WO2011003634A1 - Nanocomposite doté de nanotubes de nitrure de bore - Google Patents

Nanocomposite doté de nanotubes de nitrure de bore Download PDF

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Publication number
WO2011003634A1
WO2011003634A1 PCT/EP2010/054301 EP2010054301W WO2011003634A1 WO 2011003634 A1 WO2011003634 A1 WO 2011003634A1 EP 2010054301 W EP2010054301 W EP 2010054301W WO 2011003634 A1 WO2011003634 A1 WO 2011003634A1
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WO
WIPO (PCT)
Prior art keywords
nanocomposite
bnnt
insulating material
boron nitride
nitride nanotubes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2010/054301
Other languages
German (de)
English (en)
Inventor
Thomas Hammer
Frank Heinrichsdorff
Ursus KRÜGER
Volkmar LÜTHEN
Daniel Reznik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to EP10716306A priority Critical patent/EP2451867A1/fr
Publication of WO2011003634A1 publication Critical patent/WO2011003634A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0648—After-treatment, e.g. grinding, purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose

Definitions

  • the invention relates to a nanocomposite with semiconducting nanoparticles, such as boron nitride nanotubes (BNNT), which are distributed in an electrically insulating insulating material.
  • BNNT boron nitride nanotubes
  • Such a nanocomposite is described, for example, by N.P. Bansal et al. , "Boron Nitride Nanotubes-Reinforced Glass Composites", NASA / TM-2005-213874, pages 1 to 7, August 2005. Accordingly, it is possible to incorporate boron nitride nanotubes into glass as an electrically insulating insulator mechanical fiber stiffening of the glass.
  • nanocomposites can also be used as a field grading material when it comes to reducing peaks in the formation of electric fields, for example on the insulation of electrical conductors.
  • a material consisting of a polymer can be used for this purpose.
  • a filler is distributed whose particles are nanoparticles, so have a mean diameter of 100 nm bathtens.
  • semiconducting materials whose band section lies in a range of 0 eV and 5 eV can be used for such nanoparticles, inter alia.
  • the electrical resistance of the nanocomposite can be adjusted. If, during the admixture of the nanoparticles, a certain proportion of the volume is exceeded, which is between 10 and 20% by volume, depending on the size of the nanoparticles, the specific resistance of the nanocomposite is noticeably reduced, and in this way adjust the electrical conductivity of the nanocomposite and adapt it to the required conditions. In particular, I let a specific resistance in the order of 10 1 ⁇ cm set. This comparatively high electrical resistance leads to a load on an electrical component, which is coated with the nanocomposite, that when a DC voltage applied a certain leakage current must be accepted.
  • the field-weakening effect of the nanocomposite depends on the permittivity of the nanocomposite, the permittivity ⁇ being a measure of the permeability of a material for electric fields.
  • the Permittivitatspp of the substances used are treated.
  • CNTs nanoparticle carbon nanotubes
  • BNNTs boron nitride nanotubes
  • the percolation threshold can also be increased by measures of alignment of the CNT in the matrix of the polymer and can be less than 1% by weight with a content of CNT in the matrix.
  • C. Tang et al. "Fluorination and
  • BNNTs semiconducting properties can be influenced by doping with different dopants of their electrical conductivity similar to bulk semiconductors
  • the object of the invention is to improve a nanocomposite of the type specified at the outset such that it is comparatively well suited for use as a field-grading material.
  • This object is achieved according to the invention by the nanocomposite specified at the outset in that the insulating material which forms the matrix of the nanocomposite consists of a cellulose material or a polymer.
  • the use of the semipermeable nanoparticles initially has the advantage that significantly lower degrees of fullness of at most 5% by volume, preferably even at most 2% by volume, in the insulating material are sufficient to cause percolation of the nanoparticles and thus to increase the electrical conductivity of the nanocomposite , This is possible, although the band gap of BNNT according to C. Tang is about 5.5 eV and according to US 2007/0199729 Al and WO 2004/038735 Al it is required that the nanoparticles of semiconductors used in field-grading nanocomposites have a Band gap between 0 eV and 5 eV should have.
  • the inventive nanocomposite advantageously leads to the components produced from the nanocomposite, such as. B. insulation gen, can reliably fulfill their task over a longer period of operation.
  • the following advantages can also be obtained by using the obtained nanocomposite as a field-grading material.
  • BNNT are insulated by the band gap of 5.5 eV even at high temperatures, so that a temperature-induced breakdown can be avoided.
  • BNNTs have a high thermal conductivity of more than 300 W / mK. Like C.W. Chang et al. In addition, it can be expected that with thin BNNTs with a diameter of less than 20 nanometers, the thermal
  • Conductivity can be over 1000 W / mK.
  • the nanocomposite in addition to its property as field-grading material, can simultaneously ensure reliable heat dissipation of electrical power components such as transformers.
  • BNNTs have a permittivity of 8 BNNT , which is about 4.
  • the permittivity of common insulator materials such as polymers or cellulosic material is very similar.
  • the introduction of BNNT into these insulator materials for producing the nanocomposite according to the invention thus does not change or only slightly changes the permittivity of the nanocomposite in comparison to the solid insulator material, whereby a fluctuation of the field strength in the interior of the nanocomposite can be kept small. This occurs, as already mentioned, in an overload of the module to be isolated with an alternating voltage and can lead to unwanted partial discharges, which ultimately destroy the insulation. Due to their dimensions in the nanometer range, BNNT have a high aspect ratio, which is comparable to that of CNT. The by F.
  • silicones and resins can be selected.
  • a zeolite material is selected as the insulating material, it is particularly advantageous if it is used as paper.
  • This paper can be impregnated with the BNNT.
  • impregnation means a connection between the fibers of the cellulosic material and the BNNT.
  • the BNNT may be attached to the fibers of the cellulosic material, which may occur during papermaking.
  • impregnation can also take place in such a way that the BNNTs are added during papermaking and after the drying process of the paper are enclosed in the spaces formed by the fibers of the cellulose material.
  • the cellulosic material is the raw material for the paper.
  • paper should be understood in the broadest sense to mean any product made of the cellulosic material. the. In particular, this means thinner paper sheets or thicker cardboard or cardboard. It is also possible to produce three-dimensional structures from papier mache, which are then to be understood as paper products.
  • the cellulosic material can also be used as a wood product.
  • a wood product is understood to mean a further processing of the raw material wood from wood components glued together.
  • this can be pressboard, which is designed in particular as a block chip.
  • laminates can be produced by gluing thin layers of wood together (plywood).
  • the BNNT can be introduced into the adhesive for the purpose of jointing the press chip or the wood layer.
  • a coating with metals or doped semiconductors is provided on these semiconducting BNNT.
  • This measure advantageously serves to influence the specific resistance of the nanocomposite according to the invention by selecting suitable dopants. It is desirable, for example, to set a resistivity in the order of 10 12 ⁇ cm, which should be achieved with a degree of fill of BNNT of less than 5% by volume, preferably less than 2% by volume.
  • the doping of the BNNT or the coating can be carried out as described by C. Tang et al. described described.
  • Doping can be achieved by modifying the BNNT by adding suitable dopants such that the dopant atoms form electronic states that turn the BNNT into a p-conductor (ie, electronic states are formed, the electrons from the valence band edge capture) or to an n-conductor (ie, reaching electronic states that emit electrons by thermal excitation across the conduction band edge).
  • a dopant for a p-doping for example Be comes into question, as a dopant for n-doping Si comes into question.
  • Such doping of the BNNT can be done in situ, during the growth of the BNNT z. B. from the gas or Flussigphase the dopant atoms are incorporated.
  • the doping in a further step after the growth of the BNNT, wherein the dopants are typically taken up by the BNNT under the influence of a heat treatment.
  • the resistivity can be lowered to values typical for doped semiconductors between 0.1 and 1000 ⁇ cm.
  • Another possibility is to provide the BNNT after its production with a thin layer of a metal or a highly doped semiconductor. As a result, there is a higher electrical conductivity in this layer of the nanoparticle than in the BNNT itself. This higher conductivity influences the electrical behavior of the nanocomposite when the prepared BNNTs are introduced into the insulating matrix of the insulating material. However, the specific resistance of the nanocomposite is again higher due to the low degree of fullness of BNNT, since the electrical insulating material has a much higher specific resistance than the introduced doped BNNT.
  • the BNNT By doping the BNNT with suitable dopants or their coating with metals or highly doped semiconductors, it also being possible to carry out doping and coating at the same time, so to speak, two degrees of freedom arise for influencing the conductivity of the nanocomposites according to the invention.
  • One possibility is to change the full degree of BNNT in the nanocomposite.
  • the specific resistance decreases with increasing concentration of BNNT in the matrix of the electrically insulating insulating material.
  • the second possibility lies in the treatment according to the invention of the BNNT, wherein the doping and / or the coating reduces the specific resistance of the BNNT so that it leads to a greater reduction in the specific resistance of the nanocomposite at the same concentration in the nanocomposite.
  • the required maximum full degrees of BNNT in the nanocomposite can be maintained, for example, so that it satisfies the mechanical requirements of the application.
  • the doping of the BNNT can be used specifically for the fact that the resistivity of the nanocomposite does not change abruptly with an increasing concentration of BNNT in the matrix of the insulating material but continuously changes over a certain concentration range.
  • a more precise setting of the resistivity of the nanocomposite is advantageously possible since it is avoided that production-related, comparatively small fluctuations in the concentration of BNNT in the matrix of the insulating material lead to large deviations from the desired specific resistance of the nanocomposite.
  • a particularly advantageous use of the nanocomposite is that this is used as insulation material for a transformer.
  • the live parts such as the coils
  • the live parts must be electrically isolated from each other.
  • oil fillings are used, into which walls of paper impregnated with the oil or also pressboard boards are additionally introduced.
  • the resulting insulation must be during both operation of the transformer Applying to an AC voltage as well as for example in case of disturbances of operation with a DC voltage to ensure the electrical insulation.
  • the composite according to the invention is used as the insulating material, sufficient electrical insulation properties can be ensured both when the transformer is subjected to an alternating voltage and to a direct voltage.
  • the insulation of the transformer using the nanocomposite can be designed in a similar manner as is possible with the untreated papers.
  • the insulating properties of the combination of oil and paper can be improved in the case of the application of a DC voltage.
  • the specific resistances are of importance, which amount to a factor of 1000 for oil (po) at 10 12 ⁇ cm and for untreated paper (p p ).
  • the specific conductivity of the inventive nanocomposite can be, for example, in the form of an impregnated paper (p C o mP ) also at 10 12 ⁇ cm.
  • p C o mP impregnated paper
  • FIGS 1 and 2 schematically examples of functionalized
  • BNNT as they can be used in an exemplary embodiment of the nanocomposite according to the invention, as a three-dimensional view,
  • FIG. 3 schematically shows an exemplary embodiment of the nanocomposite according to the invention, consisting of cellulose fibers and BNNT, in a three-dimensional view and FIG. 3
  • Figure 4 schematically an exemplary embodiment of the inventive use of the nanocomposite as a transformer insulation in section.
  • a BNNT 11 is shown schematically as tubes. This BNNT has also been treated with a dopant 12, wherein it is indicated in FIG. 1 that the dopant 12 is incorporated in the lattice 13 of the BNNT formed by the boron nitride.
  • FIG. 2 An alternative embodiment of the BNNT 11 is shown in FIG.
  • the BNNT 11 according to FIG. 2 is provided with a sheath 14, which itself consists of a semiconductor provided with a dopant 12.
  • the BNNT 11 according to FIGS. 1 and 2 can be processed into a nanocomposite 15 as shown in FIG.
  • This consists of cellulose fibers 16a, 16b which were produced as paper.
  • the paper is impregnated with the BNNT IIa and / or IIb.
  • An impregnation with the BNNT IIa proceeds in such a way that the BNNT IIa is deposited on the cellulose fiber 16a. the.
  • the percolation threshold is achieved by having enough BNNT on the surface of the cellulose fiber 16a to form a two-dimensional net on the surface of the cellulose fiber 16a.
  • BNNT IIb may also be included in the interstices 17 between different cellulosic fibers 16a, 16b. This results in the interstices 16, a three-dimensional network of BNNT IIb, where the concentration of BNNT IIb must be high enough to reach the percussion threshold, ie the formation of a closed network.
  • the two mechanisms of impregnating the paper with BNNT IIa, IIb are shown together in FIG. These mechanisms can be used individually or jointly.
  • the BNNT IIa and IIb may be identical in construction or have differences.
  • An electrical insulation 18 according to Figure 4 consists of several layers of paper 19, between which Ol füren 20 lie.
  • the papers 19 are also saturated with oil, which is not shown in detail in FIG. For this, the impregnation with BNNT 11 can be seen in FIG. 4 within the papers.
  • the insulation shown according to FIG. 4 surrounds, for example, the windings used there in a transformer, which must be electrically insulated from the outside and from each other.
  • the electrical insulation of a transformer must prevent electrical breakdown in case of application of an AC voltage.
  • the isolation behavior of the insulation depends on the permittivity of the components of the insulation.
  • the permittivity is ⁇ o approximately at 2, for the paper ⁇ p at 4.
  • the voltage U 0 applied to the oil is approximately twice as high as that on the paper applied voltage U p .
  • the BNNTs do not influence the stress distribution in the insulation according to the invention since the permittivity ⁇ BNN ⁇ is also approximately 4, and therefore the permittivities - tat ⁇ cop of the impregnated paper is also at about 4.
  • the voltage U 0 acting on the oil is approximately twice as great as the voltage U COm p applied to the nanocomposite (paper).
  • the inventively introduced into the paper 19 BNNT 11 are z. B. by a suitable doping with their resistivity (between 0.1 and 1000 ⁇ cm) adjusted so that the specific resistance of the paper p p down- is set.
  • the voltage U 0 applied to the oil is in the region of the voltage Ucomp applied to the composite, so that a balanced voltage profile is established in the insulation. This advantageously improves the dielectric strength of the insulation, since the loading of the oil is noticeably reduced.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

L'invention concerne un nanocomposite (15) doté de nanoparticules semiconductrices (11a, 11b) constituées de nanotubes de nitrure de bore (BNNT) et dispersées dans un isolant électrique tel que des fibres de cellulose (16a, 16b). L'invention concerne également l'utilisation de ce nanocomposite en tant que matériau d'isolation pour un transformateur. Selon l'invention, l'isolant est un matériau en cellulose ou un polymère. En particulier, les BNNT peuvent être dopés avec des dopants ou pourvus d'un revêtement composé de métaux ou de semi-conducteurs dopés. De cette manière, il est possible de modifier de façon appropriée la résistance spécifique du nanocomposite, de sorte qu'elle se situe dans la plage de résistance de l'huile et qu'une combinaison d'huile et de nanocomposite présente, en tant qu'isolant électrique une meilleure rigidité diélectrique en cas d'application d'une tension continue. Simultanément, le pouvoir d'isolation en cas d'application d'une tension alternative demeure avantageusement inchangé.
PCT/EP2010/054301 2009-07-08 2010-03-31 Nanocomposite doté de nanotubes de nitrure de bore Ceased WO2011003634A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10716306A EP2451867A1 (fr) 2009-07-08 2010-03-31 Nanocomposite doté de nanotubes de nitrure de bore

Applications Claiming Priority (2)

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DE102009033267.7 2009-07-08
DE102009033267 2009-07-08

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012041715A1 (fr) * 2010-09-29 2012-04-05 Siemens Aktiengesellschaft Nanocomposite électro-isolant présentant des nanoparticules semi-conductrices ou non conductrices, utilisation de ce nanocomposite et procédé pour le produire
DE102011008461A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Trennstelle einer Leitungsdurchführung für eine HGÜ-Komponente
DE102011008456A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Leitungsführung für HGÜ-Transformatorspulen oder HGÜ-Drosselspulen
DE102011008462A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Schirmring für eine HGÜ-Transformatorspule oder eine HGÜ-Drosselspule
DE102011008459A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Leitungsdurchführung für die Kesselwand einer HGÜ-Komponente
DE102011008454A1 (de) 2011-01-07 2012-07-26 Siemens Aktiengesellschaft Isolationsanordnung für eine HGÜ-Komponente mit wandartigen Feststoffbarrieren
CN103554694A (zh) * 2013-10-31 2014-02-05 合肥得润电子器件有限公司 一种通讯设备线束用氯化聚乙烯绝缘料
WO2014146901A1 (fr) * 2013-03-20 2014-09-25 Siemens Aktiengesellschaft Nanocomposite comprenant des nanoparticules graduant des champs électriques, son procédé de fabrication et son utilisation
CN109370493A (zh) * 2018-09-18 2019-02-22 中国科学院深圳先进技术研究院 一种热界面材料及其制备方法
TWI823871B (zh) * 2017-10-27 2023-12-01 加拿大國家研究委員會 用於通過強脈衝光燒結金屬線路之塗有氮化硼奈米管之基板

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WO2012041715A1 (fr) * 2010-09-29 2012-04-05 Siemens Aktiengesellschaft Nanocomposite électro-isolant présentant des nanoparticules semi-conductrices ou non conductrices, utilisation de ce nanocomposite et procédé pour le produire
DE102011008461A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Trennstelle einer Leitungsdurchführung für eine HGÜ-Komponente
DE102011008456A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Leitungsführung für HGÜ-Transformatorspulen oder HGÜ-Drosselspulen
DE102011008462A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Schirmring für eine HGÜ-Transformatorspule oder eine HGÜ-Drosselspule
DE102011008459A1 (de) 2011-01-07 2012-07-12 Siemens Aktiengesellschaft Leitungsdurchführung für die Kesselwand einer HGÜ-Komponente
DE102011008454A1 (de) 2011-01-07 2012-07-26 Siemens Aktiengesellschaft Isolationsanordnung für eine HGÜ-Komponente mit wandartigen Feststoffbarrieren
WO2014146901A1 (fr) * 2013-03-20 2014-09-25 Siemens Aktiengesellschaft Nanocomposite comprenant des nanoparticules graduant des champs électriques, son procédé de fabrication et son utilisation
CN103554694A (zh) * 2013-10-31 2014-02-05 合肥得润电子器件有限公司 一种通讯设备线束用氯化聚乙烯绝缘料
TWI823871B (zh) * 2017-10-27 2023-12-01 加拿大國家研究委員會 用於通過強脈衝光燒結金屬線路之塗有氮化硼奈米管之基板
US11993719B2 (en) 2017-10-27 2024-05-28 National Research Council Of Canada Boron nitride nanotube coated substrates for sintering of metallic traces by intense pulse light
CN109370493A (zh) * 2018-09-18 2019-02-22 中国科学院深圳先进技术研究院 一种热界面材料及其制备方法
CN109370493B (zh) * 2018-09-18 2021-04-02 中国科学院深圳先进技术研究院 一种热界面材料及其制备方法

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