Title of Invention

SINTERED POLYMERIC MATERIALS AND METHOD OF MAKING THE SAME

Abstract According to the invention there is provided a composition capable of being used to form an applicator,a filtration medium, or a barrier medium, comprising: a sintered porous polymeric material consisting of a sintered mixture of particles of at least one plastic and particles of at least one thermoplastic elastomer, the sintered porous polymeric material having a porosity ranging from 20% to 80% and a rigidity of less than 5 pounds, wherein the at least one plastic is selected from the group consisting of polyethylene, polypropylene, polyesters, polycarbonates, polyvinylidene fluoride, polytetrafluoroethylene,polyethersulfones, polystyrenes, polyether imides, polyetheretherketones, and polysulfones and combinations thereof, and wherein the at least one thermoplastic elastomer is selected from the group consisting of thermoplastic polyurethanes, polyisobutylene, polybutenes, polyethylene- propylene copolymer, polyethylene-butene copolymer, polyethylene-octene copolymer, polyethylene- hexene copolymer, chlorinated polyethylene, chloro-sulfonated polyethylene, styrene-ethylene- butadiene-styrene, and 1,3-dienes and combinations thereof. There is provided also a method of producing a sintered porous polymeric material.
Full Text


RELATED APPLICATION DATA
The present application hereby claims priority under 35 U.S.C. § 119(e) to United
States Provisional Patent Application Serial Number 60/838,571 filed August 18, 2006,
United States Provisional Patent Application Serial Number 60/838,572 filed August 18,
2,006, United States Provisional Patent Application Serial Number 60/876,739 filed
December 22, 2006, and United States Provisional Patent Application Serial Number
60/900,817 filed February 12, 2007.
FIELD. OF THE INVENTION
The present invention relates generally to sintered polymeric materials and methods
of making and using the same.
BACKGROUND OF THE INVENTION
Tips or nibs used in applicators, such as highlighters, pens, cosmetic applicators, and
medicament applicators, are typically constructed of felt or thermoplastic fibrous materials
including nylon, acrylic, and polyester fibers. Tips or nibs constructed of these materials
have good mechanical strength, increasing their resistance to fracture. Moreover, such tips or
nibs demonstrate good flow properties of various liquids and have high flexibilities making
them suited for use in marking, writing, and other applications.
Several disadvantages, however, exist with felt and fibrous nibs. One disadvantage is
the difficulty encountered in producing felt and fibrous nibs having relatively complicated
shapes required by various applications. A related disadvantage is that felt and fibrous nibs
cannot be produced in a single step. Multi-step production increases costs and places
limitations on the various designs felt and fibrous nibs can assume. A farther disadvantage is
realized upon use of felt and fibrous nibs. Felt and fibrous materials can become frayed and
dissociate over the hfe of the nib. Similarly, fibers can dissolve in the solvent of inks leading
to weakening of the nib and further contributing to fraying.
Furthermore, the performance characteristics of applicators comprising felt and
fibrous nibs suffer with the deterioration of the felt and fibrous materials. Fraying and other
dissociative processes can drastically affect the fineness of an applicator making use thereof
difficult and frustrating. Additionally, dissolution of fibers in ink solvents can further
complicate matters by leading to excessive ink loss and bleeding.

In view of the foregoing problems and disadvantages, it would be desirable to provide
materials demonstrating advantageous mechanical and chemical properties operable to be
used as applicators.
Additionally, porous polymeric materials find application and play critical roles in
numerous fields. Porous polymeric materials have been widely used in filtration and fluid
barrier applications. Current filtration devices often comprise a housing with a polymeric
filtration medium disposed in fluid passageways through the housing. As fluid enters the
housing, it passes through the filtration medium to remove compositions from the fluid
stream. Fluids, as used herein, refer to gases, liquids, or combinations thereof. The efficacy
of a filtration device depends on several factors including the ability of the filtration medium
to maintain a sufficient seal with the housing to prevent fluid from circumventing the
filtration medium.
Fluid circumventing the filtration medium causes significant problems, especially
when the filtration medium also serves as a barrier to selected fluids, such as aqueous
solutions. Fluid circumventing the filtration medium can contaminate downstream apparatus
and processes leading to inconvenience, corrosion and costly repairs of equipment. Pipette
devices, for example, often comprise a filtration or barrier medium which allows the passage
of fluids such as gasses but prevents the passage of liquids which can contaminate the pipette.
Contamination of a pipette by fluids circumventing or bypassing the filtration or barrier
medium often requires destruction or decontamination of the pipette due to the potential for
subsequent contamination of other solutions.
One disadvantage of present porous polymeric filtration and barrier media is their
rigid nature making it difficult to form sufficient seals with housings. This is especially true
when either or both the housing and filtration medium have defects resulting from
manufacturing or assembly processes. Precise tolerances must therefore be maintained in
producing filters comprising filtration media disposed in housings. The requirement of
precise tolerances often results in the rejection of a significant amount of product in addition
to the potential for the filtration medium to fall out of the housing or otherwise assume an
incorrect position within the housing.
In view of the foregoing problems, it would be desirable to provide filtration and
barrier media operable to form sufficient seals with housings to prevent fluid bypass without
being subjected to the precise tolerances required by present filtration apparatus.


SUMMARY
Sintered Polymeric Materials
The present invention provides sintered polymeric materials and methods of making
and using the same. Sintered polymeric materials of the present invention can demonstrate
advantageous chemical and mechanical properties, such as resistance to solvents and
increased flexibilities, thereby facilitating application of these materials in a variety of fields,
including their use in applicators and filtration and barrier media.
In one embodiment, the present invention provides a composition comprising a
sintered polymeric material comprising at least one elastomer. In another embodiment, the
present invention provides a composition comprising a sintered polymeric material
comprising at least one plastic and at least one elastomer. In a further embodiment, the
present invention provides a continuous sintered polymeric material comprising a flexible
region and a rigid region, wherein the flexible region comprises a first plastic and at least one
elastomer, and the rigid region comprises a second plastic.
In another aspect, the present invention provides methods of producing polymeric
materials. In one embodiment, a method of producing a polymeric material comprises
providing particles of at least one plastic, providing particles of at least one elastomer, and
sintering the plastic particles and elastomer particles. In another embodiment, a method of
producing a polymeric material comprises disposing particles of a first plastic mixed with
particles of at least one elastomer in a first part of a mold, disposing particles of a second
plastic in a second part of the mold adjacent to the first part of the mold, and sintering the
first plastic particles, second plastic particles, and elastomer particles.
Applicators
The present invention additionally provides applicators comprising sintered polymeric
materials as well as methods of making applicators and using the same. Applicators
comprising sintered polymeric materials of the present invention can be made into
complicated shapes and are resistant to fraying and other dissociative processes common to
felt and fibrous applicators.
In one embodiment, the present invention provides an applicator comprising a
sintered polymeric material, the sintered polymeric material comprising at least one plastic
and at least one elastomer. In another embodiment, the present invention provides an
t applicator comprising a continuous sintered polymeric material comprising a flexible region
and a rigid region, the flexible region comprising a first plastic and at least one elastomer, and
the rigid region comprising a second plastic.


The present invention, in another aspect, provides an applicator comprising a sintered
porous polymeric component and a fibrous component coupled to the sintered porous
polymeric component. In some embodiments, the sintered porous polymeric component
comprises at least one plastic. In other embodiments, the sintered porous polymeric
component comprises a plurality of plastics. In a further embodiment, a sintered porous
polymeric component further comprises at least one elastomer. In some embodiments, an
applicator further comprises a reservoir coupled to the fibrous component. In other
embodiments, the fibrous component serves as the reservoir.
In another aspect, the present invention provides an applicator comprising a
continuous sintered porous polymeric component comprising a flexible region and a rigid
region, wherein the flexible region comprises a first plastic and at least one elastomer, and the
rigid region comprises a second plastic. A fibrous component is coupled to the continuous
sintered porous polymeric component. In some embodiments, a reservoir is coupled to the
fibrous component. In other embodiments, the fibrous component serves as the reservoir.
In some embodiments, sintered polymeric materials of applicators further comprise at
least one color change indicator. A color change indicator, according to embodiments of the
present invention, is operable to at least partially change the color of the sintered polymeric
material when contacted with an aqueous and/or organic liquid or composition. In some
embodiments, a color change indicator changes the sintered porous material of an applicator
from a first color to a second color when contacted with an aqueous and/or organic liquid or
composition. In other embodiments, the color change indicator changes the sintered
polymeric material from colorless or white to colored. The color change of the sintered
polymeric material, according to embodiments of the present invention, depends on the
identity of the color change indicator selected. The change in color provides a user an
indication that the applicator has contacted a composition for subsequent application of the
composition to a surface. In some embodiments, a color change indicator comprises a dye
including, but not limited to, organic dyes such as food dyes.
Applicators of the present invention, in some embodiments, can be used in writing,
cosmetic, healthcare, and/or industrial applications.
Methods of Producing Applicators
The present invention additionally provides methods of producing applicators
comprising sintered porous polymeric materials. In one embodiment, a method of producing
an applicator comprises providing particles of at least one plastic, providing particles of at
least one elastomer, and sintering plastic and elastomer particles. In another embodiment, a


method of producing an applicator comprises providing a sintered porous polymeric
component, providing a fibrous component, and coupling the fibrous component to the
sintered porous polymeric component. In some embodiments, the sintered porous polymeric
component comprises at least one plastic and at least one elastomer. Providing a sintered
porous polymeric component comprising at least one plastic and at least one elastomer, in
some embodiments, comprises providing particles of at least one plastic, providing particles
of at least one elastomer, and sintering the plastic particles and elastomer particles. In some
embodiments, at least one color change indicator is added to the plastic and elastomer
particles and sintered with the plastic and elastomer particles.
Moreover, in some embodiments, coupling the fibrous component to the sintered
porous polymeric component comprises inserting the fibrous component into the sintered
porous polymeric component. In other embodiments, coupling the fibrous component to the
sintered porous polymeric component comprises inserting the sintered porous polymeric
component into the fibrous component. In some embodiments, a method of producing an
applicator further comprises coupling a reservoir to the fibrous component.
In another embodiment, a method of producing an applicator comprises providing a
continuous sintered porous polymeric component comprising a flexible region and a rigid
region, providing a fibrous component, and coupling the fibrous component to the continuous
sintered porous polymeric component. In some embodiments, the flexible region of the
continuous sintered porous polymeric component comprises a first plastic and at least one
elastomer, and the rigid region comprises a second plastic. In some embodiments, providing
a continuous sintered porous polymeric component comprising a flexible region and a rigid
region comprises disposing particles of a first plastic mixed with particles of at least one
elastomer in a first part of a mold, disposing particles of a second plastic in a second part of
the mold adjacent to the first part of the mold, and sintering the first plastic particles, the
second plastic particles, and the elastomer particles. In some embodiments, at least one color
change indicator is added 19 the first plastic particles, second plastic particles, and/or
elastomer particles and sintered.
In some embodiments, coupling a fibrous component to the continuous sintered
porous polymeric component comprises inserting the fibrous component into the continuous
sintered porous polymeric component. In other embodiments, coupling the fibrous
component to the continuous sintered porous polymeric component comprises inserting the
continuous sintered porous polymeric component into the fibrous component. In some


embodiments, a method for producing an applicator further comprises couplmg a reservoir to
the fibrous component.
Methods of Applying a Composition to a Surface
In a further aspect, the present invention provides methods of applying a composition
to a surface. A method of applying a composition to a surface, in one embodiment,
comprises providing an applicator comprising a sintered polymeric material comprising at
least one plastic and at least one elastomer, disposing at least a portion of a composition on
the applicator, and contacting a surface with the composition on the applicator.
In another embodiment, a method of applying a composition to a surface comprises
providing an applicator comprising a sintered porous polymeric component and a fibrous
component coupled to the sintered porous polymeric component, disposing at least a portion
of a composition on the applicator, and contacting a surface with the composition on the
applicator. In some embodiments, the sintered porous polymeric component comprises at
least one plastic and at least one elastomer. In other embodiments, the sintered porous
polymeric component comprises a flexible region continuous with a rigid region, the flexible
region comprising a first plastic and at least one elastomer, and the rigid region comprising a
second plastic.
In some embodiments of applying a composition to a surface, disposing at least a
portion of the composition on the applicator comprises passing the composition through the
fibrous component to an exterior surface of the sintered porous polymeric component.
In some embodiments, a composition can comprise an ink, paint, cosmetic, or
pharmaceutical composition. In other embodiments, a composition can comprise
anticorrosion materials, UV-protectants, and other chemicals used in industrial applications.
Filtration Media and Barrier Media
The present invention additionally provides filtration and barrier media comprising
sintered porous polymeric materials of the present invention and methods of making and
using the same. Filtration media, according to embodiments of the present invention, are
operable to pass liquids and gases to filter contaminants or other desired species in the liquids
or gases. When a liquid or gas flows through a filtration medium of the present invention,
contaminants or other desired species, such as target molecules or substances, become
associated with the filtration medium and are removed from the liquid or gas.
Barrier media, according to some embodiments of the present invention, however,
permit the passage of gases but inhibit and/or prevent the flow of liquids through the media.
By permitting the passage of gasses and inhibiting and/or preventing the passage of liquids,


including organic and/or aqueous liquids, barrier media of the present invention can protect
downstream equipment and processes from contamination resulting from contact with
undesired fluids. Barrier media of the present invention, for example, can serve as in-line
barrier media in a pipe or a tube to prevent liquid flow through the pipe or tube. In another
embodiment, barrier media can be placed in pipette tips and act as pipette tip filters to prevent
pipetted fluid from contaminating the pipettor.
Filtration and barrier media comprising sintered polymeric materials of the present
invention can form sufficient seals with housings to prevent fluid circumventing the media
without being subjected to the precise tolerances often required by filtration apparatus.
Filtration and barrier media comprising sintered porous polymeric materials of the present
invention can demonstrate flexible properties allowing the media to conform to variations and
inconsistencies in surfaces of the housing thereby facilitating sufficient sealing with the
housing and reducing product failure and discardment due to fluid bypass. Moreover, the
flexible properties of filtration and barrier media of the present invention can permit the
porosity of the media to be adjusted according to various applications.
In one embodiment, the present invention provides a filtration medium comprising a
sintered porous polymeric material, the sintered porous polymeric material comprising at
least one plastic and at least one elastomer. In another embodiment, the present invention
provides a filtration medium comprising a sintered porous polymeric material, the sintered
porous polymeric material comprising at least one plastic, at least one elastomer, and at least
one color change indicator.
In another embodiment, the present invention provides a filtration medium
comprising a continuous sintered porous polymeric material comprising a flexible region and
a rigid region. The flexible region of the continuous sintered porous polymeric material, in
some embodiments, comprises a first plastic and at least one elastomer, and the rigid region
comprises a second plastic. In some embodiments, the flexible region comprises a first
plastic, at least one elastomer, and a first color change indicator, and the rigid region
comprises a second plastic and a second color change indicator. In another embodiment, the
color change indicator may be present in either the flexible region or the rigid region.
In another embodiment, the present invention provides a barrier medium comprising a
sintered porous polymeric material, the sintered porous polymeric material comprising at
least one plastic and at least one elastomer. In some embodiments, a liquid barrier medium
comprises a continuous sintered porous polymeric material comprising a flexible region and a
rigid region as provided herein.


In some embodiments, a barrier medium comprising a sintered porous polymeric
material comprising at least one plastic and at least one elastomer further comprises at least
one super-absorbent material. Super-absorbent materials suitable for use in barrier media,
according to embodiments of the present invention, rapidly swell when contacted with
solutions, such as water or other aqueous solutions, but do not dissolve in the solutions. The
swelling of the super-absorbent material, in some embodiments, can seal the barrier medium
preventing further flow of fluids through the barrier medium. In other embodiments, a barrier
medium comprising a sintered porous polymeric material comprising at least one plastic and
at least one elastomer does not include a super-absorbent material.
In a further embodiment, a barrier medium comprising a sintered porous polymeric
material comprising at least one plastic and at least one elastomer further comprises a
hydrophobic coating such as fluorinated molecular coating as described in United States
patent nos. 6,638,610 and 6,358,569. In one embodiment, a liquid barrier medium
comprising a sintered porous polymeric material comprising at least one plastic and at least
one elastomer further comprises at least one color change indicator.
In a further embodiment, the present invention provides an absorbent medium
comprising a sintered porous polymeric material comprising at least one plastic and at least
one elastomer, wherein the absorbent medium is operable to uptake or absorb liquids and
subsequently expel liquids when placed in compression. In such embodiments, the absorbent
medium can act as a sponge.
Filters and Apparatus Comprising Filtration Media and/or Barrier Media
In another embodiment, the present invention provides a filter comprising a housing
and at least one filtration medium, the at least one filtration medium comprising a sintered
porous polymeric material comprising at least one plastic and at least one elastomer. In some
embodiments, a filtration medium further comprises at least one color change indicator. In
other embodiments of a filter, the at least one filtration medium comprises a continuous
sintered porous polymeric material comprising a flexible region and a rigid region. The
flexible region of the continuous sintered porous polymeric material, in some embodiments,
comprises a first plastic and at least one elastomer, and the rigid region comprises a second
plastic. In some embodiments, the flexible and/or rigid region further comprises at least one
color change indicator. A housing, in one embodiment, comprises a vacuum filtration
housing, a chromatographic column, a funnel, a tube, a syringe, a catheter, a duct, or a pipette
tip.


In another embodiment, the present invention provides an apparatus comprising a
housing and at least one barrier medium, the at least one barrier medium comprising a
sintered porous polymeric material comprising at least one plastic and at least one elastomer.
In some embodiments, the at least one barrier medium comprises a continuous sintered
porous polymeric material comprising a flexible region and a rigid region. The flexible
region of the continuous sintered porous polymeric material, in some embodiments,
comprises a first plastic and at least one elastomer, and the rigid region comprises a second
plastic. In some embodiments, the flexible and/or rigid region further comprises at least one
color change indicator. Moreover, in some embodiments, an apparatus comprises a filter, a
pipettor, or a catheter.
A barrier medium, in some embodiments, further comprises a hydrophobic coating,
such as, but not limited to, a fluorinated polymeric coating. In some embodiments, a barrier
medium further comprises at least one super-absorbent material. Moreover, in some
embodiments, a housing comprises a vacuum filtration housing, a funnel, a tube, a duct, a
syringe, a catheter, or a pipette tip.
Methods of Producing Filtration Media and Barrier Media
In another aspect, the present invention provides methods of producing a filtration
medium comprising a sintered porous polymeric material. In one embodiment, a method of
producing a filtration medium comprising a sintered porous polymeric material comprises
providing particles of at least one elastomer, providing particles of at least one plastic, and
sintering the plastic and elastomer particles. In some embodiments, at least one color change
indicator is added to the particles of the at least one elastomer and/or at least one plastic and
sintered with the particles of the at least one elastomer and at least one plastic.
In another embodiment, a method of producing a filtration medium comprising a
sintered porous polymeric material comprises disposing particles of a first plastic mixed with
particles of at least one elastomer in a first part of a mold, disposing particles of a second
plastic in a second part of the mold adjacent to the first part of the mold, and sintering the
first plastic particles, elastomer particles, and second plastic particles. In some embodiments,
particles of at least one color change indicator can be added to the mixture of first plastic
particles and elastomer particles prior to sintering. In other embodiments, at least one color
change indicator can be added to second plastic particles prior to sintering.
In another aspect, the present invention provides methods of producing a barrier
medium comprising a sintered porous polymeric material. In one embodiment, a method of
producing a barrier medium comprises providing particles of at least one elastomer,


providing particles of at least one plastic, and sintering the plastic and elastomer particles. In
some embodiments, at least one super-absorbent material and/or color change indicator is
added to the particles of the at least one elastomer and at least one plastic and sintered with
the particles of the at least one elastomer and at least one plastic. In a further embodiment, a
method for producing a barrier medium comprising a sintered porous polymeric material
further comprises coating the sintered porous polymeric material with a hydrophobic coating.
In another embodiment, a method of producing a barrier medium comprising a
sintered porous polymeric material comprises disposing particles of a first plastic mixed with
particles of at least one elastomer in a first part of a mold, disposing particles of a second
plastic in a second part of the mold adjacent to the first part of the mold, and sintering the
first plastic particles, elastomer particles, and second plastic particles. In some embodiments,
at least one super-absorbent material and/or color change indicator can be added to the
mixture of first plastic particles and elastomer particles. In other embodiments, at least one
super-absorbent material and/or color change indicator can be added to the mixture of second
plastic particles. In a further embodiment, a method for producing a barrier medium
comprising a sintered porous polymeric material further comprises coating the sintered
porous polymeric material with a hydrophobic coating.
In another aspect, the present invention provides methods of producing a filter. In one
embodiment, a method for producing a filter comprises providing a filtration medium
comprising a sintered porous polymeric material, providing a housing, and disposing the
filtration medium in the housing, wherein the sintered porous polymeric material comprises
at least one elastomer and at least one plastic. In some embodiments, the sintered porous
polymeric material further comprises at least one color change indicator.
In another embodiment, a method of producing a filter comprises providing a
filtration medium comprising a continuous sintered porous polymeric material comprising a
flexible region and a rigid region, providing a housing, and disposing the filtration medium in
the housing. In some embodiments, the flexible region comprises a first plastic and at least
one elastomer, and the rigid region comprises a second plastic. In some embodiments, the
flexible region and/or rigid region can further comprise at least one'color change indicator.
The flexible region of the filtration medium, in some embodiments, conforms to the surface
of the housing to form a seal between the filtration medium and the housing. The flexible
nature of the flexible region can allow the filtration medium to conform with any variations
or inconsistencies in the surface of the housing to facilitate a tight seal resistant to fluid
bypass.


Methods of Filtering a Fluid
In another aspect, the present invention provides methods of filtering a fluid to
remove compositions from the fluid. In one embodiment, a method of filtering a fluid
comprises providing at least one filtration medium comprising a sintered porous polymeric
material and passing a fluid through the at least one filtration medium, wherein the sintered
porous polymeric material comprises at least one plastic and at least one elastomer. In some
embodiments, the sintered porous polymeric material further comprises at least one color
change indicator.
In another embodiment, a method of filtering a fluid comprises providing at least one
filtration medium comprising a continuous sintered porous polymeric material comprising a
flexible region and a rigid region and passing a fluid through the at least one filtration
medium, wherein the flexible region comprises a first plastic and at least one elastomer, and
the rigid region comprises a second plastic. In some embodiments, the flexible region and/or
rigid region can further comprise at least one color change indicator.
In further embodiment, a method for filtering a fluid comprises providing at least one
filtration medium comprising a sintered porous polymeric material, adjusting the porosity of
the at least one filtration medium, and passing a fluid through the at least one filtration
medium, wherein the sintered porous polymeric material comprises at least one elastomer and
at least one plastic. In some embodiments, adjusting the porosity of the filtration medium
comprises placing the filtration medium in tension or compression. Placing the filtration
medium in tension or compression can alter the pore size and/or pore structure of filtration
medium thereby changing the porosity of the filtration medium.
In another embodiment, a method of filtering a gas comprises providing at least one
liquid barrier medium comprising a sintered porous polymeric material, adjusting the porosity
of the at least one liquid barrier medium, and passing a gas through the liquid barrier medium
while inhibiting and/or preventing liquid from passing through the liquid barrier medium,
wherein the sintered porous polymeric material comprises at least one elastomer and at least
one plastic. In some embodiments, adjusting the porosity of the liquid barrier medium
comprises placing the liquid barrier medium in tension or compression.
In a further aspect, the present invention provides methods of cleaning filtration
media. In one embodiment, a method for cleaning a filtration medium comprises adjusting
the pore sizes of the filtration medium to release compositions disposed in the pores wherein
the filtration medium comprises at least one plastic and at least one elastomer.. In some


embodiments, adjusting the pores sizes comprises placing the filtration medium in tension or
compression.
These and other embodiments are presented in greater detail in the detailed
description which follows.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Figure 1 illustrates various applicators according to embodiments of the present
invention.
Figure 2 illustrates various applicators according to embodiments of the present
invention.
Figure 3 illustrates an applicator according to one embodiment of the present
invention.
Figure 4 illustrates a fibrous component coupled to a sintered porous polymeric
component according to one embodiment of the present invention.
Figure 5 illustrates an applicator according to one embodiment of the present
invention.
Figure 6 illustrates a top cross-sectional view of a filtration medium comprising a
continuous sintered porous polymeric material comprising a flexible region and a rigid region
according to an embodiment of the present invention.
Figure 7 illustrates a side cross-sectional view of filtration medium comprising a
continuous sintered porous polymeric material comprising a flexible region and a rigid region
according to one embodiment of the present invention.
Figure 8 illustrates a barrier medium disposed in a pipette tip according to an
embodiment of the present invention.
DETAILED DESCRIPTION
The present invention provides sintered polymeric materials and methods of making
and using the same. Sintered polymeric materials of the present invention can demonstrate
advantageous chemical and mechanical properties, such as resistance to solvents and
increased flexibilities, thereby facilitating application of these materials in a variety of fields,
including their use in applicators and filtration and barrier media.
Sintered Polymeric Materials
Sintered Polymeric Materials Comprising Elastomers
In one aspect, the present invention provides sintered polymeric materials and
methods of making and using the same. Sintered polymeric materials of the present
invention can demonstrate advantageous chemical and mechanical properties, such as


resistance to solvents and increased flexibilities, thereby facilitating application of these
materials in a variety of fields, including applicators and filtration and barrier media.
In one embodiment, a sintered polymeric material comprises at least one plastic and at
least one elastomer. A sintered polymeric material, according to some embodiments,
comprises at least one plastic and a plurality of elastomers. In another embodiment, a
sintered polymeric material comprises a plurality of plastics and at least one elastomer. In a
further embodiment, a sintered polymeric material comprises a plurality of plastics and a
plurality of elastomers.
Turning now to components that can be included in sintered polymeric materials of
the present invention, sintered polymeric materials of the present invention, in some
embodiments, comprise at least one plastic.
Plastics
In some embodiments, sintered polymeric materials of the present invention comprise
a plurality of plastics. Plastics, as used herein, include flexible plastics and rigid plastics.
Flexible plastics, in some embodiments, comprise polymers possessmg moduli ranging from
about 15,000 N/cm2 to about 350,000 N/cm2 and/or tensile strengths ranging from about 1500
N/cm2 to about 7000 N/cm2. Rigid plastics, according to some embodiments, comprise
polymers possessing moduli ranging from about 70,000 N/cm2 to about 350,000 N/cm2 and
have tensile strengths ranging from about 3000 N/cm2 to about 8500 N/cm2.
Plastics suitable for use in sintered polymeric materials of the present invention, in
some embodiments, comprise polyolefins, polyamides, polyesters, rigid polyurethanes,
polyacrylonitriles, polycarbonates, polyvinylchloride, polymethylmethacrylate,
polyvinylidene fluoride, polytetrafluoroethylene, polyethersulfones, polystyrenes, polyether
imides, polyetheretherketones, polysulfones, and combinations and copolymers thereof.
In some embodiments, a polyolefin comprises polyethylene, polypropylene, and/or
copolymers thereof. Polyethylene, in one embodiment, comprises high density polyethylene
(HDPE). High density polyethylene, as used herein, refers to polyethylene having a density
ranging from about 0.92 g/cm3 to about 0.97 g/cm3. In some embodiments, high density
polyethylene has a degree of crystallinity (% from density) ranging from about 50 to about
90. In another embodiment, polyethylene comprises ultrahigh molecular weight polyethylene
(UHMWPE). Ultrahigh molecular weight polyethylene, as used herein, refers to
polyethylene having a molecular weight greater than 1,000,000.


Elastomers
In addition to at least one plastic, sintered polymeric materials of the present invention
comprise at least one elastomer. In some embodiments, sintered polymeric materials of the
present invention comprise a plurality of elastomers. Elastomers suitable for use in sintered
polymeric materials of the present invention, according to some embodiments, comprise
thermoplastic elastomers (TPE). Thermoplastic elastomers, in some embodiments, comprise
polyurethanes and thermoplastic polyurethanes (TPU). Thermoplastic polyurethanes, in
some embodiments, include multiblock copolymers comprising a polyurethane and a
polyester or polyether.
In other embodiments, elastomers suitable for use in sintered porous polymeric
materials of the present invention comprise polyisobutylene, polybutenes, butyl rubber, or
combinations thereof. In another embodiment, elastomers comprise copolymers of ethylene
and other polymers such as polyethylene-propylene copolymer, referred to as EPM, ethylene-
butene copolymer, polyethylene-octene copolymer, and polyehtylene-hexene copolymer. In
a further embodiment, elastomers comprise chlorinated polyethylene or chloro-sulfonated
polyethylene.
In some embodiments, elastomers suitable for use in sintered polymeric materials of
the present invention comprise 1,3-dienes and derivatives thereof. 1,3-dienes include
styrene-l,3-butadiene (SBR), styrene-1,3-butadiene terpolymer with an unsaturated
carboxylic acid (carboxylated SBR), acrylonitrile-l,3-butadiene (NBR or nitrile rubber),
isobutylene-isoprene, cis-l,4-polyisoprene, l,4-poly(l,3-butadiene), polychloroprene, and
block copolymers of isoprene or 1,3-butadiene with styrene such as styrene-ethylene-
butadiene-styrene (SEBS). In other embodiments, elastomers comprise polyalkene oxide
polymers, acrylics, or polysiloxanes (silicones) or combinations thereof.
In a further embodiment, elastomers suitable for use in sintered polymeric materials
of the present invention, in some embodiments, comprise FORPRENE®, LAPRENE®,
SKYPEL®, SKYTHANE®, SYNPRENE®, RIMFLEX®, Elexar, FLEXALLOY®,
TEKRON®, DEXFLEX®, Typlax, Uceflex, ENGAGE®, HERCUPRENE®, Hi-fax,
Novalene, Kraton, Muti-Flex, EVOPRENE®, HYTREL®, NORDEL®, VITON®, Vector,
SILASTIC®, Santoprene, Elasmax, Affinity, ATTANE®, SARLINK®, etc.
Properties of Sintered Polymeric Materials Comprising Elastomers
A sintered polymeric material, according to some embodiments of the present
invention, comprises at least one elastomer in an amount ranging from about 10 weight
percent to about 90 weight percent. In other embodiments, a sintered polymeric material


comprises at least one elastomer in an amount ranging from about 20 weight percent to about
80 weight percent. In another embodiment, a sintered polymeric material comprises at least
one elastomer in an amount ranging from about 30 weight percent to about 70 weight percent.
In a further embodiment, a sintered polymeric material comprises at least one elastomer in an
amount ranging from about 40 weight percent to about 60 weight percent.
Sintered polymeric materials comprising at least one plastic and at least one
elastomer, according to some embodiments of the present invention, are porous. In one
embodiment, for example, a sintered polymeric material has a porosity ranging from about
10% to about 90%. In another embodiment, a sintered polymeric material comprising at least
one plastic and at least one elastomer has a porosity ranging from about 20% to about 80% or
from about 30% to about 70%. In a further embodiment, a sintered polymeric material
comprising at least one plastic and at least one elastomer has a porosity ranging from about
40% to about 60%.
Porous sintered polymeric materials comprising at least one plastic and at least one
elastomer, according to some embodiments of the present invention, have an average pore
size ranging from about from about 1 µm to about 200 µm. In other embodiments, porous
sintered polymeric materials comprising at least one plastic and at least one elastomer have
an average pore size ranging from about 2 µm to about 150 µm, from about 5 µm to about
100 µm, or from about 10 µm to about 50 µm. In another embodiment, a porous sintered
polymeric material has an average pore size less than about 1 µm. In one embodiment, a
porous sintered polymeric material comprising at least one plastic and at least one elastomer
has an average pore size ranging from about 0.1 µm to about 1 µm. In a further embodiment,
a porous sintered polymeric material of the present invention has an average pore size greater
than 200 µm. In one embodiment, a porous sintered polymeric material comprising at least
one plastic and at least one elastomer has an average pore size ranging from about 200 µm to
about 500 µm or from about 500 µm to about 1 mm.
Sintered polymeric materials comprising at least one plastic and at least one
elastomer, according to some embodiments, have a density ranging from about 0.1 g/cm3 to
about I g/cm3. In other embodiments, a sintered polymeric material of the present invention
has a density ranging from about 0.2 g/cm3 to about 0.8 g/cm3 or from about 0.4 g/cm3 to
about 0.6 g/cm . In a further embodiment, a sintered polymeric material comprising at least
one plastic and at least one elastomer has a density greater than about 1 g/cm3. In one


embodiment, a sintered polymeric material comprising at least one plastic and at least one
elastomer has a density less than about 0.1 g/cm3.
In some embodiments, a sintered polymeric material comprising at least one plastic
and at least one elastomer has a rigidity according to ASTM D747 of less than about 15
pounds. ASTM D747 is entitled the Standard Test Method for Apparent Bending Modulus of
Plastics by Means of a Cantilever Beam and is well suited for determining relative flexibility
of materials over a wide range. In other embodiments, a sintered polymeric material
comprising at least one plastic and at least one elastomer has a rigidity according to ASTM
D747 of less than about 10 pounds. In a further embodiment, a sintered polymeric material
comprising at least one plastic and at least on elastomer has a rigidity according to ASTM
D747 of less than about 5 pounds. In another embodiment, a sintered polymeric material
comprising at least one plastic and at least on elastomer has a rigidity according to ASTM
D747 of less than about 1 pound.
Moreover, in some embodiments, a sintered porous polymeric material comprising at
least one plastic and at least one elastomer has a tensile strength ranging from about 10 to
about 5,000 psi as measured according to ASTM D638. A sintered porous polymeric
material comprising at least one plastic and at least one elastomer, in some embodiments, has
a tensile strength ranging from about 50 to 3000 psi or from about 100 to 1,000 psi as
measured according to ASTM D638. In some embodiments, a sintered porous polymeric
material comprising at least one plastic and at least one elastomer has an elongation from
ranging from 10% to 500%.
Sintered polymeric materials comprising at least one plastic and at least one elastomer
can have any desired shape or form such as blocks, tubes, cones, cylinders, sheets, or films.
In one embodiment, for example, a sintered polymeric material comprising at least one
plastic and at least one elastomer has the shape of a nib such as nibs used in writing
instruments.
Continuous Sintered Polymeric Materials Comprising a Flexible Region and a Rigid Region
In another embodiment, the present invention provides a sintered polymeric material
comprising a flexible region continuous with a rigid region, wherein the flexible region
comprises a first plastic and at least one elastomer, and the rigid region comprises a second
plastic. In some embodiments, the first and second plastics comprise the same plastic. In
other embodiments, the first and second plastics comprise different plastics.
A sintered polymeric material comprising a flexible region continuous with a rigid
region, in some embodiments, can further comprise plastics in addition to the first and second


plastics. In one embodiment, for example, the flexible region of a sintered polymeric
material comprises one or more plastics in addition to the first plastic. Moreover, the rigid
region, in some embodiments, comprises one or more plastics in addition to the second
plastic. Plastics suitable for use in continuous sintered polymeric materials of the present
invention, in some embodiments, are consistent with any of the plastics provided herein.
Elastomers suitable for use in continuous sintered polymeric materials of the present
invention, in some embodiments, comprise elastomers consistent with those provided herein.
Properties of Continuous Sintered Polymeric Materials
In some embodiments, the flexible region of a continuous sintered polymeric material
comprises at least one elastomer in an amount ranging from about 10 weight percent to about
90 weight percent. In other embodiments, the flexible region comprises at least one
elastomer in an amount ranging from about 20 weight percent to about 80 weight percent. In
another embodiment, the flexible region comprises at least one elastomer in an amount
ranging from about 30 weight percent to about 70 weight percent. In a further embodiment,
the flexible region comprises at least one elastomer in an amount ranging from about 40
weight percent to about 60 weight percent.
The flexible region of a continuous sintered polymeric material, according to some
embodiments, is porous. In one embodiment, the flexible region comprising a first plastic
and at least one elastomer has a porosity ranging from about 10% to about 90%. In another
embodiment, the flexible region has a porosity ranging from about 20% to about 80% or from
about 30% to about 70%. In a further embodiment, the flexible region has a porosity ranging
from about 40% to about 60%.
In some embodiments, a flexible region of a continuous porous sintered polymeric
material has an average pore size ranging from about 1 µm to about 200 µm. In other
embodiments, a flexible region has an average pore size ranging from about 2 µm to about
150 µm, from about 5 µm to about 100 µm or from about 10 µm to about 50 µm. In another
embodiment, a flexible region has an average pore size less than about 1 µm. In one
embodiment, a flexible region has an average pore size ranging from about 0.1 µm to about 1
µm. In a further embodiment, a flexible region has an average pore size greater than 200 µm.
In one embodiment, a flexible region has an average pore size ranging from about 200 µm to
about 500 µm or from about 500 µm to about 1 mm.
The flexible region of a continuous sintered polymeric material, according to some
embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other


embodiments, the flexible region has a density ranging from about 0.2 g/cm3 to about 0.8
g/cm3 or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further embodiment, the flexible
region has a density greater than about 1 g/cm3. In one embodiment, the flexible region has a
density less than about 0.1 g/cm3.
In some embodiments, the flexible region of a continuous sintered polymeric material
has rigidity according to ASTM D747 of less than about 15 pounds. In other embodiments,
the flexible region of a sintered polymeric material has a rigidity according to ASTM D747
of less than about 10 pounds. In another embodiment, the flexible region of a sintered
polymeric material has a rigidity according to ASTM D747 of less than about 5 pounds. In
another embodiment, a sintered polymeric material comprising at least one plastic and at least
on elastomer has a rigidity according to ASTM D747 of less than about 1 pound.
The rigid region of a continuous sintered polymeric material, according embodiments
of the present invention, comprises a second plastic. In some embodiments, the rigid region
does not comprise any elastomeric materials in addition to the second plastic. In other
embodiments, the rigid region comprises less than about 20 weight percent elastomer. In
another embodiment, the rigid region comprises less than about 10 weight percent elastomer.
In a further embodiment, the rigid region comprises less than about 5 weight percent
elastomer.
In some embodiments, the rigid region is porous having a porosity ranging from about
10% to about 90%. In other embodiments, the rigid region has a porosity ranging from about
20% to about 80% or from about 30% to about 70%. In another embodiment, the rigid region
has a porosity ranging from about 40% to about 60%.
In some embodiments, a rigid region of a continuous sintered polymeric material has
an average pore size ranging from about 1 µm to about 200 µm. In other embodiments, a
rigid region has an average pore size ranging from about 2 µm to about 150 µm, from about 5
µm to about 100 µm or from about 10 µm to about 50 µm. In another embodiment, a rigid
region has an average pore size less than about 1 µm. In one embodiment, a rigid region has
an average pore size ranging from about 0.1 µm to about 1 µm. In a further embodiment, a
rigid region has an average pore size greater than 200 urn. In one embodiment, a rigid region
has an average pore size ranging from about 200 µm to about 500 µm or from about 500 µm
to about 1 mm.
The rigid region of a continuous sintered polymeric material, according to some
embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other


embodiments, the rigid region has a density ranging from about 0.2 g/cm3 to about 0.8 g/cm
or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further embodiment, the rigid region has a
density greater than about 1 g/cm3. In one embodiment, the rigid region has a density less
than about 0.1 g/cm .
In some embodiments, the rigid region of a sintered polymeric material has rigidity
according to ASTM D747 of greater than about 15 pounds. In other embodiments, the rigid
region of a sintered polymeric material has a rigidity according to ASTM D747 of greater
than about 10 pounds. In another embodiment, the rigid region of a sintered polymeric
material has a rigidity according to ASTM D747 of greater than about 5 pounds.
Sintered polymeric materials comprising a flexible region continuous with a rigid
region, wherein the flexible region comprises a first plastic and at least one elastomer, and the
rigid region comprises a second plastic can have any desired shape or form including blocks,
rubes, cones, cylinders, sheets, or films. In one embodiment, a sintered polymeric material
comprising a flexible region continuous with a rigid region has the shape of a nib such as nibs
used in writing instruments or other applicators.
Applicators Comprising Sintered Polymeric Materials
In another aspect, the present invention provides an applicator comprising a sintered
polymeric material, the sintered polymeric material comprising at least one plastic and at
least one elastomer as provided herein. In a further embodiment, the present invention
provides an applicator comprising a continuous sintered polymeric material comprising a
flexible region and a rigid region, the flexible region comprising a first plastic and at least
one elastomer, and the rigid region comprising a second plastic as provided herein. In some
embodiments, sintered polymeric materials of applicators of the present invention further
comprise at least one color change indicator.
Applicators comprising sintered polymeric materials of the present invention can have
any desired shape. Figure 1 illustrates several applicators according to embodiments of the
present invention. The applicators illustrated in Figure 1 comprise a sintered polymeric
material comprising at least one plastic and at least one elastomer. Figure 2 additionally
illustrates applicators according to embodiments of the present invention. The applicators
(200) illustrated in Figure 2 each comprise a flexible region (202) and a rigid region (204),
the flexible region (202) comprising a first plastic and at least one elastomer, and the rigid
.region (204) comprising a second plastic. The flexible region (202) of an applicator (200), in
some embodiments, is the tip for applying a composition to a surface. Moreover, in some


embodiments, the rigid region (204) can serve as a point of attachment for attaching the
applicator to a housing.
In some embodiments, applicators comprising sintered polymeric materials of the
present invention further comprise a hollow longitudinal axis. The hollow longitudinal axis
can facilitate attachment of the applicator to an apparatus such as a writing instrument. In
one embodiment, for example, the hollow longitudinal axis of an applicator is operable to
receive a shaft of a writing instrument, the shaft comprising ink. Attachment of the
applicator to the ink shaft can allow ink to flow into the applicator for application of the ink
to a writing surface.
Figure 3 illustrates an applicator comprising a sintered polymeric material of the
present invention having a hollow longitudinal axis according to one embodiment of the
present invention. The applicator (300) comprises a solid tip (302) and a hollow longitudinal
axis (304). The solid tip (302) comprises a flexible sintered polymeric material comprising a
first plastic and at least one elastomer while the cylindrical region (306) defining the hollow
longitudinal axis comprises a rigid second plastic. In some embodiments, the cylindrical
region (306) can comprise a first plastic and at least one elastomer.
In another aspect, the present invention provides an applicator comprising a sintered
porous polymeric component and a fibrous component coupled to the sintered porous
polymeric component. In some embodiments, the applicator further comprises a reservoir
coupled to the fibrous component. In other embodiments, the fibrous component serves as
the reservoir.
Sintered Porous Polymeric Component
A sintered porous polymeric component of an applicator, in some embodiments,
comprises at least one plastic. In other embodiments, a sintered porous polymeric component
comprises a plurality of plastics. Plastics suitable for use in applicators comprising a sintered
porous polymeric component and a fibrous component are consistent with any of the plastics
provided herein. In one embodiment, a sintered porous polymeric component comprising at
least one plastic does not comprise an elastomer.
In some embodiments, a sintered porous polymeric component comprising at least
one plastic has a porosity ranging from about 10% to about 90%. In other embodiments, a
sintered porous polymeric component has a porosity ranging from about 20% to about 80%
or from about 30% to about 70%. In another embodiment, a sintered porous polymeric
component comprising at least one plastic has a porosity ranging from about 40% to about
60%.


In some embodiments, a sintered porous polymeric component comprising at least
one plastic has an average pore size ranging from about 1 uxn to about 200 µm. In other
embodiments, a sintered porous polymeric component has an average pore size ranging from
about 2 urn to about 150 µm, from about 5 µm to about 100 µm, or from about 10 µm to
about 50 uxn. In another embodiment, a sintered porous polymeric component comprising at
least one plastic has an average pore size ranging from about 0.1 µm to about 1 µm. In a
further embodiment, a sintered porous polymeric component has an average pore size greater
than about 200 µm. In one embodiment, a sintered porous polymeric component has an
average pore size ranging from about 200 µm to about 500 µm or from about 500 µm to about
1 mm.
A sintered porous polymeric component comprising at least one plastic, according to
some embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other
embodiments, a sintered porous polymeric component has a density ranging from about 0.2
g/cm3 to about 0.8 g/cm3 or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further
embodiment, a sintered porous polymeric component has a density greater than about 1
g/cm3. In one embodiment, a sintered porous polymeric component has density less than
about 0.1 g/cm3.
In some embodiments, a sintered porous polymeric component comprising at least
one plastic has a rigidity according to ASTM D747 of greater than about 15 pounds. In other
embodiments, a sintered porous polymeric component has a rigidity according to ASTM
D747 of greater than 10 pounds. In another embodiment, the sintered porous polymeric
component has a rigidity of according to ASTM D747 of greater than 5 pounds.
In some embodiments, a sintered porous polymeric component comprising at least
one plastic further comprises at least one color change indicator. In some embodiments, a
color change indicator comprises an organic or inorganic dye, including food grade dyes.
Color change indicators comprising food grade dyes, according to embodiments of the
present invention, are operable to be used with biological samples due to the non-toxic nature
of the food dyes.
In some embodiments, a color change indicator comprises FD&C Blue No. 1, FD&C
Blue No. 2, FD&C Green No. 3, FD&C Red No. 40, FD&C Red No. 3, FD&C Yellow No. 5,
FD&C Yellow No. 6, Solvent Red 24, Solvent Red 26, Solvent Red 164, Solvent Yellow
124, Solvent Blue 35, or combinations thereof.
Color change indicators, according to some embodiments, demonstrate a pH
dependency on the color produced. As a result, color change indicators, in some



embodiments, indicate not only liquid contact with the sintered porous polymeric material of
the applicator but the relative pH of the contacting liquid as well. Color change indicators
demonstrating a pH dependency, in some embodiments, comprise methyl violet, eosin
yellow, malachite green, thymol blue, methyl yellow, bromophenol blue, congo red, methyl
orange, bromocresol green, methyl red, litmus, bromocresol purple, bromophenol red,
bromothymol blue, phenol red, neutral red, naphtholphthalein, cresol red, phenolphthalein,
thymolphthalein, alkali blue, Alizarin Yellow R, indigo carmine, epsilon blue, or
combinations thereof.
In some embodiments, a sintered porous polymeric component comprises at least one
color change indicator in an amount ranging from about 0.001 weight percent to about 2
weight percent. In other embodiments, a sintered porous polymeric component comprises at
least one color change indicator in an amount ranging from about 0.01 weight percent to
about 1 weight percent. In a further embodiment, a sintered porous component comprises at
least one color change indicator in an amount ranging from about 0.05 weight percent to
about 0.5 weight percent.
Sintered porous polymeric components comprising at least one plastic, according to
some embodiments of the present invention, can have any desired shape or form such as
blocks, tubes, cones, and cylinders. In some embodiments, for example, sintered porous
polymeric components can display various nib shapes, such as those used in writing
instruments.
In another aspect, a sintered porous polymeric component of an applicator, in some
embodiments, comprises at least one plastic and at least one elastomer. Plastics and
elastomers suitable for use in a sintered porous polymeric component, in some embodiments,
are consistent with any of those described herein.
A sintered porous polymeric component comprising at least one plastic and at least
one elastomer, according to some embodiments of the present invention, comprises at least
one elastomer in an amount ranging from about 10 weight percent to about 90 weight percent.
In other embodiments, a sintered porous polymeric component comprises at least one
elastomer in an amount ranging from about 20 weight percent to about 80 weight percent. In
another embodiment, a sintered porous polymeric component comprises at least one
elastomer in an amount ranging from about 30 weight percent to about 70 weight percent. In
a further embodiment, a sintered porous polymeric component comprises at least one
elastomer in an amount ranging from about 40 weight percent to about 60 weight percent.


A sintered porous polymeric component comprising at least one plastic and at least
one elastomer, in one embodiment, has a porosity ranging from about 10% to about 90%. In
another embodiment, a sintered porous polymeric component comprising at least one plastic
and at least one elastomer has a porosity ranging from about 20% to about 80% or from about
30% to about 70%. In a further embodiment, a sintered porous polymeric component
comprising at least one plastic and at least one elastomer has a porosity ranging from about
40% to about 60%.
Sintered porous polymeric components comprising at least one plastic and at least one
elastomer, according to some embodiments of the present invention, have an average pore
size ranging from about from about 1 urn to about 200 µm. In other embodiments, sintered
porous polymeric components comprising at least one plastic and at least one elastomer have
an average pore size ranging from about 2 µm to about 150 µm, from about 5 urn to about
100 µm, or from about 10 µm to about 50 µm. In another embodiment, a sintered porous
polymeric component has an average pore size less than about 1 µm. In one embodiment, a
sintered porous polymeric component comprising at least one plastic and at least one
elastomer has an average pore size ranging from about 0.1 µm to about 1 µm. In a further
embodiment, a sintered porous polymeric component of the present invention has an average
pore size greater than 200 µm. In one embodiment, a sintered porous polymeric component
comprising at least one plastic and at least one elastomer has an average pore size ranging
from about 200 µm to about 500 µm or from about 500 µm to about 1 mm.
Sintered porous polymeric components comprising at least one plastic and at least one
elastomer, according to some embodiments, have a density ranging from about 0.1 g/cm3 to
about 1 g/cm3. In other embodiments, a sintered porous polymeric component has a density
ranging from about 0.2 g/cm3 to about 0.8 g/cm3 or from about 0.4 g/cm3 to about 0.6 g/cm3.
In a further embodiment, a sintered porous polymeric component comprising at least one
plastic and at least one elastomer has a density greater than about 1 g/cm3. In one
embodiment, a sintered porous polymeric component comprising at least one plastic and at
least one elastomer has a density less than about 0.1 g/cm3.
In some embodiments, a sintered porous polymeric component comprising at least
one plastic and at least one elastomer has a rigidity according to ASTM D747 of less than
about 15 pounds. In other embodiments, a sintered porous polymeric component comprising
at least one plastic and at least one elastomer has a rigidity according to ASTM D747 of less
than about 10 pounds. In a further embodiment, a sintered porous polymeric component"


comprising at least one plastic and at least on elastomer has a rigidity according to ASTM
D747 of less than about 5 pounds. In another embodiment, a sintered porous polymeric
component comprising at least one plastic and at least on elastomer has a rigidity according
to ASTM D747 of less than about 1 pound.
Moreover, in some embodiments, a sintered porous polymeric component comprising
at least one plastic and at least one elastomer has a tensile strength ranging from about 10 to
about 5,000 psi as measured according to ASTM D638. A sintered porous polymeric
component comprising at least one plastic and at least one elastomer, in some embodiments,
has a tensile strength ranging from about 50 to 3000 psi or from about 100 to 1,000 psi as
measured according to ASTM D638. In some embodiments, a sintered porous polymeric
component comprising at least one plastic and at least one elastomer has an elongation from
ranging from 10% to 500%.
In some embodiments, a sintered porous polymeric component comprising at least
one plastic and at least one elastomer further comprises at least one color change indicator.
Color change indicator suitable for use in sintered porous polymeric components comprising
at least one plastic and at least one elastomer, in some embodiments, are consistent with any
of those provided herein.
In some embodiments, a sintered porous polymeric component comprising at least
one plastic and at least one elastomer comprises at least one color change indicator in an
amount ranging from about 0.001 weight percent to about 2 weight percent. In other
embodiments, a sintered porous polymeric component comprises at least one color change
indicator in an amount ranging from about 0.01 weight percent to about 1 weight percent. In
a further embodiment, a sintered porous polymeric component comprises at least one color
change indicator in an amount ranging from about 0.05 weight percent to about 0.5 weight
percent.
Sintered porous polymeric components comprising at least one plastic and at least one
elastomer, according to embodiments of the present invention, can have any desired shape or
form such as blocks, tubes, cones, and cylinders. In some embodiments, for example,
sintered porous polymeric components comprising at least one plastic and at least one
elastomer can display various nib shapes, such as those used in writing instruments.
In another aspect, a sintered porous polymeric component of an applicator, in some
embodiments, comprises a flexible region continuous with a rigid region, wherein the flexible
region comprises a first plastic and at least one elastomer and the rigid region comprises a
second plastic.


In some embodiments, the first and second plastics comprise the same plastic. In
other embodiments, the first and second plastics comprise different plastics. A sintered
porous polymeric component comprising a flexible region continuous with a rigid region, in
some embodiments, further comprises plastics in addition to the first and second plastics. In
one embodiment, for example, the flexible region comprises one or more plastics in addition
to the first plastic. Moreover, the rigid region, in some embodiments, comprises one or more
plastics in addition to the second plastic. Plastics suitable for use in sintered polymeric
materials comprising a flexible region continuous with a rigid region, in some embodiments,
are consistent with any of the plastics provided herein.
Elastomers suitable for use in sintered porous polymeric materials comprising a
flexible region continuous with a rigid region, in some embodiments, comprise elastomers
consistent with those provided herein.
In some embodiments, the flexible region comprises at least one elastomer in an
amount ranging from about 10 weight percent to about 90 weight percent. In other
embodiments, the flexible region comprises at least one elastomer in an amount ranging from
about 20 weight percent to about 80 weight percent. In another embodiment, the flexible
region comprises at least one elastomer in an amount ranging from about 30 weight percent
to about 70 weight percent. In a further embodiment, the flexible region comprises at least
one elastomer in an amount ranging from about 40 weight percent to about 60 weight percent.
In some embodiments, the flexible region comprising a first plastic and at least one
elastomer has a porosity ranging from about 10% to about 90%. In another embodiment, the
flexible region has a porosity ranging from about 20% to about 80% or from about 30% to
about 70%. In a further embodiment, the flexible region has a porosity ranging from about
40% to about 60%.
In some embodiments, the flexible region has an average pore size ranging from about
1 µm to about 200 µm. In other embodiments, the flexible region has an average pore size
ranging from about 2 µm to about 150 µm, from about 5 µm to about 100 µm or from about
10 µm to about 50 µm. In another embodiment, the flexible region has an average pore size
less than about 1 µm. In one embodiment, the flexible region has an average pore size
ranging from about 0.1 µm to about 1 µm. In a further embodiment, the flexible region has
an average pore size greater than 200 µm. In one embodiment, the flexible region has an
average pore size ranging from about 200 µm to about 500 µm or from about 500 µm to
about 1 mm.
25

The flexible region of a continuous sintered porous polymeric component, according
to some embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other
embodiments, the flexible region has a density ranging from about 0.2 g/cm3 to about 0.8
g/cm3 or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further embodiment, the flexible
region has a density greater than about 1 g/cm3. In one embodiment, the flexible region has a
density less than about 0.1 g/cm3.
In some embodiments, the flexible region of a has rigidity according to ASTM D747
of less than about 15 pounds. In other embodiments, the flexible region has a rigidity
according to ASTM D747 of less than about 10 pounds. In another embodiment, the flexible
region has a rigidity according to ASTM D747 of less than about 5 pounds. In a further
embodiment, the flexible region has a rigidity according to ASTM D747 of less than about 1
pound.
The rigid region continuous with the flexible region of a sintered porous polymeric
component, according embodiments of the present invention, comprises a second plastic. In
some embodiments, the rigid region does not comprise any elastomeric materials in addition
to the second plastic. In other embodiments, the rigid region comprises less than about 20
weight percent elastomer. In another embodiment, the rigid region comprises less than about
10 weight percent elastomer. In a further embodiment, the rigid region comprises less than
about 5 weight percent elastomer.
In some embodiments, the rigid region has a porosity ranging from about 10% to
about 90%. In other embodiments, the rigid region has a porosity ranging from about 20% to
about 80% or from about 30% to about 70%. In another embodiment, the rigid region has a
porosity ranging from about 40% to about 60%.
In some embodiments, the rigid region has an average pore size ranging from about 1
µm to about 200 µm. In other embodiments, the rigid region has an average pore size
ranging from about 2 µm to about 150 µm, from about 5 µm to about 100 µm or from about
10 µm to about 50 µm. In another embodiment, the rigid region has an average pore size less
than about 1 µm. In one embodiment, the rigid region has an average pore size ranging from
about 0.1 µm to about 1 µm. In a further embodiment, the rigid region has an average pore
size greater than 200 µm. In one embodiment, the rigid region has an average pore size
ranging from about 200 µm to about 500 µm or from about 500 µm to about 1 mm.
The rigid region of a sintered porous polymeric component, according to some
embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other


embodiments, the rigid region has a density ranging from about 0.2 g/cm3 to about 0.8 g/cm3
or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further embodiment, the rigid region has a
density greater than about 1 g/cm3. In one embodiment, the rigid region has a density less
than about 0.1 g/cm3.
In some embodiments, the rigid region of a sintered porous polymeric component has
rigidity according to ASTM D747 of greater than about 15 pounds. In other embodiments,
the rigid region has a rigidity according to ASTM D747 of greater than about 10 pounds. In
another embodiment, the rigid region has a rigidity according to ASTM D747 of greater than
about 5 pounds.
In some embodiments, the flexible region and/or rigid region of a sintered porous
polymeric component further comprises at least one color change indicator. In one
embodiment, the flexible region can comprises a first color change indicator and the rigid
region can comprise a second color change indicator.' In some embodiments, the first and
second color change indicators are the same. In other embodiments, the first and second
color change indicators are different. Color change indicators suitable for use in flexible and
rigid regions of sintered porous polymeric components, in some embodiments, are consistent
with any of the color change indicators described herein.
In some embodiments, a flexible and/or rigid region of sintered porous polymeric
component comprises at least one color change indicator in an amount ranging from about
0.001 weight percent to about 2 weight percent. In other embodiments, a flexible and/or
rigid region of a sintered porous polymeric component comprises at least one color change
indicator in an amount ranging from about 0.01 weight percent to about 1 weight percent. In
a further embodiment, a flexible and/or rigid region of a sintered porous polymeric
component comprises at least one color change indicator in an amount ranging from about
0.05 weight percent to about 0.5 weight percent.
Sintered porous polymeric components comprising a flexible region continuous with a
rigid region, according to embodiments of the present invention, can have any desired shape
or form such as blocks, tubes, cones, and cylinders. In some embodiments, for example,
sintered porous polymeric components can display various nib shapes, such as those used in
marking and writing instruments.
Fibrous Component
In addition to the various sintered porous polymeric components, an applicator of the
present invention comprises a fibrous component. In some embodiments, a fibrous
component comprises a plurality of polyester fibers, polyacrylic fibers, or combinations


thereof. In some embodiments, a fibrous component comprises a plurality of bicomponent
fibers. Bicomponent fibers, in some embodiments, comprise fibers constructed from the
following pairs of polymers: polypropylene/polyethylene terephthalate (PET),
polyethylene/PET, polypropylene/Nylon-6, Nylon-6/PET, copolyester/PET,
copolyester/NyIon-6, copolyester/Nylon-6,6, poly-4-methyl-l-pentene/PET, poly-4-mefhyl-
l-pentene/Nylon-6, poly-4-methyl-1-pentene/Nylon-6,6, PET/polyethylene naphthalate
(PEN), Nylon-6,6/poly-l,4-cyclohexanedimethy-1 (PCT), polypropylene/polybutylene
terephthalate (PBT), Nylon-6/co-poiyamide, polylactic acid/polystyrene, polyurethane/acetal,
and soluble copolyester/polyethylene.
In another embodiment, a fibrous component comprises a plurality of
monocomponent fibers including polyethylene fibers, polypropylene fibers, polystyrene
fibers, nylon-6 fibers, nylon-6,6 fibers, nylon-12 fibers, copolyamide fibers, PET fibers, PBT
fibers, CoPET fibers, and combinations thereof. In a further embodiment, a fibrous
component can comprise any type or combination of fiber known to one of skill in the art
useful in applicators including writing and marking instruments, cosmetic applicators, and
medicament applicators.
In some embodiments, the fibrous component has a density ranging from about 0.1
g/cm3 to about 1 g/cm3. In other embodiments, a fibrous component of the present invention
has a density ranging from about 0.2 g/cm3 to about 0.8 g/cm3 or from about 0.4 g/cm3 to
about 0.6 g/cm3. In a further embodiment, a fibrous component has a density greater than
about 1 g/cm3. In one embodiment, the fibrous component has a density less than about 0.1
g/cm3.
Fibrous components, according to embodiments of the present invention, can have
any desired shape or form. In some embodiments, the fibrous component comprises a
cylinder or shaft. In one embodiment, the fibrous component comprises a hollow cylinder or
shaft. In another embodiment, the fibrous component comprises a solid cylinder or shaft.
Fibrous components, in some embodiments, further comprise a resin such as a
thermoplastic and/or thermoset resin. Resins suitable for use in fibrous components of the
present invention, in one embodiment, comprise phenolic resins, melamine resins, polyester
resins, or combinations thereof. In some embodiments, the fibrous component is
impregnated with one or more resins.
Fibrous components, according to embodiments of the present invention, can
demonstrate densities, porosities, and wicking characteristics advantageous for the flow of
compositions along and through the fibrous components. Fibrous components, in some


embodiments, display advantageous flow characteristics of hydrophilic compositions.
Fibrous components, in other embodiments, display advantageous flow characteristics of
hydrophobic compositions. Fibrous components, in one embodiment, for example, display
advantageous flow characteristics of ink and/or pigment compositions.
In embodiments of applicators of the present invention, the fibrous component is
coupled to the sintered porous polymeric component. In some embodiments, the sintered
porous polymeric component comprises a hollow longitudinal portion or internal slot
operable to receive the fibrous component. In other embodiments, the fibrous component
comprises a hollow longitudinal portion or an internal slot operable to receive the sintered
porous polymeric component.
Figure 4 illustrates a fibrous component coupled to a sintered porous polymeric
component according to one embodiment of the present invention. As illustrated in Figure 4,
the sintered porous polymeric component (402) is disposed in an internal slot (406) of the
fibrous component (404).
In some embodiments, coupling a fibrous component to a sintered porous polymeric
component provides additional support to the sintered porous polymeric component allowing
the use of sintered porous polymeric components having lengths greater than about 3 cm and
diameters greater than about 5 mm. Moreover, the additional support provided by the fibrous
component, in some embodiments, increases the durability of the sintered porous polymeric
component thereby limiting breakage and other degradation pathways of the sintered porous
polymeric component.
Reservoirs
In some embodiments, an applicator of the present invention further comprises a
reservoir. Reservoirs, according to embodiments of the present invention, store or contain
compositions to be delivered to the sintered porous polymeric component for application to a
surface. In some embodiments, reservoirs contain or store inks, dyes, pigments, paints,
and/or other coating compositions. In other embodiments, reservoirs contain or store
cosmetic compositions. In a further embodiment, reservoirs contain or store medicament
and/or pharmaceutical compositions.
In some embodiments, reservoirs comprise structures having an open volume or
hollow region for containing compositions to be delivered to the sintered porous polymeric
component for application to a surface. In one embodiment, for example, a reservoir
comprises a hollow cylinder or cone. Reservoirs having an open volume, according to
embodiments of the present invention, can have any desired volume. In some embodiments,


a reservoir has a volume of at least about 1 ml. In other embodiments, a reservoir has a
volume of at least about 5 ml or at least about 10 ml. In a further embodiment, a reservoir
has a volume less than about 1 ml.
In some embodiments of the present invention, reservoirs comprise fibers and related
materials. In other embodiments, reservoirs comprise polymeric foams, such as a
polyurethane foam.
In some embodiments, the reservoir is coupled to the fibrous component. In other
embodiments, the reservoir is coupled directly to the sintered porous polymeric component.
In some embodiments wherein the reservoir is coupled directly to the sintered porous
polymeric component, the reservoir is the fibrous component. In other embodiments wherein
the reservoir is coupled directly to the sintered porous polymeric component, the applicator
does not comprise a fibrous component.
Figure 5 illustrates an applicator according to one embodiment of the present
invention. As illustrated in Figure 5, the applicator (500) comprises a sintered porous
polymeric component (502) coupled to a fibrous component (504). The sintered porous
polymeric component (502) is disposed within a hollow longitudinal portion or an internal
slot of the fibrous component (504). A reservoir (506) is coupled to the fibrous component
(504).
Applicator Housings
In some embodiments, an applicator of the present invention further comprises a
housing in which the sintered porous polymeric component, fibrous component, and/or
reservoir can be fully or partially disposed. Housings, according to embodiments of the
present invention, can comprise any desired shape including cylinders, cones, and blocks. In
some embodiments, housings comprise multiple pieces. In one embodiment, for example, a
housing comprises a first cylinder in which the fibrous component and reservoir are disposed
and a second cylinder in which the sintered porous polymeric material is disposed, wherein
the first and second cylinders are operable to engage one another. The second cylinder can
be disengaged from the first cylinder to expose the sintered porous polymeric material for
applying a composition to a surface. In some embodiments, the first and second cylinders
engage one another by a friction fit. In other embodiments, the first and second cylinders
engage one another by a threading mechanism.
In some embodiments, the densities, pore sizes, and/or porosities of the sintered
porous polymeric component, the fibrous component, and/or reservoir can be varied to
promote advantageous flow characteristics of a composition to be delivered to a surface. In


some embodiments, a density gradient can be established along the components of the
applicator to increase the flow of a composition to the continuous sintered porous polymeric
component. In one embodiment, for example, the fibrous component comprises a first
density, the rigid region of the sintered porous polymeric material comprises a second
density, and the flexible region of the sintered porous polymeric material comprises a third
density, the first density being greater than the second density and the second density being
greater than the third density. Embodiments of the present invention contemplate any
variation of densities, pore sizes, and porosities of the individual components of applicators
described herein to increase or inhibit the flow of a composition through the applicator.
In some embodiments, applicators of the present invention can be used in writing
instruments such as pens and highlighters. In other embodiments, applicators of the present
invention can be used in art utensils, including but not limited to, brushes, calligraphy pens,
and markers. Applicators of the present invention, in some embodiments, can demonstrate
desirable flow properties of inks and other writing media while providing enhanced flexibility
and durability. In another embodiment, applicators comprising sintered polymeric materials
of the present invention can be used to apply cosmetics. In a further embodiment, applicators
of the present invention can be used in the medical field for the application of medicaments
and other pharmaceutical species to surfaces, such as biological surfaces. In one
embodiment, applicators of the present invention can be used in applying coatings to
industrial surfaces.
Methods of Producing Sintered Polymeric Materials and Applicators Comprising the Same
Methods of Producing 'Sintered Polymeric Materials
In another aspect, the present invention provides methods of producing polymeric
materials. In one embodiment, a method for producing a polymeric material comprises
providing particles of at least one plastic, providing particles of at least one elastomer, and
sintering the plastic particles and elastomer particles.
In some embodiments, particles of at least one plastic and particles of at least one
elastomer are mixed in a desired ratio (weight percent) to produce a substantially uniform
mixture. The uniform mixture of plastic and elastomer particles are disposed in a mold and
sintered. The shape of the mold can be any desired shape allowing for the facile and single-
step production of applicators such as writing instrument nibs according to embodiments of
the present invention.
Plastic and elastomer particles, in some embodiments, have average sizes ranging
from about 1 µm to about 1 mm. In another embodiment, plastic and elastomer particles have


average sizes ranging from about 10 µm to about 900 µm, from about 50 urn to about 500
µm, or from about 100 µm to about 400 µm. In a further embodiment, plastic and elastomer
particles have average sizes ranging from about 200 µm to about 300 µm. In some
embodiments, plastic and elastomer particles have average sizes less than about 1 µm or
greater than about 1 mm.
Sizes of plastic and elastomer particles, in some embodiments, are selected
independently. In one embodiment, for example, the plastic particles have an average size
greater than the elastomer particles. In another embodiment, plastic particles have an average
size smaller than the elastomer particles. In a further embodiment, plastic and elastomer
particles have about the same average size.
Plastic and elastomer particles, in some embodiments, are sintered at a temperature
ranging from about 200°F to about 700°F. In some embodiments, plastic and elastomer
particles are sintered at a temperature ranging from about 300°F to about 500°F. The
sintering temperature, according to embodiments of the present invention, is dependent upon
and selected according to the identity of the plastic and elastomer particles.
Plastic and elastomer particles, in some embodiments, are sintered for a time period
ranging from about 30 seconds to about 30 minutes. In other embodiments, plastic and
elastomer particles are sintered for a time period ranging from about 1 minute to about 15
minutes or from about 5 minutes to about 10 minutes. In some embodiments, the sintering
process comprises heating, soaking, and/or cooking cycles. Moreover, in some embodiments,
sintering of plastic and elastomer particles is conducted under ambient pressure (1 arm). In
other embodiments sintering of plastic and elastomer particles is conducted under pressures
greater than ambient pressure.
In another embodiment, a method for producing a polymeric material comprises
disposing particles of a first plastic mixed with particles of at least one elastomer in a first
part of a mold, disposing particles of a second plastic in a second part of the mold adjacent to
the first part of the mold, and sintering the first plastic particles, second plastic particles and
elastomer particles.
In one embodiment, for example, particles of a first plastic are mixed with particles of
at least one elastomer in a desired ratio (weight percent) to produce a substantially uniform
mixture. The mixture is disposed in the bottom half of a mold. Particles of a second plastic
are disposed in the top half of the mold adjacent to the mixture of particles of the first plastic
and at least one elastomer. The particles of the first plastic, second plastic, and elastomer
particles are subsequently sintered to produce a polymeric material of the present invention.


In other embodiments, particles of a second plastic are disposed in the bottom half of
a mold. The mixture of elastomer and first plastic particles are disposed in the top half of the
mold adjacent to the second plastic particles. The particles of the first plastic, second plastic,
and elastomer particles are subsequently sintered to produce a polymeric material of the
present invention.
First plastic, second plastic, and elastomer particles, in some embodiments, have
average sizes ranging from about 1 µm to about 1 mm. In another embodiment, first plastic,
second plastic, and elastomer particles have average sizes ranging from about 10 µm to about
900 µm, from about 50 µm to about 500 µm, or from about 100 µm to about 400 µm. In a
further embodiment, first plastic, second plastic, and elastomer particles have average sizes
ranging from about 200 µm to about 300 µm. In some, embodiments, first plastic, second
plastic, and elastomer particles have average sizes less than about 1 µm or greater than about
1 mm. Sizes of first plastic, second plastic, and elastomer particles, in some embodiments,
are selected independently.
First plastic, second plastic, and elastomer particles, in some embodiments, are
sintered at a temperature ranging from about 200°F to about 700°F. In some embodiments,
first plastic, second plastic, and elastomer particles are sintered at a temperature ranging from
about 300°F to about 500°F. The sintering temperature, according to embodiments of the
present invention, is dependent upon and selected according to the identity of the first plastic,
second plastic and elastomer particles.
First plastic, second plastic, and elastomer particles, in some embodiments, are
sintered for a time period ranging from about 30 seconds to about 30 minutes. In other
embodiments, first plastic, second plastic, and elastomer particles are sintered for a time
period ranging from about 1 minute to about 15 minutes or from about 5 minutes to about 10
minutes. In some embodiments, the sintering process comprises heating, soaking, and/or
cooking cycles. Moreover, in some embodiments, sintering of first plastic, second plastic,
and elastomer particles is conducted under ambient pressure (1 atm). In other embodiments
sintering of first plastic, second plastic, and elastomer particles is conducted under pressures
greater than ambient pressure.
A polymeric material produced by sintering particles of a first plastic, a second
plastic, and at least one elastomer, in embodiments of the present invention, can comprise a
flexible region continuous with a rigid region, the flexible region comprising the first plastic
and the at least one elastomer, and the rigid region comprising the second plastic. The shape


of the mold can be any desired shape allowing for the facile and single-step production of
applicators such as writing instrument nibs.
Methods of Producing Applicators
In one embodiment, a method of producing an applicator comprises providing
particles of at least one plastic, providing particles of at least one elastomer, and sintering the
plastic particles and the elastomer particles.
In another aspect, a method of producing an applicator comprises providing a sintered
porous polymeric component, providing a fibrous component, and coupling the fibrous
component to the sintered porous polymeric component. Providing a sintered porous
polymeric component, according to some embodiments, comprises providing particles of at
least one plastic and sintering the plastic particles. In other embodiments, providing a
sintered porous polymeric component comprises providing a particles of a plurality of
plastics and sintering the plastic particles.
Plastic particles, in some embodiments, have average sizes ranging from about 1 µm
to about 1 mm. In another embodiment, plastic particles have average sizes ranging from
about 10 µm to about 900 µm, from about 50 urn to about 500 µm, or from about 100 µm to
about 400 µm. In a further embodiment, plastic particles have average sizes ranging from
about 200 µm to about 300 urn. In some embodiments, plastic particles have average sizes
less than about 1 µm or greater than about 1 mm.
Plastic particles, in some embodiments, are sintered at a temperature ranging from
about 200°F to about 700°F. In some embodiments, plastic particles are sintered at a
temperature ranging from about 300°F to about 500°F. The sintering temperature, according
to embodiments of the present invention, is dependent upon and selected according to the
identity of the plastic particles.
Plastic particles, in some embodiments, are sintered for a time period ranging from
about 30 seconds to about 30 minutes. In other embodiments, plastic particles are sintered
for a time period ranging from about 1 minute to about 15 minutes or from about 5 minutes to
about 10 minutes. In some embodiments, the sintering process comprises heating, soaking,
and/or cooking cycles. Moreover, in some embodiments, sintering of plastic particles is
conducted under ambient pressure (1 arm). In other embodiments sintering of plastic
particles is conducted under pressures greater than ambient pressure.
In some embodiments, particles of at least one color change indicator are mixed in a
desired weight ratio (weight percent) with the plastic and particles. Particles of a color
change indicator, according to some embodiments, have average sizes ranging from about 1


µm to about 500 µm or from about 10 µm to about 400 µm. In another embodiment,
particles of a color change indicator have average sizes ranging from about 50 µm to about
300 µm. In a further embodiment, particles of a color change indicator have average sizes
ranging from about 100 µm to about 200 µm. In some embodiments, particles of a color
change indicator have average sizes less than about 1 µm or greater than about 500 µm.
Subsequent to mixing, the plastic and color change indicator particles are sintered according
to the temperatures and time periods described herein.
In some embodiments, coupling the fibrous component to the sintered porous
polymeric component comprises inserting the fibrous component into the sintered porous
polymeric component. In some embodiments, the fibrous component is inserted into a
hollow longitudinal portion or an internal slot of the sintered porous polymeric component.
In other embodiments, coupling the fibrous component to the sintered porous polymeric
component comprises inserting the sintered porous polymeric component into the fibrous
component. In some embodiments, the sintered porous polymeric component is inserted into
a hollow longitudinal portion or an internal slot of the fibrous component.
In another embodiment, a method for producing an applicator comprises providing a
sintered polymeric component comprising at least one plastic and at least one elastomer,
providing a fibrous component, and coupling the fibrous component to the sintered porous
polymeric component. Providing a sintered porous polymeric component, in some
embodiments, comprises providing particles of at least one plastic, providing particles of at
least one elastomer, and sintering the plastic and elastomer particles.
In some embodiments, particles of at least one plastic and particles of at least one
elastomer are mixed in a desired ratio (weight percent) to produce a substantially uniform
mixture. The uniform mixture of plastic and elastomer particles are disposed in a mold and
sintered. The shape of the mold can be any desired shape, such as disks, tubes, cones, and/or
tapered shapes such as frustroconical shapes, allowing for the facile and single-step
production of the sintered porous polymeric component.
Plastic and elastomer particles, in some embodiments, have average sizes ranging
from about 1 µm to about 1 mm. In another embodiment, plastic and elastomer particles have
average sizes ranging from about 10 µm to about 900 µm, from about 50 v to about 500
µm, or from about 100 µm to about 400 urn. In a further embodiment, plastic and elastomer
particles have average sizes ranging from about 200 µm to about 300 µm. In some
embodiments, plastic and elastomer particles have average sizes less than about 1 µm or
greater than about 1 mm.


Sizes of plastic and elastomer particles, in some embodiments, are selected
independently. In one embodiment, for example, the plastic particles have an average size
greater than the elastomer particles. In another embodiment, plastic particles have an average
size smaller than the elastomer particles. In a further embodiment, plastic and elastomer
particles have about the same average size.
Plastic and elastomer particles, in some embodiments, are sintered at a temperature
ranging from about 200°F to about 700°F. In some embodiments, plastic and elastomer
particles are sintered at a temperature ranging from about 300°F to about 500°F. The
sintering temperature, according to embodiments of the present invention, is dependent upon
and selected according to the identity of the plastic and elastomer particles.
Plastic and elastomer particles, in some embodiments, are sintered for a time period
ranging from about 30 seconds to about 30 minutes. In other embodiments, plastic and
elastomer particles are sintered for a time period ranging from about 1 minute to about 15
minutes or from about 5 minutes to about 10 minutes. In some embodiments, the sintering
process comprises heating, soaking, and/or cooking cycles. Moreover, in some embodiments,
sintering of plastic and elastomer particles is conducted under ambient pressure (1 atm). In
other embodiments sintering of plastic and elastomer particles is conducted under pressures
greater than ambient pressure.
In some embodiments, particles of at least one color change indicator are mixed in a
desired weight ratio (weight percent) with the plastic and elastomer particles. Particles of a
color change indicator, according to some embodiments, have average sizes ranging from
about 1 urn to about 500 µm or from about 10 µm to about 400 µm. In another embodiment,
particles of a color change indicator have average sizes ranging from about 50 µm to about
300 µm. In a further embodiment, particles of a color change indicator have average sizes
ranging from about 100 µm to about 200 µm. In some embodiments, particles of a color
change indicator have average sizes less than about 1 µm or greater than about 500 µm.
Subsequent to mixing, the plastic, elastomer, and color change indicator particles are sintered
according to the temperatures and time periods described herein.
In some embodiments, coupling the fibrous component to the sintered porous
polymeric component comprising at least one plastic and at least one elastomer comprises
inserting the fibrous component into the sintered porous polymeric component. In some
embodiments, the fibrous component is inserted into a hollow longitudinal portion or an
internal slot of the sintered porous polymeric component comprising at least one plastic and
at least one elastomer. In other embodiments, coupling the fibrous component to the sintered


porous polymeric component comprises inserting the sintered porous polymeric component
into the fibrous component. In some embodiments, the sintered porous polymeric component
is inserted into a hollow longitudinal portion or an internal slot of the fibrous component.
In another embodiment, a method for producing an applicator comprises providing a
sintered porous polymeric component comprising a flexible region continuous with a rigid
region, providing a fibrous component, and coupling the fibrous component to the sintered
porous polymeric component. In some embodiments, the flexible region of the sintered

region comprises a second plastic.
In some embodiments, providing a sintered porous polymeric component comprising
a flexible region continuous with a rigid region comprises disposing particles of a first plastic
mixed with particles of at least one elastomer in a first part of a mold, disposing particles of a
second plastic in a second part of the mold adjacent to the first part of the mold, and sintering
the first plastic particles, the second plastic particles, and the elastomer particles.
In one embodiment, particles of a first plastic are mixed with particles of at least one
elastomer in a desired ratio (weight percent) to produce a substantially uniform mixture. The
mixture is disposed in a first part of a mold. Particles of a second plastic are disposed in a
second part of the mold adjacent to the mixture of particles of the first plastic and at least one
elastomer. The particles of the first plastic, second plastic, and elastomer particles are
subsequently sintered to produce a sintered porous polymeric material of the present
invention.
First plastic, second plastic, and elastomer particles, in some embodiments, have
average sizes ranging from about 1 µm to about 1 mm. In another embodiment, first plastic,
second plastic, and elastomer particles have average sizes ranging from about 10 µm to about
900 µm, from about 50 µm to about 500 µm, or from about 100 µm to about 400 µm. In a
further embodiment, first plastic, second plastic, and elastomer particles have average sizes
ranging from about 200 µm to about 300 µm. In some embodiments, first plastic, second
plastic, and elastomer particles have average sizes less than about 1 µm or greater than about
1 mm. Sizes of first plastic, second plastic, and elastomer particles, in some embodiments,
are selected independently.
First plastic, second plastic, and elastomer particles, in some embodiments, are
sintered at a temperature ranging from about 200°F to about 700°F. In some embodiments,
first plastic, second plastic, and elastomer particles are sintered at a temperature ranging from
about 300°F to about 500°F. The sintering temperature, according to embodiments of the


present invention, is dependent upon and selected according to the identity of the first plastic,
second plastic and elastomer particles.
First plastic, second plastic, and elastomer particles, in some embodiments, are
sintered for a time period ranging from about 30 seconds to about 30 minutes. In other
embodiments, first plastic, second plastic, and elastomer particles are sintered for a time
period ranging from about 1 minute to about 15 minutes or from about 5 minutes to about 10
minutes. In some embodiments, the sintering process comprises heating, soaking, and/or
cooking cycles. Moreover, in some embodiments, sintering of first plastic, second plastic,
and elastomer particles is conducted under ambient pressure (1 arm). In other embodiments
sintering of first plastic, second plastic, and elastomer particles is conducted under pressures
greater than ambient pressure.
In some embodiments, particles of at least one color change indicator are added in a
desired weight ratio (weight percent) to the first plastic, second plastic, and/or elastomer
particles. Particles of a color change indicator, according to some embodiments, have
average sizes ranging from about 1 µm to about 500 µm or from about 10 µm to about 400
µm. In another embodiment, particles of a color change indicator have average sizes ranging
from about 50 µm to about 300 µm. In a further embodiment, particles of a color change
indicator have average sizes ranging from about 100 µm to about 200 µm. In some
embodiments, particles of a color change indicator have average sizes less than about 1 µm or
greater than about 500 µm. Subsequent to mixing, the first plastic, second plastic, elastomer
and color change indicator particles are sintered according to the temperatures and time
periods described herein.
In some embodiments, coupling the fibrous component to the sintered porous
polymeric component comprises inserting the fibrous component into the continuous sintered
porous polymeric component. In some embodiments, the fibrous component is inserted into
a hollow longitudinal portion or an internal slot of the sintered porous polymeric component.
In some embodiments, the rigid region of the sintered porous polymeric component
comprises the hollow longitudinal portion or internal slot.
In other embodiments, coupling the fibrous component to the sintered porous
polymeric component comprises inserting the sintered porous polymeric component into the
fibrous component. In some embodiments, the continuous sintered porous polymeric
component is inserted into a hollow longitudinal portion or internal slot of the fibrous
component. In some embodiments, the rigid region of the continuous sintered porous


polymeric material is inserted into the hollow longitudinal portion or internal slot of the
fibrous component.
Methods of Applying a Composition to a Surface
In a further aspect, the present invention provides methods of applying a composition
to a surface. In one embodiment, a method for applying a composition to a surface comprises
providing an applicator comprising a sintered polymeric material comprising at least one
plastic and at least one elastomer, disposing at least a portion of the composition on the
applicator, and contacting the surface with the composition on the applicator. In another
embodiment, a method of applying a composition to a surface comprises providing an
applicator comprising a sintered polymeric material comprising a flexible region continuous
with a rigid region, the flexible region comprising a first plastic and at least one elastomer,
and the rigid region comprising a second plastic, disposing at least a portion of the
composition on the applicator, and contacting the surface with the composition on the
applicator.
In another embodiment, a method for applying a composition to a surface comprises
providing an applicator comprising a sintered porous polymeric component and a fibrous
component coupled to the sintered porous polymeric component, disposing at least a portion
of a composition on the applicator, and contacting a surface with the composition on the
applicator. In some embodiments, the sintered porous polymeric component comprises at
least one plastic and at least one elastomer. In other embodiments, the sintered porous
polymeric component comprises a continuous material comprising a flexible region and a
rigid region, the flexible region comprising a first plastic and at least one elastomer, and the
rigid region comprising a second plastic.
In some embodiments of applying a composition to a surface, disposing at least a
portion of a composition on the applicator comprises passing the composition through the
fibrous component to an exterior surface of the sintered porous polymeric component.
A surface, in some embodiments, comprises a writing or painting surface, such as
paper, parchment, and canvas. In other embodiments, a surface comprises a biological
surface, such as skin or hair or a site of injury such as a laceration. In a further embodiment,
a surface comprises a site of a topical disease or condition, such as a site of affected skin.
In some embodiments of methods of applying a composition to a surface wherein the
sintered polymeric material of the applicator comprises a color change indicator, the color of
the sintered polymeric material can change when a composition is disposed thereon for
application to a surface. The color change of the sintered polymeric material can indicate to a


user that a composition is present on the applicator and ready for subsequent application to a
surface.
Filtration Media and Barrier Media Comprising Porous Sintered Polymeric Materials
The present invention additionally provides filtration and barrier media comprising
sintered porous polymeric materials of the present invention and methods of making and
using the same. Filtration and barrier media comprising sintered polymeric materials of the
present invention can form sufficient seals with housings to prevent fluid circumventing the
material without being subjected to the precise tolerances often required by filtration
apparatus. Filtration and barrier media comprising sintered porous polymeric materials of the
present invention can demonstrate flexible properties allowing the media.to conform to
variations and inconsistencies in surfaces of the housing thereby facilitating sufficient sealing
with the housing and reducing product failure and discardment due to fluid bypass.
Moreover, the flexible properties of filtration and barrier media of the present invention can
permit the porosity of the media to be adjusted according to various applications.
Filtration media, according to embodiments of the present invention, are operable to
pass liquids and gases to filter contaminants or other desired species in the liquids or gases.
When a liquid or gas flows through a filtration medium of the present invention,
contaminants or other desired species, such as target molecules or substances, become
associated with the filtration medium and are removed the liquid or gas. In being operable to
filter both liquids and gases, filtration media of the present invention, in some embodiments,
comprise no or substantially no absorbent or super-absorbent materials.
Barrier media, according to some embodiments, however, permit the passage of
gases but inhibit and/or prevent the flow of liquids through the sintered porous polymeric
material. By permitting the passage of gases and inhibiting and/or preventing the passage of
liquids, barrier media of the present invention can protect downstream equipment and
processes from contamination resulting from contact with undesired fluids. Barrier media of
the present invention, for example, can serve as in-line barrier media in a pipe or a tube to
prevent liquid flow through the pipe or tube. In another embodiment, barrier media can be
placed in pipette tips and act as pipette tip filters to prevent pipetted fluid from contaminating
the pipettor.
Filtration Media and Barrier Media
In one embodiment, the present invention provides a filtration medium comprising a
sintered porous polymeric material, the sintered porous polymeric material comprising at
least one plastic and at least one elastomer. In some embodiments, a sintered porous


polymeric material of a filtration medium further comprises at least one color change
indicator.
In another embodiment, the present invention provides a filtration medium
comprising a sintered porous polymeric material comprising a flexible region continuous
with a and a rigid region. The flexible region of the continuous sintered porous polymeric
material, in some embodiments, comprises a first plastic and at least one elastomer, and the
rigid region comprises a second plastic. In some embodiments, the flexible region comprises

comprises a second plastic and a second color change indicator. In other embodiments, a
color change indicator is incorporated into only one of the flexible and rigid regions.
In another embodiment, the present invention provides a barrier medium comprising a
sintered porous polymeric material, the sintered porous polymeric material comprising at
least one plastic and at least one elastomer. In some embodiments, a liquid barrier medium
comprises a sintered porous polymeric material comprising a flexible region continuous with
a rigid region as provided herein.
In some embodiments, a liquid barrier medium comprising a sintered porous
polymeric material comprising at least one plastic and at least one elastomer further
comprises at least one super-absorbent material. Super-absorbent materials suitable for use in
barrier media, according to embodiments of the present invention, rapidly swell when
contacted with water or other aqueous solutions but do not dissolve in water or aqueous
solutions. The swelling of the super-absorbent material, in some embodiments, can seal the
barrier medium preventing further flow of fluids through the filtration medium.
In other embodiments, a liquid barrier medium comprising a sintered porous
polymeric material comprising at least one plastic and at least one elastomer does not include
a super-absorbent material. In a further embodiment, a liquid barrier medium comprising a
sintered porous polymeric material comprising at least one plastic and at least one elastomer
further comprises a hydrophobic coating such as fluorinated molecular coating as described
in United States patent nos. 6,638,610 and 6,358,569. In one embodiment, a liquid barrier
medium comprising a sintered porous polymeric material comprising at least one plastic and
at least one elastomer further comprises at least one color change indicator.
Color change indicators suitable for use in sintered porous polymeric materials of
filtration and barrier media, in some embodiments, are consistent with any of the color
change indicators described herein.


A color change indicator, according to embodiments of the present invention, is
operable to at least partially change the color of the sintered porous polymeric material of
filtration and barrier media when contacted with an aqueous and/or organic liquid. In some
embodiments, the color change indicator changes the sintered porous polymeric material
from a first color to a second color when contacted with an aqueous and/or organic liquid. In
other embodiments, the color change indicator changes the sintered porous polymeric
material from colorless or white to colored. The color change of the sintered porous
polymeric material of a filtration or barrier medium, according to embodiments of the present
invention, depends on the identity of the color change indicator selected. The change in color
provides a user an indication that the filtration or barrier medium has come into contact with
a liquid.
Sintered Polymeric Materials of Filtration Media and Barrier Media
A sintered polymeric material of filtration and barrier media, in some embodiments of
the present invention, comprises at least one elastomer in an amount ranging from about 10
weight percent to about 90 weight percent. In other embodiments, a sintered polymeric
material comprises at least one elastomer in an amount ranging from about 20 weight percent
to about 80 weight percent. In another embodiment, a sintered polymeric material comprises
at least one elastomer in an amount ranging from about 30 weight percent to about 70 weight
percent. In a further embodiment, a sintered polymeric material comprises at least one
elastomer in an amount ranging from about 40 weight percent to about 60 weight percent.
A sintered porous polymeric material comprising at least one plastic and at least one •
elastomer, in some embodiments, has a porosity ranging from about 10% to about 90%. In
other embodiments, a sintered porous polymeric material comprising at least one plastic and
at least one elastomer has a porosity ranging from about 20% to about 80% or from about
30% to about 70%. In a further embodiment, a sintered polymeric material comprising at
least one plastic and at least one elastomer has a porosity ranging from about 40% to about
60%.
Sintered porous polymeric materials comprising at least one plastic and at least one
elastomer, according to some embodiments of the present invention, have an average pore
size ranging from about from about 1 µm to about 200 µm. In other embodiments, sintered
porous polymeric materials comprising at least one plastic and at least one elastomer have an
average pore size ranging from about 2 µm to about 150 µm, from about 5 µm to about 100
µm, or from about 10 µm to about 50 µm. In another embodiment, a sintered porous


polymeric material has an average pore size less than about 1 µm. In one embodiment, a
sintered porous polymeric material comprising at least one plastic and at least one elastomer
has an average pore size ranging from about 0.1 µm to about 1 µm. In a further embodiment,
a sintered porous polymeric material of the present invention has an average pore size greater
than 200 µm. In one embodiment, a sintered porous polymeric material comprising at least
one plastic and at least one elastomer has an average pore size ranging from about 200 µm to
about 500 µm or from about 500 µm to about 1 mm.
Sintered porous polymeric materials comprising at least one plastic and at least one
elastomer, according to some embodiments, have a density ranging from about 0.1 g/cm3 to
about 1 g/cm3. In other embodiments, a sintered porous polymeric material of the present
invention has a density ranging from about 0.2 g/cm3 to about 0.8 g/cm3 or from about 0.4
g/cm to about 0.6 g/cm . In a further embodiment, a sintered porous polymeric material
comprising at least one plastic and at least one elastomer has a density greater than about 1
g/cm3. In one embodiment, a sintered porous polymeric material comprising at least one
. plastic and at least one elastomer has a density less than about 0.1 g/cm3.
In some embodiments, a sintered porous polymeric material of a filtration or barrier
medium comprising at least one plastic and at least one elastomer has a rigidity according to
ASTM D747 of less than about 15 pounds. ASTM D747 is entitled the Standard Test
Method for Apparent Bending Modulus of Plastics by Means of a Cantilever Beam and is
well suited for determining relative flexibility of materials over a wide range. In other
embodiments, a sintered porous polymeric material comprising at least one plastic and at
least one elastomer has a rigidity according to ASTM D747 of less than about 10 pounds. In
a further embodiment, a sintered polymeric material comprising at least one plastic and at
least on elastomer has a rigidity according to ASTM D747 of less than about 5 pounds. In
another embodiment, a sintered porous polymeric material comprising at least one plastic and
at least on elastomer has a rigidity according to ASTM D747 of less than about 1 pound.
Moreover, in some embodiments, a sintered porous polymeric material comprising at
least one plastic and at least one elastomer has a tensile strength ranging from about 10 to
about 5,000 psi as measured according to ASTM D638. A sintered porous polymeric
material comprising at least one plastic and at least one elastomer, in some embodiments, has
a tensile strength ranging from about 50 to 3000 psi or from about 100 to 1,000 psi as
measured according to ASTM D638. In some embodiments, a sintered porous polymeric


material comprising at least one plastic and at least one elastomer has an elongation from
ranging from 10% to 500%.
In some embodiments, a sintered polymeric material of a barrier medium comprising
at least one elastomer and at least one plastic further comprises at least one super-absorbent
material. In some embodiments, super-absorbent materials comprise hydrolyzed starch
acrylonitrile graft copolymer, neutralized starch-acrylic acid graft copolymer, saponified
acrylic acid ester-vinyl acetate copolymer, hydrolyzed acrylonitrile copolymer, acrylamide
copolymer, modified cross-linked polyvinyl alcohol, neutralized self-crosslinking polyacrylic
acid, crosslinked polyacrylate salts, neutralized crosslinked isobutylene-maleic anhydride
copolymers, and salts and mixtures thereof. Super-absorbent materials, in some
embodiments, comprise those disclosed by United States Patent Nos. 5,998,032, 5,939,086,
5,836,929, 5,824,328, 5,797,347, 5,750,585, 5,175,046, 4,820,577, 4,724,114, and 4,443,515.
Examples of commercially available super-absorbent materials comprise AP80HS, available
from Stockhousen of Tuscaloosa, AL, and HYSORB® P7200, available from BASF of Budd
Lake, NJ.
In some embodiments, a super-absorbent material comprises particles, fibers, or
mixtures thereof. Particulate super-absorbent materials, in some embodiments, have average
sizes ranging from about 1 µm to about 1 mm. In another embodiment, super-absorbent
particles have an average size ranging from about 10 µm to about 900 µm, from about 50 µm
to about 500 µm, or from about 100 µm to about 300 µm. In a further embodiment, super-
absorbent particles have an average size less than about 1µm or greater than about 1 mm.
Moreover, super-absorbent fibers, in some embodiments, have an average diameter
ranging from about 1 µm to about 1 mm or from about 10 µm to about 750 µm. In another
embodiment, super-absorbent fibers have an average diameter ranging from about 50 µm to
about 500 µm, from about 100 µm to about 400 µm or from about 200 µm to about 300 µm.
Super-absorbent fibers, in some embodiments, have a length ranging from about 100 µm to
about 2.5 cm or from about 250 µm to about 1 cm. In another embodiment, super-absorbent •
fibers have a length ranging from about 500 µm to about 1.5 mm or from about 750 µm to
about 1 mm.
In some embodiments, a sintered porous polymeric material of a barrier medium
comprises at least one super-absorbent material in an amount ranging from about 10 weight
percent to about 90 weight percent. In other embodiments, a sintered porous polymeric
material of a barrier medium comprises at least one super-absorbent material in an amount
ranging from about 20 weight percent to about 80 weight percent. In another embodiment, a


sintered porous polymeric material of a barrier medium comprises at least one super-
absorbent material in an amount ranging from about 30 weight percent to about 70 weight
percent. In a further embodiment, a sintered porous polymeric material of a barrier medium
comprises at least one super-absorbent material in an amount ranging from about 40 weight
percent to about 60 weight percent.
Super-absorbent materials of barrier media, in some embodiments, are incorporated
into the sintered porous matrix of the polymeric material. In other embodiments, super-
absorbent materials are located in the pores of the sintered porous polymeric material of a
barrier medium. In one embodiment, a super-absorbent material resides in the majority of the
pores of the sintered porous polymeric material of a barrier medium. In another embodiment,
a super-absorbent material resides in the minority of pores of the sintered porous polymeric
material of a barrier medium. In a further embodiment, super-absorbent materials are located
in both the sintered porous matrix and the pores of the sintered porous polymeric material of
a barrier medium.
In another embodiment, a sintered porous polymeric material of filtration and barrier
media comprising at least one plastic and at least one elastomer further comprises at least one
color change indicator. Color change indicators suitable for use in sintered polymeric
materials of filtration and barrier media of the present invention, in some embodiments, are
consistent with any of the color change indicators described herein.
In some embodiments, a sintered porous polymeric material of filtration and barrier
media comprising at least one plastic and at least one elastomer comprises at least one color
change indicator in an amount ranging from about 0.001 weight percent to about 2 weight
percent. In other embodiments, a sintered porous polymeric material comprises at least one
color change indicator in an amount ranging from about 0.01 weight percent to about 1
weight percent. In a further embodiment, a sintered porous polymeric material comprises at
least one color change indicator in an amount ranging from about 0.05 weight percent to
about 0.5 weight percent.
The sintered porous polymeric material of a barrier medium, in some embodiments of
the present invention, further comprises a hydrophobic coating. A hydrophobic coating, in
some embodiments, comprises a fluorinated hydrophobic coating. A fluorinated hydrophobic
coating, in one embodiment, comprises one or more fluorinated polymers. Fluorinated
polymers, according to some embodiments, are produced from the polymerization of
perfluorinated monomers, partially fluorinated monomers, or combinations thereof.
Fluorinated polymeric materials suitable for use in coating a barrier medium of the present


invention comprise fluorinated acrylates such as fluorinated methacrylates. Fluorinated
methacrylates, in some embodiments, comprise perfluorohexyl methacrylate, perfluoroheptyl
methacrylate, perfluorooctyl methacrylate, perfluorononylmethacrylate, perfluorodecyl
methacrlyate, perfluoroundecyl methacrylate, perfluorododecyl methacrylate, or mixtures
thereof. In another embodiment, fluorinated polymeric materials comprise fluorinated acrylic
esters.
Filtration or barrier media comprising at least one elastomer and at least one plastic
can have any desired shape or form such as disks, tubes, blocks, cones, cylinders, sheets, or
films.
Moreover, the flexible properties of filtration or barrier media comprising at least one
elastomer and at least one plastic can facilitate placement of the filtration or barrier media in
a housing. The flexible properties allow filtration or barrier media of the present invention,
in some embodiments, to conform to filtration housings and accommodate inconsistencies or
defects in the housings thereby providing enhanced sealing with the housing. As a result, the
filtration or barrier media can be correctly and securely disposed in housings without being
limited to the tight tolerances associated with previous filtration media. The secure
placement of filtration or barrier media of the present invention in housings can reduce the
occurrences of fluid circumventing the filtration media and reduce product failure and losses
due to housing inconsistencies and variations.
In another aspect, a sintered porous polymeric material of filtration and barrier media
of the present invention, in some embodiments, comprises a flexible region continuous with a
rigid region, wherein the flexible region comprises a first plastic and at least one elastomer
and the rigid region comprises a second plastic. In some embodiments, the first and second
plastics comprise the same plastics. In other embodiments, the first and second plastics
comprise different plastics.
A continuous sintered porous polymeric material comprising a flexible region and a
rigid region, in some embodiments, further comprises plastics in addition to the first and
second plastics. In one embodiment, for example, the flexible region of a continuous sintered
polymeric material comprises one or more plastics in addition to the first plastic. Moreover,
the rigid region, in some embodiments, comprises one or more plastics in addition to the
second plastic.
In some embodiments, the flexible region of a continuous sintered porous polymeric
material of a filtration or barrier medium comprises at least one elastomer in an amount
ranging from about 10 weight percent to about 90 weight percent. In other embodiments, the


flexible region comprises at least one elastomer in an amount ranging from about 20 weight
percent to about 80 weight percent. In another embodiment, the flexible region comprises at
least one elastomer in an amount ranging from about 30 weight percent to about 70 weight
percent. In a further embodiment, the flexible region comprises at least one elastomer in an
amount ranging from about 40 weight percent to about 60 weight percent.
In some embodiments, the flexible region comprising a first plastic and at least one
elastomer has a porosity ranging from about 10% to about 90%. In another embodiment, the
flexible region has a porosity ranging from about 20% to about 80% or from about 30% to
about 70%. In a further embodiment, the flexible region has a porosity ranging from about
40% to about 60%.
In some embodiments, the flexible region of a continuous sintered porous polymeric
material of a filtration or barrier medium has an average pore size ranging from about 1 urn
to about 200 µm. In other embodiments, the flexible region has an average pore size ranging
from about 2 µm to about 150 µm, from about 5 urn to about 100 µm or from about 10 µm to
about 50 µm. In another embodiment, the flexible region has an average pore size less than
about 1 µm. In one embodiment, the flexible region has an average pore size ranging from
about 0.1 µm to about 1 µm. In a further embodiment, the flexible region has an average
pore size greater than 200 µm. In one embodiment, the flexible region has an average pore
size ranging from about 200 v to about 500 µm or from about 500 µm to about 1 mm.
The flexible region of a continuous sintered porous polymeric material, according to
some embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other
embodiments, the flexible region has a density ranging from about 0.2 g/cm3 to about 0.8
g/cm3 or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further embodiment, the flexible
region has a density greater than about 1 g/cm3. In one embodiment, the flexible region has a
density less than about 0.1 g/cm3.
In some embodiments, the flexible region of a continuous sintered porous polymeric
material has rigidity according to ASTM D747 of less than about 15 pounds. In other
embodiments, the flexible region of a sintered polymeric material has a rigidity according to
ASTM D747 of less than about 10 pounds. In another embodiment, the flexible region of a
continuous sintered polymeric material has a rigidity according to ASTM D747 of less than
about 5 pounds. In a further embodiment, a sintered polymeric material comprising at least
one plastic and at least on elastomer has a rigidity according to ASTM D747 of less than
about 1 pound.


The rigid region of a continuous sintered porous polymeric material of a filtration or
barrier medium, according embodiments of the present invention, comprises a second plastic.
In some embodiments, the rigid region does not comprise elastomeric materials or
substantially no elastomeric materials in addition to the second plastic. In other
embodiments, the rigid region comprises less than about 20 weight percent elastomer. In
another embodiment, the rigid region comprises less than about 10 weight percent elastomer.
In a further embodiment, the rigid region comprises less than about 5 weight percent
elastomer.
In some embodiments, the rigid region has a porosity ranging from about 10% to
about 90%. In other embodiments, the rigid region has a porosity ranging from about 20% to
about 80% or from about 30% to about 70%. In another embodiment, the rigid region has a
porosity ranging from about 40% to about 60%.
In some embodiments, the rigid region of a continuous sintered porous polymeric
material of a filtration or barrier medium has an average pore size ranging from about 1 µm
to about 200 µm. In other embodiments, the rigid region has an average pore size ranging
from about 2 µm to about 150 µm, from about 5 µm to about 100 µm or from about 10 µm to
about 50 µm. In another embodiment, the rigid region has an average pore size less than
about 1 µm. In one embodiment, the rigid region has an average pore size ranging from
about 0.1 µm to about 1 µm. In a further embodiment, the rigid region has an average pore
size greater than 200 µm. In one embodiment, the rigid region has an average pore size
ranging from about 200 µm to about 500 µm or from about 500 µm to about 1 mm.
The rigid region of a continuous sintered porous polymeric material, according to
some embodiments, has a density ranging from about 0.1 g/cm3 to about 1 g/cm3. In other
embodiments, the rigid region has a density ranging from about 0.2 g/cm3 to about 0.8 g/cm3
or from about 0.4 g/cm3 to about 0.6 g/cm3. In a further embodiment, the rigid region has a
density greater than about 1 g/cm3. In one embodiment, the rigid region has a density less
than about 0.1 g/cm3.
In some embodiments, the rigid region of a continuous sintered porous polymeric
material has rigidity according to ASTM D747 of greater than about 15 pounds. In other
embodiments, the rigid region of a sintered polymeric material has a rigidity according to
ASTM D747 of greater than about 10 pounds. In another embodiment, the rigid region of a
continuous sintered polymeric material has a rigidity according to ASTM D747 of greater
than about 5 pounds.


In some embodiments, the flexible region of a sintered porous polymeric material of a
barrier medium further comprises a first super-absorbent material. Super-absorbent materials
suitable for use in the flexible region of a continuous sintered porous polymeric material of a
barrier medium, in some embodiments, are consistent with those provided herein.
In some embodiments, the flexible region of a continuous sintered porous polymeric
material of a barrier medium comprises a first super-absorbent material in an amount ranging
from about 10 weight percent to about 90 weight percent. In other embodiments, the flexible
region of a continuous sintered porous polymeric material of a barrier medium comprises a
first super-absorbent material in an amount ranging from about 20 weight percent to about 80
weight percent. In another embodiment, the flexible region of a continuous sintered porous
polymeric material of a barrier medium comprises a first super-absorbent material in an
amount ranging from about 30 weight percent to about 70 weight percent. In a further
embodiment, the flexible region of a continuous sintered porous polymeric material of a
barrier medium comprises a first super-absorbent material in an amount ranging from about
40 weight percent to about 60 weight percent.
In some embodiments, the rigid region of a sintered porous polymeric material of a
barrier medium further comprises a second super-absorbent material. Super-absorbent
materials suitable for use in the rigid region of a continuous sintered porous polymeric
material of a barrier medium, in some embodiments, are consistent with those provided
herein. The second super-absorbent material, in some embodiments, is the same as the first
super-absorbent material of the flexible region. In other embodiments, the second super-
absorbent material of the rigid region is different than the first super-absorbent material of the
flexible region.
In some embodiments, the rigid region of a continuous sintered porous polymeric
material of a barrier medium comprises a second super-absorbent material in an amount
ranging from about 10 weight percent to about 90 weight percent. In other embodiments, the
rigid region of a continuous sintered porous polymeric material of a barrier medium
comprises a second super-absorbent material in an amount ranging from about 20 weight
percent to about 80 weight percent. In another embodiment, the rigid region of a continuous
sintered porous polymeric material of a barrier medium comprises a second super-absorbent
material in an amount ranging from about 30 weight percent to about 70 weight percent. In a
further embodiment, the rigid region of a continuous sintered porous polymeric material of a
barrier medium comprises a second super-absorbent material in an amount ranging from
about 40 weight percent to about 60 weight percent.


In some embodiments, the flexible region of a continuous sintered porous polymeric
material further comprises at least one color change indicator. Color change indicators
suitable for use in the flexible region of a continuous sintered porous polymeric material, in
some embodiments, are consistent with those provided herein.
In some embodiments, the flexible region of a continuous sintered porous polymeric
material comprises at least one color change indicator in an amount ranging from about 0.001
weight percent to about 2 weight percent. In other embodiments, the flexible region
comprises at least one color change indicator in an amount ranging from about 0.01 weight
percent to about 1 weight percent. In a further embodiment, the flexible region comprises at
least one color change indicator in an amount ranging from about 0.05 weight percent to
about 0.5 weight percent.
In some embodiments, the rigid region of a continuous sintered porous polymeric
material further comprises at least one color change indicator. Color change indicators
suitable for use in the rigid region of a continuous sintered porous polymeric material, in
some embodiments, are consistent with those provided herein.
In some embodiments, the rigid region of a continuous sintered porous polymeric
material comprises at least one color change indicator in an amount ranging from about 0.001
weight percent to about 2 weight percent. In other embodiments, the rigid region comprises
at least one color change indicator in an amount ranging from about 0.01 weight percent to
about 1 weight percent. In a further embodiment, the rigid region comprises at least one
color change indicator in an amount ranging from about 0.05 weight percent to about 0.5
weight percent.
Figure 6 illustrates a filtration medium comprising a continuous sintered porous
polymeric material comprising a flexible region and a rigid region according to one
embodiment of the present invention. The filtration medium (600) shown in Figure 6 has the
shape of a disk wherein the flexible region (602) encircles the rigid region (604). The
flexible region (602) along the circumference of the disk facilitates placement of the filtration
medium (600) in a housing. The flexible properties of the flexible region (602), as provided
herein, allow the flexible region to conform to a filtration housing and accommodate
inconsistencies or defects in the housing thereby providing enhanced sealing with the
housing. As a result, the filtration medium (600) can be correctly and securely disposed in a
housing without being limited to the tight tolerances associated with previous filtration
media. The secure placement of the filtration medium (600) can lead to a reduction in the
occurrence of fluid by-passing the filtration medium (600).


Figure 7 illustrates a filtration medium comprising a continuous sintered porous
polymeric material comprising a flexible region and a rigid region according to one
embodiment of the present invention. The filtration medium (700) shown in Figure 7
comprises a flexible region (702) comprising at least one elastomer and at least one plastic
and a rigid region (704) comprising a second plastic.
Filters and Apparatus Comprising Filtration Media and/or Barrier Media
In another aspect, the present invention provides a filter comprising a housing and at
least one filtration medium disposed in the housing, the filtration medium comprising a
sintered polymeric material comprising at least one plastic and at least one elastomer as
provided herein. In some embodiments, the filtration medium further comprises at least one
color change indicator as provided herein.
In other embodiments, a filtration medium of a filter comprises a continuous sintered
porous polymeric material comprising a flexible region and a rigid region, the flexible region
comprising a first plastic and at least one elastomer as provided herein. The rigid region, in
some embodiments, comprises a second plastic as provided herein. In some embodiments,
the flexible and/or rigid region further comprises at least one color change indicator.
In another embodiment, the present invention provides an apparatus comprising a
housing and at least one barrier medium disposed in the housing, the barrier medium
comprising a sintered polymeric material comprising at least one plastic and at least one
elastomer as described herein. In some embodiments, the barrier medium further comprises
at least one super-absorbent material. In other embodiments, the barrier medium further
comprises a hydrophobic coating such as a fluorinated coating. In one embodiment, a
fluorinated coated comprises a fluorinated polymeric coating.
A housing, in some embodiments of the present invention, comprises a pipette tip, a
chromatographic column such as those used in liquid chromatography, a vacuum filtration
housing, a funnel, a tube, a syringe, a catheter, a duct, or combinations thereof. In some
embodiments, housings comprising pipette tips can come in a variety of shapes and sizes to
fit any type or brand of pipettor. In one embodiment, a housing comprises a tubular housing
as described in United States Patent No. 5,259,956. In some embodiments, a housing
comprises a tube wherein the filtration medium serves as an in-line filter operable to filter
fluids. In one embodiment, a barrier medium of the present invention is placed upstream
and/or downstream of the filtration medium to prevent the passage of undesired fluids. In
another embodiment, a housing comprises fluid flow control devices, such as a suction
canister as detailed in PCT Application Publication Number WO 87/00439. In another


embodiment, a housing comprises luer lock apparatus often used in medical and laboratory
applications, such as those described in United States Patent No. 5,620,427.
Figure 8 illustrates a barrier medium disposed in a pipette tip housing according to an
embodiment of the present invention. As understood by one of skill in the art, when disposed
in a pipette tip, a barrier medium can serve as a pipette tip filter. The pipette tip (800)
comprises a tapering, hollow tubular member (802) constructed of an inert material such as
glass or plastic and is open at a first end (804) and a second end (806), the first (804) and
second (806) ends are in facing opposition. A barrier medium (808) comprising a sintered
porous polymeric material comprising at least one elastomer, at least one plastic, and
optionally at least one super-absorbent material is disposed in the tubular member (802) to
define a liquid sample chamber (810) between the barrier medium (808) and second end
(806). The barrier medium (808) is additionally spaced from the first end (804) of the tubular
member (802) to define a chamber (811) between the barrier medium (808) and first end
(804)
The first end (804) of the tubular member (802) is releasably secured to a suitable
suction device (812) as known to one of skill in the art. Any suitable suction device for
drawing a predetermined volume of liquid in the chamber (810) can be used, such as a
volumetric pipetter, suction pump, elastic bulb, bellows, etc. The barrier medium (808), in
some embodiments, is force or pressure fitted securely into tubular member (802), under a
sufficient pressure so that it is securely held and frictionally sealed against the inner wall of
tubular member (802) although not attached to the inner wall by any adhesive or other
additional material. The flexible properties of the barrier medium (808) allows for a secure
seal with the wall of the tubular member (802) and can accommodate inconsistencies or
defects along interior surfaces of the tubular member (802) in contact with the filtration
medium (808).
In some embodiments, the flexible region of a filtration or barrier medium is
compressed or otherwise deformed when the medium is disposed in a housing. Compression
or deformation of the flexible region can allow a filtration or barrier medium to fit into a
variety of housings having differing dimensions thereby precluding the need to design and
manufacture a specific filtration or barrier medium for a specific housing. Moreover,
compression of the flexible region can preclude or inhibit deformation of the rigid region of
the filtration or barrier medium. Preventing deformation of the rigid region, in some
embodiments, allows the rigid region to demonstrate a uniform pore structure and porosity.
The filtration medium of Figure 6, for example, comprises a flexible region (602) encircling a


rigid region (604). When disposed in a housing, the flexible region (602), in some
embodiments, is placed in compression while the rigid region (6.04) remains in an
unperturbed state. In one embodiment, a flexible region of a filtration or barrier medium
serves as a housing sealing component and a rigid region serves as a filtration or barrier
component.
Methods for Producing Filtration and Barrier Media
In another aspect, trie present invention provides methods of producing a filtration or
barrier medium comprising a sintered porous polymeric material. In one embodiment, a
method for producing a filtration or barrier medium comprising a sintered porous polymeric
material comprises providing particles of at least one elastomer, providing particles of at least
one plastic, and sintering the plastic and elastomer particles. For barrier media, in some
embodiments, at least one super-absorbent material is added to the particles of the at least one
elastomer and at least one plastic and sintered with the particles of the at least one elastomer
and at least one plastic. In some embodiments, the at least one super-absorbent material is
added as particles. In other embodiments, the super-absorbent material is added as fibers.
In some embodiments, particles of at least one plastic and particles of at least one
elastomer are mixed in a desired ratio (weight percent) to produce a substantially uniform
mixture. The uniform mixture of plastic and elastomer particles are disposed in a mold and
sintered. The shape of the mold can be any desired shape, such as disks, tubes, cones, and/or
tapered shapes such as frustroconical shapes, allowing for the facile and single-step
production of filtration or barrier media.
Plastic and elastomer particles, in some embodiments, have average sizes ranging
from about 1 µm to about 1 mm. In another embodiment, plastic and elastomer particles have
average sizes ranging from about 10 µm to about 900 µm, from about 50 µm to about 500
µm, or from about 100 µm to about 400 µm. In a further embodiment, plastic and elastomer
particles have average sizes ranging from about 200 µm to about 300 µm. In some
embodiments, plastic and elastomer particles have average sizes less than about 1 µm or
greater than about 1 mm.
Sizes of plastic and elastomer particles, in some embodiments, are selected
independently. In one embodiment, for example, the plastic particles have an average size
greater than the elastomer particles. In another embodiment, plastic particles have an average
size smaller than the elastomer particles. In a further embodiment, plastic and elastomer
particles have about the same average size.


Plastic and elastomer particles, in some embodiments, are sintered at a temperature
ranging from about 200°F to about 700°F. In some embodiments, plastic and elastomer
particles are sintered at a temperature ranging from about 300°F to about 500°F. The
sintering temperature, according to embodiments of the present invention, is dependent upon
and selected according to the identity of the plastic and elastomer particles.
Plastic and elastomer particles, in some embodiments, are sintered for a time period
ranging from about 30 seconds to about 30 minutes or a time sufficient to produce the
sintered porous polymeric material. In other embodiments, plastic and elastomer particles are
sintered for a time period ranging from about 1 minute to about 15 minutes or from about 5
minutes to about 10 minutes. In some embodiments, the sintering process comprises heating,
soaking, and/or cooking cycles. Moreover, in some embodiments, sintering of plastic and
elastomer particles is conducted under ambient pressure (1 atm). In other embodiments
sintering of plastic and elastomer particles is conducted under pressures greater than ambient
pressure.
In some embodiments of producing filtration or barrier media, at least one color
change indicator is added to the particles of the at least one elastomer and at least one plastic
and sintered with the particles of the at least one elastomer and the at least one plastic
according to temperatures and times set forth herein. Particles of a color change indicator,
according to some embodiments, have average sizes ranging from about 1 µm to about 500
µm or from about 10 µm to about 400 µm. In another embodiment, particles of a color
change indicator have average sizes ranging from about 50 µm to about 300 µm. In a further
embodiment, particles of a color change indicator have average sizes ranging from about 100
µm to about 200 µm. In some embodiments, particles of a color change indicator have
average sizes less than about 1 urn or greater than about 500 urn.
In another embodiment, a method of producing a filtration or barrier medium
comprising a sintered porous polymeric material comprises disposing particles of a first
plastic mixed with particles of at least one elastomer in a first part of a mold, disposing
particles of a second plastic in a second part of the mold adjacent to the first part of the mold,
and sintering the first plastic particles, second plastic particles and elastomer, particles. For
barrier media, in some embodiments, at least one super-absorbent material is added to the
particles of the at least one elastomer, first plastic, and second plastic, and sintered with the
particles of the at least one elastomer, first plastic, and second plastic. In some embodiments,
the at least one super-absorbent material is added as particles. In other embodiments, the
super-absorbent material is added as fibers.


In one embodiment, for example, particles of a first plastic are mixed with particles of
at least one elastomer in a desired ratio (weight percent) to produce a substantially uniform
mixture. The mixture is disposed in a first part of a mold. Particles of a second plastic are
disposed in the second part of the mold adjacent to the mixture of particles of the first plastic
and at least one elastomer. The particles of the first plastic, second plastic, and elastomer
particles are subsequently sintered to produce a polymeric material of the present invention.
In some embodiments, the first part of a mold comprises the bottom half of the mold.
Moreover, in some embodiments, the second part of a mold comprises the top half of the
mold.
In other embodiments, particles of a second plastic are disposed in the first part of a
mold. The mixture of elastomer and first plastic particles are disposed in the second part of
the mold adjacent to the second plastic particles. The particles of the first plastic, second
plastic, and elastomer particles are subsequently sintered to produce a polymeric material of
the present invention.
First plastic, second plastic, and elastomer particles, in some embodiments, have
average sizes ranging from about 1 µm to about 1 mm. In another embodiment, first plastic,
second plastic, and elastomer particles have average sizes ranging from about 10 µm to about
900 µm, from about 50 µm to about 500 µm, or from about 100 µm to about 400 µm. In a
further embodiment, first plastic, second plastic, and elastomer particles have average sizes
ranging from about 200 µm to about 300 µm. In some embodiments, first plastic, second
plastic, and elastomer particles have average sizes less than about 1 µm or greater than about
1 mm. Sizes of first plastic, second plastic, and elastomer particles, in some embodiments,
are selected independently.
First plastic, second plastic, and elastomer particles, in some embodiments, are
sintered at a temperature ranging from about 200°F to about 700°F. In some embodiments,
first plastic, second plastic, and elastomer particles are sintered at a temperature ranging from
about 300°F to about 500°F. The sintering temperature, according to embodiments of the
present invention, is dependent upon and selected according to the identity of the first plastic,
second plastic and elastomer particles.
First plastic, second plastic, and elastomer particles, in some embodiments, are
sintered for a time period ranging from about 30 seconds to about 30 minutes. In other
embodiments, first plastic, second plastic, and elastomer particles are sintered for a time
period ranging from about 1 minute to about 15 minutes or from about 5 minutes to about 10
minutes. In some embodiments, the sintering process comprises heating, soaking, and/or


cooking cycles. Moreover, in some embodiments, sintering of first plastic, second plastic,
and elastomer particles is performed under ambient pressure (1 atm). In other embodiments
sintering of first plastic, second plastic, and elastomer particles is conducted under pressures
greater than ambient pressure.
In some embodiments of producing filtration and barrier media, at least one color
change indicator is added to the particles of the first plastic, second plastic and at least one
elastomer and sintered with the particles of the first plastic, second plastic, and at least one
elastomer according to temperatures and times set forth herein. Particles of a color change
indicator, according to some embodiments, have average sizes ranging from about 1 µm to
about 500 µm or from about 10 µm to about 400 µm. In another embodiment, particles of a
color change indicator have average sizes ranging from about 50 µm to about 300 µm. In a
further embodiment, particles of a color change indicator have average sizes ranging from
about 100 µm to about 200 µm. In some embodiments, particles of a color change indicator
have average sizes less than about 1 µm or greater than about 500 µm.
A polymeric material produced by sintering particles of a first plastic, a second
plastic, and at least one elastomer, in embodiments of the present invention, can comprise a
flexible region and a rigid region, the flexible region comprising the first plastic and the at
least one elastomer, and the rigid region comprising the second plastic. The shape of the
mold can be any desired shape, such as disks, tubes, or cones, allowing for the facile and
single-step production of filtration or barrier media. The shape of the mold can be any
desired shape, such as disks, tubes, cones, and/or tapered shapes such as frustroconical
shapes, allowing for the facile and single-step production of filtration or barrier media.
In one embodiment of method of making a barrier medium, the method further
comprises coating the sintered porous polymeric material of the barrier medium with a
hydrophobic coating. A hydrophobic coating, in some embodiments, comprises a fluorinated
hydrophobic coating. A fluorinated hydrophobic coating, in one embodiment, comprises one
or more fluorinated polymers. Fluorinated polymers, according to some embodiments, are
produced from the polymerization of perfluorinated monomers, partially fluorinated
monomers, or combinations thereof. Fluorinated polymeric materials suitable for use in
coating a barrier medium of the present invention comprise fluorinated acrylates such as
fluorinated methacrylates. Fluorinated methacrylates, in some embodiments, comprise
perfluorohexyl methacrylate, perfluoroheptyl methacrylate, perfluorooctyl methacrylate,
perfluorononylmethacrylate, perfluorodecyl methacrlyate, perfluoroundecyl methacrylate,


perfluorododecyl methacrylate, or mixtures thereof. In another embodiment, fluorinated
polymeric materials comprise fluorinated acrylic esters.
In some embodiments, a fluorinated coating is applied to a barrier medium of the
present invention by solubilizing the fluorinated molecules, such as a fluorinated polymer, in
a solvent and applying the resulting solution to the surfaces of the barrier medium.
Methods for Producing a Filter
In another aspect, the present invention provides methods of producing a filter. In one
embodiment, a method for producing a filter comprises providing a filtration medium
comprising a sintered porous polymeric material, providing a housing, and disposing the
filtration medium in the housing, wherein the sintered porous polymeric material comprises
at least one elastomer and at least one plastic. In some embodiments, the sintered porous
polymeric material further comprises at least one color change indicator. In some
embodiments, a seal is formed between a surface of the housing and the filtration medium,
the seal being operable to inhibit or prevent fluid bypass.
In another embodiment, a method for producing a filter comprises providing a
filtration medium comprising a continuous sintered porous polymeric material comprising a
flexible region and a rigid region, providing a housing, and disposing the filtration medium in
the housing. In some embodiments, the flexible region comprises a first plastic and at least
one elastomer, and the rigid region comprises a second plastic. In some embodiments, the
flexible region and'or rigid region can further comprise at least one color change indicator.
In some embodiments, a method of producing a filter further comprises forming a seal
between the flexible region of the filtration medium and a surface of the housing.
Methods for Filtering a Fluid
In another aspect, the present invention provides methods of filtering a fluid. In one
embodiment, a method of filtering a fluid comprises providing at least one filtration medium
comprising a sintered porous polymeric material and passing a fluid through the at least one
filtration medium, wherein the sintered porous polymeric material comprises at least one
plastic and at least one elastomer. In some embodiments, the sintered porous polymeric
material further comprises at least one color change indicator.
In another embodiment, a method of filtering a fluid comprises providing at least one
filtration medium comprising a continuous sintered porous polymeric material comprising a
flexible region and a rigid region and passing a fluid through the at least one filtration
medium, wherein the flexible region comprises a first plastic and at least one elastomer, and


the rigid region comprises a second plastic. In some embodiments, the flexible region and/or
rigid region can further comprise at least one color change indicator.
In further embodiment, a method for filtering a fluid comprises providing at least one
filtration medium comprising a sintered porous polymeric material, adjusting the porosity of
the at least one filtration medium, and passing a fluid through the at least one. filtration
medium, wherein the sintered porous polymeric material comprises at least one elastomer and
at least one plastic. In some embodiments, adjusting the porosity of the filtration medium
comprises placing the filtration medium in tension or compression.
The flexible properties a filtration medium of the present invention comprising a
sintered porous polymeric material comprising at least one plastic and at least one elastomer
allows the porosity of the filtration medium to be varied by placing the filtration medium in
tension or compression. Pores of a filtration medium, in some embodiments, are increased in
size by placing the filtration medium in tension. The increase in pore size concomitantly
increases the porosity of the filtration medium. Conversely, pores of a filtration medium, in
some embodiments, are decreased in size by placing the filtration medium in compression.
The decrease in pore size results in a decrease in the porosity of the filtration medium. As a
result, the pore size and porosity of a filtration medium of the present invention can be
tailored for specific filtration and barrier applications.
In another embodiment, a method of filtering a gas comprises providing at least one
liquid barrier medium comprising a sintered porous polymeric material, adjusting the porosity
of the at least one liquid barrier medium, and passing a gas through the liquid barrier medium
while inhibiting and/or preventing liquid from passing through the liquid barrier medium,
wherein the sintered porous polymeric material comprises at least one elastomer and at least
one plastic. In some embodiments, adjusting the porosity of the liquid barrier medium
comprises placing the liquid barrier medium in tension or compression.
In a further aspect, the present invention provides methods for cleaning filtration
media or barrier media. In one embodiment, a method for cleaning a filtration or barrier
medium comprises adjusting the pore sizes of the filtration or barrier medium to release
compositions disposed in the pores wherein the filtration medium or barrier medium
comprises at least one plastic and at least one elastomer. In some embodiments, adjusting the
pores sizes comprises placing the filtration or barrier medium in tension or compression.
As provided herein, placing a filtration or barrier medium of the present invention in
tension or compression, in some embodiments, results in changes to the pore size and
porosity of the medium. Changes in pore size and porosity, according to some embodiments,


are used to clean filtration or barrier media of the present invention. Placing a filtration or
barrier medium comprising a sintered porous polymeric material comprising at least one
elastomer and at least one plastic in tension, for example, results in an expansion of pore
sizes. The expansion of pore size, in some embodiments, releases compositions disposed in
the poTes thereby cleaning the filtration or barrier medium.
In another embodiment, a filtration or barrier medium of the present invention is
placed in compression to reduce pore sizes of the filtration medium. The reduction in pore
sizes, in some embodiments, forces out compositions disposed in the pores thereby cleaning
the filtration or barrier medium.
In some embodiments, a filtration or barrier medium of the present invention is cycled
through tension and compression forces during cleaning. A filtration or barrier medium, for
example, can be placed in tension followed by compression or vice versa. The flexible
properties of filtration or barrier media of the present invention reduces the potential failure
of the filtration medium due to the application of tensile and compressive forces.
Embodiments of the present invention a further illustrated in the following non-
limiting examples.
EXAMPLE 1
Sintered Porous Elastomeric Material
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenically ground to powder, the powder having an average particle size
around 200 µm. The resulting elastomer particles were filled into the cavity of an aluminum
mold and heated to 400° F for five minutes and then cooled to room temperature in five
minutes. The resulting sintered porous elastomeric material was removed from the mold. The
sintered porous elastomeric material had an open pore structure with average pore size of
about 55 µm and a porosity of about 50%.
EXAMPLE 2
Self-sealing Sintered Porous Elastomeric Material
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenically ground to powder, the powder having an average particle size of
about 200 µm. Carboxymethylcellulose (CMC) (Sigma-Aldrich) having an average particle
size of about 200 urn was mixed with the resulting elastomeric particles to produce a mixture
having about 15% by weight CMC. The mixture was filled into the cavity of an aluminum
mold and heated to 400° F for five minutes and then cooled to room temperature in five
minutes. The resulting sintered porous elastomeric material was removed from the mold. The


sintered porous elastomeric material had CMC dispersed throughout the sintered porous
matrix and demonstrated an open pore structure with average pore size around 55 µm and
50% porosity.
EXAMPLE 3
Sintered Porous Polymeric Material Comprising a Plastic and an Elastomer
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenically ground to powder, the powder having an average particle size of
about 150 µm. 30% by weight of the elastomer powder was mixed with 70% by weight
UHMWPE powder (Ticona) having an average particle size of about 150 µm. The resulting
mixture was filled into the cavity of an aluminum mold and heated to 360° F for five minutes
and then cooled to room temperature in five minutes. The resulting sintered porous polymeric
material was removed from the mold. The sintered porous polymeric material comprising the
elastomer and UHMWPE displayed an open pore structure with average pore size around 45
µm and 45% porosity.
EXAMPLE 4
Sintered Porous Polymeric Material Comprising a Plastic and an Elastomer
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenically ground to powder, the powder having an average particle size of
about 200 µm. 30% by weight of the elastomer powder was mixed with 70% by weight
UHMWPE powder (Ticona) having an average size of about 150 µm. The resulting mixture
was filled into the cavity of an aluminum mold. The volume of the mold was subsequently
compressed to 80% of the original volume. The compressed elastomer/UHMWPE mixture
was heated to 360° F for five minutes and then cooled to room temperature in five minutes.
The resulting sintered porous polymeric material was removed from the mold. The sintered
porous polymeric material comprising the elastomer and UHMWPE displayed an open pore
structure with average pore size around 30 µm and 35% porosity.
EXAMPLE 5
Barrier Medium Comprising a Super-absorbent
85% by weight of the elasotmer/UHMWPE mixture provided in Example 3 is
combined with 15% by weight carboxymethylcellulose (CMC) powder. The resulting
mixture was filed into a cavity of an aluminum mold and heated to 360° F for five minutes
and then cooled to room temperature in five minutes. The resulting sintered porous
polymeric material comprising the elastomer, UHMWPE, and CMC displayed an open pore
structure with an average pore size of about 45 µm and a 40% porosity.


EXAMPLE 6
Barrier Medium Comprising a Color Change Indicator
99.95% by weight of the elastomer/UHMWPE/CMC mixture of Example 5 was
mixed with 0.05% by weight food dye erioglaucine. The resulting mixture was filled into the
cavity of an aluminum mold and heated to 360° F for five minutes and cooled to room
temperature in five minutes. The resulting sintered porous polymeric material comprising the
elastomer, UHMWPE, CMC, and food dye displayed an open pore structure with an average
pore size of about 45 µm and a porosity of about 40%.
EXAMPLE 7
Applicator Comprising a Sintered Porous Polymeric Material
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenically ground to powder, the powder having an average particle size of
about 150 µm. 30% by weight of the elastomer powder was mixed with 70% by weight
UHMWPE powder (Ticona) having an average particle size of about 150 µm. The resulting
mixture was filled into the cavity of an aluminum mold having the shape of a nib applicator
and heated to 360° F for five minutes and then cooled to room temperature in five minutes.
The resulting nib applicator comprising the sintered porous polymeric material was removed
from the mold. The nib applicator comprising the sintered porous polymeric material
comprising the elastomer and UHMWPE displayed an open pore structure with an average
pore size of about 45 µm a porosity of about 45%.
EXAMPLE 8
Applicator Comprising a Flexible Region and a Rigid region
The bottom half of a mold was filled with the elastomer/UHMWPE powder mixture
of Example 7. The top half of the mold was filled with UHMWPE (Ticona) having an
average particle size of 150 urn. The mold, having the shape of an nib applicator with a
shank was subsequently heated 360° F for three minutes and then cooled to room temperature
in three minutes. The resulting applicator comprising a sintered porous polymeric material
displayed a flexible region corresponding to the tip of the applicator and a rigid region
corresponding to the shank of the applicator. The flexible region displayed an open pore
structure with an average pore size of about 45 µm and a porosity of about 45%, and the rigid
region demonstrated an average pore size of about 40 µm and a porosity of about 45%.


EXAMPLE 9
Applicator Comprising a Sintered Porous Polymeric Component and a Fibrous Component
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenic ground to powder form with average particle size around 150 µm.
30% by weight of the elastomer powder was mixed with 70% by weight UHMWPE powder
(Ticona) having an average particle size of about 150 µm. The resulting mixture of was filled
into a mold having the shape of a hollow nib structure and heated to 360° F for three minutes
and then cooled to room temperature in three minutes. The applicator nib comprising the
sintered porous polymeric material displayed a hollow structure having an average pore size
of about 45 µm and a porosity of about 45%. A fibrous component comprising a fiber rod
produced by sintering bi-component fibers or impregnating fibers with thermosetting resin
was inserted into the hollow structure in the elastic porous nibs. The bicomponent fibers
were sintered in accordance with the methods disclosed in United States Patent Application
Serial Number 10/464,443.
EXAMPLE 10
Applicator Comprising a Sintered Porous Polymeric Component and a Fibrous Component
The bottom part of a mold was filled with the elastomer/UHMWPE powder mixture
of Example 7. The top part of the mold was filled with UHMWPE (Ticona) having an
average particle size of 150 µm. The up part of the mold included a pin to produce hollow
structure in the applicator nib. The mold was heated to 360° F for three minutes and then
cooled to room temperature in three minutes. The applicator nib was removed from the
mold. The resulting applicator nib displayed a flexible region comprising the tip of the
applicator and a hollow rigid region comprising the shank. The flexible region comprising
the elastomer/TJHMWPE displayed an open pore structure having an average pore size of
about 45 µm and a porosity of about 45%, and the rigid region demonstrated an average pore
size of about 40 µm and a porosity of about 45%. A fibrous component comprising produced
in accordance with Example 9 was inserted into the hollow structure of the shank of the
applicator nib.
EXAMPLE 11
Filtration Medium Comprising a Sintered Porous Polymeric Material
KRATON® elastomers (styrene-ethylene-butadiene styrene) from Kraton Polymers
US, LLC were cryogenically ground to powder, the powder having an average particle size
around 100 µm. 30% by weight of the elastomer powder was mixed with 70% UHMWPE
powder (Ticona) having average particle size around 80 µm. The resulting mixture was filled


into a plurality of cylinder shaped cavities (5 mm diameter and 4 mm deep) in an aluminum
mold. The mold was heated to 360° F for three minutes and then cooled to room temperature
in three minutes. The filtration media comprising the sintered porous polymeric material were
removed from the mold. The filtration media had open pore structures with an average pore
size of about 18 µm and a porosity of about 40%.
The particulate KRATON® elastomers of Examples 3-11 can be substituted with
cryogenically ground ENGAGE® TPO (ethylene-butene copolymer) from Dow Chemical to
achieve similar materials. When ENGAGE® is used as the elastomeric material, the mold is
heated to a temperature of about 32Q°F.
EXAMPLE 12
Applying an Ink Composition to a Surface
The applicator of Example. 7 was loaded with an ink composition for application to
paper. The applicator was loaded with ink by immersing at least a portion of the applicator in
the ink. The applicator comprising the ink was subsequently placed in contact with the paper.
The applicator applied the ink to the paper in an even and controlled fashion without bleeding
or overflow.
EXAMPLE 13
Pipette Tip Comprising a Barrier Medium
The barrier medium of Example 6 was disposed in a pipette tip by inserting the barrier
medium through the end of the pipette tip operable to receive the pipettor. Sufficient pressure
was applied to the barrier medium during insertion to ensure that the barrier medium formed
a seal with the interior surfaces of the pipette tip. After insertion of the barrier medium into
the pipette tip, the pipette tip was attached to a pipettor. The pipette tip was placed in an
aqueous solution, and the aqueous solution was drawn into the sample collection chamber of
the pipette tip. As the aqueous solution was being drawn into the sample collection chamber,
the pipette tip was removed from the aqueous solution resulting in aspiration, thereby
bringing the aqueous solution into contact with the barrier medium. Upon contact with the
aqueous solution, the CMC of the barrier medium expanded and sealed the barrier medium
precluding any aqueous solution from reaching the pipettor. The barrier medium additionally
changed color indicating that the barrier medium had come into contact with the aqueous
solution. Moreover, none of the aqueous solution circumvented barrier medium.
All patents, publications and abstracts cited above are incorporated herein by
reference in their entirety. Various embodiments of the invention have been described in
fulfillment of the various objectives of the invention. It should be recognized that these


embodiments are merely illustrative of the principles of the present invention. Numerous
modifications and adaptations thereof will be readily apparent to those skilled in the art
without departing from the spirit and scope of the invention.
That which is claimed is:

We claim
1. A composition comprising:
a sintered porous polymeric material consisting of a sintered mixture of particles of at least
one plastic and pailicles of at least one thermoplastic elastomer, the sintered porous polymeric
material having a porosity ranging from 20% to 80% and a rigidity of less than 5 pounds,
wherein the at least one plastic is selected from the group consisting of polyethylene,
polypropylene, polyesters, polycarbonates, polyvinylidene fluoride, polytetrafluoroethylene,
polyethersulfones, polystyrenes, polyether imides, polyetheretherketones, and polysulfones and
combinations thereof, and wherein the at least one thermoplastic elastomer is selected from the
group consisting of thermoplastic polyurethanes, polyisobutylene, polybutenes, polyethylene-
propylene copolymer, polyethylene-butene copolymer, polyethylene-octene copolymer,
polyethylene-hexene copolymer, chlorinated polyethylene, chloro-sulfonated polyethylene, styrene-
ethylene-butadiene-styrene, and 1, 3-dienes and combinations thereof.
2. The composition as claimed in claim 1, wherein the 1,3-dienes comprises styrene-1,3-
butadiene, carboxylated styrene-1,3-butadiene, acrylonitrile-1,3-butadiene, or isobutylene-isoprene
or combinations thereof.
3. The composition as claimed in claim 1, wherein polyethylene comprises high density
polyethylene or ultrahigh molecular weight polyethylene.
4. The composition as claimed in claim 1, wherein the particles of the at least one
thermoplastic elastomer are present in an amount ranging from 10 weight percent to 90 weight
percent.

5. The composition as claimed in claim 1, wherein the sintered porous polymeric material has
an average pore size ranging from 1 µm to 200 µm.
6. The composition as claimed in any of the preceding claims, containing at least one super-
absorbent material, such as herein described.
7. The composition as claimed in any of the preceding claims, which is capable of being used


to form an applicator, a filtration medium, or a barrier medium.
8. A composition as claimed in claim 1, wherein the sintered porous polymeric material
comprises a flexible region and a rigid region, the flexible region having a porosity ranging from
20% to 80% and a rigidity of less than 5 pounds, and the rigid region comprising a sintered
particles of a second plastic, wherein the first plastic and the second plastic are independently
selected from the group consisting of polyethylene, polypropylene, polyesters, polycarbonates,
polyvinylidene fluoride, polytetrafluoroethylene, polyethersulfones, polystyrenes, polyether imides,
polyetheretherketones, and polysulfones and combinations thereof, and wherein the at least one
thermoplastic elastomer is selected from the group consisting of thermoplastic polyurethanes,
polyisobutylene, polybutenes, polyethylene-propylene copolymer, polyethylene-butene copolymer,
polyethylene-octene copolymer, polyethylene-hexene copolymer, chlorinated polyethylene, chloro-
sulfonated polyethylene, styrene-ethylene-butadiene-styrene, and 1,3-dienes and combinations
thereof.
9. The composition as claimed in claim 8, which is capable of being used to form an applicator,
a filtration medium, or a barrier medium.
10. An applicator formed of the composition as claimed in any of the preceding claims, with a
fibrous component being coupled to the sintered porous polymeric material.

11. The applicator as claimed in claim 10, having a reservoir coupled to the fibrous component.
12. The applicator as claimed in claim 10, wherein the fibrous component is a reservoir.
13. An apparatus comprising:
a housing with at least one filtration medium or at least one barrier medium being disposed
in the -housing,said filtration medium or the barrier medium being formed of a composition as
claimed in any of claims 1 to 7.
14. The apparatus as claimed in claim 13, wherein the housing is a vacuum filtration housing, a
chromatographic column, a funnel, a tube, a duct, a syringe, a catheter, or a pipette tip.


15. A method of producing a sintered porous polymeric material as claimed in any of claims 1
to 7, said method comprising the steps of:
providing particles of said at least one thermoplastic elastomer;
providing particles of said at least one plastic;
mixing the thermoplastic elastomer particles and the plastic particles uniformly; and
sintering the plastic particles and the elastomer particles;
wherein the sintered porous polymeric material has a porosity ranging from 20% to 80% and
a rigidity of less than 5 pounds.
16. A method of producing a sintered porous polymeric material as claimed in claim 8, said
method comprising the steps of:
disposing particles of said first plastic mixed with particles of said at least one
thermoplastic elastomer in a first part of a mold;
disposing particles of said second plastic in a second part of the mold adjacent to the first
part of the mold; and
sintering the first plastic particles, the thermoplastic elastomer particles, and the second
plastic particles to produce the flexible region comprising particles of the first plastic and the at
least one thermoplastic elastomer, and the rigid region comprising particles of the second plastic.
17. An apparatus comprising a housing with a filtration medium or a barrier medium formed of
composition having a continuous sintered porous polymeric material consisting of a flexible
region and a rigid region, as claimed in claim 8.
18. The apparatus as claimed in claims 17 , wherein a seal is formed between the flexible
region and the housing.
19. The apparatus as claimed in claim 17 or 18 , wherein the housing comprises a pipette tip.


20. The composition as claimed in claim 8, wherein the flexible region has an average pore size
ranging from 1 µm to 200 µm.


ABSTRACT

SINTERED POLYMERIC MATERIALS AND METHOD
OF MAKING THE SAME
According to the invention there is provided a composition capable of being used to form an
applicator,a filtration medium, or a barrier medium, comprising: a sintered porous polymeric material
consisting of a sintered mixture of particles of at least one plastic and particles of at least one
thermoplastic elastomer, the sintered porous polymeric material having a porosity ranging from 20% to
80% and a rigidity of less than 5 pounds, wherein the at least one plastic is selected from the group
consisting of polyethylene, polypropylene, polyesters, polycarbonates, polyvinylidene fluoride,
polytetrafluoroethylene,polyethersulfones, polystyrenes, polyether imides, polyetheretherketones, and
polysulfones and combinations thereof, and wherein the at least one thermoplastic elastomer is selected
from the group consisting of thermoplastic polyurethanes, polyisobutylene, polybutenes, polyethylene-
propylene copolymer, polyethylene-butene copolymer, polyethylene-octene copolymer, polyethylene-
hexene copolymer, chlorinated polyethylene, chloro-sulfonated polyethylene, styrene-ethylene-
butadiene-styrene, and 1,3-dienes and combinations thereof.
There is provided also a method of producing a sintered porous polymeric material.

Documents:

729-KOLNP-2009-(22-05-2012)-ABSTRACT.pdf

729-KOLNP-2009-(22-05-2012)-AMANDED CLAIMS.pdf

729-KOLNP-2009-(22-05-2012)-AMANDED PAGES OF SPECIFICATION.pdf

729-KOLNP-2009-(22-05-2012)-DESCRIPTION (COMPLETE).pdf

729-KOLNP-2009-(22-05-2012)-DRAWINGS.pdf

729-KOLNP-2009-(22-05-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

729-KOLNP-2009-(22-05-2012)-FORM-1.pdf

729-KOLNP-2009-(22-05-2012)-FORM-2.pdf

729-KOLNP-2009-(22-05-2012)-FORM-3.pdf

729-KOLNP-2009-(22-05-2012)-OTHERS.pdf

729-kolnp-2009-abstract.pdf

729-KOLNP-2009-ASSIGNMENT.pdf

729-kolnp-2009-claims.pdf

729-kolnp-2009-correspondence.pdf

729-KOLNP-2009-CORRESPONDENCE1.1.pdf

729-kolnp-2009-description (complete).pdf

729-kolnp-2009-drawings.pdf

729-KOLNP-2009-EXAMINATION REPORT.pdf

729-kolnp-2009-form 1.pdf

729-KOLNP-2009-FORM 13.1.pdf

729-kolnp-2009-form 13.pdf

729-KOLNP-2009-FORM 18.pdf

729-KOLNP-2009-FORM 3.1.pdf

729-kolnp-2009-form 3.pdf

729-KOLNP-2009-FORM 5.1.pdf

729-kolnp-2009-form 5.pdf

729-KOLNP-2009-GPA.pdf

729-KOLNP-2009-GRANTED-ABSTRACT.pdf

729-KOLNP-2009-GRANTED-CLAIMS.pdf

729-KOLNP-2009-GRANTED-DESCRIPTION (COMPLETE).pdf

729-KOLNP-2009-GRANTED-DRAWINGS.pdf

729-KOLNP-2009-GRANTED-FORM 1.pdf

729-KOLNP-2009-GRANTED-FORM 2.pdf

729-KOLNP-2009-GRANTED-SPECIFICATION.pdf

729-kolnp-2009-international publication.pdf

729-kolnp-2009-international search report.pdf

729-kolnp-2009-others.pdf

729-KOLNP-2009-OTHERS1.1.pdf

729-kolnp-2009-pct priority document notification.pdf

729-kolnp-2009-pct request form.pdf

729-KOLNP-2009-REPLY TO EXAMINATION REPORT.pdf

729-kolnp-2009-specification.pdf

abstract-729-kolnp-2009.jpg


Patent Number 254740
Indian Patent Application Number 729/KOLNP/2009
PG Journal Number 50/2012
Publication Date 14-Dec-2012
Grant Date 13-Dec-2012
Date of Filing 24-Feb-2009
Name of Patentee POREX CORPORATION
Applicant Address 500 BOHANNON ROAD, FAIRBURN, GEORGIA
Inventors:
# Inventor's Name Inventor's Address
1 KUNTH, GERALD BLUMENSTRASSE 21, D-02692 DOBERSCHAU
2 MAERTENS, ANDRE NAUNDOREER STRASSE 19, D-01139 DRESDEN
3 FULLERTON, DANIEL, GEORGE 2627 RANGWOOD COURT, ATLANTA, GEORGIA 30345
4 WITOVER, MICHAEL 68 MANCHESTER LANE, STONY BROOK, NEW YORK 11790
5 WINGO, JAMES, P. 116 WINDALIER RIDGE, PEACHTREE CITY, GEORGIA 30269
6 HALDOPOULOS, IKE, IAOKIM 8305 GLEDSTONE WAY, FAIRBURN, GEORGIA 30213
7 TAN, TAKE, HUAT 23 B LORONG KELULI 1C, KAWASAN PERINDUSTRIAN BUKIT RAJA SELATAN, SEKSYEN 7, BANDAR SHAH ALAM, SELANGOR, 41050
8 MAO, GUOQIANG 4951 DURLEY WALK, SMYRNA, GEORGIA 30082
9 REED, DEBORAH, B. 110 KEYLAND DRIVE, FAYETTEVILLE, GEORGIA 30215
PCT International Classification Number C08J 9/00
PCT International Application Number PCT/US2007/018355
PCT International Filing date 2007-08-20
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/876,739 2006-12-22 U.S.A.
2 60/838,572 2006-08-18 U.S.A.
3 60/838,571 2006-08-18 U.S.A.
4 60/900,817 2007-02-12 U.S.A.