U.S. patent application number 17/176058 was filed with the patent office on 2021-08-19 for three-dimensional freeze extrusion for the manufacture of homogeneous and graded rods and tubes.
This patent application is currently assigned to Trustees of Dartmouth College. The applicant listed for this patent is Trustees of Dartmouth College. Invention is credited to Claire Adner, Amalie Hildebrandt Brynjulfsson, Peyton Weber, Ulrike G. K. Wegst, Kaiyang Yin.
Application Number | 20210252773 17/176058 |
Document ID | / |
Family ID | 1000005465132 |
Filed Date | 2021-08-19 |
United States Patent
Application |
20210252773 |
Kind Code |
A1 |
Wegst; Ulrike G. K. ; et
al. |
August 19, 2021 |
THREE-DIMENSIONAL FREEZE EXTRUSION FOR THE MANUFACTURE OF
HOMOGENEOUS AND GRADED RODS AND TUBES
Abstract
In an aspect, the present disclosure pertains to a method of
making a material. Generally, the method includes one or more of
the following steps of: (1) placing a mixture having one or more
components in a container; and (2) extruding the mixture out of at
least one opening of at least one nozzle. In an additional aspect,
the present disclosure pertains to a material. In some embodiments,
the material includes one or more components. In some embodiments,
the one or more components are in the form of a multi-layered
structure.
Inventors: |
Wegst; Ulrike G. K.;
(Hanover, NH) ; Yin; Kaiyang; (West Lebanon,
NH) ; Adner; Claire; (Hanover, NH) ; Weber;
Peyton; (Hanover, NH) ; Brynjulfsson; Amalie
Hildebrandt; (Hanover, NH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Trustees of Dartmouth College |
Hanover |
NH |
US |
|
|
Assignee: |
Trustees of Dartmouth
College
Hanover
NH
|
Family ID: |
1000005465132 |
Appl. No.: |
17/176058 |
Filed: |
February 15, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62976734 |
Feb 14, 2020 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29C 64/255 20170801;
B29C 64/209 20170801; B33Y 10/00 20141201; B29C 64/393 20170801;
B33Y 80/00 20141201; B29L 2023/22 20130101; B33Y 50/02 20141201;
B33Y 40/10 20200101; B29C 64/106 20170801; B29C 64/314
20170801 |
International
Class: |
B29C 64/106 20060101
B29C064/106; B29C 64/314 20060101 B29C064/314; B29C 64/255 20060101
B29C064/255; B29C 64/393 20060101 B29C064/393; B29C 64/209 20060101
B29C064/209; B33Y 10/00 20060101 B33Y010/00; B33Y 40/10 20060101
B33Y040/10; B33Y 50/02 20060101 B33Y050/02; B33Y 80/00 20060101
B33Y080/00 |
Goverment Interests
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
[0002] This invention was made with government support under
1538094 awarded by the National Science Foundation and
80NSSC18K0305 awarded by the National Aeronautics and Space
Administration. The government has certain rights in the invention.
Claims
1. A method of making a material, said method comprising: placing a
mixture comprising a plurality of different components in a
container, wherein the container comprises a first end and a second
end, and wherein the second end of the container comprises at least
one opening; and extruding the mixture out of the at least one
opening, wherein the mixture comprises a plurality of layers during
the extruding, wherein the extruding comprises freezing the
mixture, and wherein the freezing results in the solidification of
the mixture into the material.
2. The method of claim 1, wherein the mixture is in the form of a
solution, a colloid, a gel, a slurry, a suspension, a particle
suspension, an emulsion, or combinations thereof.
3. The method of claim 1, wherein the plurality of different
components are selected from the group consisting of water,
polymers, ceramics, metals, composites, particles, solid beads,
hollow beads, platelets, flakes, fibers, fibrils, whiskers, tubes,
hydrogels, capsules, hydrogel capsules, carbohydrates, mono-, di-
and polysaccharides, lipids, peptides, proteins, blood, cells,
biological factors, hormones, growth factors, viral vectors,
antibacterial agents, stains, magnetic materials, piezoelectric
materials, semiconductors, electrically conducive materials,
thermally conductive materials, solutions thereof, colloids
thereof, emulsions thereof, gels thereof, slurries thereof, ice
particles thereof, ice crystals thereof, and combinations
thereof.
4. The method of claim 1, wherein each of the plurality of layers
comprise a gradient, wherein the gradient is selected from the
group consisting of a property gradient, a compositional gradient,
a concentration gradient, a structural gradient, a mechanical
property gradient, a physical property gradient, or combinations
thereof.
5. The method of claim 1, wherein the at least one opening is at
the center of the second end of the container.
6. The method of claim 1, wherein the freezing comprises
directional freezing of the mixture through a temperature gradient
in the mixture, wherein the temperature gradient gradually
decreases in the mixture from the first end of the container to the
second end of the container.
7. The method of claim 1, wherein the freezing occurs within the at
least one opening.
8. The method of claim 1, wherein the freezing occurs during the
extruding.
9. The method of claim 1, wherein the freezing occurs while the
mixture exits the at least one opening.
10. The method of claim 1, wherein the freezing occurs after the
mixture exits the at least one opening.
11. The method of claim 1, wherein the freezing occurs by
freeze-casting.
12. The method of claim 1, wherein the freezing occurs by exposure
of the mixture to a cooling source.
13. The method of claim 12, wherein the cooling source does not
contact the mixture or any component of the container.
14. The method of claim 12, wherein the cooling source directly
contacts the at least one opening.
15. The method of claim 12, wherein the cooling source comprises a
plurality of cooling units, wherein the plurality of cooling units
are positioned at different regions of the container in order to
create the temperature gradient in the mixture.
16. The method of claim 1, wherein the at least one opening is in
the form of a nozzle that protrudes out of the second end of the
container, wherein the at least one nozzle comprises a first end
proximal to the second end of the container and a second end distal
to the second end of the container.
17. The method of claim 16, wherein the at least one nozzle has a
shorter length and a narrower diameter than the container
18. The method of claim 16, wherein a cooling source is in direct
contact with the nozzle for freezing the mixture during the
extruding.
19. The method of claim 18, wherein the freezing comprises
directional freezing of the mixture through a temperature gradient
in the mixture, wherein the temperature gradient gradually
decreases in the mixture from the first end of the nozzle to the
second end of the nozzle.
20. The method of claim 1, further comprising a step of applying
the material to a surface, wherein the application occurs as the
material exits the extruder.
21. The method of claim 1, further comprising a step of subliming
the material.
22. The method of claim 21, wherein the subliming forms a hollow
cavity within the material.
23. The method of claim 21, wherein the hollow cavity comprises a
non-uniform diameter.
24. The method of claim 21, wherein the hollow cavity comprises a
graded diameter, and wherein the graded diameter becomes narrower
from one end of the material to another end of the material
25. The method of claim 1, wherein the material comprises a
diameter of less than about 50 mm and a length of more than about
50 mm.
26. The method of claim 1, wherein the method occurs in a
continuous manner, wherein the mixture is continuously placed in a
container and continuously extruded out of the container in order
to continuously make the materials of the present disclosure for a
certain amount of time.
27. The method of claim 1, further comprising controlling a
temperature of the container; wherein the temperature of the
container is controlled before extruding, during extruding, after
extruding, or combinations thereof; wherein the temperature of the
container is controlled spatially, temporally, or combinations
thereof; wherein the controlling comprises controlling the
temperature of a nozzle associated with the container, controlling
a temperature profile within the container, controlling a
temperature profile along a nozzle of the container, controlling a
temperature gradient of the container or a nozzle of the container,
controlling a profile of the temperature gradient of the container
or a nozzle of the container, or combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 62/976,734, filed on Feb. 14, 2020. The entirety of
the aforementioned application is incorporated herein by
reference.
BACKGROUND
[0003] Freeze-casting is a technique for the manufacture of
materials. However, with its current mold-based approach,
freeze-casting has reached limitations. Various embodiments of the
present disclosure seek to address such limitations.
SUMMARY
[0004] In an aspect, the present disclosure pertains to a method of
making a material. Generally, the method includes one or more of
the following steps of: (1) placing a mixture in a container; and
(2) extruding the mixture out of the container. In some
embodiments, the mixture includes a plurality of different
components. In some embodiments, the container has a first end and
a second end. In some embodiments, the first end and the second end
are on opposite sides of one another. In some embodiments, the
second end of the container has at least one opening. In some
embodiments, the mixture is extruded out of the at least one
opening. In some embodiments, the mixture includes a plurality of
layers during the extruding. In some embodiments, the extruding
includes freezing the mixture. In some embodiments, the freezing
includes directional freezing of the mixture through a temperature
gradient. In some embodiments, the temperature gradient gradually
decreases from the first end of the container to the second end of
the container.
[0005] In some embodiments, the freezing results in the
solidification of the mixture into the material.
[0006] In some embodiments, the methods of making the materials of
the present disclosure occur in a continuous manner. For instance,
in some embodiments, a mixture is continuously placed in a
container and continuously extruded out of the container in order
to continuously make the materials of the present disclosure for a
certain amount of time.
[0007] In an additional aspect, the present disclosure pertains to
a material. In some embodiments, the material includes one or more
components. In some embodiments, the one or more components are in
the form of a multi-layered structure.
DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1A depicts a method of making a material according to
aspects of the present disclosure.
[0009] FIG. 1B illustrates a container suitable for making the
materials of the present disclosure.
[0010] FIG. 1C1 and FIG. 1C2 depict exemplary materials of the
present disclosure.
[0011] FIG. 2A illustrates a schematic of flow for the manufacture
of graded scaffolds.
[0012] FIG. 2B illustrates a syringe connected to a pump and
feeding into a cold ring.
[0013] FIG. 2C illustrates a three-dimensional (3D) printer
modified for low temperature extrusion.
[0014] FIG. 2D illustrates an expanded view of the syringe and cold
ring in FIG. 2B. The inner nozzle diameter is 0.06 inches (1.54 mm)
while the outer nozzle diameter is 0.072 inches (1.83 mm).
[0015] FIG. 3A, FIG. 3B, and FIG. 3C illustrate that not only
polymer solutions, but also "slush" (half-frozen) solutions or
slurries can be extruded and solidified during the extrusion
process.
[0016] FIG. 4A, FIG. 4B, FIG. 4C, and FIG. 4D illustrate
longitudinal cross-sections of extrudites without (FIG. 4A) and
with (FIGS. 4B, 4C, and 4D) property gradients of the following
compositions: 4% (w/v) (FIG. 4A), 4% (w/v) (FIG. 4B), and 8% (w/v)
(FIG. 4C) three-component chitosan with a property gradient along
the length, and 4% (w/v) (FIG. 4D) three-component chitosan with
both a radial (through the thickness) and a longitudinal property
gradient.
[0017] FIG. 5 illustrates dimensions along the length of the pure
4% (w/v) chitosan extrudite shown in FIG. 4A.
[0018] FIG. 6 illustrates dimensions and phase distribution along
the length of the two-composition 4% (w/v) chitosan extrudite shown
in FIG. 4B.
[0019] FIG. 7 illustrates dimensions and phase distribution along
the length of the two-composition 8% (w/v) chitosan extrudite shown
in FIG. 4C.
[0020] FIG. 8 illustrates width and relative presence of chitosan
layers for a 4% treble colored sample shown in FIG. 4D.
DETAILED DESCRIPTION
[0021] It is to be understood that both the foregoing general
description and the following detailed description are illustrative
and explanatory, and are not restrictive of the subject matter, as
claimed. In this application, the use of the singular includes the
plural, the word "a" or "an" means "at least one", and the use of
"or" means "and/or", unless specifically stated otherwise.
Furthermore, the use of the term "including", as well as other
forms, such as "includes" and "included", is not limiting. Also,
terms such as "element" or "component" encompass both elements or
components comprising one unit and elements or components that
include more than one unit unless specifically stated
otherwise.
[0022] The section headings used herein are for organizational
purposes and are not to be construed as limiting the subject matter
described. All documents, or portions of documents, cited in this
application, including, but not limited to, patents, patent
applications, articles, books, and treatises, are hereby expressly
incorporated herein by reference in their entirety for any purpose.
In the event that one or more of the incorporated literature and
similar materials defines a term in a manner that contradicts the
definition of that term in this application, this application
controls.
[0023] Freeze-casting, the directional solidification of solutions,
colloids, emulsions, gels, and slurries, is a technique for the
manufacture of porous materials. However, with its current
mold-based approach, the process has reached limitations which need
to be overcome. Currently, a process with which slender materials
and structures longer than 50 mm and 1-4 mm diameter made via
freeze-cast methods with suitable microstructures and property
gradients (e.g., compositional gradients, structural gradients,
mechanical property gradients, and/or physical property gradients)
is not available.
[0024] As such, a need exists for more effective systems and
methods for making materials, such as, but not limited to, porous
materials with uniform sizes and distributions. Various embodiments
of the present disclosure address the aforementioned need.
[0025] In some embodiments, the present disclosure pertains to a
method of making materials. In some embodiments illustrated in FIG.
1A, the method of making the materials of the present disclosure
can include one or more of the following steps of: placing a
mixture with one or more components in a container (step 10),
extruding the mixture out of the container (step 12), and forming a
material from the mixture (step 14). In some embodiments, the
materials may be applied to a surface as the materials exit the
extruder (step 16). In some embodiments, the materials may be
sublimed (e.g., lyophilized) (step 18).
[0026] In some embodiments, after the material is formed (step 14),
the processes can be repeated until the desired amount of the
material is formed or processed further. In some embodiments, the
methods of making the materials of the present disclosure occur in
a continuous manner. In particular embodiments, a mixture is
continuously placed in a container and continuously extruded out of
the container in order to continuously make the materials of the
present disclosure for a certain amount of time.
[0027] The methods of the present disclosure can utilize various
containers to make the materials of the present disclosure. For
instance, in some embodiments illustrated in FIG. 1B, the
containers of the present disclosure are in the form of container
20, which has a first end 22 and a second end 24 on opposite sides
of one another. In this embodiment, second end 24 has at least one
nozzle 26 that protrudes out of the second end. The at least one
nozzle 26 has a first end 30 proximal to the second end 24, a
second end 32 distal to the second end 24, and at least one opening
28 at second end 32. Additionally, the at least one nozzle 26 has a
shorter length and a narrower diameter than container 20. In this
embodiment, container 20 is filled with a mixture that has layers
34 and 36. In some embodiments, each layer has one or more
components that are different from one or more components of other
layers. In some embodiments, each layer has one or more components
that are the same as one or more components of the other
layers.
[0028] The methods of the present disclosure can utilize numerous
containers to extrude mixtures. For instance, in some embodiments,
container 20 illustrated in FIG. 1B may be utilized to extrude
mixtures. In some embodiments, the mixture is extruded out of the
at least one opening 28 of the at least one nozzle 26. In some
embodiments, the extruding includes freezing the mixture during or
after the extruding. In some embodiments, the freezing includes
directional freezing of the mixture through a temperature gradient
in the mixture. In some embodiments, the temperature gradient
gradually decreases from first end 22 to second end 24 of container
20. In some embodiments, the temperature gradient gradually
decreases from first end 30 to second end 32 of nozzle 26. In some
embodiments, the freezing results in the solidification of the
mixture into the material.
[0029] The methods of the present disclosure may form various types
of materials. Additional embodiments of the present disclosure
pertain to such materials. For instance, in some embodiments
illustrated in FIG. 1C1 and FIG. 1C2, the materials of the present
disclosure may be in the form of material 40 with layers 42 and 44,
which are formed from the extrusion of layers 34 and 36 from
container 20, respectively. In some embodiments where material 40
is sublimed (e.g., lyophilized), the materials of the present
disclosure are in the form of material 40' with a single remaining
layer 44'.
[0030] As set forth in more detail herein, the methods and
materials of the present disclosure can have numerous embodiments.
For instance, the methods for making the materials of the present
disclosure can utilize various mixtures, components, containers,
and nozzles. Moreover, the methods of making the materials of the
present disclosure may utilize various extruding methods and
freezing methods, or can further include additional steps, such as,
but not limited to, application of the material to a surface (e.g.,
as the material exits the extruder), sublimation (e.g.,
lyophilization of the material), and combinations thereof.
Additionally, the methods of the present disclosure can form
various materials having various properties.
[0031] Methods of Making a Material
[0032] As set forth in further detail herein, an aspect of the
present disclosure relates to methods of making a material. Such
methods generally include one or more of the steps of: (1) placing
a mixture in a container; and (2) extruding the mixture out of the
container.
[0033] In some embodiments, the mixture includes one or more
components. In some embodiments, the mixture includes a plurality
of different components.
[0034] In some embodiments, the container has a first end and a
second end. In some embodiments, the first end and the second end
are on opposite sides of one another. In some embodiments, the
second end of the container has at least one opening.
[0035] In some embodiments, the mixture is extruded out of the at
least one opening. In some embodiments, the mixture includes a
plurality of layers during the extruding. In some embodiments, each
of the plurality of layers includes one or more components that are
different from one or more components of other layers. In some
embodiments, each of the plurality of layers includes one or more
components that are the same as one or more components of the other
layers.
[0036] In some embodiments, the extruding includes freezing the
mixture. In some embodiments, the freezing results in the
solidification of the mixture into the material.
[0037] Additionally, the methods of making the materials as
disclosed herein can utilize various mixtures, components,
containers, and openings. Moreover, the methods of making the
materials of the present disclosure may utilize various extruding
methods and freezing methods. Furthermore, the methods of the
present disclosure can further include additional steps, such as,
but not limited to, application of the material to a surface (e.g.,
as the material exits the extruder), sublimation (e.g.,
lyophilization) of the material, and combinations thereof.
[0038] Mixtures
[0039] As set forth in further detail herein, the methods of making
the materials of the present disclosure can utilize various types
of mixtures. For instance, in some embodiments, the mixture is in
the form of a liquid, a solid, a gas, or combinations thereof. In
some embodiments, the mixture may include a liquid, a solid, and an
applied gas source (e.g., CO.sub.2). In some embodiments, the
mixture is in the form of a semi-frozen mixture, a partially frozen
mixture, a semi-solidified mixture, an unfrozen mixture, a
partially solidified mixture, and combinations thereof.
[0040] In some embodiments, the mixture is in the form of a slurry,
a solution, a colloid, a gel, a suspension, a particle suspension,
an emulsion, or combinations thereof. In some embodiments, the
mixture is in the form of a solution. In some embodiments, the
solution is a homogenous mixture (e.g., a homogenous solution,
slurry, colloid, gel, suspension, particle suspension, emulsion, or
combinations thereof). In some embodiments, the mixture is a
heterogeneous mixture (e.g., a heterogeneous solution, slurry,
colloid, gel, suspension, particle suspension, emulsion, or
combinations thereof). In some embodiments, the mixture is in the
form of a liquid oil in water-based mixture (e.g., a liquid oil in
water-based solution). In some embodiments, the mixture is in the
form of an emulsion.
[0041] In some embodiments, the mixture is in the form of a liquid
and a solid. In some embodiments, the mixture is in the form of a
slurry. In some embodiments, the mixture is in the form of a
homogenous slurry. In some embodiments, the mixture is in the form
of a heterogeneous slurry.
[0042] In some embodiments, the mixtures of the present disclosure
have one or more solvents. In some embodiments, the one or more
solvents include aqueous solvents, such as water-based solvents. In
some embodiments, the one or more solvents include non-aqueous
solvents. In some embodiments, the non-aqueous solvents include,
without limitation, camphene, cyclohexane, dioxane, tert-butyl
alcohol (TBA), dimethyl sulfoxide (DMSO), or combinations
thereof.
[0043] Components
[0044] The mixtures of the present disclosure can include various
components. For instance, in some embodiments, the component
includes one or more components. In some embodiments, the one or
more components include a single component.
[0045] In some embodiments, the one or more components include a
plurality of different components. In some embodiments, the
plurality of different components in a mixture are in the form of a
plurality of layers during the extruding process. In some
embodiments, each layer includes one or more components that are
the same as one or more components in other layers. In some
embodiments, each layer includes one or more components that are
different from one or more components in other layers.
[0046] In some embodiments, each or one of the plurality of layers
include a gradient. In some embodiments, the gradient includes a
property gradient, a compositional gradient, a concentration
gradient, a structural gradient, a mechanical property gradient, a
physical property gradient, or combinations thereof. In some
embodiments, the gradient includes a concentration gradient.
[0047] In some embodiments, the plurality of layers of the
plurality of different components include different layers. In some
embodiments, the different layers can be in various forms described
previously. For instance, in some embodiments, each of the
different layers can be in the form of liquid, solid, gas,
semi-frozen mixtures, partially frozen mixtures, semi-solidified
mixtures, unfrozen mixtures, partially solidified mixtures, or
combinations thereof.
[0048] In some embodiments, the one or more components have the
same freezing characteristics. In some embodiments, the one or more
components have different freezing characteristics.
[0049] In some embodiments, the one or more components can include,
without limitation, water, polymers, ceramics, metals, composites,
particles, solid beads, hollow beads, platelets, flakes, fibers,
fibrils, whiskers, tubes, hydrogels, capsules, hydrogel capsules,
carbohydrates, mono-, di- and polysaccharides, lipids, peptides,
proteins, blood, cells, biological factors, hormones, growth
factors, viral vectors, antibacterial agents, stains, magnetic
materials, piezoelectric materials, semiconductors, electrically
conducive materials, thermally conductive materials, solutions
thereof, colloids thereof, emulsions thereof, gels thereof,
slurries thereof, ice particles thereof, ice crystals thereof, and
combinations thereof.
[0050] In some embodiments, the one or more components include one
or more metals. In some embodiments, the one or more metals
include, without limitation, Al, Zr, Ti, V, Sr, Mg, Fe, Ni, Zn, Co,
Cu, Ag, Au, Ca, Si, Gd, Cd, alloys thereof, oxides thereof,
carbides thereof, nitrides thereof, and combinations thereof. In
some embodiments, the one or more components include barium
titanate, lead zirconate titanate, lithium niobate, or combinations
thereof.
[0051] In some embodiments, the one or more components include rate
earth elements, such a neodymium or samarium. In some embodiments,
the one or more components include ferrite, Alnico, Sendust, AN,
BN, SiC, or combinations thereof.
[0052] In some embodiments, the one or more components are
polymers. In some embodiments, the polymer can include, without
limitation, water soluble polymers, biopolymers, hydrogels,
carbohydrates, mono-, di- and polysaccharides, lipids, peptides,
proteins, nanocellulose, carboxymethyl cellulose, guar gum, xantham
gum, alginate, agar, agarose, chitin, chitosan, chitosan-alginate,
glucose, fructose, sucrose, trehalose, collagen, silk, keratin,
polylactic acid (PLA), poly(glycolic acid) (PGA), polycaprolactone,
polydioxanone, and combinations thereof.
[0053] In some embodiments, the polymers are in the form of
slurries. In some embodiments, the polymers are in the form of
suspensions. In some embodiments, the polymers are in the form of
emulsions. In some embodiments, the polymers may be in an acid,
such as acetic acids.
[0054] In some embodiments, the one or more components are
particles. In some embodiments, the particles can include, without
limitation, nanoparticles, microparticles, thermally conductive
particles, electrically conductive particles, piezoelectric
particles, magnetic particles, and combinations thereof.
[0055] In some embodiments, the particles include diameters that
range from about 1 nanometer to about 100 micrometer. In some
embodiments, the particles include diameters that range from about
1 nanometer to about 900 nm. In some embodiments, the particles
include diameters of about 300 nanometer. In some embodiments, the
particles include diameters of about 5 micrometer. In some
embodiments, the particles include diameters of about 50
micrometer.
[0056] In some embodiments, the one or more components include
antimicrobials. In some embodiments, the antimicrobials include
antibacterial components. In some embodiments, the antimicrobials
include antiviral components.
[0057] In some embodiments, the one or more components are blood.
In some embodiments, the blood can include, without limitation,
blood plasma, platelet-rich plasma, and combinations thereof.
[0058] In some embodiments, the one or more components are cells.
In some embodiments, the cells are fat cells, Schwann cells, stem
cells, microorganisms, or combinations thereof.
[0059] In some embodiments, the one or more components include
viruses. In some embodiments, the one or more components includes
viral vectors.
[0060] Containers
[0061] As set forth in further detail herein, the methods of making
the materials of the present disclosure can utilize various types
of containers. For instance, in some embodiments, the container is
a component of a three-dimensional (3D) printer. In some
embodiments, the container is attached to or associated with a
three-dimensional printer. In some embodiments, the container is in
the form of a syringe.
[0062] In some embodiments, the container can have various shapes.
For instance, in some embodiments, the shapes can include, without
limitation, a square shape, a circular shape, a cylindrical shape,
a rectangular shape, a hexagonal shape, a concave shape, a convex
shape, a tapered shape, and combinations thereof. In some
embodiments, the containers of the present disclosure are in the
form of container 20 shown in FIG. 1B.
[0063] In some embodiments, the containers of the present
disclosure have a first end and a second end. In some embodiments,
the second end contains the at least one opening. In some
embodiments, the first end and the second end are on opposite sides
of one another. In some embodiments, the first end and the second
end have an angular relation to one another.
[0064] In some embodiments, the containers of the present
disclosure have a length ranging from about 50 mm to about 80 mm.
In some embodiments, the containers of the present disclosure have
a diameter ranging from about 4 mm to about 15 mm
[0065] Openings
[0066] As set forth in further detail herein, the methods of making
the materials of the present disclosure can utilize various types
of openings. For instance, in some embodiments, the openings
include at least one opening. In some embodiments, the at least one
opening is a single opening. In some embodiments, the at least one
opening is a plurality of openings. In some embodiments, the
plurality of openings are co-axial to one another.
[0067] The openings of the present disclosure can be in various
positions of a container. For instance, in some embodiments, the at
least one opening is at the center of the second end of the
container.
[0068] In some embodiments, the at least one opening is not at the
center of the second end of the container. For instance, in some
embodiments, the at least one opening is at an edge of a
container.
[0069] The openings of the present disclosure can also have various
shapes. For instance, in some embodiments, the opening shapes can
include, without limitation, a circular shape, a square shape, a
rectangular shape, and combinations thereof.
[0070] In some embodiments, the at least one opening is in the form
of a needle. In some embodiments, the needle may have a tapered
tip, a stainless steel tip, a poly tube flexible tip, a Teflon.RTM.
lined tip, or combinations thereof. In some embodiments, the needle
may have a length ranging from about 0.1 inches (2.5 mm) to about 2
inches (50 mm). In some embodiments, the needle may have an inner
diameter ranging from about 0.004 inches (0.1 mm) to about 0.06
inches (1.54 mm).
[0071] In some embodiments, the opening is in the form of a nozzle.
In some embodiments, the nozzle protrudes out of the second end of
the container. In some embodiments, the nozzle has a first end
proximal to the second end of the container and a second end distal
to the second end of the container. In some embodiments, the nozzle
has a shorter length and a narrower diameter than the container. In
some embodiments, the second end of the nozzle has at least one
opening.
[0072] The nozzles of the present disclosure can have various
lengths. For instance, in some embodiments, the nozzles of the
present disclosure have lengths ranging from about 0.1 mm to about
1 cm. In some embodiments, the nozzles of the present disclosure
have lengths ranging from about 5 mm to about 50 mm. In some
embodiments, the nozzles of the present disclosure have lengths
ranging from about 12.7 mm to about 38.1 mm.
[0073] The nozzles of the present disclosure can also have various
diameters. For instance, in some embodiments, the nozzles of the
present disclosure have an inner diameter ranging from about 0.05
mm to about 2 mm. In some embodiments, the nozzles of the present
disclosure have an inner diameter ranging from about 5 mm to about
50 mm. In some embodiments, the nozzles of the present disclosure
have an inner diameter ranging from about 0.1 mm to about 10 mm. In
some embodiments, the nozzles of the present disclosure have an
inner diameter ranging from about 0.2 mm to about 1.55 mm.
[0074] In some embodiments, the nozzles of the present disclosure
are in the form of nozzle 26 shown in FIG. 1B. In some embodiments,
the nozzles of the present disclosure are in the form of extrusion
dies.
[0075] The nozzles and containers of the present disclosure can
include various materials. For instance, in some embodiments, the
nozzles and containers of the present disclosure can each
independently include metals, polymers, ceramics, thermally
conducting materials, thermally insulating materials, or
combinations thereof.
[0076] Extruding
[0077] As set forth in further detail herein, the methods of making
the materials of the present disclosure can utilize various methods
of extruding. For instance, in some embodiments, extruding occurs
by application of pressure to the container. In some embodiments,
the pressure pushes the mixture out from the at least one opening.
In some embodiments, the application of pressure is via a syringe.
In some embodiments, the application of pressure is via a pump.
[0078] In some embodiments, the application of pressure is through
a syringe pump, a standard pump, a piston, a plunger, or
combinations thereof. In some embodiments, the application of
pressure can be performed while controlling a flow rate (e.g., via
a syringe pump). In some embodiments, the application of pressure
can be performed while controlling the pressure (e.g., via a
standard pump). In some embodiments, the application of pressure
can be performed through the application of a force (e.g., through
a plunger).
[0079] Freezing
[0080] As set for in further detail below, the methods of making
materials of the present disclosure can utilize various methods of
freezing. For instance, in some embodiments, the freezing occurs by
freeze-casting, freeze drying, subliming, or combinations thereof.
In some embodiments, the freezing occurs by freeze-casting.
[0081] Freezing of mixtures can occur through various mechanisms.
For instance, in some embodiments, the freezing occurs by
directional freezing of the mixture through a temperature gradient
in the mixture, where the temperature gradient gradually decreases
in the mixture from a first end of a container to a second end of
the container. In some embodiments, freezing occurs by directional
freezing of the mixture through a temperature gradient in the
mixture, where the temperature gradient gradually decreases in the
mixture from a first end of a nozzle to a second end of a
nozzle.
[0082] In some embodiments, the temperature gradient is concentric
within the mixture. In some embodiments, the temperature gradient
is non-concentric within the mixture.
[0083] Freezing of mixtures can occur at various times. For
instance, in some embodiments, the freezing occurs during the
extruding of a mixture from a container. In some embodiments, the
freezing occurs while the mixture exits an opening of the
container. In some embodiments, the freezing occurs within the
opening. In some embodiments, the freezing occurs after the mixture
exits an opening of the container.
[0084] In some embodiments, the freezing occurs within at least one
nozzle of a container. In some embodiments, the freezing occurs
while the mixture exits the at least one nozzle. In some
embodiments, the freezing occurs proximal to the at least one
nozzle.
[0085] In some embodiments, the freezing occurs by applying a
cooling source to a mixture of the present disclosure. In some
embodiments, the cooling source does not contact the mixture or any
components of the container (e.g., the openings or the nozzle). In
some embodiments, the cooling source contacts the mixture, a
component of the container (e.g., the openings or the nozzle), or
combinations thereof. In some embodiments, the cooling source
directly contacts the at least one opening. In some embodiments,
the cooling source is in direct contact with the nozzle.
[0086] In some embodiments, the cooling source surrounds the
nozzle. In some embodiments, the cooling source is in the form of a
ring that surrounds the nozzle (e.g., the cooling ring shown in
FIG. 2D).
[0087] In some embodiments, the application of the cooling source
to the mixture occurs by applying the cooling source to at least
one opening of a container. In some embodiments, the application of
the cooling source to the mixture occurs by applying the cooling
source to at least one nozzle. In some embodiments, the cooling
source is utilized to generate a uniform temperature through the at
least one nozzle. In some embodiments, the cooling source is
utilized to generate a temperature gradient through the at least
one nozzle.
[0088] .In some embodiments, the cooling source can include,
without limitation, dry ice, liquid nitrogen, FREON, a chilling
block, cooling rings, surface-coated cooling rings, and
combinations thereof. In some embodiments, the cooling source
includes one or more chilling blocks. In some embodiments, the
cooling source is in the form of chilling blocks, such as copper
chilling blocks.
[0089] In some embodiments, the cooling source cools the mixture
through concentric cooling. In some embodiments, the cooling source
cools the mixture through linear cooling.
[0090] In some embodiments, the cooling source includes a plurality
of cooling sources (e.g., a plurality of chilling blocks). In some
embodiments, the plurality of cooling sources are positioned at
different regions of a container or a nozzle in order to create a
temperature gradient in the mixture. For instance, in some
embodiments, a plurality of cooling sources are placed at the first
and second ends of a container in order to create a temperature
gradient in the mixture between the first end and the second end of
the container. In some embodiments, a plurality of cooling sources
are placed at the first and second ends of a nozzle in order to
create a temperature gradient in the mixture between the first end
and the second end of the nozzle.
[0091] In some embodiments, the methods of the present disclosure
also include a step of controlling a temperature of the container.
In some embodiments, a temperature of the container can be
controlled before, during and/or after the extruding process. In
some embodiments, the temperature of the container can be
controlled spatially, temporally, or combinations thereof.
[0092] In some embodiments, controlling a temperature of the
container includes controlling the temperature of a nozzle
associated with the container (e.g., spatially and/or temporally).
In some embodiments, controlling a temperature of the container
includes controlling a temperature profile within the container
(e.g., spatially and/or temporally). In some embodiments,
controlling a temperature of the container includes controlling a
temperature profile along a nozzle of the container (e.g.,
spatially and/or temporally). In some embodiments, controlling a
temperature of the container includes controlling the temperature
gradient of the container or a nozzle of the container (e.g.,
spatially and/or temporally). In some embodiments, controlling a
temperature of the container includes controlling a profile of the
temperature gradient of the container or a nozzle of the container
(e.g., spatially and/or temporally).
[0093] Various methods may be utilized to control a temperature of
a container. For instance, in some embodiments, the temperature of
the container is controlled by controlling the temperature of one
or more cooling sources associated with the container. For
instance, in some embodiments, the temperature of one or more
cooling sources can be controlled to define an applied temperature
gradient spatially and/or temporally. In some embodiments, the
temperature of one or more cooling sources can be controlled to
define the profile of a temperature gradient spatially and/or
temporally.
[0094] Application to a Surface
[0095] As set forth in further detail herein, the methods of making
the materials of the present disclosure can include the additional
step of applying the material to a surface. For instance, in some
embodiments, the application occurs as the material exits the
extruder. In some embodiments, the application occurs after
extrusion. In some embodiments, the application is direct
application. In some embodiments, the application can occur through
various methods. For instance, in some embodiments, the application
can occur via dropping, pouring, brushing, spraying, and
freeze-spraying, and combinations thereof. In some embodiments, the
surface is a cold surface. In some embodiments, the cold surface
maintains the materials of the present disclosure in a frozen
state.
[0096] In some embodiments, the surface of the materials of the
present disclosure are coated with an additional material. In some
embodiments, the coating occurs after the materials are extruded.
For instance, in some embodiments, the application can occur via
spraying, brushing, freeze-spraying, dipping, and combinations
thereof.
[0097] Sublimation
[0098] In some embodiments, the methods of making the materials of
the present disclosure can include the additional step of subliming
the material. For instance, in some embodiments, the materials are
sublimed after they exit an opening of a container. In some
embodiments, the sublimation removes one or more additives or
impurities from the material. In some embodiments, the sublimation
removes one or more of the one or more components from the material
(e.g., water). In some embodiments, the sublimation forms a hollow
cavity within the material. In some embodiments, the hollow cavity
has a non-uniform diameter. In some embodiments, the hollow cavity
has a graded diameter. In some embodiments, the graded diameter
becomes narrower from one end of the material to another end of the
material.
[0099] Sublimation can occur by various methods. For instance, in
some embodiments, sublimation can occur by methods that include,
without limitation, lyophilization, freeze-drying, evaporation, or
combinations thereof. In some embodiments, sublimation occurs by
evaporation.
[0100] Materials
[0101] As set forth in further detail herein, the methods of the
present disclosure can form various materials having various
properties. Additional embodiments of the present disclosure
pertain to the materials.
[0102] In some embodiments, the materials of the present disclosure
include one or more components. In some embodiments, the one or
more components are in the form of a multi-layered structure.
[0103] Components
[0104] As detailed herein, the materials of the present disclosure
can include various components such as those outlined above in
detail. For instance, in some embodiments, the components are one
or more components. In some embodiments, the one or more components
are a single component. In some embodiments, the one or more
components are a plurality of different components. In some
embodiments, the one or more components have the same freezing
characteristics. In some embodiments, the one or more components
have different freezing characteristics.
[0105] In some embodiments, the one or more components can include,
without limitation, water, polymers, ceramics, metals, composites,
particles, solid beads, hollow beads, platelets, flakes, fibers,
fibrils, whiskers, tubes, hydrogels, capsules, hydrogel capsules,
carbohydrates, mono-, di- and polysaccharides, lipids, peptides,
proteins, blood, cells, biological factors, hormones, growth
factors, viral vectors, antibacterial agents, stains, magnetic
materials, piezoelectric materials, semiconductors, electrically
conducive materials, thermally conductive materials, solutions
thereof, colloids thereof, emulsions thereof, gels thereof,
slurries thereof, ice particles thereof, ice crystals thereof, and
combinations thereof.
[0106] In some embodiments, the one or more components are
polymers. In some embodiments, the polymer can include, without
limitation, water soluble polymers, biopolymers, hydrogels,
carbohydrates, mono-, di- and polysaccharides, lipids, peptides,
proteins, nanocellulose, carboxymethyl cellulose, guar gum, xantham
gum, alginate, agar, agarose, chitin, chitosan, chitosan-alginate,
glucose, fructose, sucrose, trehalose, collagen, silk, keratin,
polylactic acid (PLA), poly(glycolic acid) (PGA), polycaprolactone,
polydioxanone, and combinations thereof.
[0107] In some embodiments, the one or more components are
particles. In some embodiments, the particles can include, without
limitation, nanoparticles, microparticles, thermally conductive
particles, electrically conductive particles, piezoelectric
particles, magnetic particles, and combinations thereof.
[0108] In some embodiments, the particles include diameters that
range from about 1 nanometer to about 100 micrometer. In some
embodiments, the particles include diameters that range from about
1 nanometer to about 900 nm. In some embodiments, the particles
include diameters of about 300 nanometer. In some embodiments, the
particles include diameters of about 50 micrometer.
[0109] In some embodiments, the one or more components are blood.
In some embodiments, the blood can include, without limitation,
blood plasma, platelet-rich plasma, and combinations thereof.
[0110] In some embodiments, the one or more components are cells.
In some embodiments, the cells are fat cells, Schwann cells, stem
cells, microorganisms, or combinations thereof.
[0111] In some embodiments, the one or more components include
viruses. In some embodiments, the one or more components includes
viral vectors.
[0112] In some embodiments, the one or more components have various
alignments. For instance, in some embodiments, the one or more
components are uniformly aligned. In some embodiments, the one or
more components are angularly aligned. In some embodiments, the
alignment is in the direction of flow and/or ice crystals.
[0113] Properties
[0114] The materials of the present disclosure can have various
properties, such as those outlined above in detail. For instance,
in some embodiments, the material has a hollow cavity within the
material. In some embodiments, the hollow cavity has a non-uniform
diameter. In some embodiments, the hollow cavity has a graded
diameter. In some embodiments, the graded diameter becomes narrower
from one end of the material to another end of the material.
[0115] In some embodiments, the one or more components of the
material are uniformly aligned. In some embodiments, the one or
more components of the material are angularly aligned.
[0116] In some embodiments, the material is in the form of a solid,
a semi-solid, gels, and combinations thereof. In some embodiments,
the materials have uniform dimensions. In some embodiments, the
materials are three-dimensional.
[0117] In some embodiments, the materials have a hierarchical
architecture. In some embodiments, the material has an outer layer
and an inner layer. In some embodiments, the material has multiple
outer layers and multiple inner layers.
[0118] In some embodiments, the material is porous. In some
embodiments, the material has uniform pore sizes. In some
embodiments, 50% of pores have the same size. In some embodiments,
60% of pores have the same size. In some embodiments, 75% of pores
have the same size. In some embodiments, 85% of pores have the same
size.
[0119] The materials of the present disclosure can have various
pore sizes. For instance, in some embodiments, the material has
microscopic pores (e.g., pores with diameters between 1 and 500
micrometers), macropores (e.g., pores with diameters larger than 50
nm), mesopores (e.g., pores with diameters between 2 and 50 nm),
micropores (e.g., pores with diameters less than 2 nm), nanopores
(e.g., pores with nanometer sized diameters), and combinations
thereof.
[0120] In some embodiments, the materials of the present disclosure
have varying porosities. For instance, in some embodiments, the
porosity of the materials of the present disclosure can vary from
nanopores to microscopic pores.
[0121] In some embodiments, the porosity of the materials of the
present disclosure can vary in a hierarchical manner. For instance,
in some embodiments, the materials of the present disclosure have a
hierarchical architecture that encompasses microscopic pores,
macropores, mesopores, micropores, nanopores, and combinations
thereof.
[0122] In some embodiments, the materials of the present disclosure
have a plurality of layers with different porosities within each
layer. In some embodiments, one or more of each of the layers may
have regions (e.g., cell walls or lattices or lattice struts) with
different porosities. For instance, in some embodiments, the pore
size within a layer, of which the regions (e.g., cell walls or
lattices) are composed, is smaller than that within the regions
(e.g., cell walls or lattices or lattice struts) of the layers. In
some embodiments, the pores within the regions (e.g., cell walls or
lattices or lattice struts) are smaller than pore sizes between
each of the regions.
[0123] In some embodiments, a majority of the material includes
uniform pore sizes. For instance, in some embodiments, at least 50%
of the surface area of the material includes uniform pore sizes. In
some embodiments, at least 60% of the surface area of the material
includes uniform pore sizes. In some embodiments, at least 70% of
the surface area of the material includes uniform pore sizes. In
some embodiments, at least 80% of the surface area of the material
includes uniform pore sizes. In some embodiments, at least 90% of
the surface area of the material includes uniform pore sizes. In
some embodiments, at least 95% of the surface area of the material
includes uniform pore sizes.
[0124] In some embodiments, the material is in the form of rods,
graded rods, tubes, scaffolds, composites, and combinations
thereof. In some embodiments, the material is in the form of
scaffolds.
[0125] In some embodiments, the material has one or more gradients
along a length, across a section, or combinations thereof. In some
embodiments, the gradient includes a property gradient, a
compositional gradient, a concentration gradient, a structural
gradient, a mechanical property gradient, a physical property
gradient, or combinations thereof.
[0126] In some embodiments, the material has a diameter of less
than about 100 mm. In some embodiments, the material has a diameter
of less than about 75 mm. In some embodiments, the material has a
diameter of less than about 50 mm. In some embodiments, the
material has a diameter of less than about 25 mm. In some
embodiments, the material has a diameter of less than about 10 mm.
In some embodiments, the material has a diameter of less than about
5 mm. In some embodiments, the material has a diameter between
about 1 mm to about 4 mm. In some embodiments, the material has a
diameter of less than about 1 mm.
[0127] In some embodiments, the material has a length of more than
about 5 mm. In some embodiments, the material has a length of more
than about 10 mm. In some embodiments, the material has a length of
more than about 25 mm. In some embodiments, the material has a
length of more than about 35 mm. In some embodiments, the material
has a length of more than about 50 mm. In some embodiments, the
material has a length of more than about 75 mm. In some
embodiments, the material has a length of more than about 100 mm.
In some embodiments, the material has a length of more than about
200 mm. In some embodiments, the material has a length of more than
about 300 mm.
[0128] In some embodiments, the materials are homogenous. In some
embodiments, the materials have no layers. In some embodiments, the
materials are graded. In some embodiments, the materials are
multi-layered. In some embodiments, the materials exhibit a
hierarchical architecture. In some embodiments, the materials
include a random distribution.
[0129] In some embodiments, the materials of the present disclosure
have one or more property gradients. In some embodiments, the one
or more property gradients span across a length of the material. In
some embodiments, the one or more property gradients span across a
width of the material. In some embodiments, the one or more
property gradients include, without limitation, compositional
gradients, structural gradients, mechanical property gradients, and
physical property gradients. In some embodiments, the one or more
gradients include a concentration gradient.
Additional Embodiments
[0130] Reference will now be made to more specific embodiments of
the present disclosure and experimental results that provide
support for such embodiments. However, Applicants note that the
disclosure below is for illustrative purposes only and is not
intended to limit the scope of the claimed subject matter in any
way.
EXAMPLE 1
Continuous Manufacture of Homogeneous and Graded Rods by
Low-Temperature Extrusion
[0131] This Example describes the continuous manufacture of
homogenous and graded rods by low temperature extrusions according
to aspects of the present disclosure.
[0132] Freeze-casting, the directional solidification of solutions,
colloids, emulsions, gels, and slurries, is a technique for the
manufacture of porous materials. However, with its current
mold-based approach, the process has reached limitations which need
to be overcome. Needed is a process with which slender materials
and structures longer than 50 mm and 1-4 mm diameter can be
freeze-cast with suitable microstructures and mechanical properties
for numerous applications.
[0133] A low-temperature extrusion system has been developed for
this purpose and is demonstrated in this Example. With it, the
manufacture of slender rods of uniform or graded structures and
compositions can be extruded in a continuous processing approach.
The length of rods produced and the graded features achieved are
currently unobtainable by any other method of manufacture.
Highlighted are three samples types: rods with a uniform structure
and properties, and rods with graded properties, both
through-thickness and along the length composed of two or three
compositions. The principles of structure formation are explained
and illustrated herein.
[0134] FIG. 2A illustrates a schematic of flow for the manufacture
of graded scaffolds. FIG. 2B illustrates a syringe connected to a
pump and feeding into a cold ring. FIG. 2C illustrates a
three-dimensional (3D) printer modified for low temperature
extrusion. FIG. 2D illustrates an expanded view of the syringe and
cold ring in FIG. 2B.
[0135] FIGS. 3A, 3B and 3C illustrate that not only polymer
solutions, but also "slush" (partially-frozen) solutions, colloids,
emulsions, gels, or slurries can be extruded and solidified during
the extrusion process. If one of the components is water-based, a
hollow cylinder results after lyophilization.
[0136] FIGS. 4A, 4B, 4C, and 4D illustrate longitudinal
cross-sections of extrudites without (FIG. 4A) and with (FIGS. 4B,
4C, and 4D) property gradients of the following compositions: 4%
(w/v) chitosan (FIG. 4A), 4% (w/v) (FIG. 4B), and 8% (w/v) (FIG.
4C) three-component chitosan (colored white and green) with
property gradient along the length, and 4% (w/v) (FIG. 4D)
three-component chitosan (colored white, green, and blue) with both
a radial (through the thickness) and a longitudinal property
gradient.
[0137] FIG. 5 illustrates dimensions along the length of the pure
4% (w/v) chitosan extrudite shown in FIG. 4A. FIG. 6 illustrates
dimensions and phase distribution along the length of the
two-composition 4% (w/v) chitosan extrudite shown in FIG. 4B. FIG.
7 illustrates dimensions and phase distribution along the length of
the two-composition 8% (w/v) chitosan extrudite shown in FIG. 4C.
FIG. 8 illustrates dimensions and phase distribution along the
length of the three-composition 4% (w/v) chitosan extrudite shown
in FIG. 4D.
[0138] Without further elaboration, it is believed that one skilled
in the art can, using the description herein, utilize the present
disclosure to its fullest extent. The embodiments described herein
are to be construed as illustrative and not as constraining the
remainder of the disclosure in any way whatsoever. While the
embodiments have been shown and described, many variations and
modifications thereof can be made by one skilled in the art without
departing from the spirit and teachings of the invention.
Accordingly, the scope of protection is not limited by the
description set out above, but is only limited by the claims,
including all equivalents of the subject matter of the claims. The
disclosures of all patents, patent applications and publications
cited herein are hereby incorporated herein by reference, to the
extent that they provide procedural or other details consistent
with and supplementary to those set forth herein.
* * * * *