Composites with oriented particles and particle networks with method
A method and types of composites in which particles are oriented within a melt-processable material or are arranged into networks in response to chaotic advection. A masterbatch comprising a melt-processable material and particles is supplied to a blender in which chaotic advection is maintained for a specified period. A second, melt-processable material may be supplied to the blender simultaneously. Resulting composites include extrusions with oriented inorganic platelets that reduce permeation or electrically conducting plastics and other functional materials.
This patent application claims the benefit and priority of U.S. Provisional patent Application 60/508,708 filed Oct. 3, 2003 and hereby incorporated by reference in its entirety.
The invention involves plastic materials with particulate matter embedded in the plastic to form a composite or nanocomposite. The invention is fully applicable to other materials that are processable in a viscous, liquid-like state, such as glass. The invention describes composites, including nanocomposites with controllably oriented particles and interlocking networks that affect the physical properties of the composite including permeability, directional electrical conductivity, and mechanical strength. In addition, the invention describes smart blending technology derived from chaotic advection to controllably form the composite.
BACKGROUNDPlastics in their varied formulations and applications are effectively a part of nearly every element of modern commerce, science and technology. The development and use of polymer blends and composites represent a significant advance through which desired characteristics of two or more components may be combined in a single material.
Among the various methods available to produce plastic components, increased understanding of a new process of blending polymeric constituents of plastic composites has led to novel and improved composites and methods to produce them. Fundamental to one rapidly emerging process is the understanding that particles can be advected along complex paths in even simple flow fields, and the motion over time can become chaotic, a behavior known as chaotic advection, and, because of the newly discovered ability to control the in situ structure development, a process now referred to as smart blending. See U.S. Pat. No. 6,770,340 issued Aug. 3, 2004 to Zumbrunnen and U.S. patent application Ser. No. 10/385,118 (Zumbrunnen et al. filed Mar. 10, 2003), both of which are hereby incorporated by reference in their entirety.
SUMMARY OF THE INVENTIONA purpose of the invention is a composite that reduces gas permeability while retaining suitable characteristics for various types of food product packaging.
A parallel purpose of the invention is a composite that displays directional electrical conductivity. Plastic films with conductive capabilities may find wide and varied uses in the computer/electronic components and packaging industry.
Related purposes of the invention are methods to produce composites suitable for food packaging and methods to produce composites with controlled, directional electrical conductivity.
Additional related purposes include products with increased flexural rigidity and method to produce such products.
These and other goals and purposes of the invention are achieved by a method that controls of the distribution and orientation of particles in a composite and includes steps of selection of an appropriate melt-processable material and a particle, and processing the plastic and particle to yield a master batch, and subsequently processing the master batch utilizing a blender that will instill chaotic advection and after feeding the master batch into the blender, operating the blender for a time to instill chaotic advection, discharging the composite, and processing it into a product; these goals and purposes are further achieved by a composite with oriented particles that increases gas permeability resistance of the composite, a composite with oriented particles that imparts directional electrical conductivity, and a composite with oriented particles that increases the strength of the composite; these goals and purposes are further achieved by method to produce composites with oriented particles by first producing a master batch from a selected, melt-processable material and a particle introducing the master batch to device capable of inducing chaotic advection concurrently introducing to the device a second, melt-processable material, and operating the device to induce chaotic advection for a specified period of time discharging the resulting composite, and processing it for use; these goals and objectives are further achieved by a method of producing a composite in which particles included in a master batch form interconnecting networks that are separated into layers when the master batch is concurrently subjected to chaotic advection with a second, melt-processable material.
BRIEF DESCRIPTION OF THE FIGURES
Overview
Chaotic advection conditions can be accomplished by batch and continuous devices. A continuous flow, smart blender has proved to be very useful in the formation of a variety of composites and provides a basis for explaining smart blending devices and the chaotic advection process as it relates to the production of certain composites.
As used herein with respect to particles, the term clay is used in a broad sense and includes clay in addition to similar, inorganic material that subdivides into small, discrete, flat particles, including, but not limited to graphite and silica. Clay and such other materials are capable of being oriented in composites by chaotic advection. Similarly, the term carbon black with respect to particles is used in a broad sense and includes carbon black as well as other conductive materials in a powder-like form that may form clusters including, but not limited to nickel, iron, and copper. Carbon black and such other particulate materials are capable of forming interconnecting networks in composites by chaotic advection. Particles can vary in size from microns to nanometers.
Melt-processable materials include, but are not limited to nylon, polypropylene, polypropylene-g-maleic anhydride, and linear, low density polyethylene. Additional melt-processable materials include for example other plastics and glass.
Composites comprise at least two components (or melts). Commonly the more prevalent material is designated the major component (or melt), and the other, the minor component. In this invention, the major component may be a master batch comprised of a melt-processable material plus a particle material (such as clay or carbon black). There is no required, second melt-processable material, although composites with particles with and without a second, melt-processable material can be used.
The device 101 illustrates a first flow (melt-processable material) 104 being delivered via a first metering pump 105 to the barrel 102. The second flow (melt-processable material) 106 is similarly delivered by a second metering pump 107 to the barrel 102. The stir rods 103 are driven by independent motors units 108A and 108B. Rotation of the stir rods is a major factor in inducing chaotic advection. By rotating the rods sequentially and periodically and with adequate rotational displacement, chaotic advection arises.
In
The process of chaotic advection is characterized by recursive stretching and folding of compounds in a fluid-like state. When generally immiscible plastics or plastic-like materials are processed, the resulting composite may develop characteristic encapsulates as a function of the degree of exposure to chaotic advection.
When a master batch comprising a melt-processable material and particles is subjected to chaotic advection, the particles may become oriented in the melt-processable material (as is the case with clay), or form inter-connecting networks (as is the case with carbon black). The degree of orientation or network formation and interconnectivity among particles depends on the degree of chaotic advection to which the master batch is exposed.
In an alternative example, a second, melt-processable material may be introduced to the smart blender separately from but simultaneously with a master batch (a melt-processable material plus particles). See
The extent of particle orientation and particle network characteristics in a melt and processing time are related to the number (N) of chaotic advection periods. One period can comprise the separate and sequential rotation of individual stir rods that can be rotated in the same direction. Perturbation strength (u) equals the fraction of a complete rotation for each rod during one period. In the following examples, in which the continuous chaotic advection blender was used, unless otherwise noted, u=3.0. Chaotic advection was induced by the rotation of stir rods. In a preferred configuration (embodiment), rods were rotated by separate stepper motors independently controlled by a computer interface.
Example 1The addition of inorganic materials to plastic with appropriate processing yields plastic material with high barrier properties suitable for many food packaging applications. Clay is a suitable source of particulate material having very thin platelets (approximately 1 nm) and having high frontal area with low mass diffusivity. See Okada, et al., 1997.
The obvious effect of the inclusion of the oriented clay particles on permeability is seen in the comparison of the PP 303 and with the PP and clay not subjected to smart blending 304 and the PP with clay particles subjected to smart blending 305. Clay particle orientation occurs as N increases. Clearly the presence of clay reduces permeability. The reduction in permeability resulting with blending, greater than N=8 306, demonstrates the impact of the chaotic advection process on orienting the platelets thereby pinching paths for diffusion.
In
Blending for the masterbatches of
The inclusion of particles of electrically conductive material in a composite subjected to various levels of smart blending affects the directional conductivity of the composite. Carbon black, CB, may be used as the conductor particle. One skilled in the art recognizes that the phenomenon associated with CB in the composite will be produced by similar conductors including, but not limited to nickel powder, which conductors are included in the scope of the invention. An important, unique property is particles that are oriented or placed into networks in a continuous chaotic advection process are retained in a predictable orientation or network configuration in the extrusion.
The organized distribution of carbon CB in the composite affects a variety of directional electrical properties of extruded composite films,
Resistivity is affected less by percent CB in the composite than by the degree of blending, due in great part to the effects of the networks formed.
The arrangements of CB particles into networks and connecting branches which instill directional electrical properties are illustrated in
Similar results were achieved with carbon black concentrations of about 1.5% to about 6.5% by weight. Processing temperatures ranged from about 175C to 220C. Film edges of extruded films from the smart blender were removed before resistivity measurements were done in accordance with standard procedures.
Example 3
As one skilled in the art recognizes, the basic properties and technology described in Example 1 and Example 3, above, also affect thermal properties of composites. It is widely recognized that similarities in transport mechanisms for electrical conductivity and thermal conductivity exist. The addition of inorganic materials, such as clay particles and the organization generated by the application of smart blending technology yields composites with characteristic and useful thermal transfer properties not expressed in those plastics having random distribution of particles typical conventional mixing methods. Increased stiffness and strength of the material is a widely recognized, additional property resulting from the addition of clay.
In the interest of clarity and precision, specific terms and conditions have been presented in the figures and examples. Such limited terms and conditions are used to aid in understanding and to appreciate more fully the scope and intent of the invention, not as limitations in the interpretation of the following, appended claims which are applications to particles having similar processing characteristics.
Claims
1. A method to produce a composite with controllably oriented particles comprising:
- a. selecting a melt-processable material;
- b. selecting a particle type;
- c. processing said polymer melt and said particle to yield a masterbatch;
- d. feeding said masterbatch into a machine capable of inducing chaotic advection;
- e. discharging the resulting composite following a predefined amount of chaotic advection; and
- f. processing said resultant composite into a product.
2. The method of claim 1 wherein said melt-processable material is polyethylene.
3. The method of claim 1 wherein said particle type is a low permeation material.
4. The method of claim 3 wherein said particle type is a clay.
5. The method of claim 3 wherein said low permeation material is graphite.
6. The method of claim 1 wherein said particle type is an electrical conducting material.
7. The method of claim 6 wherein said electrical conducting material is carbon black.
8. The method of claim 6 where said electrical conducting material is a metal.
9. A method of producing composites with controllably oriented particles comprising the steps of:
- a. selecting a first melt-processable material;
- b. selecting a particle type;
- c. processing said first melt-processable material and particles of said selected particle type to yield a master batch;
- d. selecting a second melt-processable polymer;
- e. feeding said master batch and said second melt-processable material simultaneously into a machine capable of chaotic advection;
- f. operating said machine so as to subject said master batch and said second melt-processable material to a defined amount of chaotic advection to produce a composite with oriented particles;
- g. discharging the resultant composite from said machine; and
- h. processing said discharged composite for a use.
10. A method of producing networks among particles to yield a composite with unique features comprising the steps of:
- a. selecting a first melt-processable material;
- selecting a particle type;
- b. processing said first melt-processable material and particles of said particle type to yield a master batch;
- c. selecting a second melt-processable material;
- d. feeding said master batch and said second melt-processable material simultaneously into a machine capable of inducing chaotic advection;
- e. operating said machine so as to subject said masterbatch and said second melt-processable material to chaotic advection to a degree to produce a composite with networks formed among particles;
- f. discharging the resultant composite from machine; and
- g. processing said discharged composite for use.
11. The method of claim 10 wherein said unique feature is directed to directional electrical conductivity.
12. The method of claim 10 wherein said unique property is electrical conductivity attained at particle concentrations as low as 1%.
13. A composite derived from a masterbatch wherein said masterbatch comprises a first melt-processable material and particles and further wherein said particles are oriented into numerous layers.
14. The composite of claim 13 wherein said first melt-processable material is one of the following materials: nylon, polypropylene, polypropylene-g-maleic anhydride or linear, low density polyethylene.
15. The composite of claim 13 wherein said particles are one of the following (clay, graphite, or silica).
16. A composite derived from a masterbatch wherein said masterbatch comprises a first melt-processable material, and particles, and further wherein said composite further is derived from a second melt-processable material and wherein said particles are oriented into numerous layers.
17. The composite of claim 16 wherein said first melt-processable material is one of the following (nylon, polypropylene, polypropylene-g-maleic anhydride, or low density polyethylene), and said second melt-processable material is one of the following (nylon, polypropylene, polypropylene-g-malaeic acid, or low density polyethylene), and said particles are one of the following (clay, graphite, or silica), and further wherein said particles are oriented into numerous layers.
18. A composite derived from a masterbatch wherein said masterbatch comprises a first melt-processable material and particles wherein said particles form numerous, interconnecting networks.
19. The composite of claim 18 wherein said first melt-processable material is one of the following (nylon, polypropylene, polypropylene-g-maleic anhydride, or low density polyethylene).
20. The composite of claim 18 wherein said particles are one of the following (carbon black, nickel, iron, or copper).
21. A composite derived from a masterbatch wherein said masterbatch comprises a first melt-processable material and particles and further derived from a second melt-processable material wherein said particles form numerous, interconnecting networks.
22. The composite of claim 21 wherein said first melt-processable material is one of the following nylon, polypropylene, propylene-g-maleic anhydride, or low density polyethylene), said second melt-processable material is one of the following (nylon, polypropylene, propylene-g-maleic anhydride, or low density polyethylene), and said particles are one of the following (carbon black, nickel, iron, or copper).
Type: Application
Filed: Oct 1, 2004
Publication Date: May 26, 2005
Inventor: David Zumbrunnen (Seneca, SC)
Application Number: 10/956,753