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WO2010104710A1 - Composites - Google Patents

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Publication number
WO2010104710A1
WO2010104710A1 PCT/US2010/026012 US2010026012W WO2010104710A1 WO 2010104710 A1 WO2010104710 A1 WO 2010104710A1 US 2010026012 W US2010026012 W US 2010026012W WO 2010104710 A1 WO2010104710 A1 WO 2010104710A1
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WIPO (PCT)
Prior art keywords
recited
nanoparticles
polymer pellets
composition
polymers
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Application number
PCT/US2010/026012
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French (fr)
Inventor
Dongsheng Mao
Zvi Yaniv
Original Assignee
Applied Nanotech Holdings, Inc.
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Publication of WO2010104710A1 publication Critical patent/WO2010104710A1/en

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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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

Definitions

  • Nanocomposites are composite materials that contain particles in the size range of 1-100 nm. These materials bring into play the submicron structural properties of molecules. These particles, such as clay and carbon nanotubes (CNTs), generally have excellent properties, a high aspect ratio, and a layered structure that maximizes bonding between the polymer and particles. Adding a small quantity of these additives (0.5-5%) can increase many of the properties of polymer materials, including higher strength, greater rigidity, high heat resistance, higher UV resistance, lower water absorption rate, lower gas permeation rate, and other improved properties (T. D. Fornes, D. L. Hunter, and D. R. Paul, "Nylon-6 nanocomposites from Alkylammonium-modified clay: The role of Alkyl tails on exfoliation,” Macromolecules 37, pp. 1793-1798 (2004)).
  • CNTs carbon nanotubes
  • Fig. 1 illustrates a schematic diagram of a ball milling apparatus
  • Fig. 2 illustrates a flow diagram of manufacturing nylon 11/clay/styrene- ethylene/butylene-styrene(SEBS)/composite resins
  • SEBS nylon 11/clay/styrene- ethylene/butylene-styrene
  • Fig. 3 illustrates a photograph of neat nylon 6 pellets on the left, which are transparent in contrast with nylon 6/CNT pellets on the right.
  • Improved mechanical properties of both clay and carbon nanotube (CNT)- reinforced polymer matrix nanocomposites are obtained by pre-treating nanoparticles and polymer pellets prior to a melt compounding process.
  • the nanoparticles are coated onto the surface of the polymer pellets by a ball-milling process.
  • the nanoparticle thin film is formed onto the surface of the polymer pellets after the mixture is ground for a certain time.
  • fillers such as graphite particles, carbon fibers, fullerenes, carbon nanotubes, ceramic particles, or any combination thereof may also be used.
  • Nylon 11/clay nanocomposites Nylon 1 1 pellets were obtained from Arkema Co., Japan (product name: RILSAN ® BMV-P20 PAI l). Clay was provided by Southern Clay Products, US (product name: CLOISITE ® series 93A). It is a natural montmorillonite modified with a ternary ammonium salt. Referring to Fig. 2, in step 201 , both clay and nylon 1 1 pellets were dried in a vacuum oven at 8O 0 C for at least 16 hours to fully eliminate the moisture. Then they were put in a glass container to go through the ball milling process in step 202.
  • Fig. 1 is a schematic diagram of a typical ball milling apparatus.
  • the speed of this machine is about 50 ⁇ 60 revolutions per minute.
  • 5 wt. % and 10 wt. % of the clay powders were chosen for the experiment.
  • the mixture was ground at least half an hour to allow the clay particles to be attached onto the surface of the nylon 1 1 pellets.
  • Solvents such as IPA, water, or acetone may be added into the mixture.
  • a direct mixing method was also used.
  • the clay and nylon 1 1 were put in a plastic bag and hand shaken for at least half an hour.
  • HAAKE Rheomex CTW 100 twin screw extruder (Germany) was used to blend nylon 6/clay/SEBS nanocomposites in step 203. Following are the parameters used in this process:
  • a quantity of the nylon 1 1 pellets and clay for each operation is 1 pound because the twin screw needs to be cleaned using the mixture before collecting the composite resin.
  • the synthesized resin may make 20 bars by the following injection molding process.
  • step 204 the nanocomposite fiber was quenched in water and palletized using a Haake PPl Pelletizer POSTEX after extrusion process.
  • step 205 the nanocomposite pellets were dried at 70 0 C prior to the injection molding process to make specimens.
  • a Mini-Jector Model 55, Mini-Jector Machinery Corp. Newbury, Ohio, USA laboratory-scale injection molding machine was used in step 206 to make impact bars for physical testing in step 207. Samples were added with specific dimensions using ASTM-specified molds (ASTM D256 for impact strength testing, ASTM D790 for flexural modulus testing). Following are the parameters used:
  • the specimens were dried in a desiccator for at least 40 hours' conditioning before the testing process. Flexural modulus and impact of the samples were characterized using standard 3-point bending method.
  • Table 1 shows the mechanical properties (flexural modulus and impact strength) of the nylon 11/clay/SEBS composites with different weight ratios.
  • Nylon 6 pellets were obtained from UBE Co., Japan (product name: SFlOl 8A). Clay was provided by Southern Clay Products, US (product name: CLOISITE ® series 93A). The carbon nanotubes used in this case were double wall CNTs (DWNTs). DWNTs were obtained from Nanocyl, Inc., Belgium.
  • Fig. 3 shows a picture of neat nylon 6 pellets (left) and nylon 6/CNT right.
  • Neat nylon 6 is transparent, while it was black after the ball milling process with CNTs because CNTs have a black color. It means that CNTs were evenly coated onto the surface of the nylon 6 pellets.
  • a HAAKE Rheomex CTW 100 twin screw extruder Germany was used to blend nylon 6/clay/SEBS nanocomposites. Following are the parameters used in this process:
  • a quantity of the nylon 6 pellets and CNTs for each operation was 1 pound because the twin screw needed to be cleaned using the mixture before collecting the composite resin.
  • the synthesized resin made 20 bars by following injection molding process.
  • the nanocomposite fiber was quenched in water and palletized using a Haake PPl Pelletizer POSTEX after the extrusion process.
  • the nanocomposite pellets were dried at 70 0 C prior to the injection molding process to make specimens.
  • a Mini-Jector Model 55, Mini- Jector Machinery Corp. Newbury, Ohio, USA laboratory-scale injection molding machine was used to make impact bars for physical testing. Samples were molded with specific dimensions using ASTM-specified molds (ASTM D638 for tensile strength testing, ASTM D790 for flexural modulus testing). Following are the parameters used:
  • nylon 6/CNT nanocomposites pre -treated by the ball milling process were better than those of neat nylon 6.
  • Nylon 6/CNT nanocomposites synthesized by melt compounding process hold worse mechanical properties than neat nylon 6 (Dhanote, “Nanocomposites with functionalized carbon nanotubes", Mat. Res. Soc. Symp. Proc. Vol. 788, Ll 1.17.1-L11.17.6).
  • thermoplastic and thermosetting polymers may be used in the cases described above in place of, or together with, nylon 6 and nylon 11.
  • Thermoplastic polymers that may be used as described herein include, but are not limited to, polycarbonates, polyamides, polyesters (e.g., polybutylene terephthalate and polyethylene terephthalate), polyethers, thermoplastic polyurethanes, polyacetals, fluorinated polymers (e.g., polyvinylidene fluoride), polyethersulfones, polyolefins (e.g., polyethylene and polypropylene), polyimides, polyacrylates (polymethylmethacrylate), polyphenylene oxides, polyphenylene sulfides, polyether ketones, polyarylether ketones, styrene polymers (e.g., polystyrene), styrene copolymers (e.g., styrene acrylonitrile copolymers), acrylate rubbers, acrylonitrile -butadiene-styrene block copolymers, polyviny
  • Thermosetting polymers that may be used as described herein include, but are not limited to, epoxies, phenolics, cyanate esters (CEs), bismaleimides (BMIs), polyimides, or any combination thereof. Nanoparticles such as clay or CNTs may be coated onto the surface of thermosetting pellets by a milling process. The pellets are then heated to form a molten liquid at certain temperatures and cured to form a nanocomposite. Further mixing such as stirring or ultrasonication provided before the curing process.
  • Thermosetting polymers e.g., EPON® Resin 828 epoxy
  • Thermosetting polymers that are in liquid form at room temperature may be cooled to a lower temperature to form a solid material. The solid material may then be broken into pellets.
  • the milling process may be performed at lower temperatures for polymers that are liquid at room temperature than polymers that are solid at room temperature.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Improved mechanical properties of both clay and carbon nanotube (CNT)-reinforced polymer matrix nanocomposites are obtained by pre-treating nanoparticles and thermosetting or thermoplastic polymer pellets prior to a melt compounding process. The nanoparticles are coated onto the surface of the polymer pellets by a ball-milling process. The nanoparticle thin film is formed onto the surface of the polymer pellets after the mixture is ground for a certain time.

Description

Composites
CROSS-REFERENCE TO RELATED APPLICATIONS
This application for patent is a continuation-in-part of U.S. Application Serial No. 11/695,877, filed April 3, 2007, which claims priority to U.S. Provisional Patent Application Serial Nos. 60/810,394, filed June 2, 2006, and 60/789,300, filed April 5, 2006, all of which are hereby incorporated by reference herein.
BACKGROUND INFORMATION
Nanocomposites are composite materials that contain particles in the size range of 1-100 nm. These materials bring into play the submicron structural properties of molecules. These particles, such as clay and carbon nanotubes (CNTs), generally have excellent properties, a high aspect ratio, and a layered structure that maximizes bonding between the polymer and particles. Adding a small quantity of these additives (0.5-5%) can increase many of the properties of polymer materials, including higher strength, greater rigidity, high heat resistance, higher UV resistance, lower water absorption rate, lower gas permeation rate, and other improved properties (T. D. Fornes, D. L. Hunter, and D. R. Paul, "Nylon-6 nanocomposites from Alkylammonium-modified clay: The role of Alkyl tails on exfoliation," Macromolecules 37, pp. 1793-1798 (2004)).
However, dispersion of the nanoparticles is very important to reinforce polymer matrix nanocomposites. Such dispersion of nanoparticles in the polymer matrix has been a problem. That is why those nanoparticle-reinforced nanocomposites have not achieved excellent properties as expected (Shamal K. Mhetre, Yong K. Kim, Steven B. Warner, Prabir K. Patra, Phaneshwar Katangur, and Autumn Dhanote "Nanocomposites with functionalized carbon nanotubes," Mat. Res. Soc. Symp. Proc. Vol. 788 (2004)). Researchers have claimed that in-situ polymerization of the nanocomposites can improve the dispersion of the nanoparticles. Better properties of the nanocomposites were somehow obtained. But in-situ polymerization is not proven to be an acceptable manufacturing process for the polymer production. Also used has been a melt compounding process, which is a more popular and manufacturable process to make those nanoparticle-reinforced polymer nanocomposites. But the results have not been satisfactory.
BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 illustrates a schematic diagram of a ball milling apparatus; Fig. 2 illustrates a flow diagram of manufacturing nylon 11/clay/styrene- ethylene/butylene-styrene(SEBS)/composite resins; and
Fig. 3 illustrates a photograph of neat nylon 6 pellets on the left, which are transparent in contrast with nylon 6/CNT pellets on the right.
DETAILED DESCRIPTION
Improved mechanical properties of both clay and carbon nanotube (CNT)- reinforced polymer matrix nanocomposites are obtained by pre-treating nanoparticles and polymer pellets prior to a melt compounding process. The nanoparticles are coated onto the surface of the polymer pellets by a ball-milling process. The nanoparticle thin film is formed onto the surface of the polymer pellets after the mixture is ground for a certain time.
The ball-milling process:
1. Allows nanoparticles to attach onto the surface of the polymer pellets; and
2. Breaks the big clusters of the nanoparticles by the bombardment of the polymer pellets, which further disperse the nanoparticles in the polymer matrix after the melt compounding process.
In addition to clay and CNTs, other fillers such as graphite particles, carbon fibers, fullerenes, carbon nanotubes, ceramic particles, or any combination thereof may also be used.
Two cases are provided to illustrate embodiments of the invention.
Case 1 : Nylon 11/clay nanocomposites Nylon 1 1 pellets were obtained from Arkema Co., Japan (product name: RILSAN® BMV-P20 PAI l). Clay was provided by Southern Clay Products, US (product name: CLOISITE® series 93A). It is a natural montmorillonite modified with a ternary ammonium salt. Referring to Fig. 2, in step 201 , both clay and nylon 1 1 pellets were dried in a vacuum oven at 8O0C for at least 16 hours to fully eliminate the moisture. Then they were put in a glass container to go through the ball milling process in step 202. Fig. 1 is a schematic diagram of a typical ball milling apparatus. The speed of this machine is about 50~60 revolutions per minute. In this method, 5 wt. % and 10 wt. % of the clay powders were chosen for the experiment. The mixture was ground at least half an hour to allow the clay particles to be attached onto the surface of the nylon 1 1 pellets. Solvents such as IPA, water, or acetone may be added into the mixture. For comparison, a direct mixing method was also used. The clay and nylon 1 1 were put in a plastic bag and hand shaken for at least half an hour.
After the mixtures were mixed by ball milling and direct mixing processes, a
HAAKE Rheomex CTW 100 twin screw extruder (Germany) was used to blend nylon 6/clay/SEBS nanocomposites in step 203. Following are the parameters used in this process:
Screw zone 1 temperature - 2300C; Screw zone 1 temperature - 2200C;
Screw zone 1 temperature - 2200C; Die temperature - 2300C; Screw speed - 100 rpm.
A quantity of the nylon 1 1 pellets and clay for each operation is 1 pound because the twin screw needs to be cleaned using the mixture before collecting the composite resin. The synthesized resin may make 20 bars by the following injection molding process. In step 204, the nanocomposite fiber was quenched in water and palletized using a Haake PPl Pelletizer POSTEX after extrusion process. In step 205, the nanocomposite pellets were dried at 700C prior to the injection molding process to make specimens. A Mini-Jector (Model 55, Mini-Jector Machinery Corp. Newbury, Ohio, USA) laboratory-scale injection molding machine was used in step 206 to make impact bars for physical testing in step 207. Samples were added with specific dimensions using ASTM-specified molds (ASTM D256 for impact strength testing, ASTM D790 for flexural modulus testing). Following are the parameters used:
Injection pressure - 70 bar; Holding pressure - 35 bar; Holding time - 40 seconds; Heating zone 1 temperature - 2200C; Heating zone 2 temperature - 2200C; Nozzle temperature -2300C; Mold temperature - 60-800C.
The specimens were dried in a desiccator for at least 40 hours' conditioning before the testing process. Flexural modulus and impact of the samples were characterized using standard 3-point bending method.
Table 1 shows the mechanical properties (flexural modulus and impact strength) of the nylon 11/clay/SEBS composites with different weight ratios.
Table 1
Figure imgf000005_0001
It can be seen clearly that the mechanical properties of nylon 11 /clay nanocomposites pre -treated by ball milling process are better than those by the direct mixing process at the same loading of clay. Case 2: Nylon 6/carbon nanotube nanocomposites
Nylon 6 pellets were obtained from UBE Co., Japan (product name: SFlOl 8A). Clay was provided by Southern Clay Products, US (product name: CLOISITE® series 93A). The carbon nanotubes used in this case were double wall CNTs (DWNTs). DWNTs were obtained from Nanocyl, Inc., Belgium.
A similar process as described above with respect to Fig. 2 was used. Both CNTs and nylon 6 pellets were dried in a vacuum oven at 8O0C for at least 16 hours to fully eliminate the moisture. Then they were put in a glass container to go through the ball milling process. In this case, 0.4 wt. % CNTs was used in nylon 6 matrix.
Fig. 3 shows a picture of neat nylon 6 pellets (left) and nylon 6/CNT right. Neat nylon 6 is transparent, while it was black after the ball milling process with CNTs because CNTs have a black color. It means that CNTs were evenly coated onto the surface of the nylon 6 pellets. After the mixtures were mixed by ball milling, a HAAKE Rheomex CTW 100 twin screw extruder (Germany) was used to blend nylon 6/clay/SEBS nanocomposites. Following are the parameters used in this process:
Screw zone 1 temperature - 2400C; Screw zone 1 temperature - 2300C; Screw zone 1 temperature - 2300C;
Die temperature - 2200C; Screw speed - 100 rpm.
A quantity of the nylon 6 pellets and CNTs for each operation was 1 pound because the twin screw needed to be cleaned using the mixture before collecting the composite resin. The synthesized resin made 20 bars by following injection molding process. The nanocomposite fiber was quenched in water and palletized using a Haake PPl Pelletizer POSTEX after the extrusion process. The nanocomposite pellets were dried at 700C prior to the injection molding process to make specimens. A Mini-Jector (Model 55, Mini- Jector Machinery Corp. Newbury, Ohio, USA) laboratory-scale injection molding machine was used to make impact bars for physical testing. Samples were molded with specific dimensions using ASTM-specified molds (ASTM D638 for tensile strength testing, ASTM D790 for flexural modulus testing). Following are the parameters used:
Injection pressure - 70 bar; Holding pressure - 35 bar; Holding time - 40 seconds; Heating zone 1 temperature - 2300C; Heating zone 2 temperature - 2300C; Nozzle temperature -2400C; Mold temperature - 60-800C.
For comparison, neat nylon 6 specimens were also molded. The specimens were dried in a desiccator for at least 40 hours' conditioning before the testing process. Table 2 shows the mechanical properties (tensile strength and impact strength) of the nylon 6/CNT nanocomposite.
Table 2
Figure imgf000007_0001
It can be seen clearly that the mechanical properties of nylon 6/CNT nanocomposites pre -treated by the ball milling process were better than those of neat nylon 6. Nylon 6/CNT nanocomposites synthesized by melt compounding process hold worse mechanical properties than neat nylon 6 (Dhanote, "Nanocomposites with functionalized carbon nanotubes", Mat. Res. Soc. Symp. Proc. Vol. 788, Ll 1.17.1-L11.17.6).
Other types of polymers including, but not limited to thermoplastic and thermosetting polymers, may be used in the cases described above in place of, or together with, nylon 6 and nylon 11.
Thermoplastic polymers that may be used as described herein include, but are not limited to, polycarbonates, polyamides, polyesters (e.g., polybutylene terephthalate and polyethylene terephthalate), polyethers, thermoplastic polyurethanes, polyacetals, fluorinated polymers (e.g., polyvinylidene fluoride), polyethersulfones, polyolefins (e.g., polyethylene and polypropylene), polyimides, polyacrylates (polymethylmethacrylate), polyphenylene oxides, polyphenylene sulfides, polyether ketones, polyarylether ketones, styrene polymers (e.g., polystyrene), styrene copolymers (e.g., styrene acrylonitrile copolymers), acrylate rubbers, acrylonitrile -butadiene-styrene block copolymers, polyvinyl chloride, or any combination thereof.
Thermosetting polymers that may be used as described herein include, but are not limited to, epoxies, phenolics, cyanate esters (CEs), bismaleimides (BMIs), polyimides, or any combination thereof. Nanoparticles such as clay or CNTs may be coated onto the surface of thermosetting pellets by a milling process. The pellets are then heated to form a molten liquid at certain temperatures and cured to form a nanocomposite. Further mixing such as stirring or ultrasonication provided before the curing process. Thermosetting polymers (e.g., EPON® Resin 828 epoxy) that are in liquid form at room temperature may be cooled to a lower temperature to form a solid material. The solid material may then be broken into pellets. The milling process may be performed at lower temperatures for polymers that are liquid at room temperature than polymers that are solid at room temperature.

Claims

WHAT IS CLAIMED IS:
1. A method comprising: blending nanoparticles with polymer pellets in a predetermined relative wt.% concentration; and mixing the nanoparticles with the polymer pellets and a solvent, resulting in a sufficient coating of the nanoparticles on surfaces of the polymer pellets so that the predetermined relative wt.% is substantially maintained after the mixing, wherein the polymer pellets are selected from the group consisting of thermoplastic polymers and thermosetting polymers.
2. The method as recited in claim 1, wherein the thermoplastic polymers are selected from the group consisting of polycarbonates, polyamides, polyesters, polyethers, thermoplastic polyurethanes, polyacetals, fiuorinated polymers, polyethersulfones, polyolefins, polyimides, poly aery lates, polyphenylene oxides, polyphenylene sulfides, polyether ketones, polyarylether ketones, styrene polymers, styrene copolymers, acrylate rubbers, acrylonitrile-butadiene-styrene block copolymers, polyvinyl chloride, or any combination thereof.
3. The method as recited in claim 1, wherein the thermosetting polymers are selected from the group consisting of epoxies, phenolics, cyanate esters, bismaleimides, polyimides, or any combination thereof.
4. The method as recited in claim 1, wherein the nanoparticles comprise clay nanoparticles.
5. The method as recited in claim 1, wherein the nanoparticles comprise carbon nanotubes.
6. The method as recited in claim 1, wherein the nanoparticles comprise graphite particles.
7. The method as recited in claim 1, wherein the nanoparticles comprise carbon fibers.
8. The method as recited in claim 1, wherein the nanoparticles comprise fullerenes.
9. The method as recited in claim 1, wherein the nanoparticles comprise ceramic particles.
10. The method as recited in claim 1, wherein the mixing is performed with a ball milling apparatus.
11. A composition of matter comprising polymer pellets with nanoparticles attached to the surface thereof, wherein the polymer pellets are selected from the group consisting of thermoplastic polymers and thermosetting polymers.
12. The composition as recited in claim 11, wherein the thermoplastic polymers are selected from the group consisting of polycarbonates, polyamides, polyesters, poly ethers, thermoplastic polyurethanes, polyacetals, fiuorinated polymers, polyethersulfones, polyolefϊns, polyimides, polyacrylates, polyphenylene oxides, polyphenylene sulfides, polyether ketones, polyarylether ketones, styrene polymers, styrene copolymers, acrylate rubbers, acrylonitrile-butadiene-styrene block copolymers, polyvinyl chloride, or any combination thereof.
13. The composition as recited in claim 11 , wherein the thermosetting polymers are selected from the group consisting of epoxies, phenolics, cyanate esters, bismaleimides, polyimides, or any combination thereof.
14. The composition as recited in claim 11, wherein the nanoparticles comprise clay nanoparticles.
15. The composition as recited in claim 11 , wherein the nanoparticles comprise carbon nano tubes.
16. The composition as recited in claim 11 , wherein the nanoparticles comprise graphite particles.
17. The composition as recited in claim 11 , wherein the nanoparticles comprise carbon fibers.
18. The composition as recited in claim 11 , wherein the nanoparticles comprise fullerenes.
19. The composition as recited in claim 11 , wherein the nanoparticles comprise ceramic particles.
20. The composition as recited in claim 11 , wherein the polymer pellets are covered with the nanoparticles after mixing using the ball milling apparatus.
21. The method as recited in claim 1 , further comprising after the mixing of the nanoparticles with the polymer pellets and the solvent, the nanoparticles are coated on the entire surfaces of the polymer pellets.
22. The method as recited in claim 1, further comprising after the mixing of the nanoparticles with the polymer pellets and the solvent, extruding the mixture.
23. The method as recited in claim 1, wherein the nanoparticles comprise multi-wall carbon nano tubes.
24. The method as recited in claim 1, wherein the predetermined relative wt.% concentration is 0.4.
25. The method as recited in claim 1, wherein the predetermined relative wt.% concentration is 5.
26. The method as recited in claim 1, wherein the predetermined relative wt.% concentration is 10.
PCT/US2010/026012 2009-03-11 2010-03-03 Composites WO2010104710A1 (en)

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Cited By (2)

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US20110064940A1 (en) * 2009-09-14 2011-03-17 The Regents Of The University Of Michigan Dispersion method for particles in nanocomposites and method of forming nanocomposites
CN105711094A (en) * 2016-03-15 2016-06-29 东华大学 Three-dimensional printing method

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US20050191491A1 (en) * 2003-04-08 2005-09-01 Yulu Wang Polymer coating/encapsulation of nanoparticles using a supercritical antisolvent process
US7094367B1 (en) * 2002-08-13 2006-08-22 University Of Florida Transparent polymer carbon nanotube composites and process for preparation
WO2006104689A1 (en) * 2005-03-24 2006-10-05 3M Innovative Properties Company Polymer nanocomposite having surface modified nanoparticles and methods of preparing same
US20070183959A1 (en) * 2003-03-20 2007-08-09 Armines Association Pour la Recherche et le Development des Methodes et Processis Industriels Carbon nanostructures and process for the production of carbon-based nanotubes, nanofibres and nanostructures
US20080152913A1 (en) * 2006-12-22 2008-06-26 3M Innovative Properties Company Method of making compositions including particles

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Publication number Priority date Publication date Assignee Title
US20030099798A1 (en) * 2001-11-29 2003-05-29 George Eric R. Nanocomposite reinforced polymer blend and method for blending thereof
US7094367B1 (en) * 2002-08-13 2006-08-22 University Of Florida Transparent polymer carbon nanotube composites and process for preparation
US20070183959A1 (en) * 2003-03-20 2007-08-09 Armines Association Pour la Recherche et le Development des Methodes et Processis Industriels Carbon nanostructures and process for the production of carbon-based nanotubes, nanofibres and nanostructures
US20050191491A1 (en) * 2003-04-08 2005-09-01 Yulu Wang Polymer coating/encapsulation of nanoparticles using a supercritical antisolvent process
WO2006104689A1 (en) * 2005-03-24 2006-10-05 3M Innovative Properties Company Polymer nanocomposite having surface modified nanoparticles and methods of preparing same
US20080152913A1 (en) * 2006-12-22 2008-06-26 3M Innovative Properties Company Method of making compositions including particles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110064940A1 (en) * 2009-09-14 2011-03-17 The Regents Of The University Of Michigan Dispersion method for particles in nanocomposites and method of forming nanocomposites
US9902819B2 (en) * 2009-09-14 2018-02-27 The Regents Of The University Of Michigan Dispersion method for particles in nanocomposites and method of forming nanocomposites
CN105711094A (en) * 2016-03-15 2016-06-29 东华大学 Three-dimensional printing method

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