The invention relates to additives for cellular foams. More particularly, the invention relates to the addition of kinetic mixing particles to a foam for promoting improved dispersion of blowing agents, reactive and non-reactive additives.
In the early 20th century, various types of specially manufactured solid foams came into use. The low density of these foams made them excellent for use as thermal insulators and flotation devices, and their lightness and compressibility made the foams ideal for use as packing materials and stuffing. In the last 40 years foam development has progressed from a simple material into complex, highly advanced, cellular structural materials that are lightweight and durable. These new foam materials are out-performing fiberglass, composites, sheet steel and plastics in a variety of diverse markets including automobiles, agricultural equipment, boats, bathroom showers and tubs, fencing, doors, window frames and decorative molding trim, to mention a few. Today the cellular foam industry continues to strive for product improvements including consistency of the cellular structure, dispersion of formula components, improved strength, and reduced costs.
In the field of fluid dynamics, the boundary layer of a flowing fluid has always been considered fixed and immovable. In the laminar region, the boundary layer creates a steady form of resistance to fluid flow. Applicant's U.S. patent application Ser. No. 12/412,357, entitled, “STRUCTURALLY ENHANCED PLASTICS WITH FILLER REINFORCEMENTS” teaches that the addition of kinetic mixing particles kinetically moves the boundary layer when the fluid is moving, for promoting flow and decreasing film drag. U.S. patent application Ser. No. 12/412,357 is hereby incorporated by reference. The reduction of drag is similar to comparing static friction to the kinetic friction of a moving body and applying it to a fluid flow. Using Applicant's invention, the boundary layer can be moved kinetically, thereby reducing drag and increasing flow. If the fluid is not moving, the inert structural particle, i.e., the kinetic mixing particle, acts like a filler in the nano and micron size range, thereby creating nucleating sites during the foaming process. When the micron nano sized particles are moving, the unique three-dimensional shape of the kinetic mixing particles promotes kinetic mixing of additives and fillers throughout polymer matrix thereby converting a stagnant boundary layer region into a dynamic mixing zone.
The highly specialized particles, i.e., the kinetic mixing particles, may be incorporated into solids such as plastics. In an extruder, the solid is melted. The melted plastic develops a boundary layer over the entire surface area of the screw and barrels in a high shear environment. The boundary layer kinetic mixing is activated whenever and wherever the fluid is moving. In the case where the material is a fluid, such as a polyurethane, the materials can be mixed using simple agitation, such as a turbine mixer or an advanced impinge jet mixing system. In both cases, movement of the particles is activated due to fluid movement. Initial kinetic mixing occurs as the components are being mixed using high shear. As the fluid moves, kinetic mixing is propagated.
Applicant's invention directly improves all four categories of consistency of the cellular structure, dispersion of formula components, improved strength, and reduced costs through the use of inert micro and nano sized structural particles.
The method of the invention provides a unique solution to the above mentioned problems. The addition of the kinetic mixing particles of the invention provides kinetic mixing of the boundary layer, which produces a homogenous dispersion with micro and nano mixing that allows for reduction of expensive additives that may be environmentally damaging while still maintaining benefits associated with the additives. The technology of the invention uses environmentally safe, chemically stable solid particles to continuously mix materials as long as the fluid is flowing.
The addition of kinetic mixing particles results in improvements in boundary layer mixing, i.e., the invention relates to the effects of structural mechanical fillers on fluid flow, wherein the particles have sizes ranging from nano to micron. In particular, the size ranges of the particles are preferably from approximately 500 nm to 1μ, and more preferably, from 1μ to 30μ. However, any sub ranges within the defined ranges are also contemplated as being effective. The invention uses the principles of boundary layer static film coupled with frictional forces associated with a particle being forced to rotate or tumble in the boundary layer due to fluid velocity differentials. As a result, kinetic mixing is promoted through the use of the kinetic mixing or structural particles.
As an example, consider that a hard sphere rolling on a soft material travels in a moving depression. The soft material is compressed in front of the rolling sphere and the soft material rebounds at the rear of the rolling sphere. If the material is perfectly elastic, then energy stored during compression is returned to the sphere by the rebound of the soft material at the rear of the rolling sphere. In practice, actual materials are not perfectly elastic. Therefore, energy dissipation occurs, which results in kinetic energy, i.e., rolling. By definition, a fluid is a material continuum that is unable to withstand a static shear stress. Unlike an elastic solid, which responds to a shear stress with a recoverable deformation, a fluid responds with irrecoverable flow. The irrecoverable flow may be used as a driving force for kinetic mechanical mixing in the boundary layer. By using the principle of rolling, kinetic friction and an increase of fluid sticking at the surface of the no-slip zone, adherents are produced. Fluid flow that is adjacent to the boundary layer produces an inertial force upon the adhered particles. Inertial force rotates the particles along the surface of mechanical process equipment regardless of mixing mechanics used, i.e., regardless of static, dynamic or kinetic mixing.
Geometric design or selection of structural particles is based on the fundamental principle of surface interaction with the sticky film in the boundary layer where the velocity is zero. Mechanical surface adherence is increased by increasing particle surface roughness. Particle penetration deep into the boundary layer produces kinetic mixing. Particle penetration is increased by increasing sharpness of particle edges or bladelike particle surfaces. A particle having a rough and/or sharp particle surface exhibits increased adhesion to the non-slip zone, which promotes better surface adhesion than a smooth particle having little to no surface characteristics. The ideal particle size will differ depending upon the fluid due to the viscosity of a particular fluid. Because viscosity differs depending on the fluid, process parameters such as temperature and pressure as well as mixing mechanics produced by shear forces and surface polishing on mechanical surfaces will also differ, which creates a variation in boundary layer thickness. A rough and/or sharp particle surface allows a particle to function as a rolling kinetic mixing blade in the boundary layer. Hardened particles having rough and/or sharp edges that roll along a fluid boundary layer will produce micro mixing by agitating the surface area of the boundary layer.
Solid particles used for kinetic mixing in a boundary layer, i.e., kinetic boundary layer mixing material or kinetic mixing material, preferably have following characteristics:
Particles should have a physical geometry characteristic that allows the particle to roll or tumble along a boundary layer surface.
Particles should have a surface roughness sufficient to interact with a zero velocity zone or a non-slip fluid surface to promote kinetic friction rather than static friction. The mixing efficiency of particles increases with surface roughness.
Particles should be sufficiently hard so that the fluid is deformed around a particle for promoting kinetic mixing through the tumbling or rolling effect of the particle.
Particles should be size proportional to the boundary layer of a fluid being used so that the particles roll or tumble due to kinetic rolling friction.
Particles should not be too small. If the particles are too small, the particles will be caught in the boundary layer and will lose an ability to tumble or roll which increases friction and promotes mechanical wear throughout the contact zone of the boundary layer.
Particles should not be too large. If the particles are too large, the particles will be swept into the bulk fluid flow and have a minimal, if any, effect on kinetic boundary layer mixing. The particles should have size and surface characteristics, such as roughness and/or sharp bladelike characteristics, to be able to reconnect in the boundary layer from the bulk fluid during the mixing process.
Particles can be solid or porous materials, manmade or naturally occurring minerals and or rocks.
Physical Geometry of Particles:
Particle shapes can be spherical, triangular, diamond, square or etc., but semi-flat or flat particles are less desirable because they do not tumble well. Semi-flat or flat particles tumble less well because the cross-sectional surface area of a flat particle has little resistance to fluid friction applied to its small thickness. However, since agitation in the form of mixing is desired, awkward forms of tumbling are beneficial since the awkward tumbling creates dynamic random generated mixing zones at the boundary layer. Random mixing zones are analogous to mixing zones created by big mixing blades operating with little mixing blades. Some of the blades turn fast and some of the blades turn slow, but the result is that the blades are all mixing. In a more viscous fluid, which has less inelastic properties, kinetic mixing by particles will produce a chopping and grinding effect due to particle surface roughness and due to sharp edges of the particles.
Spherical particles having extremely smooth surfaces are not ideal for the following reasons. First, surface roughness increases friction between the particle and the fluid, which increases the ability of the particle to remain in contact with the sticky and/or the non-slip zone. In contrast, a smooth surface, such as may be found on a sphere, limits contact with the sticky layer due to poor surface adhesion. Second, surface roughness directly affects the ability of a particle to induce mixing through tumbling and/or rolling, whereas a smooth surface does not. Thirdly, spherical shapes with smooth surfaces tend to roll along the boundary layer, which can promote a lubricating effect. However, spherical particles having surface roughness help to promote dynamic mixing of the boundary layer as well as promote lubricating effects, especially with low viscosity fluids and gases.
Advantages of Adding Kinetic Mixing Materials to Polymers Include:
The kinetic mixing material of the invention will help meet current and anticipated environmental regulatory requirements by reducing the use of certain toxic additives and replacing the toxic additives with an environmentally friendly, inert solid, i.e., with a kinetic mixing material that is both chemically and thermally stable.
FIG. 32C shows a base polystyrene foam with direct gas injection, wherein the weight % of additives is 0.35 wt % wherein the cells sizes include cells of 217 microns.
The introduction of kinetic mixing particles results in excellent dispersion capabilities, as illustrated by
Mixing and Blending of Dissimilar Materials
Image 2 of
Typically, additives in polymers are used to promote durability. However, in the case of fire retardants, fillers, de-foamers, surface tension modifiers and biocides etc., fillers often have a negative effect on the polymer, which produces fatigue throughout the cross-linked polymer system. The addition of kinetic mixing particles does more than improve mixing. The addition of kinetic mixing particles mechanically reduces the size of additives, which produces better interaction in the polymer matrix. Therefore, by reducing the size of additives and improving dispersion, the amount of additives can be reduced. This homogenous mixing characteristic increases cross-linking strength of the polymer by reducing the amount of additives needed to produce the desired result.
In a reactive two-component foam, the addition of kinetic mixing particles will help mix the liquid-to-liquid interface, which promotes better cross linking throughout the polymer. The additive of kinetic mixing particles will additionally improve adhesive strength and impart better flow properties.
As can be seen by reference to
A static mixing test was conducted for dual component reactive materials, the results of which can be seen in
Material: Loctite two component 60 min. epoxy, 2 pigments, i.e., one yellow one green was used.
Equipment: Standard 50 mL dual caulking gun with ¼ inch diameter 6 inch long disposable static mixer tip was used.
Experiment Set Up:
100 ml of epoxy was reacted mixed and a small amount of yellow pigment was mixed in;
100 ml of epoxy was reacted mixed and a small amount of green pigment was mixed in:
The two 100 ml reacted epoxies with pigment within was then split in half. 50 ml of yellow reacted epoxy was put in one half of a single dual component cartridge in a static mixer. In the other half of the static mixer, 50 ml of green reacted epoxy was located in the single dual component cartridge.
The 50 ml yellow reacted epoxy had 1% by mass kinetic mixing particles hand mixed therein. The yellow reacted epoxy was put in one half of the static mixer cartridge. 50 ml green reacted epoxy had 1% by mass kinetic mixing particles hand mixed therein. The 50 ml green reacted epoxy was then placed in the other side of the dual component cartridge. The mixing process was conducted for approximately 5 minutes before the material was ejected out of the static mixer at the same low rate. The static mixing tubes were then allowed to be fully cured. The tubes were then cut in half using a water jet cutter. As can be seen by reference to
Application in Foam Technologies
When the highly specialized structural material of the invention, i.e., the kinetic mixing particles, is incorporated with a foaming technology, the unique characteristics of kinetic mixing do not stop when a mixing step is complete. The kinetic mixing particles continue to remain active as fluids move during the expansion process. The post mixing step particle activity promotes better dispersion of blowing agents as well as increased mobility through better dispersion of reactive and nonreactive additives throughout the polymer during expansion of the foam. The better dispersion and increased mobility result in improved cellular consistency. The unique characteristic shape of three-dimensional, pointed, blade-like structures of the kinetic mixing particles produces excellent nucleation sites, thereby increasing cellular wall consistencies and strength.
It is desirable to reduce cell sizes of a foam from a 700-1000 micron sized cellular structure to 10 microns and lower. This breakthrough would allow the industry to make lighter, stronger foams than have ever been commercially available.
In a gas injected foam process using gases such as (N2, CO2, Ar, etc.), the most difficult part of the process is to dissolve the gases into the molten plastic or reactive material. Different gases have different solubility constants with different polymers.
Solubility Constants
Variation of solubility constants results in inconsistencies in gas loading of various materials. Structural and thermal variations are caused by the inconsistent cellular structures where the foam has produced both large and small cell sizes. Attempts to overcome these difficulties include increasing extruder length or using multiple extruders to increase dispersion time for mechanical mixing. The addition of kinetic mixing particles incorporates nano and micron size three-dimensional hard structural particles. Kinetic mixing particles produce micro and nano size mechanical openings in the plastic during the mixing process. The openings allow gas dispersion into the polymer, thereby greatly reducing mixing time and the effects of gas solubility. The three-dimensional, kinetic mixing particles of the invention can be tailored to have a variety of sizes and shapes where the structural features, such as blade length, cavity depth, particle void size, protruding member size, spine-like structure length, etc., can produce cells in foam of a desired size.
For example, a study was conducted wherein type I kinetic mixing particles were used and critical CO2 gas was added into polypropylene with various concentrations of type I kinetic mixing particles. The results may be seen in
The relationship between the particles and the resulting cell size is a function of surface characteristics of the kinetic particle being used.
For example, using the previously mentioned gas injected testing to illustrate particle size characteristics in relationship to cell formation, when an expanded perlite particle with the appropriate kinetic boundary layer mixing surface characteristics rolls and tumbles in kinetic motion, the perlite particle will produce low surface energy regions in the polymer that are proportional in size to a void cavity of the particle where the vertex of the void forms a very small angle. In one embodiment, i.e., where the void is defined by a hyperbolic surface, the vertex becomes infinite, in the same manner as the vertices of a non-conformal hyperbolic triangle. Expanded perlite having the characteristics of a type I mixing particle looks like the fletching on the back in of an arrow, i.e., the particle possesses three-dimensional bladelike characteristics, which allows bubble formation in between blades. The bubble will stay adhered to the bladelike structure until resistance forces applied by the fluid overcomes adhesive forces of the expanding and protruding bubble forming on the kinetic boundary layer mixing particle. The example above discussed an average mean particle size of 30μ. Therefore, the particle radius in this example is 15μ. A bubble will release from a type I kinetic mixing particle at approximately three times the radius. The 3:1 relationship changes depending on the types of kinetic mixing particles because the geometric contact between surfaces directly affects the adhesive forces of the bubble. Therefore, different geometric configurations change the surface to fluid removal energy to produce bigger or smaller cell sizes. The dynamics of the mixing and the selection of polymers and additives will have a significant effect on fluid force applied to the kinetic mixing particles to overcome the adhesive force of the bubble on a surface of the kinetic mixing particle, which can vary from application to application. A general rule of thumb is that the desired bubble size, i.e., foam void size, is expected to be from 0.025 to 8 times larger than the particle size diameter and/or of a protruding arm of a particle. For particle type 1, we expect the void size to be 1-8 times larger than the particle size diameter and/or of a protruding arm of a particle.
The addition of Applicant's kinetic mixing particles improves four areas of current foam technology: 1. Consistency of the Cellular Structure; 2. Dispersion of Formula Components; 3. Improved Strength; 4. Reduced Costs. These four areas of impact will be discussed below.
Consistency of Cellular Structure
The kinetic mixing particles of the invention have unique characteristics including three-dimensional, sharp points, blade-like, holes, cavities, protruding arms, spine-like characteristics, jagged edges, smooth corners, etc., shape. As these kinetic mixing particles move with the fluid during foam expansion, the edges produce excellent nucleation sites that cause the fluid to expand in such a way as to increase the consistency of the cellular structure. This can be seen in
Dispersion of Formula Components
The boundary layer kinetic mixing particle type I made from expanded perlite resulted in better dispersion of all formula components, including blowing agents, throughout the polymer without changing chemical properties of the formula. Even during post-extruder expansion, the particles continue to influence the foam through mixing, thereby creating better dispersion of formula components throughout the polymer.
Improved Strength
An Izod impact strength test was conducted on polypropylene foam at standard at ½″ Izod profiles:
Polypropylene with 1%* Blowing Agent=7.14 g
Polypropylene with 1%* Blowing Agent+1%* Additive=8.11 g
*by formula weight
The improved dispersion of formula components combined with the improved cellular makeup of the foam structure, produced by the introduction of the type I kinetic mixing particles, resulted in a 13.5% increase in impact strength.
Reduced Cost
Weight reduction analysis on polypropylene foam, standard ½″ Izod profiles
Polypropylene with 1%* Blowing Agent=21.5 g
Polypropylene with 1%* Blowing Agent+1%* Additive=13.5 g
*by formula weight
The improved dispersion of formula components combined with the improved cellular makeup of the foam structure, produced by the introduction of the kinetic mixing particles, resulted in a 25.0% reduction in the weight of the same geometrically shaped part.
The benefits of application of kinetic mixing particles are not limited to application in foam plastics such as polypropylene, polyethylene, polystyrene, PVC, ABS, etc.; nor are the benefits limited to reactive foams such as single component urethanes, plural component urethanes, epoxies, ureas, etc. The addition of kinetic mixing particles will produce similar results in any structural foam material that uses endothermic blowing agents, an exothermic blowing agents, nitrogen or CO2 gas foam injection systems.
size
1
2
3
4
5
Injection Pressure
Time
Pressure
indicates data missing or illegible when filed
Chemical Blowing Agents
The particles of the invention provide a mechanical assistance to commercially used blowing agents in three ways. The first is increased dispersion of the blowing agents produced by nano and micro mechanical mixing. The second is the nano and micron size perforations that occur during mixing that allow dispersion of chemical blowing agents into the polymer. The third is nano and micro mechanical kinetic blending process that lowers the surface tension in the mixing zone giving mechanical blowing agents the ability to nucleate more freely. These kinetic mixing particles can also be commercially incorporated into a blowing agent formulation through a coating and/or doping process to produce the same results. The base particle can be used to produce better blowing agents.
Nucleation Sites
There have been a variety of materials that have been used to produce better nucleation and more unified cell sizes. The most common commercially used material is talc along with some more exotic materials such as nano clay and carbon nano tubes. There has been a lot discussion and debate over of the nucleation particle size to foam cell size relationship.
The technology of the invention focuses on a fundamental principle of geometrical shapes to increase nucleation sites by promoting low surface energy inside a polymer. Lowered surface energy of a fluid surrounding a particle is produced by a geometrical shape having a very sharp vertex. In one embodiment, i.e., where the void is defined by a hyperbolic surface, the vertex becomes infinite in the same manner as the vertices of a non-conformal hyperbolic triangle. These geometrical shapes include, but are not limited to points, sharp edges and accessible internal structures, voids or pockets whose geometric shapes produce corners, diamonds, triangles etc.
Polymers are chain-like materials that naturally bend over surfaces and around particles in a manner similar to water flowing down a river. The more abrupt the shape of the particle, the greater turbulence that is produced. For example, consider rocks in a river, where smooth rocks create little to no turbulence while rocks that have abrupt edges and cavities produce lots of turbulence. The turbulence creates an area or region of low surface energy. Low surface energy areas allow for nucleation sites to occur. Nucleation sites are the beginning of bubble formation that turns into a chain reaction of cell formation throughout the polymer.
Discussion of the geometric shapes of commonly used nucleation materials and new materials that are being developed follows.
Talc: flat plate-like shape, held together by weak Vander Wal forces which allows material to cleave during high shear. Talc can be processed into small particle sizes and may or may not have sharp or jagged edges depending on processing conditions.
Nano Clay: irregular shape, most likely spherical or cylindrical having an aspect ratio of approximately one. Nano clay is a hard organic and can be processed in nano size shapes.
Carbon nanotubes: cylindrical shaped or fiber-like. Carbon nanotubes are strong and are molecularly produced.
All of the above mentioned materials have attributes that produce low energy regions in a flowing fluid thereby stimulating adjacent nucleation sites based on size and geometry. For example, nano-sized particles promote low energy regions because long chain polymers have difficulty bending around a small radius. Therefore nano-sized particles produce small regions around particles for nucleation sites. A difficulty with nano materials is related to difficulties associated with dispersing the small particles uniformly throughout the polymer. Uniform dispersion is crucial to producing low surface energy regions based on particle radius in relationship of polymer bending. If the nano particles stay in conglomerated regions, the conglomerations may not produce low surface energy regions suitable for nucleation sites. Additionally, conglomerations make it difficult to calculate predictable nucleation based on nano particle count.
Talc has unique physical properties. Talc is not a rigid solid. Talc is held together by weak Vander Wal forces and is used in many cases as a lubricant. The natural shape of talc is thin small plate-like structures that undergo transformation of physical shape when under high pressure and shear produced by an extruder. Talc can be used to produce low energy sites by edge effects coupled with lubricating properties throughout the polymer. Talc is not a structural material. Therefore, talc changes size and shape within a extrusion process with different polymers because of the mechanical load imparted upon talc particles, making it difficult to accurately predict nucleation outcome, unlike talc. Applicant's kinetic mixing particles are ideal for nucleation sites because surface characteristics are predictable and repeatable based on their dispersability and structural integrity throughout a polymer, regardless of operating parameters inside the extruder.
Applicant's kinetic mixing particles are rigid structural particles with diverse surface characteristics that produce repeatable low surface energy interaction regardless of polymer or shear effects that are applied. Kinetic mixing particles are self-dispersing, which overcomes the complication of using nano materials as nucleation sites.
Method of Application
The additive, i.e., the kinetic mixing particles, can be incorporated into a plastic or foam formula in different ways, including:
1. Directly into plastic pellets from a manufacturer or a compounding company at total formula weight percent of 0.20% to 70.0%
2. Compounded as an additive with a blowing agent from the manufacturer of a blowing agent in powder or granular form.
3. Fed into a plastic or foam mixture as a raw powder or as a specialized, compounded plastic pellet for feeding directly into the extruder using a hopper system to control percent loading.
4. Incorporated as a dry powder directly into fluids prior to the fluids being mixed or during the mixing process.
An example formulation of a blowing agent and a description of the equipment used to process may be found in Table 1.
Particle Type I
Particle type I embeds deep into the boundary layer to produce excellent kinetic mixing of foam constituent fluids in both the boundary layer and in the mixing zone. Type I particles increase dispersion of chemical and mineral additives. Type I particles increase fluid flow. The surface area of Type I particles is large compared to the mass of Type I particles. Therefore Type I particles stay in suspension well. In one example, a type (I) kinetic mixing particle is made from expanded perlite with a Mohs scale hardness of 5.5 (equivalent to a high-quality steel knife blade). For effectiveness, particles of all types preferably have a hardness of 2.5 or higher on the Mohs scale.
Referring to
Referring to
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Particle Type II
Particle type II achieves medium penetration into a boundary layer for producing minimal kinetic boundary layer mixing and minimal dispersion capabilities. Type II particles result in minimal fluid flow improvement and are easily suspended due to the large surface and extremely low mass of Type II particles.
The majority of materials that form hollow spheres can undergo mechanical processing to produce egg shell-like fragments with surface characteristics to promote kinetic boundary layer mixing.
Referring now to
Referring now to
Referring now to
Referring now to
Particle Type III
Particles categorized as Particle type III exhibit minimal penetration into a boundary layer. Type III particles exhibit minimal kinetic mixing in the boundary layer and have excellent dispersion characteristics with both soft chemical and hard mineral additives. Type III particles increase fluid flow and do not suspend well but are easily mixed back into suspension. Some solid materials have the ability to produce conchordial fracturing to produce surface characteristics that promote kinetic boundary layer mixing.
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Particle Type IV
Some solid clustering material have the ability to produce fracturing of the cluster structure to produce individual unique uniform materials that produce surface characteristics that promote kinetic boundary layer mixing.
Referring now to
Referring now to
Referring now to
Particle Type V
Particles of Type V result in medium penetration into the boundary layer. Type V particles create medium kinetic mixing of the boundary layer similar to a leaf rake on dry ground. Type V particles have excellent adhesive forces to the gluey region of the boundary layer, which is required for two-phase boundary layer mixing. Particle of Type V produce minimal dispersion of additives. Therefore, addition of Type V particles increases fluid flow and the particles will tend to stay in suspension. Some hollow or solid semi-spherical clustering material with aggressive surface morphology, e.g., roughness, groups, striations and hair-like fibers, promote excellent adhesion to the boundary layer with the ability to roll freely and can be used in low viscosity fluids and phase change materials, e.g., liquid to a gas and gas to a liquid. Type V particles possess the desired surface characteristics to promote boundary layer kinetic mixing.
Referring now to
Particle Type VI
Referring now to
Referring now to
Referring now to
Thus, the present invention is well adapted to carry out the objectives and attain the ends and advantages mentioned above as well as those inherent therein. While presently preferred embodiments have been described for purposes of this disclosure, numerous changes and modifications will be apparent to those of ordinary skill in the art. Such changes and modifications are encompassed within the spirit of this invention as defined by the claims.
This application is a Continuation of U.S. Utility patent application Ser. No. 13/217,200, titled, “CELLULAR FOAM ADDITIVE”, filed Aug. 24, 2011, which claims the priority of U.S. Provisional Patent Application No. 61/376,607 entitled “CELLULAR FOAM ADDITIVE,” filed Aug. 24, 2010, and this application also claims the priority of U.S. Provisional Patent Application No. 61/392,558 entitled “CELLULAR FOAM ADDITIVE,” filed Oct. 13, 2010, and this application additionally claims the priority of U.S. patent application Ser. No. 13/181,476, entitled “BOUNDARY BREAKER PAINT, COATINGS AND ADHESIVES,” filed Jul. 12, 2011, the contents of each of which are hereby incorporated by reference.
Number | Date | Country | |
---|---|---|---|
61376607 | Aug 2010 | US | |
61392558 | Oct 2010 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13217200 | Aug 2011 | US |
Child | 16726472 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13181476 | Jul 2011 | US |
Child | 13217200 | US |