WO2015198657A1 - 複合強化素材及び造形材料 - Google Patents
複合強化素材及び造形材料 Download PDFInfo
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- WO2015198657A1 WO2015198657A1 PCT/JP2015/058331 JP2015058331W WO2015198657A1 WO 2015198657 A1 WO2015198657 A1 WO 2015198657A1 JP 2015058331 W JP2015058331 W JP 2015058331W WO 2015198657 A1 WO2015198657 A1 WO 2015198657A1
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- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a composite reinforcing material and a modeling material.
- composite reinforcing materials are disclosed in which exfoliated graphite and an inorganic filler are added to improve physical properties (tensile modulus, rigidity, impact resistance) (Patent Documents 2 and 3).
- Graphene is superior to other carbon materials in terms of performance as well as mass productivity and handling properties, and is expected in various fields.
- When graphene and other reinforcing materials are mixed with resin In order to obtain a sufficient physical property improving effect, it is necessary to uniformly disperse the reinforcing material.
- JP 2010-254822 A ([0032]-[0038]) JP 2014-201676 A ([0048]-[0064]) Japanese Patent Laying-Open No. 2014-210916 ([0043]) International Publication No. 2014/064432 (Page 19, Line 4-Line 9) JP 2013-79348 A ([0083]) JP 2009-114435 A ([0044])
- Patent Document 5 In Patent Documents 2 and 3 described above, physical properties contributing to rigidity (hardness) such as elastic modulus and impact resistance are improved by adding a reinforcing material. Similar results were obtained in Example 5 of the present specification (an unpublished invention before the present application).
- Patent Document 1 In order to improve the tensile strength (tensile strength), a reinforcing material is added (for example, Patent Document 1).
- a string-like material such as carbon fiber, glass fiber, or cellulose fiber is suitable as a reinforcing material (filler).
- a compatibilizing agent in order to make it difficult to remove the string-like material from the base material, a material in which the tensile yield stress is improved by using a compatibilizing agent has been proposed (Patent Document 6).
- Patent Document 6 it has been found that mechanical strength such as tensile strength is not sufficiently improved by simply adding a string-like material. This is presumably because the base material is soft and the string-like material comes off together with the base material.
- graphene precursor graphite-based carbon material that can be easily separated into graphene and can be highly concentrated or dispersed is obtained by subjecting graphite as a material to a predetermined treatment.
- This graphene precursor is partly or entirely peeled off by ultrasonic waves, stirring, and kneading, and becomes a mixture “graphene-like” from the graphene precursor to the graphene.
- the size, thickness, and the like vary depending on the amount of graphene precursor added, the process time, and the like.
- graphite that easily peels and disperses like graphene by an existing stirring or kneading process or apparatus is a graphite-based carbon material (graphene precursor).
- graphene precursor graphite-based carbon material
- the present inventors have found that the composite reinforcing material can be produced without any problems.
- the present invention has been made paying attention to such problems, and an object thereof is to provide a composite reinforcing material and a modeling material that are excellent in mechanical strength. Another object of the present invention is to provide a composite reinforcing material that exhibits desired properties even if the amount of graphene-like material dispersed and blended in the base material is small. Furthermore, it aims at providing the composite reinforcement
- the composite reinforcing material of the present invention is A composite reinforcing material in which a graphene-like material and a reinforcing material separated from at least a reinforcing material and a graphite-based carbon material are dispersed in a base material,
- the graphite-based carbon material has a rhombohedral graphite layer (3R) and a hexagonal graphite layer (2H), and the rhombohedral graphite layer (3R) and the hexagonal graphite layer (2H).
- the rate Rate (3R) defined by the following (Expression 1) by the X-ray diffraction method is 31% or more.
- Rate (3R) P3 / (P3 + P4) ⁇ 100 (Equation 1) here, P3 is the peak intensity of the (101) plane of the rhombohedral graphite layer (3R) by X-ray diffraction method P4 is the peak intensity of the (101) plane of the hexagonal graphite layer (2H) by X-ray diffraction method.
- the composite material is excellent in mechanical strength. This is presumably because the graphene-like dispersed in the base material synergistically exhibited the effect of increasing the elastic modulus of the base material itself and the function of making it difficult for the reinforcing material to escape.
- examples of the mechanical strength include bending elastic modulus, compressive strength, tensile strength, Young's modulus, and the like, for example, excellent tensile strength.
- the reinforcing material is string-like, linear or flaky fine particles. According to this feature, since graphene-like exists around the fine particles, the strengthening function of the fine particles can be sufficiently exhibited.
- the fine particles have an aspect ratio of 5 or more. According to this feature, the reinforcing function of the fine particles can be sufficiently exhibited.
- the weight ratio of the graphite-based carbon material to the reinforcing material is 1/100 or more and less than 10. According to this feature, the reinforcing function of the reinforcing material can be sufficiently exhibited.
- the base material is a polymer. According to this feature, a composite reinforcing material having excellent mechanical strength can be obtained.
- the base material is an inorganic material. According to this feature, a composite reinforcing material having excellent mechanical strength can be obtained.
- the modeling material is characterized by using the composite reinforcing material. According to this feature, it is possible to obtain a modeling material for 3D printing or the like having excellent mechanical strength.
- FIG. 6 is a diagram showing an X-ray diffraction profile of a graphite-based carbon material of Sample 6 manufactured by the manufacturing apparatus A of Example 1.
- FIG. It is a figure which shows the X-ray-diffraction profile of the graphite-type carbon raw material of the sample 1 which shows a comparative example.
- FIG. 1 It is a figure which shows the dispersion
- FIG. It is a TEM imaging figure of the graphite type carbon material (graphene) dispersed in the dispersion. It is a figure which shows the distribution state of the graphite type
- graphite type carbon material graphene
- FIG. 7 is a diagram showing the distribution of the number of layers of a graphite-based carbon material dispersed in a dispersion prepared using Sample 1-7 as a precursor. It is a figure which shows the ratio of the graphene of 10 layers or less with respect to the content rate of the rhombohedral crystal
- FIG. 5 It is a figure which shows an elasticity modulus when the graphite-type carbon raw material of Example 5 is knead
- NMP N-methylpyrrolidone
- (a) is the distribution state of the sample 12
- (B) is a figure which shows the distribution state of the sample 2.
- FIG. It is a graph which shows the tensile strength and bending elastic modulus of the test piece of Example 6.
- the present invention pays attention to the crystal structure of graphite, and the matters related to this crystal structure will be described first.
- natural graphite is classified into three types of crystal structures, hexagonal, rhombohedral and disordered, depending on how the layers overlap.
- the hexagonal crystal has a crystal structure in which layers are stacked in the order of ABABAB ⁇
- the rhombohedral crystal has a crystal structure in which layers are stacked in the order of ABCABCABC ⁇ .
- Natural graphite has almost no rhombohedral crystals at the stage of excavation, but is crushed and the like at the purification stage. Therefore, about 14% of rhombohedral crystals are present in a general natural graphite-based carbon material.
- the rhombohedral crystal ratio converges at about 30% even when crushing during purification is performed for a long time (Non-Patent Documents 1 and 2).
- the rhombohedral crystal is used in addition to the physical force such as crushing.
- Non-patent Document 3 Is about 25% (Non-patent Document 3). Furthermore, even when an extremely high temperature of 3000 degrees Celsius is applied, the temperature is about 30% (Non-patent Document 2). Thus, it is possible to increase the ratio of rhombohedral crystals by treating natural graphite with physical force or heat, but the upper limit is about 30%.
- Equation 3 the van der Waals force between the graphenes is expressed by (Equation 3) (Patent Document 2).
- graphene peels off.
- the energy required for exfoliation is inversely proportional to the cube of the thickness, so graphene exfoliates with weak physical force such as ultrasonic waves in a very thin state where the layers are infinitely thick. To do so, a very large amount of energy is required. In other words, even if the graphite is treated for a long time, only the weak part of the surface peels off, and the majority remains unpeeled.
- the inventors of the present application give a ratio of rhombohedral crystals (3R), which is increased to only about 30% by pulverization or heating to an ultra-high temperature, by subjecting natural graphite to a predetermined treatment as described below.
- rhombohedral crystals (3R) of the graphite-based carbon material is increased, particularly when the content is 31% or more, the use of this graphite-based carbon material as a precursor tends to be easily separated into graphene.
- graphene is easily exfoliated by applying a predetermined treatment to natural graphite, and a graphite-based carbon material capable of highly dispersing or dispersing graphene is referred to as a graphene precursor.
- a graphene precursor manufacturing method showing a predetermined treatment, a graphene precursor crystal structure, and a graphene dispersion using the graphene precursor will be described in this order.
- graphene is a crystal having an average size of 100 nm or more, is not a microcrystal having an average size of several nm to several tens of nm, and is a flaky or sheet-shaped graphene having 10 or less layers Say. Since graphene is a crystal having an average size of 100 nm or more, artificial graphite and carbon black, which are amorphous (microcrystalline) carbon materials other than natural graphite, do not yield graphene even when they are processed ( Non-patent document 4).
- the graphene composite is a graphite-based carbon material used as the graphene precursor according to the present invention, that is, a graphite-based carbon material having a Rate (3R) of 31% or more (for example, a sample of Example 1 described later) 2-7, a composite produced using Sample 2, 21 of Example 5).
- reference numeral 1 is a natural graphite material having a particle size of 5 mm or less (manufactured by Nippon Graphite Industries, scaly graphite ACB-50), 2 is a hopper containing the natural graphite material 1, and 3 is a jet of the natural graphite material 1 from the hopper 2.
- Venturi nozzle 4, jet mill for injecting air pumped from the compressor 5 into 8 locations and causing the natural graphite material to collide with the chamber by jet jet, 7 for oxygen, argon, nitrogen, hydrogen, etc.
- a plasma generator that generates a plasma in the chamber of the jet mill 4 by injecting a gas 9 from the nozzle 8 and applying a voltage from a high voltage power source 10 to a coil 11 wound around the outer periphery of the nozzle 8.
- 13 is a pipe connecting the jet mill 4 and the dust collector 14, 14 is a dust collector, 15 is a collecting container, 16 is a graphite-based carbon material (graphene precursor), and 17 is a blower.
- the conditions of the jet mill and the plasma are as follows.
- the conditions of the jet mill are as follows. Pressure: 0.5 MPa Air volume: 2.8m3 / min Nozzle inner diameter: 12mm Flow velocity: about 410m / s
- the plasma conditions are as follows. Output: 15W Voltage: 8kV Gas type: Ar (purity 99.999 Vol%) Gas flow rate: 5L / min
- the natural graphite material 1 put into the chamber of the jet mill 4 from the venturi nozzle 3 is accelerated in the chamber at a speed higher than the speed of sound, and is pulverized by the impact of hitting the natural graphite materials 1 and the walls, and at the same time, the plasma 12 is natural.
- the graphite material 1 By discharging or exciting the graphite material 1, it is considered that it directly acts on atoms (electrons), increases the distortion of the crystal and promotes pulverization.
- the natural graphite material 1 becomes a fine powder to a certain particle size (about 1 to 10 ⁇ m) the mass is reduced and the centrifugal force is weakened, so that the natural graphite material 1 is sucked out from the pipe 13 connected to the center of the chamber.
- a graphite-based carbon material (graphene precursor) 16 used as a graphene precursor of about 800 g was obtained from 1 kg of natural graphite material 1 as a raw material (recovery efficiency: about 80%) ).
- the manufacturing apparatus B uses a case where a microwave is applied as a process using radio wave force and a ball mill is used as a process using physical force.
- reference numeral 20 is a ball mill
- 21 is a microwave generator (magnetron)
- 22 is a waveguide
- 23 is a microwave inlet
- 24 is a medium
- 25 is a particle of 5 mm or less.
- Natural graphite material (Nippon Graphite Industries, scaly graphite ACB-50), 26 is a collection container, 27 is a filter, and 28 is a graphite-based carbon material (graphene precursor).
- the conditions of the ball mill and the microwave generator are as follows.
- the conditions of the ball mill are as follows.
- the conditions of the microwave generator (magnetron) are as follows.
- ⁇ X-ray diffraction profile of graphite-based carbon material (precursor)> Referring to FIG. 5 to FIG. 7, a graphite-based natural material (sample 6, sample 5) manufactured by manufacturing apparatuses A and B and a graphite system of about 10 ⁇ m powder obtained using only the ball mill of manufacturing apparatus B The X-ray diffraction profile and crystal structure of a natural material (Sample 1: Comparative Example) will be described.
- the measurement conditions of the X-ray diffractometer are as follows.
- each sample is composed of hexagonal crystal 2H face (100), face (002), face (101), and rhombohedron, respectively. Since the peak intensities P1, P2, P3, and P4 are shown on the surface (101) of the crystal 3R, these will be described.
- a so-called standardized value has been used in recent years regardless of domestic and foreign countries.
- the sample 5 manufactured by the manufacturing apparatus B that performs the processing by the ball mill and the microwave processing has a high ratio of the peak intensity P3 and the peak intensity P1, and P3 and P4 of P3.
- the Rate (3R) defined by (Equation 1) indicating the ratio to the sum of is 46%.
- the intensity ratio P1 / P2 was 0.012.
- Rate (3R) P3 / (P3 + P4) ⁇ 100 (Equation 1) here, P1 is peak intensity of (100) plane of hexagonal graphite layer (2H) by X-ray diffraction method P2 is peak intensity of (002) plane of hexagonal graphite layer (2H) by X-ray diffraction method P3 is rhomboid (4) is the peak intensity of the (101) plane of the hexagonal graphite layer (2H) by the X-ray diffraction method.
- the sample 6 manufactured by the manufacturing apparatus A that performs the processing by the jet mill and the processing by the plasma has a high ratio of the peak intensity P3 and the peak intensity P1, as shown in FIG. (3R) was 51%.
- the intensity ratio P1 / P2 was 0.014.
- the sample 1 showing the comparative example manufactured only by the ball mill has a smaller peak intensity P3 than the samples 5 and 6, and the rate (3R) is 23. %Met.
- the intensity ratio P1 / P2 was 0.008.
- Rate (3R) is 46% and 51%, which are shown in FIG. It was shown to be 40% or more or 50% or more compared with natural graphite or Sample 1 showing a comparative example.
- a graphene dispersion was prepared, and the ease of peeling of the graphene was compared.
- FIG. 8 shows an example in which ultrasonic treatment and microwave treatment are used in combination when preparing a graphene dispersion.
- the ultrasonic horn 44 is operated and 20 kHz (100 W) ultrasonic waves are continuously applied for 3 hours. (4) While the ultrasonic horn 44 is operated, the microwave generator 43 is operated to apply microwave 2.45 GHz (300 W) intermittently (irradiation every 5 minutes for 10 seconds).
- FIG. 9 shows that the graphene dispersion prepared as described above has passed 24 hours. It was confirmed that the graphene dispersion 30 using the sample 5 manufactured by the manufacturing apparatus B was partially precipitated but the whole was black. This is considered that many of the graphite-based carbon materials used as the graphene precursor are dispersed in a state of being separated from the graphene. It was confirmed that in the dispersion liquid 31 using the sample 1 showing the comparative example, most of the graphite-based carbon material is precipitated, and a part thereof is floating as a supernatant liquid. From this, it is considered that a small part peels off to graphene and floats as a supernatant.
- the graphene dispersion prepared as described above is diluted and applied to an observable concentration on a sample stage (TEM grid), dried, and shown in FIG. 10 of a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the size and number of layers of graphene were observed from various captured images.
- the sample 1 what diluted and apply
- the size is about 600 nm, which is the maximum length L of the flake 33 from FIG. 10A
- the number of layers from FIG. 10B is the number of layers by observing the end face of the flake 33 and counting the overlap of the graphene layers 6 layers (region indicated by reference numeral 34).
- the size and the number of layers of each flake were measured, and the number and size of the graphene layers shown in FIGS. 11 and 12 were obtained.
- the particle size distribution (size distribution) of flaky flakes contained in the graphene dispersion of sample 5 (Rate (R3) is 46%) manufactured by the manufacturing apparatus B of Example 1 ) was a distribution having a peak at 0.5 ⁇ m.
- the number of layers was distribution with the peak of 3 layers and graphene of 10 layers or less becoming 68%.
- the particle size distribution (size distribution) of flaky flakes contained in the dispersion of Sample 1 of Comparative Example (Rate (R3) is 23%) is a distribution having a peak at 0.9 ⁇ m. Met.
- the number of layers was a distribution in which most of the layers were 30 layers or more, and the graphene of 10 layers or less was 10%. From this result, when the sample 5 manufactured by the manufacturing apparatus B is used as a graphene precursor, there are many graphenes of 10 layers or less, excellent dispersibility of graphene, and high concentration graphene dispersion. I found that it was obtained.
- Samples 1, 5, and 6 in FIG. 13 are as described above.
- Samples 2, 3, and 4 are manufactured by a manufacturing apparatus B that performs processing by a ball mill and microwave processing, and graphene using a graphene precursor that is manufactured with a shorter microwave irradiation time than Sample 5 is used.
- a dispersion is prepared.
- Sample 7 was manufactured by a manufacturing apparatus A that performs processing by a jet mill and plasma processing, and a graphene dispersion was prepared using a graphene precursor that was manufactured by applying plasma with a higher output than sample 6. Is.
- Samples 2 and 3 having a Rate (3R) of 31% and 38% have a shape close to a normal distribution in which the shape of the distribution of the number of layers has peaks around 13 layers (a dispersion using the samples 2 and 3 ).
- Sample 4-7 having a Rate (3R) of 40% or more has a so-called log-normal distribution shape in which the distribution of the number of layers has a peak at a portion of several layers (thin graphene).
- Sample 1 having a Rate (3R) of 23% has a shape having a peak at a portion where the number of layers is 30 or more (a dispersion using Sample 1).
- the rate (3R) is 31% or more, the shape of the layer number distribution is different from less than 31%, and when the rate (3R) is 40% or more, the shape of the layer number distribution is less than 40%. It can be seen that the trends are clearly different.
- the ratio of graphene in 10 layers or less is 38% for the rate (3R) of the dispersion using the sample 3, whereas the rate (3R) for the dispersion using the sample 4 is 62%. It can be seen that when the Rate (3R) is 40% or more, the proportion of graphene in 10 layers or less is rapidly increasing.
- Rate (3R) is 31% or more, it becomes easy to exfoliate into graphene of 10 layers or less, and as Rate (3R) increases to 40%, 50%, 60%, 10 layers or less It is thought that it becomes easier to peel off the graphene.
- Sample 2 to Sample 7 have a relatively narrow value within a range of 0.012 to 0.016, and the crystal structure is distorted and easily peeled off from graphene. Since it exceeds 0.01 considered, all are preferable.
- FIG. 14 shows the result of comparison between Rate (3R) and the ratio of 10 layers or less of graphene.
- Rate (3R) when the rate (3R) is 25% or more, the graphene of 10 layers or less starts to increase from around 31% (inclining to the right), and the graphene of 10 layers or less is around 40%.
- the ratio of graphene in 10 layers or less is 38% for the dispersion (3R) of the dispersion using the sample 3 whereas the rate (3R) of the dispersion using the sample 4 is 62%).
- the rate of graphene of 10 layers or less rapidly increases so that Rate (3R) increases by 4%), and the graphene of 10 layers or less occupies 50% or more of the total. Note that the black square points in FIG. 14 are different samples, and the above-described sample 1-7 and other samples are also included.
- Rate (3R) is more preferably 40% or more from the viewpoint that the proportion of 10 or less layers of graphene rapidly increases to 50% or more.
- Rate (3R) when Rate (3R) is 31% or more, preferably 40% or more, and more preferably 50% or more, the ratio of being separated into 10 or less layers of graphene and 10 or less layers of graphitic carbon material It has been found that when these graphite-based carbon materials are used as a graphene precursor, it is excellent in graphene dispersibility and a high-concentration graphene dispersion can be obtained.
- Example 5 described later clarified that it is useful as a graphitic carbon material graphene precursor when Rate (3R) is 31% or more.
- the upper limit of Rate (3R) needs to be specified in particular, it is possible to separate into graphene when creating a dispersion liquid or the like so that the intensity ratio R1 / R2 satisfies 0.01 or more at the same time. It is preferable because it is easy.
- the upper limit is about 70% from the viewpoint that the graphene precursor is easily manufactured.
- the method using the treatment with the jet mill of the production apparatus A and the plasma treatment in combination is more preferable because a material having a high Rate (3R) can be easily obtained. Note that it is only necessary that the rate (3R) is 31% or more by combining the processing by physical force and the processing by radio wave force.
- Example 1 the case of using ultrasonic treatment and microwave treatment in combination when obtaining the graphene dispersion was described. However, in Example 2, only ultrasonic treatment was performed and microwave treatment was not performed. Other conditions are the same as in the first embodiment.
- Example 3 an example used for conductive ink will be described.
- Is a graphene precursor, and INK1, INK3, INK5, and INK6 are prepared in a mixed solution of water and an alcohol having a carbon number of 3 or less, which is a conductivity-imparting agent, and the respective resistance values are set. Compared. From this result, as the Rate (3R) becomes higher, the resistance value becomes lower.
- Example 4 an example of kneading into a resin will be described.
- the tensile strength of the glass fiber added was very good, and the cause was investigated.
- the compatibilizer added simultaneously with the glass fiber was converted into graphene precursor. It was found as a finding that it contributes to Then, what mixed the dispersing agent and the compatibilizing agent with resin was examined.
- the degree of grapheneization and dispersion can be inferred relatively by measuring the tensile strength of the resin. Can do.
- the tensile strength was measured with a tabletop precision universal testing machine (AUTOGRAPH AGS-J) manufactured by Shimadzu Corporation at a test speed of 500 mm / min.
- FIG. 17 shows a measurement result.
- the circle marks are resin materials using the sample 1 of the comparative example
- the square marks are resin materials using the sample 5 of the first embodiment.
- examples of the dispersant include an anionic (anionic) surfactant, a cationic (cationic) surfactant, a zwitterionic surfactant, and a nonionic (nonionic) surfactant.
- anionic surfactants and nonionic surfactants are preferred. More preferably, it is a nonionic surfactant.
- Nonionic surfactants are surfactants that do not dissociate into ions, such as sugar chains such as oxyethylene groups, hydroxyl groups, and glucosides, and are hydrophilic by hydrogen bonding with water.
- an X acid salt (X acid is, for example, cholic acid or deoxycholic acid), for example, SDC: sodium deoxycholate, phosphate ester, or the like is preferable.
- nonionic surfactant glycerin fatty acid ester, sorbitan fatty acid ester, fatty alcohol ethoxylate, polyoxyethylene alkylphenyl ether, alkyl glycoside and the like are preferable.
- Example 5 In order to further verify that the rate (3R) described in Example 1 is 31% or more, it will be further explained using an example of kneading into a resin in Example 5. The elastic modulus of a resin molded article using the Rate (3R) graphite-based carbon material plotted in FIG. 14 including the samples 1 to 7 in Example 1 as a precursor will be described.
- a test piece JIS K7161 1A type (full length 165 mm, width 20 mm, thickness 4 mm) is prepared with an injection molding machine using the pellets prepared in (2).
- the elastic modulus (Mpa) of the test piece prepared in (3) was tested with a tabletop precision universal testing machine (AUTOGRAPH AGS-J) manufactured by Shimadzu Corporation at a test speed of 500 mm / min. Measured under conditions.
- Kneading temperature 135 ° C
- Rotor rotation speed 30 rpm
- Kneading time 15 minutes
- Furnace pressurization 10 minutes after starting 0.3 MPa, 10 minutes after depressurization to atmospheric pressure
- the dispersion of the graphene dispersion of (2) described above into the resin since the melting point of the resin is generally 100 ° C. or higher, water evaporates in the atmosphere, but the pressure kneader can pressurize the furnace. . In the furnace, an emulsion of the dispersion and the resin can be obtained by raising the boiling point of water and keeping the dispersion liquid. When the pressure is gradually released after pressurizing for a predetermined time, the boiling point of water decreases and the water evaporates. At that time, the graphene trapped in the water remains in the resin. Thereby, it is considered that the graphene graphite-based carbon material is highly dispersed in the resin. In addition, since the graphene dispersion tends to precipitate the graphene-based carbon material over time, it is preferable to knead the resin immediately after obtaining the graphene dispersion.
- the means for obtaining the emulsion of the dispersion and the resin may be a chemical thruster, vortex mixer, homomixer, high pressure homogenizer, hydro shear, flow jet mixer, wet jet mill, ultrasonic generator, etc. good.
- IPA 2-propanol
- acetone toluene
- NMP N-methylpyrrolidone
- DMF N-dimethylformamide
- Table 4 shows the relationship between the rate (3R) of which the rate (3R) is around 30% and the elastic modulus of the resin molded product.
- sample 00 is a blank sample in which the precursor was not kneaded.
- Samples 11 and 12 have Rate (3R) between Sample 1 and Sample 2, and Sample 21 had Rate (3R) as a sample. Sample between 2 and sample 3.
- the difference in elastic modulus (increase rate of elastic modulus) with respect to the sample 00 (blank) is approximately constant up to about 10% until Rate (3R) is 31%, and Rate (3R) is The difference suddenly increases to 32% after 31%, the rate increases monotonically from 50% to 31% from 31% to 42%, and the difference slightly increases until the rate (3R) is 42% or later. It turned out to converge at around%.
- Rate (3R) is 31% or more, a resin molded product having an excellent elastic modulus can be obtained.
- the graphene or graphite-based carbon material contained in the resin molded product is a small amount of 0.5 wt%, the resin has little influence on the inherent properties.
- the ratio of the thin layer of less than 15 layers in Sample 2 is larger than that of Sample 12, that is, the surface area of the graphite-based carbon material dispersed as a precursor is large, and the area in contact with the resin is large. This is thought to have spread rapidly.
- the Rate (3R) is 31% or more, the graphite-based carbon material used as the graphene precursor tends to be separated into 10 layers or less of graphene or a thin-layer graphite-based carbon material. was clearly shown.
- Example 5 only graphene-like was dispersed, but only an increase in elastic modulus was observed, and an increase in tensile strength was not so much observed. Therefore, an experiment was conducted in which the graphene precursor and graph fiber produced by the above-described method were added to the resin.
- Step 1 Glass fiber (GF) 40 wt%, compatibilizer 4 wt% and resin 56 wt% are mixed in advance with a tumbler mixer under mixing condition 1 and then kneaded with a twin screw extruder (extruder) under kneading condition 1 to obtain a master. Batch 1 is obtained.
- Step 2. 12 wt% of graphene precursors with different Rate (3R) shown in Table 5 and 88 wt% of resin are mixed in advance with a tumbler mixer under mixing condition 1, and then kneaded under kneading condition 1 with a twin screw extruder (extruder). Then, master batch 2 is obtained.
- Step 3R Rate 3R
- the master batch 1 is mixed with 25 wt%, the master batch 2 is 25 wt%, and the resin is 50 wt% with a tumbler mixer in advance under the mixing condition 1 and then kneaded under the kneading condition 1 with a twin screw extruder (extruder).
- Step 4 A test piece was molded from the kneaded product in Step 3 with an injection molding machine, and changes in mechanical strength were observed at a test speed of 500 mm / min in accordance with JIS K7139.
- Rate (3R) is 23% (Sample 1), 31% (Sample 2), 35% (Sample 21), 42% (Sample 4) according to the mixing ratio shown in Table 5. The experiment was conducted.
- the flexural modulus is higher in Examples 6-2, 6-3, and 6-4 than in Example 6-1 and Comparative Examples 6-1, 6-2, and 6-3, similarly to the tensile strength. It was observed.
- the ratio Rate (3R) of the graphene precursor is 31% or more
- the flexural modulus is improved by 40% or more compared to 0% (Comparative Example 6-2) and 23% (Example 6-1). A trend to be observed was observed.
- the graphene-like that comes into contact with the GF that has become difficult to pull out causes a so-called wedge action, and the tensile strength and the flexural modulus have increased due to the synergistic effect of the increase in the elastic modulus of the PP itself and the wedge action.
- a stake with a barb is easy to pull out even if it is stabbed into a muddy ground, but it is the same state as it is difficult to pull out on a ground that has been hardened.
- the addition of a compatibilizing agent promotes the exfoliation of graphene-like materials from the graphite-based carbon material, and it is speculated that there are many thin graphene-like materials. Note that when the Rate (3R) is less than 31% (Example 6-1), the amount of graphene-like dispersed is small, and it is considered that the effect of adding the graphene precursor is not sufficiently exhibited.
- the Rate (3R) is 35% or more (Examples 6-3 and 6-4), the flexural modulus and the tensile strength are better than those when the rate is 3% or less.
- the rate (3R) is considered to be more than 31% (Example 6-2) because the graphene-like number that increases the elastic modulus of PP increases.
- the graphene precursor obtained in Example 1 is a laminate of thin-layer graphite having a length of 7 ⁇ m and a thickness of 0.1 ⁇ m, for example, as shown in FIGS.
- FIG. 23 shows a cross section of a resin in which carbon nanotubes and graphene-like are dispersed, in which linear portions are carbon nanotubes and white spots are graphene-like.
- This graphene-like is a laminate of thin graphite having a thickness of 3.97 nm, for example, as shown in FIG.
- Step 1 Glass fiber (GF) 40 wt%, compatibilizer 4 wt% and resin 56 wt% are mixed in advance with a tumbler mixer under mixing condition 1 and then kneaded under a kneading condition 2 with a twin screw extruder (extruder). Batch 1 is obtained.
- Step 2. 12 wt% of graphene precursors with different Rate (3R) shown in Table 6 and 88 wt% of resin are mixed in advance with a tumbler mixer under mixing condition 1, and then kneaded under kneading condition 2 with a twin-screw extruder (extruder). Then, master batch 2 is obtained.
- Step 3R graphene precursors with different Rate (3R) shown in Table 6
- 88 wt% of resin are mixed in advance with a tumbler mixer under mixing condition 1, and then kneaded under kneading condition 2 with a twin-screw extruder (extruder). Then, master batch 2 is obtained.
- Master batch 1 37.5 wt%, masterbatch 2 25 wt%, and resin 37.5 wt% were mixed in advance with a tumbler mixer under mixing condition 1, and then kneaded with a twin screw extruder (extruder) under kneading condition 2 Knead.
- Step 4 A test piece was molded from the kneaded product in Step 3 with an injection molding machine, and changes in mechanical strength were observed at a test speed of 500 mm / min in accordance with JIS K7139.
- Rate (3R) is 23% (Sample 1), 31% (Sample 2), 35% (Sample 21), 42% (Sample 4) according to the mixing ratio shown in Table 6. The experiment was conducted.
- Example 7-2, 7-3, and 7-4 the tensile strength of Examples 7-2, 7-3, and 7-4 is higher than that of Example 7-1 and Comparative Examples 7-1, 7-2, and 7-3. Observed. In particular, when the rate (3R) of the graphene precursor is 31% or more, the tensile strength is improved by 20% or more compared to 0% (Comparative Example 7-2) and 23% (Example 7-1). A power trend was observed. In FIG. 25, Comparative Examples 7-1 and 7-3 not including GF are not plotted.
- the flexural modulus is higher in Examples 7-2, 7-3, and 7-4 than in Example 7-1 and Comparative Examples 7-1, 7-2, and 7-3, similarly to the tensile strength. It was observed.
- the ratio Rate (3R) of the graphene precursor is 31% or more
- the flexural modulus is improved by 20% or more compared to 0% (Comparative Example 7-2) and 23% (Example 7-1). A trend to be observed was observed.
- Example 8 the influence of the shape of the reinforcing material was confirmed using glass fiber (GF), carbon fiber (CF), talc, and silica as the reinforcing material.
- the experimental conditions other than the reinforcing material are the same as in Example 6.
- GF and CF are string-like or linear with a diameter of several tens of ⁇ m and a length of several hundreds of ⁇ m.
- Talc is in the form of flakes with a representative length of several to several tens of ⁇ m and a thickness of several hundreds of nanometers, and silica is granular with a diameter of several tens of nanometers to several ⁇ m.
- the tensile strength and the flexural modulus are improved in all of the materials to which the reinforcing material is added as compared with Comparative Example 6-1 in which the reinforcing material is not added.
- strengthening material (Comparative Examples 6-2,8-1, 8-2, 8-3) when the reinforcing material added with the graphene precursor is GF, the tensile strength and flexural modulus were 1.4 times and 1.4 times, respectively (implementation for Comparative Example 6-2) The rate of change in Example 6-2.)
- the CF was 1.3 times and 1.3 times
- the graphene precursor is preferable when used in combination with a string-like, linear or flaky reinforcing material because the tensile strength and the flexural modulus are improved by 10% or more.
- the string-like, linear or flaky nano-strengthened material has a large surface area per unit mass due to its shape, so it has a high effect of improving tensile strength and can increase the flexural modulus. Is presumed to be good.
- the reinforcing material is particularly preferably a string-like, linear or flaky shape having an aspect ratio of 5 or more.
- a reinforcing material with an aspect ratio of 5 or less such as silica
- what is necessary is just to obtain
- the aspect ratio referred to here is obtained from an average value of diameter or thickness and an average value of length described in a catalog or the like of the reinforcing material. In particular, when there is no catalog or the like, an arbitrary number is observed with an electron microscope such as SEM, and the average value of the length and thickness is obtained.
- the lower limit of the mixing ratio is 1/100 or more, preferably 1/10 or more, and the upper limit is 10 or less, preferably 1 or less.
- Comparative Example 6-1 not including GF is not plotted.
- examples of the base material in which the reinforcing material and the graphite-based carbon material are dispersed include the following.
- the ratio of the base material may be smaller than that of the reinforcing material or the graphite-based carbon material. In use, it may disappear due to combustion, oxidation, vaporization, evaporation, or the like.
- the base material such as a coating agent is a volatile solvent
- the base material is burned and carbonized like a C / C composite.
- polyethylene polyethylene
- PP polypropylene
- PS polystyrene
- PVC polyvinyl chloride
- ABS resin ABS resin
- PLA polylactic acid
- PMMA acrylic resin
- PA Polyacetal
- PC polycarbonate
- PET polyethylene terephthalate
- COP polyphenylene sulfide
- PTFE polytetrafluoroethylene
- PSF polysulfone
- PAI heat Thermoplastic resins such as plastic polyimide (PI), polyether ether ketone (PEEK), and liquid crystal polymer (LCP) can be mentioned.
- PI plastic polyimide
- PEEK polyether ether ketone
- LCP liquid crystal polymer
- thermosetting resin or an ultraviolet curable resin among synthetic resins conductive materials such as epoxy resin (EP), phenol resin (PF), melamine resin (MF), polyurethane (PUR), unsaturated polyester resin (UP), etc.
- polymers PEDOT, polythiophene, polyacetylene, polyaniline, polypyrrole, etc., fibers such as fibrous nylon, polyester, acrylic, vinylon, polyolefin, polyurethane, rayon, etc., isoprene rubber (IR), butadiene rubber (BR), styrene as elastomers Butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), polyisobutylene rubber / butyl rubber (IIR), ethylene propylene rubber (EPM / EPDM), chlorosulfonated polyethylene (CSM), Ryl rubber (ACM), epichlorohydrin rubber (CO / ECO) and other thermosetting resin elastomers,
- metal materials include silver nanoparticles, copper nanoparticles, silver nanowires, copper nanowires, flaky silver, flaky copper, iron powder, zinc oxide, and fibrous metals (boron, tungsten, alumina, silicon carbide). Carbon black, carbon fiber, CNT, graphite, activated carbon, etc. as carbon materials.
- Non-metallic materials other than carbon include glass fiber, nanocellulose, nanoclay (clay minerals such as montmorillonite), aramid fiber, and polyethylene fiber.
- a natural graphite for producing a graphitic carbon material used as a graphene precursor a natural graphite material having a particle size of 5 mm or less (scale graphite ACB-50 manufactured by Nippon Graphite Industry Co., Ltd.) has been described as an example.
- Graphite is flaky graphite and is pulverized to 5 mm or less, and is preferable from the viewpoint that a rate (3R) of less than 25% and a strength ratio P1 / P2 of less than 0.01 are easily available.
- 3R rate
- P1 / P2 strength ratio
- the metal content needs to be controlled, it is preferable to use artificial graphite with high purity. Further, if the Rate (3R) is 31% or more, artificial graphite obtained by a method other than the above-described physical force treatment or radio wave force treatment may be used.
- the graphite-based carbon material used as the graphene precursor is generally called graphene, graphene precursor, graphene nanoplatelet (GNP), fulayer graphene (FLG), nanographene, etc. It is not a thing.
- the present invention is directed to a composite reinforcing material having strength, and its application field is not limited.
- the base material is an organic material (resin, plastic)
- Vehicles Structural members such as airplanes, automobiles (passenger cars, trucks, buses, etc.), ships, playground equipment, etc.
- Structural members are composite resin, modified resin, fiber reinforced resin, etc.
- General-purpose products Structural members such as housings and parts such as furniture, home appliances, household items, and toys.
- Coating agent Used for hot melt additive manufacturing (FDM), stereolithography (SLA), powder fixation, powder sintered modeling (SLS), multi-jet modeling (MLM, inkjet modeling), Various modeling materials such as resin filaments and UV curable resins.
- Coating agent A coating agent is dispersed together with a resin in an organic solvent and applied by spraying or painting to coat the surface. In addition to improving strength, it has effects such as water repellency, rust prevention, and UV resistance. Applications include building (piers, buildings, walls, roads, etc.), automobiles, airplanes and other surfaces and interior coatings, helmets, protectors and other resin moldings.
- the base material is an inorganic material Fiber reinforced structural member such as cement (concrete, mortar), gypsum board, ceramics, C / C composite (carbon fiber reinforced carbon composite material). Graphene-like and reinforcing materials dispersed with these inorganic materials as base materials.
- the base material is a metal material Structural members such as aluminum, stainless steel, titanium, brass, bronze, mild steel, nickel alloy, tungsten carbide. (Structural members such as fiber reinforced metal). Graphene-like and reinforcing materials are dispersed using these metal materials as a base material.
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Abstract
Description
例えば、ポリオレフィンなどの熱可塑性樹脂に、薄片化黒鉛などの炭素素材を添加してなる樹脂複合強化素材が開示されている(特許文献1)。また、薄片化黒鉛と無機フィラーとを添加し、物性(引張弾性率、剛性、耐衝撃性)の改善を求めた複合強化素材が開示されている(特許文献2、特許文献3)。
中でもグラフェンは、性能的にはもちろん、量産性、ハンドリング性などの面からも他の炭素素材より優れており、様々な分野で期待されているが、グラフェンなどの強化素材と樹脂を混練した際に物性改善効果を十分に得るには、強化素材を均一に分散させることが必要となる。
上述した、特許文献2、3では、強化素材を添加し、弾性率や耐衝撃性など、剛性(硬さ)に寄与する物性が向上している。本明細書の実施例5(本出願以前に未公開の発明。)でも同様の結果となった。
このグラフェン様を母材に強化素材とともに少量分散させることによって、機械的強度、例えば曲げ弾性率、圧縮強度、引張強度、ヤング率などの向上が可能となり、しかも、製造方法を従来法と大きく変えることなく、該複合強化素材を製造できることを見出した。
また、母材に分散・配合させるグラフェン様の量が少なくても所望する性状を奏する複合強化素材を提供することを目的とする。
さらにまた、従来の製造プロセスを用いて機械的強度に優れる複合強化素材を提供することを目的とする。
母材に少なくとも強化素材と黒鉛系炭素素材から剥離されたグラフェン様と強化素材とが分散された複合強化素材であって、
前記黒鉛系炭素素材は、菱面晶系黒鉛層(3R)と六方晶系黒鉛層(2H)とを有し、前記菱面晶系黒鉛層(3R)と前記六方晶系黒鉛層(2H)とのX線回折法による次の(式1)により定義される割合Rate(3R)が31%以上であることを特徴としている。
Rate(3R)=P3/(P3+P4)×100・・・・(式1)
ここで、
P3は菱面晶系黒鉛層(3R)のX線回折法による(101)面のピーク強度
P4は六方晶系黒鉛層(2H)のX線回折法による(101)面のピーク強度
である。
この特徴によれば、複合素材は機械的強度に優れる。これは、母材にグラフェン様が分散し、母材自体の弾性率を上昇させる作用と、強化素材が抜けにくくなる作用とが相乗的に発揮されたためであると推察される。また、機械的強度として、曲げ弾性率、圧縮強度、引張強度、ヤング率などが挙げられるが、例えば、引張強度に優れる。
この特徴によれば、微粒子の周りにグラフェン様が存在するため、微粒子の有する強化機能を十分に発揮させられる。
この特徴によれば、さらに微粒子の有する強化機能を十分に発揮させられる。
この特徴によれば、強化素材の有する強化機能を十分に発揮させられる。
この特徴によれば、機械的強度に優れる複合強化素材を得ることができる。
この特徴によれば、機械的強度に優れる複合強化素材を得ることができる。
この特徴によれば、機械的強度に優れる3Dプリントなどのための造形材料を得ることができる。
また、破砕などの物理的力以外でも加熱によって黒鉛を膨張させて薄片化する方法も知られているが、黒鉛に1600K(摂氏約1300度)の熱をかけて処理を行っても菱面体晶の比率は25%程度である(非特許文献3)。更に超高温の摂氏3000度の熱をかけても30%程度までとなっている(非特許文献2)。
このように、天然黒鉛を物理的力や熱によって処理することで、菱面体晶の比率を増加させることが可能であるがその上限は30%程度である。
Fvdw:ファンデルワールス力
H :Hamaker定数
A :黒鉛又はグラフェンの表面積
t :黒鉛又はグラフェンの厚み
なお、グラフェンは平均サイズが100nm以上の結晶であるため、天然黒鉛以外の非晶質(微結晶)炭素素材である、人造黒鉛、カーボンブラックは、これらを処理してもグラフェンは得られない(非特許文献4)。
また、本明細書において、グラフェン複合体は、本発明に係るグラフェン前駆体として用いられる黒鉛系炭素素材、すなわちRate(3R)が31%以上の黒鉛系炭素素材(例えば後述する実施例1の試料2-7、実施例5の試料2、21・・・)を用いて作成した複合体を意味する。
図3に示されるジェットミルとプラズマとを用いた製造装置Aにより、グラフェン前駆体として用いられる黒鉛系炭素素材を得る方法について説明する。製造装置Aは、電波的力による処理としてプラズマを施し、また、物理的力による処理としてジェットミルを用いた場合を例にしている。
ジェットミルの条件は次のとおりである。
圧力 : 0.5MPa
風量 : 2.8m3/min
ノズル内直径 :12mm
流速 : 約410m/s
プラズマの条件は次のとおりである。
出力 : 15W
電圧 : 8kV
ガス種 : Ar(純度99.999Vol%)
ガス流量: 5L/min
ボールミルの条件は次のとおりである。
回転数 : 30rpm
メディアサイズ: φ5mm
メディア種 : ジルコニアボール
粉砕時間 : 3時間
マイクロ波発生装置(マグネトロン)の条件は次のとおりである。
出力 : 300W
周波数 : 2.45GHz
照射方法 : 断続的
図5-図7を参照して、製造装置A、Bにより製造された黒鉛系天然材料(試料6、試料5)及び製造装置Bのボールミルのみを用いて得た10μm程度の粉体の黒鉛系天然材料(試料1:比較例)のX線回折プロファイルと結晶構造について説明する。
X線回折装置の測定条件は次のとおりである。
線源 : Cu Kα線
走査速度 : 20°/min
管電圧 : 40kV
管電流 : 30mA
各試料は、X線回折法(リガク社製試料水平型多目的X線回折装置 Ultima IV)によれば、それぞれ六方晶2Hの面(100)、面(002)、面(101)、及び菱面体晶3Rの面(101)にピーク強度P1,P2,P3,P4を示すことからこれらについて説明する。
ここで、X線回折プロファイルの測定は、近年では国内外を問わずいわゆる標準化された値が用いられている。当該、リガク社製試料水平型多目的X線回折装置 Ultima IVは、X線回折プロファイルを、JIS R 7651:2007「炭素材料の格子定数及び結晶子の大きさ測定方法」に準拠して測定可能な装置である。なお、Rate(3R)は、Rate(3R)=P3/(P3+P4)×100で求められる回折強度の比であり、回折強度の値が変化しても、Rate(3R)の値が変化するものではない。つまり、回折強度の比は規格化されており、絶対値で物質の同定を行うのを回避するために一般に用いられおり、その値が測定装置に依存することはない。
Rate(3R)=P3/(P3+P4)×100・・・・(式1)
ここで、
P1は六方晶系黒鉛層(2H)のX線回折法による(100)面のピーク強度
P2は六方晶系黒鉛層(2H)のX線回折法による(002)面のピーク強度
P3は菱面晶系黒鉛層(3R)のX線回折法による(101)面のピーク強度
P4は六方晶系黒鉛層(2H)のX線回折法による(101)面のピーク強度
である。
次に、上述で製造されたグラフェン前駆体を用いて、グラフェン分散液を作成し、グラフェンの剥離し易さを比較した。
グラフェン分散液の作成方法について図8を参照して説明する。図8においては、グラフェン分散液を作成する際に、液中にて超音波処理とマイクロ波処理とを併用する場合を例にしている。
(1)ビーカー40にグラフェン前駆体として用いられる黒鉛系炭素素材0.2gと分散液であるN-メチルピロリドン(NMP)200mlを入れる。
(2)ビーカー40をマイクロ波発生装置43のチャンバ42に入れ、上方から超音波ホーン44の超音波の振動子44Aを分散液41に挿入する。
(3)超音波ホーン44を作動させ20kHz(100W)の超音波を連続的に3時間付与する。
(4)上記超音波ホーン44を作動させている間に、マイクロ波発生装置43を作動させマイクロ波2.45GHz(300W)を断続的(5分おきに10秒照射)に付与する。
製造装置Bにより製造された試料5を用いたグラフェン分散液30は一部沈殿しているものの全体が黒色を呈するものが確認された。これは、グラフェン前駆体として用いた黒鉛系炭素素材の多くがグラフェンに剥離した状態で分散していると考えられる。
比較例を示す試料1を用いた分散液31は黒鉛系炭素素材のほとんどが沈殿しており、一部が上澄み液として浮いていることが確認された。このことから、ごく一部がグラフェンに剥離し、上澄みとして浮いていると考えられる。
図12を参照して、比較例の試料1(Rate(R3)が23%)の分散液に含まれた薄片状のフレークの粒度分布(サイズの分布)は、0.9μmをピークとする分布であった。また、層数は、30層以上のものが大部分を占め、10層以下のグラフェンが10%となる分布であった。
この結果から、製造装置Bにより製造された試料5のものは、グラフェン前駆体として用いた場合に、10層以下のグラフェンが多く、グラフェンの分散性に優れ、かつ、高濃度のグラフェン分散液を得られることが分った。
図15(b)は、製造装置Bで製造した試料5(Rate(3R)=46%)のグラフェン前駆体を用い超音波処理を施して得られたグラフェン分散液の層数の分布を示す。なお、図15(a)は実施例1の製造装置Bにより製造された試料5の図11(b)に示される分布と同じである。
その結果、層数の分布の傾向は概ね同様であるが、10層以下のグラフェンの割合は64%であり、実施例1の68%に比較し、少し低下している。このことから、グラフェン分散液を作成する際は物理的力と電波的力の処理を2つ同時に行った方がより効果があることが判明した。
実施例1の試料1(Rate(3R)=23%)、試料3(Rate(3R)=38%)、試料5(Rate(3R)=46%)、試料6(Rate(3R)=51%)をグラフェン前駆体として、水と導電性付与剤たる炭素数3以下のアルコールとの混合溶液に導電性インクに使用する濃度にしたINK1,INK3,INK5,INK6を作成し、それぞれの抵抗値を比較した。この結果から、Rate(3R)が高くなるにつれ、抵抗値は低いという結果となった。
グラフェンを分散した樹脂シートを作成する際に、ガラス繊維を添加したものの引張強度が非常に良好であったためその要因を調べたところ、ガラス繊維と同時に添加する相溶化剤が、前駆体がグラフェン化することに寄与していることが知見として得られた。そこで、分散剤と相溶化剤とを樹脂に混ぜたものについて検討した。
実施例1の試料5(Rate(3R)=46%)を前駆体としてLLDPE(ポリエチレン)に1wt%直接添加し、ニーダーや2軸混練機(エクストルーダー)等でシェア(せん段力)をかけながら混練した。
樹脂中で黒鉛系炭素素材がグラフェン化し、高分散すると、引張強度が増加することは公知であることから、樹脂の引張強度を測定することによりグラフェン化と分散の度合いを相対的に推察することができる。引張強度は、島津製作所社製の卓上型精密万能試験機(AUTOGRAPH AGS-J)で試験速度500mm/minの条件で測定した。
(a)添加剤無
(b)一般的分散剤(ステアリン酸亜鉛)
(c)相溶化剤(グラフト変性ポリマー)
(a)の添加剤を加えない場合は、引っ張り強さの差は小さかった。
(b)の分散剤を添加した場合は、試料5のグラフェン前駆体はグラフェン化がある程度促進されることがわかる。
(c)の相溶化剤を添加した場合は、試料5のグラフェン前駆体はグラフェン化がかなり促進されることがわかる。これは、相溶化剤は、グラフェン分散させる効果の他に、グラフェン層結合体と樹脂を結合させ、その状態でシェアを加えると、グラフェン層結合体を引きはがすように作用すると考えられるからである。
(2)(1)において得られたグラフェン分散液0.6kgを直ちに、ニーダー(モリヤマ株式会社製 加圧型ニーダー WDS7-30)を用いて樹脂5.4kgに混練し、ペレットを作成する。混練条件については後述する。なお、樹脂と分散液との配合比率は最終的にグラフェン乃至黒鉛系炭素素材の添加量が0.5wt%になるように選定した。
(3)(2)において作成されたペレットを使用して射出成型機で試験片 JIS K7161 1A形(全長165mm、幅20mm、厚み4mm)を作成する。
(4)(3)により作成された試験片の弾性率(Mpa)をJIS K7161に基づいて、株式会社島津製作所製の卓上精密万能試験機(AUTOGRAPH AGS-J)により試験速度:500mm/minの条件で測定した。
混練温度:135℃
ローター回転数 :30rpm
混練時間:15分
炉内加圧:開始後10分間.0.3MPa、10分経過後大気圧まで除圧
また、グラフェン分散液は時間の経過とともにグラフェン黒鉛系炭素素材が沈降する傾向にあることから、グラフェン分散液を得た直後に樹脂に混練することが好ましい。
また、分散液の溶媒として水の他に2-プロパノール(IPA)、アセトン、トルエン、N-メチルピロリドン(NMP)、N,N-ジメチルホルムアミド(DMF)などを用いても良い。
このように、実施例5により、Rate(3R)が31%以上であると、グラフェン前駆体として用いられる黒鉛系炭素素材は10層以下のグラフェン乃至薄層の黒鉛系炭素素材に分離される傾向が明確に示された。
そこで、上述の方法により製造したグラフェン前駆体とグラフファイバーを樹脂に添加する実験を行った。
樹脂:PP(ポリプロピレン) プライムポリマー製 J707G、
相溶化剤:カヤブリッド(化薬アクゾ社製006PP 無水マレン酸変性PP)
グラスファイバー(GF):セントラルグラスファイバー社製 ECS03-631K(径13μm、長さ3mm)、
黒鉛系炭素素材:グラフェン前駆体(上述の方法により製造)、
混合機:タンブラーミキサー(セイワ技研社製)、
<混合条件1:回転数25rpm×1分>、
混練機:2軸エクストルーダー (神戸製鋼社製 HYPERKTX 30)、
<混練条件1:シリンダー温度 180℃、ローター回転数 100rpm、吐出量8kg/h>
試験片:JIS K7139(170mm×20mm×t4mm )、
測定装置:島津製作所製 卓上精密万能試験機 AUTOGRAPH AGS-J
ステップ1.グラスファイバー(GF)40wt%、相溶化剤4wt%、樹脂56wt%をタンブラーミキサーで事前に混合条件1で混合し、その後、2軸エクストルーダー(押出機)にて混練条件1で混練し、マスターバッチ1を得る。
ステップ2.表5に示されるRate(3R)の異なるグラフェン前駆体12wt%と樹脂88wt%をタンブラーミキサーで事前に混合条件1で混合し、その後、2軸エクストルーダー(押出機)にて混練条件1で混練し、マスターバッチ2を得る。
ステップ3.マスターバッチ1を25wt%、マスターバッチ2を25wt%、樹脂を50wt%をタンブラーミキサーで事前に混合条件1で混合し、その後、2軸エクストルーダー(押出機)にて混練条件1で混練する。
ステップ4.ステップ3で混練したものを射出成型機にて試験片を成型し、JIS K7139に準拠して試験速度500mm/minで機械強度の変化を観察した。
なお、Rate(3R)が31%未満(実施例6-1)では分散するグラフェン様の量が少なく、グラフェン前駆体を添加することによる効果が十分に発揮されていないと考えられる。
樹脂:PA66(66ナイロン) 旭化成製 1300S、
相溶化剤:カヤブリッド(化薬アクゾ社製006PP 無水マレン酸変性PP)
グラスファイバー(GF):セントラルグラスファイバー社製 ECS03-631K(径13μm、長さ3mm)、
黒鉛系炭素素材:グラフェン前駆体(上述の方法により製造)、
混合機:タンブラーミキサー(セイワ技研社製)、
<混合条件1:回転数25rpm×1分>、
混練機:2軸エクストルーダー (神戸製鋼社製 HYPERKTX 30)、
<混練条件2:シリンダー温度 280℃、ローター回転数 200rpm、吐出量12kg/h>
試験片:JIS K7139(170mm×20mm×t4mm)、
測定装置:島津製作所製 卓上精密万能試験機 AUTOGRAPH AGS-J
ステップ1.グラスファイバー(GF)40wt%、相溶化剤4wt%、樹脂56wt%をタンブラーミキサーで事前に混合条件1で混合し、その後、2軸エクストルーダー(押出機)にて混練条件2で混練し、マスターバッチ1を得る。
ステップ2.表6に示されるRate(3R)の異なるグラフェン前駆体12wt%と樹脂88wt%をタンブラーミキサーで事前に混合条件1で混合し、その後、2軸エクストルーダー(押出機)にて混練条件2で混練し、マスターバッチ2を得る。
ステップ3.マスターバッチ1を37.5wt%、マスターバッチ2を25wt%、樹脂を37.5wt%をタンブラーミキサーで事前に混合条件1で混合し、その後、2軸エクストルーダー(押出機)にて混練条件2で混練する。
ステップ4.ステップ3で混練したものを射出成型機にて試験片を成型し、JIS K7139に準拠して試験速度500mm/minで機械強度の変化を観察した。
Rate(3R)が31%であるグラフェン前駆体の強化素材に対する混合比率を表8に示される条件で実験を行った。実験条件等は実施例6と同様である。
このことから、混合比率は、下限は1/100以上、好ましくは1/10以上、上限は10以下好ましくは1以下であることが好ましい。
なお、図28には、GFを含まない比較例6-1はプロットしていない。
無機材料として、コンクリート、セラミックス、石膏、金属粉末などが挙げられる。
金属材料として、銀ナノ粒子、銅ナノ粒子、銀ナノワイヤ、銅ナノワイヤ、鱗片状銀、鱗片状銅、鉄粉、酸化亜鉛、繊維状金属(ボロン、タングステン、アルミナ、炭化ケイ素)など。
炭素素材として、カーボンブラック、カーボンファイバー、CNT、黒鉛、活性炭など。
炭素以外の非金属材料として、ガラス繊維、ナノセルロース、ナノクレイ(モンモリロナイトなどの粘土鉱物)、アラミド繊維、ポリエチレン繊維など。
なお、グラフェン前駆体として用いられる黒鉛系炭素素材は、一般的にグラフェン、グラフェン前駆体、グラフェンナノプレートレット(GNP)、フューレイヤーグラフェン(FLG)、ナノグラフェンなどと呼ばれているが、特に限定するものではない。
(1)母材が有機材料(樹脂、プラスチック)の例
(1-1)乗り物
飛行機、自動車(乗用車、トラック、バスなど)、船舶、遊具などの筐体、部品などの構造部材。(構造部材は複合樹脂、改質樹脂、繊維強化樹脂など)
(1-2)汎用品
家具、家電、家庭用品、玩具などの筐体、部品などの構造部材。
(1-3)3Dプリンタ
熱溶解積層造形法(FDM)、光造形法(SLA)、粉末固着、粉末焼結造形法(SLS)、マルチジェット造形法(MLM、インクジェット造形法)に用いられる、樹脂フィラメント、UV硬化樹脂などの各種造形材料。
(1-4)コート剤
有機溶媒に樹脂と共に分散させ、スプレーまたは塗装等で塗布し、表面をコーティングする。強度向上の他に、撥水、防錆、耐紫外線などの効果がある。用途は、建築物(橋脚、ビル、壁、道路など)、自動車、飛行機などの表面・内部塗装、ヘルメット、プロテクタなどの樹脂成型物など。
(2)母材が無機材料の例
セメント(コンクリート、モルタル)、石膏ボード、セラミックス、C/Cコンポジット(炭素繊維強化炭素複合材料)など繊維強化構造部材。これら無機材料を母材としてグラフェン様及び強化素材を分散させたもの。
(3)母材が金属材料
アルミニウム、ステンレス、チタン、真鍮、ブロンズ、軟鋼、ニッケル合金、炭化タングステンなどの構造部材。(構造部材は繊維強化金属など)。これら金属材料を母材としてグラフェン様及び強化素材を分散させたもの。
Claims (7)
- 母材に少なくとも黒鉛系炭素素材から剥離されたグラフェン様と強化素材とが分散された複合強化素材であって、
前記黒鉛系炭素素材は、菱面晶系黒鉛層(3R)と六方晶系黒鉛層(2H)とを有し、前記菱面晶系黒鉛層(3R)と前記六方晶系黒鉛層(2H)とのX線回折法による次の(式1)により定義される割合Rate(3R)が31%以上であることを特徴とする複合強化素材。
Rate(3R)=P3/(P3+P4)×100・・・・(式1)
ここで、
P3は菱面晶系黒鉛層(3R)のX線回折法による(101)面のピーク強度
P4は六方晶系黒鉛層(2H)のX線回折法による(101)面のピーク強度
である。 - 前記強化素材は、ひも状、線状又は薄片状の微粒子であることを特徴とする請求項1に記載の複合強化素材。
- 前記微粒子はアスペクト比が5以上であることを特徴とする請求項2に記載の複合強化素材。
- 前記強化素材に対する前記黒鉛系炭素素材の重量比は、1/100以上10未満であることを特徴とする請求項1又は2に記載の複合強化素材。
- 前記母材は、ポリマーであることを特徴とする請求項1に記載の複合強化素材。
- 前記母材は、無機材料であることを特徴とする請求項1に記載の複合強化素材。
- 請求項1に記載の前記複合強化素材を用いたことを特徴とする、3Dプリントなどのための造形材料。
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Also Published As
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GB201510240D0 (en) | 2015-07-29 |
CA2905717A1 (en) | 2015-08-21 |
CA2905717C (en) | 2019-10-15 |
GB201601711D0 (en) | 2016-03-16 |
GB2528381A (en) | 2016-01-20 |
GB201601710D0 (en) | 2016-03-16 |
GB2532375A (en) | 2016-05-18 |
GB2528381B (en) | 2017-08-02 |
GB2533709A (en) | 2016-06-29 |
GB2533709B (en) | 2017-03-29 |
GB2532375B (en) | 2017-04-12 |
GB2533494A (en) | 2016-06-22 |
AU2015203587A1 (en) | 2015-10-29 |
GB201601712D0 (en) | 2016-03-16 |
AU2015203587B2 (en) | 2015-11-12 |
GB2533494B (en) | 2017-04-12 |
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