CN101191007B - Method for preparing resin-base composite material containing metal particle - Google Patents
Method for preparing resin-base composite material containing metal particle Download PDFInfo
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- CN101191007B CN101191007B CN2007101684253A CN200710168425A CN101191007B CN 101191007 B CN101191007 B CN 101191007B CN 2007101684253 A CN2007101684253 A CN 2007101684253A CN 200710168425 A CN200710168425 A CN 200710168425A CN 101191007 B CN101191007 B CN 101191007B
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Abstract
The invention relates to a preparation method of a resin matrix composite material filled with metal particles, in particular to a preparation method of a resin matrix composite material containing metal particles. The invention is characterized in that: the invention comprises the steps: 1) dried metal powder and surface modifier are mixed with solvent, and then the mixture obtained is heated and refluxed with the protection of inert gas under 80-150 DEG C, thus forming suspension; 2) the suspension is classified to obtain suspension with single particle-sized particles, which is then extracted and filtered, thus obtaining single particle-sized modified metal powder; 3) the modified metal powder obtained in the step 2) is added into the resin matrix, in which thixotropic agent and curingagent are added, and then a vacuum stirrer and a ultrasonic vibrating device are used together to stir and vibrate the mixture obtained; 4) the mixture obtained in the step 3) after mixed is poured into a die for casting moulding, thus obtaining the resin matrix composite material containing metal particles through curing technique. The method is characterized by good dispersion effective of the metal particles and preventing the metal particles from a secondary aggregation.
Description
Technical field
The present invention relates to a kind of method for preparing rigid particles potting resin matrix material, specially refer to the preparation method of the polymer matrix composites of metallic particles filling.
Background technology
Traditional polymer toughening mainly be add rubber elastomer as toughner reaching toughness reinforcing purpose, but the intensity of resin material, modulus and thermotolerance but decline to a great extent.In order to overcome the shortcoming that descends significantly in the intensity, modulus and the thermotolerance that improve polymeric matrix flexible while material, from 1984, the new thought of rubber toughened polymkeric substance has abroad appearred replacing with inelastic body, it has solved the problem that elastic body toughening occurs, but there are some problems in the toughness reinforcing preparation technology of polymkeric substance inelastic body, i.e. reducing along with the particle filled composite size, because Van der Waals force effect, particle is more little, its agglomeration is obvious more, very easily self takes place to assemble to form macroparticle shape agglomerated masses.The reunion of rigid particles makes its effect forfeiture toughness reinforcing to polymeric matrix.Therefore how rigid particles is dispersed into the maximum difficult point for the toughness reinforcing preparation technology of polymkeric substance inelastic body equably in polymeric matrix.
The most representative as rigid particles is metallic particles, and the purposes of the resin composite materials that metallic particles is filled is very many, as the pre-adult of metal complex component, conductive polymer body, electromagnetic shielding material, antistatic material, exothermic material etc.But there is difficult point in the preparation technology of metal filled polymer matrix composites always, mainly is that pellet density is big owing to adopt the metallic particles of big particle diameter, easily sedimentation takes place and demixing phenomenon takes place cause the size distribution of matrix material inhomogeneous in resin; And the metallic particles of employing small particle size, reunite easily, particle is skewness in resin matrix, and the particulate reunion causes the bubble in the resin to increase with the particles settling phenomenon obvious, directly have influence on the content of metallic particles in the matrix material, thereby cause the bonding strength between the size distribution of matrix material inhomogeneous and matrix and the particle relatively poor.In this case, overcome the key that the dispersion effect in resin of metallic particles and sedimentation phenomenon and containing metal particulate resin solidification technology become preparation technology's difficult point of containing metal particulate polymer matrix composites.
Particles dispersed is divided by dispersing mode can be divided into physics dispersion and chemical dispersion.Physics is dispersed with mechanical dispersion, ultra-sonic dispersion, electromagnetism dispersion and percussion flow method etc.; Chemical dispersion is to utilize dispersion agent to reach dispersion to superfine powder by different mechanism.Physics disperses to exist a common problem to be, in case leave the field of turbulent flow that physical method produces, powder granule may be reunited again, and dispersion effect is not obvious.Though chemical dispersion is discrete particles effectively, owing to change the character of particle surface, influence the mechanism that is connected of particle and matrix, thereby influence the performance of the product that obtains.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of containing metal particulate polymer matrix composites, this method has that the metallic particles dispersion effect is good, the characteristics of the secondary agglomeration phenomenon that can prevent metallic particles.
In order to realize above purpose, technical scheme of the present invention is: a kind of preparation method of containing metal particulate polymer matrix composites is characterized in that it comprises the steps:
1) will treat that the vacuum-drying of dispersed metal powder removes the moisture that absorption is gone up on the surface, then exsiccant metal-powder and surface-modifying agent and solvent be mixed, and under 80～150 ℃ of temperature, protection of inert gas reflux, form suspension;
Wherein, the weight percent that exsiccant metal-powder, solvent account for dispersion system is: exsiccant metal-powder 1～90%, solvent 10%～99%, the content of surface-modifying agent are 0.5～5% of exsiccant metal-powder weight; Described dispersion system is exsiccant metal-powder and solvent; Described metal-powder is one of in the heavy metal powder, purity＞99%, and the powder particle particle diameter is between 0.2 μ m～2 μ m;
2) suspension is carried out classification and obtain to contain single particle size particulate suspension, suction filtration contains single particle size particulate suspended emulsion, obtains the modified metal powder (metal-powder of surface grafting surface-modifying agent) of single particle size;
3) with step 2) the modified metal powder add in the resin matrix, carry out ultra-sonic oscillation and vacuum machine simultaneously and stir, mix 10～30min, metallic particles/resin compound; Add thixotropic agent and solidifying agent in metallic particles/resin compound, utilize vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shake (mixing); The weight ratio of modified metal powder and resin matrix is 1～4: 1, and the add-on of thixotropic agent is 0.1～2% of a resin matrix weight, and the add-on of solidifying agent is 2～7% of a resin matrix weight;
4) after the mixing, pour casting in the mould into, through obtaining containing metal particulate polymer matrix composites behind the curing process.
The described surface-modifying agent of step 1) is silane coupling agent (as the KH550/KH560 silane coupling agent) or titanate coupling agent.
The described solvent of step 1) is a non-aqueous solvent, as analytical pure ethanol or acetone.
Described rare gas element is Ar or N
2Deng.
Step 2) the particulate fractionated time determines that by Stocks ' law law grading time is 1～10min.
Described resin matrix is a Resins, epoxy.
Described thixotropic agent is general amorphous Si O
2Powder.
Described solidifying agent is an epoxy curing agent, as 2-ethyl-4-methylimidazole (EMI-2,4), glyoxal ethyline (EMI-2).
Described curing process is: put into the heating under vacuum case behind the casting, vacuumize; When vacuum tightness is better than 1 * 10-2Pa, begin the heating that heats up, be heated to 70～90 ℃ and solidify 1～2h, be warming up to 160～200 ℃ of after fixing 1～2h again.
Compared with prior art, the present invention has significantly following beneficial effect: 1, select both dispersed metal particles well of this dispersion method for use, the surface that meanwhile dispersion agent is grafted on metal-powder prevents the secondary agglomeration of metal-powder, and secondly the adding of thixotropic agent has prevented the sedimentation phenomenon of heavy metal particles at solidification process; The containing metal particulate polymer matrix composites that obtain have in the resin particles dispersed evenly, particle and firm, the particles filled content height of matrix bond, characteristics such as the control accuracy height of granule content.2, method of the present invention have cost little, operate easy characteristics.
The present invention overcome that simple physics disperses and chemical dispersion in separately shortcoming, solved dispersion, secondary agglomeration and the sedimentation difficult problem of metallic particles at resin; Easy and simple to handle, and dispersed metal particle and can prevent that metallic particles is in resin settled well.Method of the present invention can be used for the research fields such as pre-adult, conductive polymer body, electromagnetic shielding material, antistatic material, exothermic material and polymer toughening of metal complex component.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is not surface treatment and the infrared test that carries out a surface-treated W powder comparison diagram as a result;
Fig. 3 is the micrograph results figure that does not carry out the W powder potting resin of dispersion treatment;
Fig. 4 is the micrograph results figure that carries out the W powder potting resin after the dispersion treatment;
Fig. 5 is the cut apart synoptic diagram of containing metal particulate resin-cast body along short transverse;
Fig. 6 is the W resin composite materials of filling along the density measurement of short transverse comparison diagram as a result;
Fig. 7 is the Mo resin composite materials of filling along the density measurement of short transverse comparison diagram as a result;
Fig. 8 is the Ni resin composite materials of filling along the density measurement of short transverse comparison diagram as a result.
Embodiment
In order to understand the present invention better, the preparation method with the particles filled Resins, epoxy of three heavy metal species is an example below, in conjunction with the accompanying drawings the present invention is described in further detail, but content of the present invention not only is confined to the following examples.
Embodiment 1:
As shown in Figure 1, a kind of preparation method of containing metal particulate polymer matrix composites, it comprises the steps:
1) the W particle surface modification is handled: with W powder (median size 0.95 μ m, Chaozhou Xianglu Tungsten Industry Co., Ltd.), (KH550, molecular formula is N to silane coupling agent
2N (CH
2)
3Si (OC
2H
5)
3, organosilicon novel material company limited of Hubei Wuhan University) and ethanol (chemical reagents corporation of Shanghai traditional Chinese medicines group) mixing, wherein the KH550 silane coupling agent is the 2wt% of W powder, the part by weight of ethanol and W powder is 1: 1; Adopt the concussion of agitator and ultrasonic device to stir 10min simultaneously, and at 100 ℃ of following reflux (N
2Protection), form suspension (metal particle suspension of grafting surface-modifying agent).
2) classification: suspension is carried out classification obtain to contain single particle size particulate suspension, grading time is 2min, and suction filtration contains single particle size particulate suspended emulsion, obtains the modification W powder (metal-powder of surface grafting surface-modifying agent) of single particle size.The infrared detection of the W powder after disperseing is found W powder surface grafting one deck silane coupling agent, and the existence of this layer coupling agent had both prevented the secondary agglomeration (as shown in Figure 2) of W particle in resin.
3) modification W powder and the Resins, epoxy (CYD-127, head factory Resins, epoxy factory of China Petrochemical Industry) with single particle size mixes according to weight ratio at 1: 1, carries out ultra-sonic oscillation and vacuum machine simultaneously and stirs, and mixes 30min, gets metallic particles/resin compound; Intermediate temperature setting agent (2-ethyl-4-methylimidazole (the EMI-2 that adds weight epoxy 4% in metallic particles/resin compound, 4), Wuhan grand chemical reagent factory), amorphous SiO2 powder (the CAB-O-SIL that adds weight epoxy 1%, LM-150), utilize vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shake (mixing).
4) pour the mixture of metallic particles and resin in mould casting, put into vacuum heater, when vacuum tightness is better than 1 * 10
-2During Pa, begin to be warming up to 80 ℃, insulation 1h continues to be heated to 160 ℃ again, insulation 2h, and naturally cooling obtains containing metal particulate polymer matrix composites (the particles filled resin composite materials of W).As shown in Figure 4, the W particle after the modification is at the favorable dispersity of resin, with the microstructure (as shown in Figure 3) of the particles filled resin material of dispersive W not relatively, the dispersion effect of particle in resin improves significantly.As shown in Figure 6, along pour mass short transverse (Fig. 5), before relatively disperseing with disperse after the composite density of W/ resin, the result shows that the even property of density unevenness obviously improves.
Embodiment 2:
A kind of preparation method of containing metal particulate polymer matrix composites, it comprises the steps:
1) the Mo particle surface modification is handled: with Mo powder (median size 1.50 μ m, the Beijing Non-Ferrous Metal Research General Academy), KH550 silane coupling agent and ethanol mix, wherein the KH560 silane coupling agent is the 2wt% of Mo powder, and the part by weight of ethanol and Mo powder is 1: 1; Adopt the concussion of agitator and ultrasonic device to stir 10min simultaneously, and, form suspension in 100 ℃ of following reflux (N2 protection).
2) suspension is carried out classification and obtain to contain single particle size particulate suspension, grading time is 1min, suction filtration suspended emulsion, the modification Mo powder (metal-powder of surface grafting surface-modifying agent) of acquisition single particle size.
3) with step 2) modification Mo powder add in the Resins, epoxy, modification Mo powder mixes according to weight ratio with Resins, epoxy at 1: 1, carries out ultra-sonic oscillation and vacuum machine simultaneously and stirs, and mixes 30min, must metallic particles/resin compound; The intermediate temperature setting agent [2-ethyl-4-methylimidazole (EMI-2,4)] that adds weight epoxy 4% in metallic particles/resin compound, the amorphous Si O of adding weight epoxy 1%
2(CAB-O-SIL LM-150), utilizes vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shakes (mixing) powder;
4) after the mixing, pour casting in the mould into, put into vacuum heater, when vacuum tightness is better than 1 * 10
-2During Pa, begin to be warming up to 80 ℃, insulation 1h continues to be heated to 160 ℃ again, insulation 2h, and naturally cooling obtains to contain the particles filled resin composite materials of Mo.As shown in Figure 7, along the pour mass short transverse, before relatively disperseing with disperse after the composite density difference of Mo/ resin obviously improve, more approaching with theoretical density, this shows employing method of the present invention dispersed metal particle well, and prevent from the sedimentation of metallic particles to obtain the metal/resin based composites that is evenly distributed.
Embodiment 3:
A kind of preparation method of containing metal particulate polymer matrix composites, it comprises the steps:
1) the Ni particle surface modification is handled: with Ni powder (median size 2.0 μ m, the Beijing Non-Ferrous Metal Research General Academy), titanate coupling agent (NDZ-401, NanJing Shuguang Chemical Group Co., Ltd.) and ethanol mix, wherein coupling agent is the 2wt% of Ni powder, and the part by weight of ethanol and Ni powder is 1: 1; Adopt the concussion of agitator and ultrasonic device to stir 10min simultaneously, and at 100 ℃ of following reflux (N
2Protection), form suspension.
2) classification: suspension is carried out classification obtain to contain single particle size particulate suspension, grading time is 1min, suction filtration suspended emulsion, the modification Ni powder (metal-powder of surface grafting surface-modifying agent) of acquisition single particle size.
3) with step 2) modification Ni powder add in the Resins, epoxy, modification Ni powder mixes according to weight ratio with Resins, epoxy at 1: 1, carries out ultra-sonic oscillation and vacuum machine simultaneously and stirs, and mixes 30min, must metallic particles/resin compound; The intermediate temperature setting agent 2-ethyl-4-methylimidazole (EMI-2,4) that adds weight epoxy 4% in metallic particles/resin compound, the amorphous Si O of adding weight epoxy 1%
2(CAB-O-SIL LM-150), utilizes vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shakes (mixing) powder;
4) after the mixing, pour casting in the mould into, put into vacuum heater, when vacuum tightness is better than 1 * 10
-2During Pa, begin to be warming up to 80 ℃, insulation 1h continues to be heated to 160 ℃ again, insulation 2h, and naturally cooling obtains to contain the particles filled resin composite materials of Ni.As shown in Figure 8, along the pour mass short transverse, before relatively disperseing with disperse after the test result of composite density of Ni/ resin, the middle portion homogeneity of the resin after disperseing as can be seen is better, shows the dispersion of sample and prevents that settled effect is remarkable.
Embodiment 4:
A kind of preparation method of containing metal particulate polymer matrix composites, it comprises the steps:
1) will treat that the vacuum-drying of dispersed metal powder removes the moisture that absorption is gone up on the surface, then exsiccant metal-powder and surface-modifying agent and solvent be mixed, and under 150 ℃, protection of inert gas reflux, form suspension;
Wherein, the weight percent of exsiccant metal-powder, the shared exsiccant metal-powder of solvent and solvent is: exsiccant metal-powder 1%, solvent 99%, the content of surface-modifying agent are 0.5% of exsiccant metal-powder weight; Described metal-powder is the W powder, purity＞99%, and the powder particle median size is 0.2 μ m; Described surface-modifying agent is silane coupling agent (as the KH550/KH560 silane coupling agent); Described solvent is a non-aqueous solvent analytical pure ethanol; Described rare gas element is Ar;
2) suspension is carried out classification and obtain to contain single particle size particulate suspension, grading time is 1min, suction filtration suspended emulsion, the modified metal powder (metal-powder of surface grafting surface-modifying agent) of acquisition single particle size;
3) with step 2) the modified metal powder add in the resin matrix, carry out ultra-sonic oscillation and vacuum machine simultaneously and stir, mix 10min, metallic particles/resin compound; Add thixotropic agent and solidifying agent in metallic particles/resin compound, utilize vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shake (mixing); The weight ratio of modified metal powder and resin matrix 1: 1, the add-on of thixotropic agent are 0.1% of resin matrix weight, and the add-on of solidifying agent is 2% of a resin matrix weight; Described resin matrix is a Resins, epoxy; Described thixotropic agent is general amorphous Si O
2Powder; Described solidifying agent is 2-ethyl-4-methylimidazole (EMI-2,4);
4) after the mixing, pour casting in the mould into, put into the heating under vacuum case behind the casting, vacuumize; When vacuum tightness is better than 1 * 10
-2Begin the heating that heats up during Pa, be heated to 70 ℃ and solidify 1h, be warming up to 160 ℃ of after fixing 1h again; Acquisition contains W particulate polymer matrix composites.
Embodiment 5:
A kind of preparation method of containing metal particulate polymer matrix composites, it comprises the steps:
1) will treat that the vacuum-drying of dispersed metal powder removes the moisture that absorption is gone up on the surface, then exsiccant metal-powder and surface-modifying agent and solvent be mixed, and under 150 ℃, protection of inert gas reflux, form suspension;
Wherein, the weight percent of exsiccant metal-powder, the shared exsiccant metal-powder of solvent and solvent is: exsiccant metal-powder 90%, solvent 10%, the content of surface-modifying agent are 5% of exsiccant metal-powder weight; Described metal-powder is the Mo powder, purity＞99%, and the powder particle particle diameter is between 2 μ m; Described surface-modifying agent is a titanate coupling agent; Described solvent is a non-aqueous solvent, as analytical pure ethanol; Described rare gas element is N
2
2) suspension is carried out classification and obtain to contain single particle size particulate suspension, grading time is 10min, suction filtration suspended emulsion, the modified metal powder (metal-powder of surface grafting surface-modifying agent) of acquisition single particle size;
3) with step 2) the modified metal powder add in the resin matrix, carry out ultra-sonic oscillation and vacuum machine simultaneously and stir, mix 30min, metallic particles/resin compound; Add thixotropic agent and solidifying agent in metallic particles/resin compound, utilize vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shake (mixing); The weight ratio of modified metal powder and resin matrix 4: 1, the add-on of thixotropic agent are 2% of resin matrix weight, and the add-on of solidifying agent is 7% of a resin matrix weight; Described resin matrix is a Resins, epoxy; Described thixotropic agent is general amorphous Si O
2Powder; Described solidifying agent is the agent of Resins, epoxy intermediate temperature setting, as 2-ethyl-4-methylimidazole (EMI-2,4);
4) after the mixing, pour casting in the mould into, put into the heating under vacuum case behind the casting, vacuumize; When vacuum tightness is better than 1 * 10
-2Begin the heating that heats up during Pa, be heated to 90 ℃ and solidify 2h, be warming up to 200 ℃ of after fixing 2h again, obtain the metallic particles/resin composite materials of even particle distribution.
Claims (4)
1. the preparation method of containing metal particulate polymer matrix composites is characterized in that it comprises the steps:
1) will treat that the vacuum-drying of dispersed metal powder removes the moisture that absorption is gone up on the surface, then exsiccant metal-powder and surface-modifying agent and solvent be mixed, and under 80～150 ℃ of temperature, protection of inert gas reflux, form suspension;
Described surface-modifying agent is silane coupling agent or titanate coupling agent, and solvent is analytical pure ethanol or acetone;
Wherein, the weight percent that exsiccant metal-powder, solvent account for dispersion system is: exsiccant metal-powder 1～90%, solvent 10%～99%, the content of surface-modifying agent are 0.5～5% of exsiccant metal-powder weight; Described dispersion system is exsiccant metal-powder and solvent; Described metal-powder is one of in the heavy metal powder, purity＞99%, and the powder particle particle diameter is between 0.2 μ m～2 μ m;
2) suspension is carried out classification and obtain to contain single particle size particulate suspension, suction filtration contains single particle size particulate suspended emulsion, obtains the modified metal powder of single particle size;
3) with step 2) the modified metal powder add in the resin matrix, carry out ultra-sonic oscillation and vacuum machine simultaneously and stir, mix 10～30min, metallic particles/resin compound; Add thixotropic agent and solidifying agent in metallic particles/resin compound, utilize vacuum stirring device and ultrasonic oscillation device to stir simultaneously and shake; The weight ratio of modified metal powder and resin matrix is 1～4: 1, and the add-on of thixotropic agent is 0.1～2% of a resin matrix weight, and the add-on of solidifying agent is 2～7% of a resin matrix weight;
Described thixotropic agent is general amorphous Si O
2Powder, described solidifying agent are epoxy curing agent; Described resin matrix is a Resins, epoxy;
4) after the mixing, pour casting in the mould into, through obtaining containing metal particulate polymer matrix composites behind the curing process.
2. the preparation method of a kind of containing metal particulate polymer matrix composites according to claim 1 is characterized in that: described rare gas element is Ar or N
2
3. the preparation method of a kind of containing metal particulate polymer matrix composites according to claim 1 is characterized in that: step 2) the particulate fractionated time determine that by Stocks ' law law grading time is 1～10min.
4. the preparation method of a kind of containing metal particulate polymer matrix composites according to claim 1 is characterized in that: the described curing process of step 4) is: put into the heating under vacuum case behind the casting, vacuumize; When vacuum tightness is better than 1 * 10
-2Begin the heating that heats up during Pa, be heated to 70～90 ℃ and solidify 1～2h, be warming up to 160～200 ℃ of after fixing 1～2h again.
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| CN2007101684253A CN101191007B (en) | 2007-11-23 | 2007-11-23 | Method for preparing resin-base composite material containing metal particle |
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| CN2007101684253A CN101191007B (en) | 2007-11-23 | 2007-11-23 | Method for preparing resin-base composite material containing metal particle |
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| CN103723289B (en) * | 2014-01-26 | 2015-09-23 | 南通通洋机电制造有限公司 | A kind of radiation shielded components for artificial satellite |
| CN108215233B (en) * | 2017-12-11 | 2019-12-24 | 湖北耐创新材料洁具有限公司 | Pressure forming process of resin and mineral mixed casting part |
| CN108481654B (en) * | 2018-03-25 | 2020-12-29 | 昆山益兴荣电子科技有限公司 | Composite material injection molding process |
| CN109607672B (en) * | 2018-12-21 | 2022-07-15 | 翁乾铭 | Polymer curing agent for bearing metal particles and application thereof |
| CN110752189B (en) | 2019-10-23 | 2020-08-21 | 杭州见闻录科技有限公司 | EMI shielding material, EMI shielding process and communication module product |
| CN111361180B (en) * | 2020-02-14 | 2021-02-19 | 大连交通大学 | Carbon fiber structural component and preparation method thereof |
| CN111905700B (en) * | 2020-08-24 | 2023-04-07 | 中蓝长化工程科技有限公司 | Resin-based inorganic nanoparticle composite lithium extraction particle |
| CN112538246A (en) * | 2020-12-04 | 2021-03-23 | 惠州莹光塑胶颜料有限公司 | Plastic master batch with metallic luster and preparation method thereof |
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| CN1422741A (en) * | 2001-11-08 | 2003-06-11 | 希普利公司 | Method for forming resin composite material |
| CN1465621A (en) * | 2002-07-03 | 2004-01-07 | 北京崇高纳米科技有限公司 | Polyester/lamellar silicate nano composite material and preparation method thereof |
| WO2004034409A1 (en) * | 2002-10-04 | 2004-04-22 | Rensselaer Polytechnic Institute | Nanometric composites as improved dielectric structures |
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| CN1422741A (en) * | 2001-11-08 | 2003-06-11 | 希普利公司 | Method for forming resin composite material |
| CN1465621A (en) * | 2002-07-03 | 2004-01-07 | 北京崇高纳米科技有限公司 | Polyester/lamellar silicate nano composite material and preparation method thereof |
| WO2004034409A1 (en) * | 2002-10-04 | 2004-04-22 | Rensselaer Polytechnic Institute | Nanometric composites as improved dielectric structures |
| JP2007197655A (en) * | 2005-05-30 | 2007-08-09 | Admatechs Co Ltd | Microparticle-containing composition and method for producing the composition |
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