite material 10. If the temperature is lower than 2200° C., a crystalline structure required for heat-conveying part(s) 1 may not be formed, and an amount of beat conveyance by the resulting graphite material 10 may be decreased.
[0030] As for the pressure, if the applied pressure is smaller than 5 MPa, thin carbonaceous films may not be adhered tightly to each other, and, consequently, it may be impossible to obtain heat-conveying parts 1 having desirable thicknesses.
[0031] If the applied pressure is larger than 20 MPa, the porosity may be smaller than 1%, and, in that case, the conveying parts 1 become very hard. By applying a pressure of 5 MPa to 20 MPa only to at least one part of the monolayer or multilayer structure (i.e., to at least one part thereof that will serve as a heat-conveying part 1), a graphite material having a heat-conveying part(s) 1 and a flexible part 2 can be obtained. In addition, any pressure may not be applied to a part of the monolayer or multilayer structure (i.e. a part that will serve as a flexible part 2). However, both of the parts that will serve as a heat-conveying part (s) 1 and a flexible part 2 may be subjected to the same heat treatment. Therefore, in that case, the heat-conveying part(s) 1 and the flexible part 2 may be produced from the same polymer film (s). The heat-conveying part (s) 1 and the flexible part 2 may be continuous with each other, and graphite basal planes in heat-conveying part (s) 1 and the flexible part 2 may be continuous with each other.
[0032] As for the above-mentioned rate of temperature increase, if the rate is smaller than 1° C./minute, the porosity of the flexible part 2 may be 30% or less. On the other hand, if the rate is larger than 5° C./minute, the porosity of the flexible part 2 may be larger than 50%. In addition, the heat-conveying part(s) 1 would be provided without causing any problems, at the above-mentioned range of the rate of temperature increase.
[0033] If the porosity of the flexible part 2 is 30% or less, the flexible part 2 may lose sufficient flexibility, and therefore, cracks may be caused therein, and the heat-radiation properties may be deteriorated.
[0034] On the other hand, the porosity of the flexible part 2 is larger than 50%, then, the heat conductivity of the flexible part 2 may be lowered, and therefore, the heat-radiation properties would be deteriorated.
[0035] Furthermore, the flexible part 2 is preferably placed between heat-conveying parts 1. As shown in
[0036] In addition, oxygen, hydrogen, etc. have been removed from the graphite material 10 through the heat treatment, and the graphite material 10 consists essentially of carbon (i.e. approximately 100% of carbon). However, the graphite material 10 can include inevitable elements.
<Films Usable as Materials>
[0037] Possible films usable as materials in present disclosure (hereinafter, the film(s) may be referred to simply as “material film(s)”) may be polymer films. For example, polyimides (PI), polyamides (PA), polyoxadiazoles (POD), polybenzothiaxoles (PBT), poilybensobisthiazoles (PBBT), polybenzoxazoles (PBO), polybenzobisoxazoles (PBBQ) polyparaphenylenevinylenes (PPV), polyphenylene benzoimidazoles (PBI), polyphenylene benzobisimidasoles (PPBI), and polythiazoles (PT) can be mentioned.
[0038] A heat-resistant aromatic polymer film including at least one polymer selected from these materials is preferably used. This is because the electrical conductivity and the heat conductivity of the resulting graphite material 10 will be higher in cases where such a polymer film is used as a material. The above types of polymer films may be produced by known techniques.
[0039] Among the above polymers, polyimides are particularly preferable since polyimides having various structures and properties can be obtained by selecting various types of material monomers.
[0040] Moreover, a material film having a thickness of 75 μm or less is preferably used. In cases in which a material film having a thickness larger than 75 μm is used, the crystallinity may be distorted depending on timing of gas generation, and this results in deterioration of the heat conductivity. Therefore, the resulting material may be unsuitable as a heat-conveying material.
[0041] Furthermore, since the above polymer film is subjected to the heat treatment, oxygen, hydrogen, and the like are removed from graphite generated in the neat-conveying part (s) 1 through the sintering process. In the graphite generated in the heat-conveying part(s) 1 (or in the produced graphite material 10), a content of oxygen is preferably 3.1 at % or less, and/or a content of nitrogen is preferably 4.1 at % or less.
[0042] Additionally, a gap between layers each having a six-membered carbon ring structure in the graphite present in the heat-conveying part(s) 1 is preferably from 3.3 angstroms to 3.73 angstroms. Graphite obtained by subjecting the polymer film to the heat treatment would have a layer structure originated from the polymer. A half-value width of 2θ/θ of the X ray diffraction peaks of the (002) plane of the graphite in the heat-conveying part(s) 1 is preferably 0.5 or smaller, i.e., the produced graphite is preferably highly crystalline.
[0043] In addition, graphite forming the flexible part 2 may have the same physical properties described above.
[0044] Hereinafter, embodiments will more specifically be described based on examples. However, it should be noted that the examples below do not limit embodiments of the disclosure.
EXAMPLES 1-3
[0045] 20 pieces of polyimide films (Kapton films manufactured by DU PONT-TORAY CO., LTD) each having a thickness of 25 82 m were layered as material films that were graphitized through the product ion process. Graphite materials were prepared, based on conditions shown, in Table 1 with regard to welding pressures, rates of temperature increase, porosities of each of the parts, and lengths of flexible parts 2. Results of evaluation of heat-radiation properties of the produced graphite materials are also shown in Table 1. Variations in the porosities in the examples and the comparative examples are further shown in Table 1.
TABLE-US-00001 TABLE 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 EXAMPLE 7 Thickness of 25 25 25 25 25 25 25 film (μm) Pressures 20 10 5 10 10 10 5 applied to parts corresponding to the heat- conveying parts 1 (MPa) Rates of 3 3 3 1 3 5 5 temperature increase (° C./minute) Porosities of 1 10 30 10 10 10 30 heat-conveying parts 1 (%) Porosities 40 40 40 30 40 50 50 of flexible parts 2 (%) Lengths of 1 1 1 1 1 1 1 flexible parts 2 (mm) Heat-radiation 5 6 7 6 7 8 10 properties (° C.) (Measurements based on FIG. 3) Evaluations Superior Superior Superior Superior Superior Superior Superior COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 Thickness of 25 25 25 25 25 film (μm) Pressures 25 3 10 20 10 applied to parts corresponding to the heat- conveying parts 1 (MPa) Rates of 3 1 0.5 7 8 temperature increase (° C./minute) Porosities of 0.5 40 10 1 10 heat-conveying parts 1 (%) Porosities 40 30 20 60 40 of flexible parts 2 (%) Lengths of 1 1 1 1 0.5 flexible parts 2 (mm) Heat-radiation 11 15 20 15 22 properties (° C.) (Measurements based on FIG. 3) Evaluations Inferior Inferior Inferior Inferior Inferior
COMPARATIVE EXAMPLES 1-4
[0046] Film materials were treated in the same: manner as the above examples except that conditions specified in Table 1 were adopted.
<Evaluations on Heat-Radiation Properties>
[0047] Heat-radiation properties of graphite materials obtained in the examples and the comparative examples were evaluated by use of a simple jig.
<Discussion>
(1) Porosities of Heat-Conveying Parts 1
[0048] According to results of COMPARATIVE EXAMPLE 1, when porosities of heat-conveying parts 1 were arranged to be smaller (0.5%), graphite in the heat-conveying parts 1 became highly crystalline and hard, and, when the graphite material was pressed against the heat-generating component, minute cracks were caused, resulting in deterioration of heat-radiation effects.
[0049] To the contrary, when porosities of heat-conveying parts 1 were arranged to be larger (40%) in COMPARATIVE EXAMPLE 2, it was considered that a sufficient, amount, of neat cannot be conveyed through the heat-conveying parts 1, and this resulted in deterioration, of heat-radiation properties. On the other hand, according to EXAMPLES 1-3, when the porosities were arranged to range from 1% to 30%, high heat-radiation properties were realized. Therefore, the porosities of the: heat-conveying parts 1 are preferably from 1% to 30%.
(2) Porosity of the Flexible Part 2
[0050] The graphite material in COMPARATIVE EXAMPLE 3 could, not tolerate the difference in level of the components through its flexible part 2, and thus, cracks were caused therein, resulting in decreased heat-radiation properties. To the contrary, although no cracks were caused in COMPARATIVE EXAMPLE 4, it was considered that heat-radiation properties were deteriorated since heat-conveying properties of the flexible part 2 was inferior. On the other hand, according to EXAMPLES 4-6, when the porosities were adjusted so as to range from 30% to 50%, higher heat-radiation properties were realized. However, the porosity is more preferably adjusted to be larger than 30% in order to further enhance the flexibility. Hence, preferably, the porosity of the flexible part 2 is larger than 30%, and is 50% or less.
(3) Length of the Flexible Part 2
[0051] According to COMPARATIVE EXAMPLE 5, it was revealed that, when the length of the flexible part 2 is excessively small, cracks may be caused, thereby resulting in significantly deteriorated heat-radiation properties. Therefore, the length of the flexible part 2 is preferably 1 mm or more.
[0052] The above observations are summarized as follows. [0053] (1) Porosities of heat-conveying parts 1 are preferably from 1% to 30%. [0054] (2) Preferably, a porosity of the flexible part 2 is larger than 30%, and is 50% or less. [0055] (3) A length of the flexible part 2 is preferably 1 mm or more.
[0056] Graphite materials produced according to the disclosure will have high heat conductivity. Therefore, the graphite materials are suitable not only as heat-conveying materials used in electronic devices (e.g., servers, server computers and desktop computers) and portable electronic devices (e.g., notebook computers, electronic dictionaries, PDAs, portable phones, PDPs and portable music players) but also as heat-conveying materials for heat equalization in vehicle batteries. Furthermore, according to the production, method of the disclosure, such useful graphite materials can be produced. Therefore, the graphite materials and the production method according to the disclosure are highly industrially applicable.