WO2011032791A1 - Matériau composite comprenant un métal et des nanoparticules - Google Patents

Matériau composite comprenant un métal et des nanoparticules Download PDF

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Publication number
WO2011032791A1
WO2011032791A1 PCT/EP2010/061890 EP2010061890W WO2011032791A1 WO 2011032791 A1 WO2011032791 A1 WO 2011032791A1 EP 2010061890 W EP2010061890 W EP 2010061890W WO 2011032791 A1 WO2011032791 A1 WO 2011032791A1
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WIPO (PCT)
Prior art keywords
composite material
metal
cnt
cnts
nanoparticles
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PCT/EP2010/061890
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English (en)
Inventor
Horst Adams
Original Assignee
Bayer International Sa, Ftb
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
Priority claimed from PCT/EP2009/006737 external-priority patent/WO2010091704A1/fr
Application filed by Bayer International Sa, Ftb filed Critical Bayer International Sa, Ftb
Priority to BR112012005829A priority Critical patent/BR112012005829A2/pt
Priority to IN2285DEN2012 priority patent/IN2012DN02285A/en
Priority to CA2783939A priority patent/CA2783939A1/fr
Priority to AU2010294797A priority patent/AU2010294797A1/en
Priority to JP2012529186A priority patent/JP2013505353A/ja
Priority to US13/496,564 priority patent/US20120175547A1/en
Priority to RU2012114872/02A priority patent/RU2012114872A/ru
Priority to CN2010800410966A priority patent/CN102630252A/zh
Priority to EP10745206A priority patent/EP2478124A1/fr
Publication of WO2011032791A1 publication Critical patent/WO2011032791A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04—Light metals
    • C22C49/06—Aluminium

Definitions

  • a compound material comprising a metal and nanoparticles
  • the present invention relates to compound materials comprising a metal and nanoparticles, in particular carbon nano tubes (CNT), characterized in that the compound has a metal crystallite structure of crystallites having an average size which is in the range of higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • CNT carbon nano tubes
  • Carbon nano tubes sometimes also referred to as “carbon fibrils” or “hollow carbon fibrils”, are typically cylindrical carbon tubes having a diameter of 3 to 100 nm and a length which is a multiple of their diameter.
  • CNTs may consist of one or more layers of carbon atoms and are characterized by cores having different morphologies. CNTs have been known from the literature for a long time. While Iijima (s. Iijima, Nature 354, 56 - 58, 1991) is generally regarded as the first to discover CNTs, in fact fibre shaped graphite materials having several graphite layers have been known since the 1970s and 1980s.
  • the most common structure of carbon nano tubes is cylindrical, wherein the CNT may be either comprised of a single graphene layer (single-wall carbon nano tubes) or of a plurality of concentric gra- phene layers (multi-wall carbon nano tubes).
  • Standard ways to produce such cylindrical CNTs are based on arch discharge, laser ablation, CVD and catalytic CVD processes.
  • Iijima Nature 354, 56 - 58, 1991
  • the formation of CNTs having two or more graphene layers in the form of concentric seamless cylinders using the arch discharge method is described.
  • roll up vector chiral and antichiral arrangements of the carbon atoms with respect to the CNT longitudinal axis are possible.
  • CNTs have a hardness exceeding that of diamond and a tensile strength ten times higher than steel. Consequently, there has been a continuous effort to use CNTs as constituent in compound or composite materials such as ceramics, polymer materials or metals trying to transfer some of these advantageous characteristics to the compound material.
  • a method of producing a CNT dispersed composite material in which a mixed powder of ceramics and metal and long-chain carbon nano tubes are kneaded and dispersed by a ball mill, and the dispersed material is sintered using discharge plasma. If aluminum is used for the metal, the preferred particle size is 50 to 150 ⁇ .
  • the directionality is imparted to the nano fibrils by application of a mechanical mass flowing process to the compos- ite material with the nano fibrils uniformly dispersed in the metal, where the mass flowing process could for example be extrusion, rolling or injection of the composite material.
  • WO 2008/052 642 and WO 2009/010 297 of the present inventors disclose a further method of producing a composite material containing CNTs and a metal.
  • the composite material is produced by mechanical alloying using a ball mill, where the balls are accelerated to very high velocities up to 11 m/s or even 14 m/s.
  • the resulting composite material is characterized by a layered structure of alternating metal and CNT layers, where the individual layers of the metal material may be between 20 and 200,000 nm thick and the individual layers of the CNT may be between 20 and 50,000 nm thickness.
  • the layer structure of this prior art is shown in Fig. 1 lb.
  • JP 2009 03 00 90 yet an alternative way of forming the CNT metal compound material is proposed.
  • a metallic powder having an average primary particle size of 0.1 ⁇ to 100 ⁇ is immersed in a solution containing CNTs, and the CNTs are attached to the metal particles by hydrophilization, thereby forming a mesh-shaped coating film on top of the metal powder particles.
  • the CNT coated metallic powder can then be further processed in a sintering process.
  • a stacked metal composite may be formed by stacking the coated metal composite on a substrate surface. The resultant composite is reported to have superior mechanical strength, electric conductivity and thermal conductivity.
  • a further and equally important object of the invention to provide such a composite material which shows these superior beneficial mechanical properties under further processing to a semimanufactured or finished product, preserving the beneficial properties while the product is in use. This will allow that the material can be manufactured with great precision and efficiency while preserving the advantageous mechanical properties, and that the finished product itself will have a high- temperature stability as well.
  • a further object of the invention is to provide a method which allows for a simple and cost-efficient handling of the separate constituents as well as of the composite material while minimizing the potential for exposure for persons involved in the production.
  • a method of producing a composite material comprising a metal and nanoparticles, in particular carbon nanotubes (CNT) is provided, in which a metal powder and the nanoparticles are processed by mechanical alloying, such as to form a composite comprising metal crystallites having an average size in the range of higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • CNT carbon nanotubes
  • the composite material differs structurally from the composite of JP 2009 03 00 90 or US 2007/0134496 in that the metal crystallites are at least one order of magnitude smaller.
  • the composite material of the invention differs from previous inventions of the inventors in that in the present composite, independent metal crystallites of below 200 nm but more than 100 nm are formed, while according to the above patent documents the compound has a structure of alternating thin layers of metal and CNT, in which the in-plane extension of the metal layer however is way beyond 200 nm.
  • CNT- INV a specific type of CNTs as described later on in this specification (further below in this specification referred to as "CNT- INV") proves to be extremely useful with regard to processing of the educts, and to resulting proper- ties of the inventive composition and of the semi-finished and finished products made therefrom.
  • the strengthening effects of the CNTs on mechanical alloys is most pronounced when the average crystallite size in the CNT-metal compound is in the range of higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • the alloys thus produced have superior properties inter alia with regard to Young modulus and hardness. Due to their high temperature stability, these properties are preserved when the alloys are or have been exposed to high temperatures.
  • some CNTs are also contained or embedded in crystallites. One can think of this as a CNT sticking out like a "hair" from a crystallite.
  • CNTs are believed to play an important role in preventing grain growth and internal relaxation, i.e. preventing a decrease of the dislocation density when energy is supplied in form of pressure and/or heat upon compacting the compound material.
  • CNTs are embedded in crystallites.
  • the crystallites of the inventive CNT-metal compound are stabilized in sizes of higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • the metal of the compound is a light metal, and in particular, Al, Mg, Ti or an alloy includ- ing one or more of the same.
  • the metal may be Cu or a Cu alloy.
  • the invention allows to circumvent many problems currently encountered with Al alloys. While high strength Al alloys are known, such as A17xxx incorporating Zinc or A18xxx incorporating Li according to standard EN 573-3/4, unfortunately, coating these alloys by anodic oxidation proves to be difficult. Also, if different Al alloys are combined, due to a different electro- chemical potential of the alloys involved, corrosion may occur in the contact region.
  • Al alloys of the series lxxx, 3xxx and 5xxx based on solid-solution hardening can be coated by anodic oxidation, they have comparatively poor mechanical properties, a low temperature stability and can only be hardened to a quite narrow degree by cold working.
  • an aluminum based composite material can be provided which due to the nano-stabilization effect has a strength and hardness comparable with or even beyond high strength aluminum alloys available today, which also has an increased high-temperature stability due to the nano-stabilization and is open for anodic oxidation.
  • the strength of the compound can even be further raised. Also, by adequately adjusting the percentage of CNTs in the composite, the mechanical properties can be adjusted to a desired value. Therefore, materials having the same metal component but different concentrations of CNT and thus different mechanical properties can be manufactured, which will have the same electro-chemical potential and therefore will not be prone to corrosion when connected with each other. It has been found that the tensile strength and the hardness can be varied approximately proportionally with the content of CNT in the composite material. For light metals, such as aluminum, it has been found that the Vickers hardness increases nearly lineally with the CNT content.
  • the composite material becomes extremely hard and brittle. Accordingly, depending on the desired mechanical properties, a CNT content from 0.5 to 10.0 wt% will be preferable. In particular, a CNT content in the range of 5.0 to 9.0 % is extremely useful as it allows to make composite materials of extraordinary strength in combination with the aforementioned advantages of nano- stabilization, in particular high-temperature stability. In another preferred embodiment, the CNT content is between 3.0 and 6.0 wt%.
  • the most pronounced effects may be achieved when using CNTs which in form of a powder of tangled CNT-agglomerates have a mean size sufficiently large to ensure easy handling because of a low potential for dustiness.
  • preferably at least 95% of the CNT-agglomerates have a cluster size larger than 100 ⁇ .
  • the mean diameter of the CNT-agglomerates is between 0.05 and 5.0 mm, preferably 0.1 and 2.0 mm and most preferably 0.2 and 1.0 mm.
  • the nanoparticles to be processed with the metal powder can be easily handled e.g. with regard to dustiness and filtering by standard filters.
  • the powder comprised of agglomerates being larger than 100 ⁇ , has a pourability and flowability which allows an easy handling of the CNT source material.
  • the length-to- diameter ratio of the CNT also called aspect ratio, is preferably larger than 3, more preferably larger than 5 but most preferably smaller than 15.
  • a high aspect ratio of the CNT again assists in the nano-stabilization of the metal crystallites.
  • At least a fraction of the CNT have a scrolled structure comprised of one or more rolled up graphite layers, each graphite layer consisting of two or more graphene layers on top of each other.
  • This type of nanotubes has for the first time been described in DE 10 2007 044 031 Al .
  • This new type of CNT structure is called a "multi-scroll" structure to dis- tinguish it from "single-scroll” structures comprised of a single rolled-up graphene layer.
  • the relationship between multi-scroll and single-scroll CNTs is therefore analogous to the relationship between single-wall and multi-wall cylindrical CNTs.
  • the multi-scroll CNTs have a spiral shaped cross section and typically comprise 2 or 3 graphite layers with 6 to 12 graphene layers each.
  • the multi-scroll type CNT have found to be extraordinarily suitable for the above mentioned nano- stabilization.
  • One of the reasons is that the multi-scroll CNT have the tendency to not extend along a straight line but to have a curvy or kinky, multiply bent shape, which is also the reason why they tend to form large agglomerates of highly tangled CNTs.
  • This tendency to form a curvy, bent and tangled structure facilitates the formation of a three-dimensional network interlocking with the crystallites and stabilizing them.
  • a further reason why the multi-scroll structure is so well suited for nano-stabilization is believed to be that the individual layers tend to fan out when the tube is bent like the pages of an open book, thus forming a rough structure for interlocking with the crystallites which in turn is believed to be one of the mechanisms for stabilization of defects.
  • the CNT When processing conventional CNT at high kinetic energies, the CNT may be worn down or destroyed to an extent that the interlocking effect with the metal crystallites, i.e. the nano-stabilization no longer occurs.
  • CNT as described in DE 10 2007 044 031 Al prove to be very stable in the production process of the inventive CNT -metal compound.
  • the respective CNT are most effective in stabilizing the crystallite structure and enhancing the macroscopic properties of the CNT -metal compound.
  • the processing of the respective CNT is carried out until the length of the CNT's is in the order of magnitude of the average size or average diameter of the metal crystallites, e.g. higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • the nanoparticles are functionalized, in particular sur- face roughened prior to the mechanical alloying.
  • the roughening may be performed by causing at least the outermost layer of at least some of the CNTs to break by submitting the CNTs to high pressure, such as a pressure of 5.0 MPa or higher, preferably 7.8 MPa or higher, as will be explained below with reference to a specific embodiment. Due to the roughening of the nanoparticles, the interlocking effect with the metal crystallites and thus the nano-stabilization
  • the processing is conducted such as to increase and stabilize the dislocation density of the crystallites by the nanoparticles sufficiently to increase the average Vickers hardness of the composite material to exceed the Vickers hardness of the original metal by 40% or more, preferably by 80% or more.
  • FIG. 1 is a schematic diagram illustrating the production setup for high quality CNTs.
  • Fig.2 is a sketch schematically showing the generation of CNT-agglomerates from agglomerated primary catalyst particles.
  • Fig. 3 is an SEM picture of a CNT-agglomerate.
  • Fig. 4 is a close-up view of the CNT-agglomerate of Fig. 3 showing highly en-tangled
  • Fig. 5 is a graph showing the size distribution of CNT-agglomerates obtained with a production setup shown in Fig. 1
  • Fig. 6a is an SEM image of CNT-agglomerates prior to functionalization.
  • Fig. 6b is an SEM image of the same CNT-agglomerates after functionalization.
  • Fig. 6c is a TEM image showing a single CNT after functionalization.
  • Fig. 7 is a schematic diagram showing a setup for spray atomization of liquid alloys into an inert atmosphere.
  • Figs. 8a and 8b show sectional side and end views respectively of a ball mill designed for high energy milling.
  • Fig. 9 is a conceptional diagram showing the mechanism of mechanical alloying by high energy milling.
  • Fig. 10 is a diagram showing the rotational frequency of the HEM rotor versus time in a cyclic operation mode.
  • Fig. 11a shows the nano structure of a compound of the invention in a section through a compound particle.
  • Fig. l ib shows, in comparison to Fig. 11 a, a similar sectional view for the corn-pound material as known from WO 2008/052642 Al and WO 2009/010297 Al .
  • Fig. 12 shows an SEM image of the composite material according to an embodi-ment of the invention in which CNTs are embedded in metal crystallites.
  • Fig. 13 shows the same SEM image, the white lines illustrating the boundaries of the crystallites.
  • the processing strategy comprises the following steps:
  • CNTs of the multi-scroll type as known from DE 10 2007 044 031 Al are used. These CNTs are commercially available as Baytubes® CI 50 P from Bayer MaterialScience AG, Germany. Typical values for product properties are shown in the following table:
  • Fig. 5 shows a graph of the particle-size distribution of the CNT-agglomerates.
  • the abscissa represents the particle size in ⁇ , while the ordinate represents the cumulative volumetric content.
  • almost all of the CNT-agglomerates have a size larger than 100 ⁇ . This means that practically all of the CNT-agglomerates can be filtered by standard filters.
  • These CNT-agglomerates have a low respirable dustiness under EN 15051-B.
  • the extraordinarily large CNT-agglomerates used in the preferred embodiment of the invention allow for a safe and easy han- dling of the CNT, which again is of highest importance when it comes to transferring the technology from the laboratory to the industrial scale.
  • the CNT powder has a good pourability, which also greatly facilitates the handling.
  • the CNT- agglomerates allow to combine macroscopic handling properties with nanoscopic material characteristics.
  • a method of producing a composite material comprising a metal and nanoparticles, in particular carbon nano tubes (CNT) is provided, in which a metal powder and the nanoparticles are processed by mechanical alloying, such as to form a composite comprising metal crystallites having an average size which is in the range of higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • the CNTs may be functionalized prior to performing the mechanical alloying.
  • the purpose of the functionalizing is to treat the CNTs such that the nano-stabilization of the metal crystallites in the composite material will be enhanced.
  • this functionalization is achieved by roughening the surface of at least some of the CNTs.
  • the CNT-agglomerates are submitted to a high pressure of 100 kg/cm 2 (9.8 MPa). Upon exert- ing this pressure, as is shown in Fig. 6b, the agglomerate structure as such is preserved, i.e. the functionalized CNTs are still present in the form of agglomerates preserving the aforementioned advantages with respect to low respirable dustiness and easier handling. Also, it is found that while the CNT retain the same inner structure, the outermost layer or layers burst or break, thereby developing a rough surface, as is shown in Fig. 6c. With the rough surface, the interlocking effect between CNT and crystallites is increased, which in turn increases the nano-stabilization effect.
  • a setup 24 for generating a metal powder through atomization is shown.
  • the setup 24 com- prises a vessel 26 with heating means 28 in which a metal or metal alloy to be used as a constituent of the composite of the invention is melted.
  • the liquid metal or alloy is poured into a chamber 30 and forced by argon driving gas, represented by an arrow 32 through a nozzle assembly 34 into a chamber 36 containing an inert gas.
  • the liquid metal spray leaving the nozzle assembly 34 is quenched by an argon quenching gas 38, so that the metal droplets are rapidly solidified and form a metal powder 40 piling up on the floor of chamber 36.
  • Such a kind of powder forms the metal constituent of the composite material of the invention.
  • the CNTs need to be dispersed within the metal.
  • a high energy ball mill similar as disclosed in DE 196 35 500, DE 43 07 083 and DE 195 04 540 Al is used.
  • the dispersion is achieved by using the mechanical alloying technique which is a process where powder particles are treated by repeated deformation, fracture and welding by highly energetic collisions of grinding balls. Ball velocities of advantageously above 4 m/s or even above 11 m/s or between 11 - 14 m/s are necessary.
  • a process as disclosed in EP 1918249 Al , paragraphs [0011-0013], is used.
  • the CNT- agglomerates are deconstructed and the metal powder particles are fragmentized, and by this process, single CNTs are dispersed in the metal matrix.
  • the mechanical al- loying is carried out until the average length of the single CNT's is in the order of magnitude of the average size or average diameter of the metal crystallites, e.g. higher than 100 nm and up to 200 nm, preferably between 120 nm and 200 nm.
  • a CNT-metal compound having a crystallite size between more than 100 nm and up to 200 nm, preferably between 120 nm - 200 nm, will be formed. Also observed is a work hardening effect due to an increase of dislocation density in the crystallites. The dislocations accumulate, interact with each other and serve as pinning points or obstacles that significantly impede their motion. This again leads to an increase in the yield strength a y of the material and a subsequent decrease in ductility.
  • the integrity of the disentangled CNTs in the metal matrix it is believed that using the agglomerates of the CNT-INV according to the invention is advantageous, since the CNTs inside the agglomerates are to a certain extent protected by the outside CNTs.
  • many metals, in particular light metals such as aluminum have a fairly high ductility which makes processing by high energy milling difficult. Due to the high ductility, the metal may tend to stick at and bake to the inside wall of the milling chamber or the rotating element and may thereby not be completely milled. Such sticking can be counteracted by using milling aids such as stearic acids, alcohol or the like.
  • the use of a milling agent may be avoided when using CNTs, as is explained in WO 2009/010297 by the same inventors, because the CNT itself may act as a milling agent which avoids sticking of the metal powder.
  • a powder composite material can be obtained in which metal crystallites having a high dislocation density and are at least partially separated and micro-stabilized by ho- mogeneously distributed CNTs.
  • Fig. 11a shows a cut through a composite material particle according to an embodiment of the invention.
  • the metal constituent is aluminum and the CNTs are of the multi-scroll type obtained in a process as described in section 1 above.
  • the average length of the CNTs is in the range of the average size of the metal crystallites.
  • the composite material of WO 2008/052642 shown in Fig. l ib has a non-isotropic layer structure, leading to non- isotropic mechanical properties.
  • FIG. 12 shows an SEM image of a composite material comprised of aluminum with CNT dispersed therein.
  • examples of CNT extending along a boundary of crystallites can be seen (see also Fig. 13).
  • CNTs can be seen which are contained or embedded within a nanocrystallite and stick out from the nanocrystallite sur- face like a "hair". It is believed that these CNTs have been pressed into the metal crystallites like needles in the course of the high energy milling described above. It is believed that these CNTs embedded or contained within individual crystallites play an important role in the nano-stabilization effect, which in turn is responsible for the superior mechanical properties of the composite material and of compacted articles formed thereby.
  • the composite material powder can be used as a source material for forming semi-finished or finished articles by powder metallurgic methods.
  • the powder material of the invention can very advantageously be further processed by cold isostatic pressing (CIP) and hot isostatic pressing (HIP).
  • the composite material can be further processed by hot working, powder milling or powder extrusion at high temperatures up to the melting temperature of some of the metal phases. It has been observed that the viscosity of the composite material even at high temperatures is increased such that the composite material may be processed by powder extrusion or flow pressing.
  • the powder can be directly processed by continuous powder rolling.
  • the beneficial mechanical properties of the powder particles can be maintained in the compacted finished or semi-finished article.
  • a composite material having a Vickers hardness of more than 390 HV was obtained.
  • the Vickers hardness remains at more than 80% of this value.
  • the stabilizing nano structure the hardness of the individual composite powder particles can largely be transferred to the compacted article.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention porte sur des matériaux composites comprenant un métal et des nanoparticules, en particulier des nanotubes de carbone (CNT), caractérisés en ce que le composite a une structure de cristallites métalliques constituée de cristallites ayant une taille moyenne qui est dans la plage de valeurs supérieures à 100 nm et allant jusqu'à 200 nm, de préférence comprises entre 120 nm et 200 nm.
PCT/EP2010/061890 2009-09-17 2010-08-16 Matériau composite comprenant un métal et des nanoparticules WO2011032791A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BR112012005829A BR112012005829A2 (pt) 2009-09-17 2010-08-16 material compósito compreendendo um metal e nanopartículas
IN2285DEN2012 IN2012DN02285A (fr) 2009-09-17 2010-08-16
CA2783939A CA2783939A1 (fr) 2009-09-17 2010-08-16 Materiau composite comprenant un metal et des nanoparticules
AU2010294797A AU2010294797A1 (en) 2009-09-17 2010-08-16 A compound material comprising a metal and nanoparticles
JP2012529186A JP2013505353A (ja) 2009-09-17 2010-08-16 金属およびナノ粒子を含む複合材料
US13/496,564 US20120175547A1 (en) 2009-09-17 2010-08-16 Compound material comprising a metal and nanoparticles
RU2012114872/02A RU2012114872A (ru) 2009-09-17 2010-08-16 Композитный материал, содержащий металл и наночастицы
CN2010800410966A CN102630252A (zh) 2009-09-17 2010-08-16 包含金属和纳米颗粒的复合材料
EP10745206A EP2478124A1 (fr) 2009-09-17 2010-08-16 Matériau composite comprenant un métal et des nanoparticules

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EPPCT/EP2009/006737 2009-09-17
PCT/EP2009/006737 WO2010091704A1 (fr) 2009-02-16 2009-09-17 Matière composite comprenant un métal et des nanoparticules et son procédé de production
PCT/EP2010/000520 WO2010091790A1 (fr) 2009-02-16 2010-01-28 Matériau composite comprenant un métal et des nanoparticules et procédé de production associé
EPPCT/EP2010/000520 2010-01-28

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Cited By (6)

* Cited by examiner, † Cited by third party
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CN102851557A (zh) * 2011-06-30 2013-01-02 鸿富锦精密工业（深圳）有限公司 石墨烯掺杂的镁合金及镁合金结构件
WO2013117241A1 (fr) 2012-02-10 2013-08-15 Adamco Ag Renforcement de matériau par des microcouples de torsion par ancrage par point de fibres
DE102012222230A1 (de) 2012-12-04 2014-06-05 Pfeiffer Vacuum Gmbh Vakuumpumpe
CN106222591A (zh) * 2016-08-04 2016-12-14 北京工业大学 一种提高碳纳米管增强镁基复合材料力学性能的方法
CN109182820A (zh) * 2018-09-17 2019-01-11 宜春学院 一种异型结构纳米碳材料增强镁基复合材料的方法
CN111151765A (zh) * 2020-01-20 2020-05-15 西安稀有金属材料研究院有限公司 一种三维结构纳米碳材料增强铜基复合材料的制备方法

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EP2740943A2 (fr) 2012-12-04 2014-06-11 Pfeiffer Vacuum Gmbh Pompe à vide
CN106222591A (zh) * 2016-08-04 2016-12-14 北京工业大学 一种提高碳纳米管增强镁基复合材料力学性能的方法
CN109182820A (zh) * 2018-09-17 2019-01-11 宜春学院 一种异型结构纳米碳材料增强镁基复合材料的方法
CN111151765A (zh) * 2020-01-20 2020-05-15 西安稀有金属材料研究院有限公司 一种三维结构纳米碳材料增强铜基复合材料的制备方法

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