JP2009191399A - Diamond fiber, nonwoven fabric containing the same, and method for producing them - Google Patents

Diamond fiber, nonwoven fabric containing the same, and method for producing them Download PDF

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JP2009191399A
JP2009191399A JP2008033253A JP2008033253A JP2009191399A JP 2009191399 A JP2009191399 A JP 2009191399A JP 2008033253 A JP2008033253 A JP 2008033253A JP 2008033253 A JP2008033253 A JP 2008033253A JP 2009191399 A JP2009191399 A JP 2009191399A
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diamond
fiber
nonwoven fabric
polymer
spinning solution
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JP5188827B2 (en
Inventor
Masaaki Kawabe
Eiji Osawa
Takashi Tarao
Hiroaki Yamazaki
隆 多羅尾
映二 大澤
洋昭 山崎
雅章 川部
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Japan Vilene Co Ltd
Nanocarbon Research Institute Co Ltd
日本バイリーン株式会社
株式会社ナノ炭素研究所
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a diamond fiber having excellent handleability and exhibiting the inherent characteristic performance of diamond such as heat conductivity, and to provide a nonwoven fabric containing the diamond fiber and a method for producing the fiber and the fabric. <P>SOLUTION: The diamond fiber consists essentially of diamond and has an aspect ratio of 200 or more. The nonwoven fabric contains the diamond fiber. The method for the production of the diamond fiber includes preparation of a spinning liquid by mixing diamond nanoparticles and a polymer; supply of the spinning liquid to a spinning space; formation of a composite fine fiber of the diamond nanoparticles and the polymer by thinning the spinning liquid with an electric field; removal of the polymer from the composite fine fiber to form a fiber composed solely of the diamond nanoparticles; and the application of CVD treatment to the fiber consisting of diamond nanoparticles, thereby forming the diamond fiber. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a diamond fiber, a nonwoven fabric including the same, and a method for producing the same.

Since diamond has the largest hardness and elastic modulus among the substances on the earth, the hardness and elastic modulus of the resin can be improved by mixing the diamond with the resin.
Further, since diamond has high thermal conductivity and insulation, application as a heat dissipation material or an electrical insulation material is expected.
Since this diamond is excellent in chemical stability, it is generally provided in a particle state or a thin film state. If a fiber sheet (nonwoven fabric) made of diamond fibers is present, the performance (for example, thermal conductivity, insulation) and air permeability are excellent. However, only diamond fibers in the fiber state have been proposed.

  For example, Japanese Patent Laid-Open No. 1-246116 discloses that “a diamond synthesized by a plasma chemical vapor deposition method or a chemical vapor deposition method or a film thereof is made of oxygen, carbon dioxide, water vapor, hydrogen, halogenated hydrocarbon, or halogenated. Needle-like, fibrous, porous diamond or plasma-treated in a stream containing carbon, or etched by thermal oxidation in a stream containing oxygen, carbon dioxide, or water vapor The manufacturing method of those aggregates "is disclosed. According to this production method, a diamond fiber can be produced. This diamond fiber is a short fiber having a fiber diameter of about 0.2 to 5 μm and an aspect ratio (= fiber length / fiber diameter) of at most 150. In order to obtain a fiber sheet (nonwoven fabric), a further manufacturing process is required. However, such a thin fiber has poor handleability, and an adhesive is required to form a fiber sheet. Moreover, since the fiber is a very short short fiber, the performance such as the thermal conductivity of the fiber sheet is likely to deteriorate. .

JP-A-1-246116

  Accordingly, an object of the present invention is to provide a diamond fiber that is excellent in handleability and can exhibit the performance inherent in diamond such as thermal conductivity, a nonwoven fabric including the same, and a method for producing the same. It is in.

  The above-mentioned problem can be solved by the diamond fiber according to the present invention, which consists essentially of diamond and has an aspect ratio of 200 or more.

The present invention also includes (1) a step of mixing a diamond nanoparticle and a polymer to prepare a spinning solution (hereinafter referred to as a spinning solution preparation step),
(2) Supplying the spinning solution to a spinning space and reducing the diameter by applying an electric field to the spinning solution to form composite fine fibers of diamond nanoparticles and a polymer (hereinafter referred to as a spinning step). And (3) a step of removing the polymer from the composite fine fiber to form a fiber composed only of diamond nanoparticles (hereinafter referred to as a removal step).
The manufacturing method of a diamond fiber containing this.
The present invention also provides (4) a step of performing CVD (chemical vapor deposition) on the fiber composed only of diamond nanoparticles obtained in the removing step to form diamond fiber (hereinafter referred to as CVD step). Called)
Further, the present invention relates to a method for producing a diamond fiber.

  The diamond fiber of the present invention includes, for example, a fiber made of only diamond nanoparticles, which can be obtained by performing the spinning solution preparation step, the spinning step, and the removal step in the manufacturing method, or further a CVD step. Diamond fibers that can be obtained by practice are included.

Moreover, this invention relates to the nonwoven fabric containing the said diamond fiber.
According to the preferable aspect of the nonwoven fabric of this invention, the diamond fibers which comprise a nonwoven fabric have adhere | attached, More preferably, it consists only of diamond fibers.

The present invention also includes (1) a step of mixing a diamond nanoparticle and a polymer to prepare a spinning solution,
(2) supplying the spinning solution to a spinning space and reducing the diameter by applying an electric field to the spinning solution to form composite fine fibers of diamond nanoparticles and a polymer;
(3) a process of accumulating the composite microfibers to form a fiber web (hereinafter referred to as an accumulation process); and (4) removing the polymer from the composite microfibers forming the fiber web to obtain only diamond nanoparticles. A step of forming a fiber web made of the fibers (hereinafter referred to as a removal step)
The manufacturing method of the nonwoven fabric which consists of diamond fiber containing.
In the present invention, (5) a step of performing CVD on a fiber web composed of fibers composed only of the diamond nanoparticles to form diamond fibers (hereinafter referred to as a CVD step).
The manufacturing method of the nonwoven fabric which consists of diamond fiber further.

  The non-woven fabric made of diamond fibers, which is an embodiment of the non-woven fabric of the present invention, can be obtained, for example, by performing the spinning solution preparation step, the spinning step, the accumulation step, and the removal step in the manufacturing method. Non-woven fabrics made of fibers consisting only of nanoparticles, or non-woven fabrics made of diamond fibers that can be obtained by carrying out a CVD process are included.

  Since the diamond fiber of the present invention is basically a continuous fiber, it has excellent performance such as thermal conductivity. Moreover, since the nonwoven fabric of this invention contains the said diamond fiber, it is excellent in performance, such as heat conductivity. In the nonwoven fabric in which the diamond fibers constituting the nonwoven fabric are bonded to each other, which is a preferred embodiment of the nonwoven fabric of the present invention, since it has a self-supporting property (shape retention), it has excellent handleability and has thermal conductivity, etc. Excellent performance. According to the production method of the present invention, the diamond fiber or the nonwoven fabric can be produced.

  The diamond fiber of the present invention consists essentially of diamond, and has an aspect ratio of 200 or more, preferably 500 or more. In the present specification, the “aspect ratio” means a value (L / D) obtained by dividing an average fiber length (L: unit = μm) by an average fiber diameter (D: unit = μm), and “average fiber length”. Means the average length of 50 fibers measured from a 2000 times scanning electron microscope (SEM) photograph, and the “average fiber diameter” refers to the 50 fibers measured from a 5000 times SEM photograph. It means the average value of the diameter of the cross section. “Substantially consisting only of diamond” means that 99% or more is composed of diamond. The diamond fiber includes a fiber composed only of diamond nanoparticles.

The average fiber diameter of the diamond fiber of the present invention is usually 5 μm or less, preferably 2 μm or less. Moreover, it is 10 nm or more normally, Preferably it is 50 nm or more.
Moreover, the average fiber length of the diamond fiber of this invention is 100 micrometers or more normally, Preferably it is 500 micrometers or more, More preferably, it is a continuous fiber.
In the nonwoven fabric of the present invention, the diamond fiber contained in the nonwoven fabric is preferably 50% or more, more preferably 70% or more, and 90% or more in terms of excellent thermal conductivity. More preferably, it is most preferably composed of only diamond fibers. When the diamond fibers are bonded to each other, the bonding is preferably performed through a part of the diamond fibers.

Although the diamond fiber or nonwoven fabric of this invention is not limited to this, For example, it can manufacture with the manufacturing method of this invention.
The production method of the present invention is based on the electrospinning technique, and when producing diamond fibers, the spinning solution preparation step, the spinning step, and the removal step are performed in this order, or these A CVD process is further performed after the process. When manufacturing a nonwoven fabric made of diamond fibers, the spinning solution preparation process, spinning process, accumulation process, and removal process are performed in this order, or a CVD process is further performed after these processes. It is characterized by doing.

  Examples of the diamond nanoparticles used in the spinning solution preparation step in the production method of the present invention include nanodiamonds obtained by an explosion method (see, for example, JP-A-2005-1983). In the explosion method, explosives having an oxygen-deficient composition are exploded in an inert medium without adding a carbon source in addition to the explosives, and diamond particles contained in a high concentration are taken out to obtain diamond particles. it can. However, explosive nanodiamonds are remarkable aggregates. For example, commercially available diamond particles are a group of particles having an average of about 300 nm or / and about 10 microns. The explosive nanodiamond agglomerates are, for example, ceramic beads or metal beads having a diameter of 0.1 to 0.05 mm, and an average diameter of 4 to 5 nm of nanodiamonds by bead milling at a peripheral speed of 5 m / s or more. Can be peptized.

  The polymer used in the spinning solution preparation step is not particularly limited as long as it can be spun by electrostatic spinning and does not impair the dispersion of diamond nanoparticles. For example, polyethylene glycol, partially saponified polyvinyl alcohol, fully saponified polyvinyl Examples include alcohol, polyvinylpyrrolidone, polylactic acid, polyglycolic acid, polyacrylonitrile (PAN), polymethacrylic acid, polymethyl methacrylate, polycarbonate, polystyrene, polyamide, polyimide, polyethersulfone, polysulfone, and the like. Polystyrene and polyvinyl pyrrolidone are preferred.

  In the spinning solution preparation step, the spinning solution is prepared by mixing the diamond nanoparticles and the polymer together with a suitable solvent. The solvent is not particularly limited as long as it is capable of dissolving the polymer and does not cause aggregation of diamond nanoparticles. For example, N, N-dimethylformamide (DMF), N, N-dimethyl Examples include acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), alcohol solvents (methanol, ethanol, propanol, etc.), water and the like. When PAN is used as the polymer, DMF or DMSO is preferred as the solvent.

  The order of mixing the diamond nanoparticles, the polymer, and the solvent is not particularly limited as long as a spinning solution that can be electrospun can be obtained, and any order or two or three components may be mixed simultaneously. it can. For example, an aggregate of diamond nanoparticles can be ultrasonically dispersed in a solvent to disperse particles of 100 nm or less, preferably 10 nm or less, and then the polymer can be mixed and dissolved. In addition, after dispersing the nanoparticles, aggregates having a large particle diameter (for example, more than 1 μm) can be removed by filtration or centrifugation. Further, even when it is difficult to mix and dissolve the polymer in the nanoparticle dispersion, the polymer can be mixed and dissolved after replacing the solvent of the nanoparticle dispersion.

Since the preferred range of the molecular weight of the polymer varies depending on the type of polymer, it may be in a range where electrospinning is possible. In the case of polyacrylonitrile, the weight average molecular weight (Mw) is preferably 50,000 to 2,000,000, and more preferably 400,000 to 700,000.
The amount of diamond nanoparticles added to the polymer is preferably 5 to 50 wt%, and more preferably 20 to 30 wt%.
The concentration of diamond nanoparticles in the spinning solution is preferably 0.1 to 10 wt%, and more preferably 1 to 5 wt%.
The polymer concentration in the spinning solution is preferably 1 to 30 wt%, and more preferably 5 to 20 wt%.
The viscosity of the spinning solution is preferably 100 to 5000 mPa · s, and more preferably 500 to 2000 mPa · s.

  The spinning step, or the spinning step and the accumulating step in the production method of the present invention can be carried out based on a normal electrostatic spinning method except that the spinning solution obtained in the spinning solution preparation step is used. A known production apparatus capable of performing the electrospinning method and a production method using the same are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2003-73964, 2004-238749, and 2005-194675. ing. Hereinafter, the spinning process and the accumulating process in the manufacturing method of the present invention will be described with reference to FIG. 1 showing a manufacturing apparatus disclosed in Japanese Patent Laid-Open No. 2005-194675.

  The manufacturing apparatus shown in FIG. 1 has a spinning solution supply device 1 that can supply a spinning solution to the nozzle 2, a nozzle 2 that discharges the spinning solution supplied from the spinning solution supply device 1 to the spinning space 5, and a nozzle 2 that discharges the electric field. In order to form an electric field between the grounded collector 3 and the nozzle 2 and the grounded collector 3 for collecting the fibers drawn by the above, a voltage applying device 4 that can apply a voltage to the nozzle 2 and the nozzle 2 And a collecting container 3, a gas supply device 7 that can supply a gas having a predetermined relative humidity to the spinning vessel 6, and an exhaust device 8 that can exhaust the gas in the spinning vessel 6.

  The spinning solution obtained in the spinning solution preparation step is supplied to the nozzle 2 by the spinning solution supply device 1. The supplied spinning solution is pushed out from the nozzle 2 to the spinning space 5 and is subjected to a drawing action by an electric field between the grounded collector 3 and the nozzle 2 applied by the voltage application device 4 and is captured while being fiberized. Fly toward the assembly 3 (so-called electrostatic spinning method). The flying fibers are directly accumulated on the collecting body 3 to form a fiber web. In addition, although the spinning solution supply apparatus 1 is not specifically limited, For example, a syringe pump, a tube pump, a dispenser, etc. can be used.

  The pushing direction of the spinning solution from the nozzle 2 in FIG. 1 is a direction orthogonal to the gravity and the direction of the collecting body 3, so that the spinning solution does not drop on the collecting body 3. However, the direction in which the spinning solution is pushed out from the nozzle 2 may be different from that in FIG.

  The diameter of the nozzle 2 that pushes out the spinning solution varies depending on the fiber diameter of the fiber to be obtained, and is not particularly limited. In the present invention, the fiber diameter of the composite fine fiber obtained in the spinning step is usually 10 nm to 5 μm, preferably 50 nm to 2 μm, more preferably 100 nm to 1 μm. The inner diameter of the nozzle is preferably 0.2 to 1 mm so that electrostatic spinning can be performed stably.

  The nozzle 2 may be made of metal or non-metal. If the nozzle 2 is made of metal, the nozzle 2 can be used as one electrode by applying a voltage from the voltage application device 4. If the nozzle 2 is made of non-metal, the inside of the nozzle 2 By applying an electrode to the inner electrode and applying a voltage to the internal electrode from the voltage application device 4, an electric field can be applied to the extruded spinning solution.

  In FIG. 1, a voltage is applied to the nozzle 2 by the voltage application device 4 and an electric field is formed by grounding the collector 3. However, contrary to FIG. 1, the nozzle 2 is grounded and captured. A voltage may be applied to the collector 3 to form an electric field, or a voltage may be applied to both the nozzle 2 and the collector 3, but an electric field may be formed by applying a potential difference. The electric field varies depending on the fiber diameter of the fiber, the distance between the nozzle 2 and the collector 3, the main solvent of the spinning solution, the viscosity of the spinning solution, etc., and is not particularly limited, but is 0.2 to 5 kV. / Cm is preferred. When the electric field strength exceeds 5 kV / cm, there is a tendency that dielectric breakdown of air tends to occur, and when it is less than 0.2 kV / cm, there is a tendency that the spinning solution is insufficiently stretched and hardly forms a fiber shape.

  The voltage application device 4 is not particularly limited, and for example, a DC high voltage generator or a Van de Graf electromotive machine can be used. The applied voltage is not particularly limited as long as the electric field strength can be set as described above, but is preferably about 5 to 50 KV.

  Although the collection body 3 in FIG. 1 is a drum, it should just be a thing which can collect a fiber, and is not specifically limited. For example, a non-woven fabric, a woven fabric, a knitted fabric, a net, a flat plate, or a belt made of a conductive material made of metal or carbon, or a non-conductive material made of an organic polymer can be used as the collector 3. In some cases, a liquid such as water or an organic solvent can be used as the collector 3.

As shown in FIG. 1, when the collector 3 is used as the other electrode, the collector 3 is preferably made of a conductive material (for example, made of metal) having a volume resistance of 10 9 Ω or less. On the other hand, when the conductive material is arranged as the counter electrode behind the collector 3 as viewed from the nozzle 2 side, the collector 3 does not necessarily need to be made of a conductive material. When the counter electrode is arranged behind the collector 3 as in the latter case, the collector 3 and the counter electrode may be in contact with each other or may be separated from each other.

  In the removing step in the production method of the present invention, the polymer is removed from the composite fine fiber obtained in the spinning step, thereby forming a fiber composed only of diamond nanoparticles (one aspect of diamond fiber). Alternatively, if the polymer is removed from the composite fine fiber of the fiber web made of composite fine fibers, a fiber web made of fibers consisting only of diamond nanoparticles can be formed. This fiber web is an embodiment of the nonwoven fabric of the present invention because it contains fibers consisting only of diamond nanoparticles. The removal of the polymer can be performed, for example, by calcination.

  The calcination temperature is usually 400 to 800 ° C, preferably 500 to 600 ° C. The rate of temperature increase is usually 10 to 500 ° C./hour, preferably 100 to 400 ° C./hour, more preferably 200 to 300 ° C./hour. The calcination time is usually 1 to 24 hours, preferably 2 to 12 hours, and more preferably 4 to 6 hours.

Diamond fibers made of only diamond can be formed by growing diamond by CVD on the fibers made only of diamond nanoparticles after calcination. Since diamond nanoparticles are used as crystal nuclei, diamond can be grown efficiently and diamond fibers can be produced efficiently. In addition, as CVD method, well-known CVD, such as plasma CVD (for example, direct current | flow, a high frequency, a microwave etc.) and thermal CVD, can be utilized, for example.
Similarly, a non-woven fabric consisting only of diamond fibers can be formed by growing diamond by CVD on a fiber web consisting only of diamond nanoparticles after calcination. Since diamond nanoparticles are used as crystal nuclei, diamond can be grown efficiently and a diamond nonwoven fabric can be produced efficiently.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

Example 1
(1) Preparation of spinning solution An ethanol dispersion (5% concentration) of nanodiamond [product name “Nanoamand”, New Metals End Chemical Corporation (manufacturer: Nanocarbon Laboratory), Ltd.] was added to polyacrylonitrile (PAN). Was replaced with a soluble solvent, N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). A rotary evaporator was used for solvent replacement. The nanodiamond concentration after solvent replacement was 5%. The visual dispersibility of the nanodiamond with respect to DMF or DMSO was good.

  A PAN resin (Mw: 500,000) was dissolved in a DMF or DMSO dispersion of nanodiamond to prepare a spinning solution. The ratio of nanodiamond and PAN was nanodiamond / PAN = 1/10, 3/10, and 5/10, respectively, in weight ratio. The concentration of the PAN resin in the solution was 10 wt%. Table 1 shows the blending conditions and the state of the spinning solution.

[Table 1]
Compound condition Solution state
Conditions Solvent Nanodia PAN Appearance Viscosity
1 DMF 1% 10% cloudiness 1200cP
2 DMF 3% 10% Transparent gel 3 DMF 5% 10% Transparent Gel 4 DMSO 1% 10% White turbidity 3800cP
5 DMSO 3% 10% Transparent Gel
6 DMSO 5% 10% Transparent Gel

  In the case of nanodiamond / PAN = 1/10, cloudiness was observed in the solution regardless of the type of solvent. It is presumed that the particles are aggregated. On the other hand, in the case of nanodiamond / PAN = 3/10, 5/10, the solution is colored black, but it is transparent and the dispersion state of the particles is considered good. However, when the PAN concentration was 10%, regardless of the type of solvent, when nanodiamond / PAN = 3/10 or higher, the solution lost its fluidity and became a gel. Gelation was more remarkable in the DMSO solvent, and it was difficult to uniformly dissolve the nanodiamond / PAN = 5/10 solution in the DMSO solvent. In the case of nanodiamond / PAN = 3/10, the gel recovered fluidity and became a solution capable of electrospinning by setting the PAN concentration to 7% by dilution regardless of the type of solvent. At this time, no cloudiness of the solution was observed even after dilution. In addition, the nanodiamond / PAN = 5/10 solution of DMF solvent also recovered the fluidity of the gel by diluting the PAN concentration to 5% by dilution, and became a solution capable of electrospinning.

(2) Fabrication of fiber web by electrostatic spinning A fiber web was fabricated by electrostatic spinning using each spinning solution (conditions 1-5) prepared in (1) above. In the spinning solution under condition 2 (DMF solvent nanodiamond / PAN = 3/10 solution) and condition 5 (DMSO solvent nanodiamond / PAN = 3/10 solution), the PAN concentration was set to 7%. For the spinning solution under the condition 3 (DMF solvent nanodiamond / PAN = 5/10 solution), the diluted solution so that the PAN concentration is 5% is used for electrostatic spinning. did.

  The electrostatic spinning was performed under the conditions of a nozzle inner diameter of 0.25 mm, a discharge amount of 0.5 g / hour, a nozzle-collector distance of 10 cm, a spinning atmosphere temperature and humidity of 26 ° C./30% RH, and an applied voltage of 10 kV.

  Scanning electron microscope (SEM) photographs of the obtained fiber web are shown in FIGS. Depending on the conditions, droplets were observed (for example, Condition 1 and Condition 3), but even with a nanodiamond / PAN = 1/10 solution in which the solution was cloudy, a fiber web with few droplets could be obtained. The tensile strength of the fiber web decreased with increasing amount of nanodiamond added.

(3) Removal of polymer component by calcination The fiber web prepared using the spinning solution of condition 5 (DMO solvent nanodiamond / PAN = 3/10 solution) is calcined in air, thereby polymer component Was removed. The calcination temperature was 500 ° C., the heating rate was 250 ° C./hr, and the holding time was 4 hours. The calcined fiber web after calcination (one aspect of the nonwoven fabric of the present invention) was brittle, but it could be handled with tweezers, etc., and SEM observation confirmed that the fiber shape was retained. (FIGS. 12-13). The weight retention before and after calcination was 18 to 21%, which was slightly lower than the theoretical value (23%). The area of the fiber web contracted by calcination by about 30%, and the average fiber diameter was reduced from 300 nm before calcination to about 150 nm after calcination.

(4) Formation of diamond fiber by CVD Using a microwave plasma CVD apparatus, a diamond is grown using a calcined fiber web made of only the diamond nanoparticles from which the polymer component has been removed. A nonwoven fabric in which fibers were bonded together was produced. Microwave plasma CVD was performed for 30 minutes under a pressure of 35 Torr using a mixed gas with a microwave power of 3500 W, a processing temperature of 700 ° C., and hydrogen / methane = 97/3%. The average fiber diameter of the nonwoven fabric constituting diamond fibers was 250 nm, and the aspect ratio was 1000 or more. Moreover, this nonwoven fabric was excellent in thermal conductivity and handleability.

Example 2
In this example, a diamond nanoparticle DMSO dispersion was directly prepared and spun.
Specifically, 7 g of diamond nanoparticles [product name “Nanoamand Flakes”, New Metals End Chemical Corporation, Inc.] and 93 g of DMSO were used with an ultrasonic device (Branson's ultrasonic homogenizer “Sonifer 450 type”). Sonication was performed for 10 minutes.
Subsequently, centrifugation was performed at 10,000 rpm to remove undispersed aggregates, and a dispersion of diamond nanoparticles was produced. The dispersion was black and transparent, and the dispersion state of the particles was good. Using a DMSO dispersion of diamond nanoparticles, the concentration was adjusted and a polyacrylonitrile resin having a molecular weight of 500,000 was dissolved to prepare a spinning solution composed of 3 wt% diamond nanoparticles, 7 wt% PAN, and 90 wt% DMSO. The spinning solution was black and transparent, and the dispersion state of the particles was good.

Using this spinning solution, a fiber web was formed by electrostatic spinning under the same conditions as in Example 1 (2). Subsequently, after removing the polymer by calcination, microwave plasma CVD was performed, and only from diamond fibers. And a nonwoven fabric in which the fibers were bonded to each other was produced.
The average fiber diameter of the nonwoven fabric constituting diamond fibers was 250 nm, and the aspect ratio was 1000 or more. Moreover, the obtained diamond fiber nonwoven fabric was excellent in thermal conductivity and handleability.

  The diamond fiber of the present invention can be applied to non-woven fabric applications. Moreover, the nonwoven fabric of this invention is applicable to the use which requires hardness, an elasticity modulus, heat conductivity, and / or insulation.

It is explanatory drawing which shows the outline | summary of the spinning apparatus which can implement the manufacturing method of this invention. Photomicrograph (× 1) instead of a drawing showing the structure of a composite fine fiber constituting a fiber web (before calcination) produced using a spinning solution of condition 1 (DMD solvent nanodiamond / PAN = 1/10 solution) 1,000 times). FIG. 3 is a photomicrograph (× 10,000 times) in place of the drawing, showing the structure of the composite fine fiber constituting the fiber web shown in FIG. 2 at a higher magnification. The structure of a composite fine fiber constituting a fiber web (before calcination) prepared using a spinning solution (diluted to a PAN concentration of 7%) under condition 2 (DMD solvent nanodiamond / PAN = 3/10 solution), It is the microscope picture (x1,000 times) which replaces drawing. FIG. 5 is a photomicrograph (× 10,000 times) in place of the drawing, showing the structure of the composite fine fiber constituting the fiber web shown in FIG. 4 at a higher magnification. The structure of a composite fine fiber constituting a fiber web (before calcination) prepared using a spinning solution (diluted to a PAN concentration of 5%) of condition 3 (DMF solvent nanodiamond / PAN = 5/10 solution) is shown. It is the microscope picture (x1,000 times) which replaces drawing. It is the microscope picture (x10,000 time) which replaces drawing which shows the structure of the composite fine fiber which comprises the fiber web shown in FIG. 6 further at high magnification. A photomicrograph (× 1) instead of a drawing showing the structure of a composite fine fiber constituting a fiber web (before calcination) prepared using a spinning solution of condition 4 (DMSO solvent nanodiamond / PAN = 1/10 solution) 1,000 times). FIG. 9 is a photomicrograph (× 10,000 times) in place of the drawing, showing the structure of the composite fine fiber constituting the fiber web shown in FIG. 8 at a higher magnification. The structure of a composite fine fiber constituting a fiber web (before calcination) produced using a spinning solution (diluted to a PAN concentration of 7%) under condition 5 (DMSO solvent nanodiamond / PAN = 3/10 solution), It is the microscope picture (x1,000 times) which replaces drawing. FIG. 11 is a photomicrograph (× 10,000 times) in place of the drawing, showing the structure of the composite fine fiber constituting the fiber web shown in FIG. 10 at a higher magnification. The fiber component prepared using the spinning solution (diluted to a 7% PAN concentration) under condition 5 (DMSO solvent nanodiamond / PAN = 3/10 solution) was calcined in air to remove the polymer component. It is the microscope picture (x1,000 times) which replaces drawing which shows the structure of the fiber which consists only of the diamond nanoparticle which comprises the done calcination fiber web. FIG. 13 is a photomicrograph (× 10,000 times) in place of the drawing, showing the structure of the fiber consisting only of diamond nanoparticles constituting the calcined fiber web shown in FIG. 12 at a higher magnification.

Claims (7)

  1.   A diamond fiber which consists essentially of diamond and has an aspect ratio of 200 or more.
  2.   A nonwoven fabric comprising the diamond fiber according to claim 1.
  3.   The nonwoven fabric according to claim 2, wherein diamond fibers constituting the nonwoven fabric are bonded to each other.
  4. (1) A step of preparing a spinning solution by mixing diamond nanoparticles and a polymer,
    (2) supplying the spinning solution to a spinning space and reducing the diameter by applying an electric field to the spinning solution to form composite fine fibers of diamond nanoparticles and a polymer; and (3) the composite fine A method for producing a diamond fiber, comprising a step of removing a polymer from the fiber to form a fiber composed only of diamond nanoparticles.
  5. (4) The method for producing diamond fiber according to claim 4, further comprising a step of performing CVD on the fiber composed only of diamond nanoparticles obtained in the step (3) to form diamond fiber.
  6. (1) A step of preparing a spinning solution by mixing diamond nanoparticles and a polymer,
    (2) supplying the spinning solution to a spinning space and reducing the diameter by applying an electric field to the spinning solution to form composite fine fibers of diamond nanoparticles and a polymer;
    (3) a step of accumulating the composite fine fibers to form a fiber web; and (4) removing a polymer from the composite fine fibers forming the fiber web to form a fiber web composed of fibers consisting only of diamond nanoparticles. The manufacturing method of the nonwoven fabric which consists of a diamond fiber including the process to form.
  7. (5) From the diamond fiber according to claim 6, further comprising a step of performing CVD on the fiber web made of only the diamond nanoparticles obtained in the step (4) to form a nonwoven fabric made of diamond fiber. The manufacturing method of the nonwoven fabric which becomes.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01246116A (en) * 1988-03-29 1989-10-02 Natl Inst For Res In Inorg Mater Production of acicular, fibrous or porous diamond or their aggregate
JPH0571070A (en) * 1991-09-04 1993-03-23 Seiko Epson Corp Diamond fiber
JP2006240937A (en) * 2005-03-04 2006-09-14 Tokyo Univ Of Agriculture & Technology Carbon material and method for manufacturing the same
JP2007092210A (en) * 2005-09-28 2007-04-12 Teijin Ltd Method and equipment for producing fibrous structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01246116A (en) * 1988-03-29 1989-10-02 Natl Inst For Res In Inorg Mater Production of acicular, fibrous or porous diamond or their aggregate
JPH0571070A (en) * 1991-09-04 1993-03-23 Seiko Epson Corp Diamond fiber
JP2006240937A (en) * 2005-03-04 2006-09-14 Tokyo Univ Of Agriculture & Technology Carbon material and method for manufacturing the same
JP2007092210A (en) * 2005-09-28 2007-04-12 Teijin Ltd Method and equipment for producing fibrous structure

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