(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization
International Bureau (10) International Publication Number
(43) International Publication Date WO 2019/036126 Al
2 1 February 2019 (21.02.2019) W !P O PCT

(51) International Patent Classification: (72) Inventors: NATARAJAN, Arunkumar; 1 Research C ir

B29C 64/209 (2017.01) B33Y 70/00 (2015.01) cle, CEB2585, Niskayuna, NY 12309 (US). BONILLA
B29C 64/165 (2017.01) B33Y 30/00 (2015.01) GONZALEZ, Carlos; 9701 Windisch Rd, West Chester,
B22F 3/105 (2006.01) OH 45069 (US). CHAN, Kwok, Pong; One Research
Cricle, Niskayuna, NY 12309 (US).
(21) International Application Number:
PCT/US20 18/040983 (74) Agent: OVERBECK, Brian, P. et al; General Electric
Company, GE Aviation Patent Operation, 1 Neumann Way,
(22) International Filing Date:
Mail Drop F16, Cincinnati, OH 45215 (US).
06 July 2018 (06.07.2018)
(81) Designated States (unless otherwise indicated, for every
(25) Filing Language: English
kind of national protection available): AE, AG, AL, AM,
(26) Publication Language: English AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
(30) Priority Data:
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
15/680,733 18 August 2017 (18.08.2017) US
HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP,
(71) Applicant: GENERAL ELECTRIC COMPANY KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME,
[US/US]; 1 River Road, Schenectady, NY 12345 (US). MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,

(54) Title: THERMOPLASTIC BINDERS FOR USE IN BINDER JETTING ADDITIVE MANUFACTURING

10

Deposit layer of metal powder

ileotively deposit linkable thermoplastic binder into metal

powder layer 24

Cure linkable thermoplastic binder to form layer of green .- 74

body metal part

Remove portion of linkable thermoplastic binder from green 78

body metal part to generate a brown body metal part

Pre-sinfer brown body metal part to remove remaining linkable

thermoplastic binder

Sinter brown body metal part to consolidate printed iayers

and to generate consolidated metal part substantially free o f 4
char residue

F!G. 1

(57) Abstract: A method of binder jet printing a part including depositing a layer of a powder on a working surface of a binder jet
printer and selectively printing a binder solution having a linkable thermoplastic binder into the layer of the powder in a pattern to
generate a printed layer. The pattern is representative of a structure of a layer of the part. The linkable thermoplastic binder includes
a first polymer strand and a second polymer strand, the first polymer strand includes a first functional group and the second polymer
strand includes a second functional group, and the first and second functional groups non-covalently couple the first polymer strand
© with the second polymer strand. The method of binder jet printing a part also includes curing the linkable thermoplastic binder in the
printed layer to generate a layer of a green body part, heating the green body part above a first temperature to remove at least a portion
o of the linkable thermoplastic binder and generate a brown body part, and heating the brown body part above a second temperature to

o
[Continued on next page]
 WO 2019/036126 Al llll I I I I 11III III llll II I I I III III II I II
SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.

(84) Designated States (unless otherwise indicated, for every

kind of regional protection available): ARIPO (BW, GH,
GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).

Declarations under Rule 4.17:

— as to applicant's entitlement to apply for and be granted a
patent (Rule 4.1 7(H))
— as to the applicant's entitlement to claim the priority of the
earlier application (Rule 4.17 (in))
Published:
— with international search report (Art. 21(3))

sinter the powder to generate the part. The part is substantially free o f char residue.
 THERMOPLASTIC BINDERS FOR USE IN BINDER JETTING ADDITIVE MANUFACTURING

[0001] The subject matter disclosed herein relates to additive manufacturing, and more particularly,
to thermoplastic binders for use in binder jetting additive manufacturing techniques.

[0002] Additive manufacturing, also known as 3D printing, generally involves printing an article one
layer at a time using specialized systems. In particular, a layer of a material (e.g., a metal powder bed)
may be deposited on a working surface and bonded with another layer of the same or a different
material. Additive manufacturing may be used to manufacture articles (e.g., fuel nozzles, fuel injectors,
turbine blades, etc.) from computer aided design (CAD) models using techniques such as, but not
limited to, metal laser melting, laser sintering, and binder jetting. These additive manufacturing
techniques melt, sinter, or chemically bind layers of material to generate the desired article. Additive
manufacturing may facilitate manufacturing of complex articles and enable flexibility for customization
of articles compared to techniques such as molding (e.g., cast molding, injection molding)
Additionally, additive manufacturing can reduce the overall manufacturing costs associated with
generating these complex articles compared to molding techniques generally used.

BRIEF DESCRIPTION

[0003] In one embodiment, a method of binder jet printing a part includes depositing a layer of a
powder on a working surface of a binder jet printer and selectively printing a binder solution having a
linkable thermoplastic binder into the layer of the powder in a pattern to generate a printed layer. The
pattern is representative of a structure of a layer of the part. The linkable thermoplastic binder includes
a first polymer strand and a second polymer strand, the first polymer strand includes a first functional
group and the second polymer strand includes a second functional group, and the first and second
functional groups non-covalently couple the first polymer strand with the second polymer strand. The
method of binder jet printing the part also includes curing the linkable thermoplastic binder in the
printed layer to generate a layer of a green body part, heating the green body part above a first
temperature to remove at least a portion of the linkable thermoplastic binder and generate a brown body
part, and heating the brown body part above a second temperature to sinter the powder to generate the
part. The part is substantially free of char residue.

[0004] In a second embodiment, a part manufactured via a binder jet printing process includes the
steps of depositing a layer of a powder on a working surface of a binder jet printer and selectively
printing a binder solution having a linkable thermoplastic binder into the layer of powder in a pattern to
generate a printed layer. The pattern is representative of a structure of a layer of the part. The linkable
thermoplastic binder includes a first polymer strand and a second polymer strand, the first polymer
strand includes a first functional group and the second polymer strand includes a second functional
group, and the first and second functional groups non-covalently couple the first polymer strand with the
second polymer strand. The binder jet printing process also includes curing the linkable thermoplastic
binder in the printed layer to generate a layer of a green body part, heating the green body part above a
first temperature to remove at least a portion of the linkable thermoplastic binder and generate a brown
body part, and heating the brown body part above a second temperature to sinter the powder to generate
the part. The part is substantially free of char residue.

[0005] In a third embodiment, a binder solution that may be used in binder jet printing, including a
binder solution having a linkable thermoplastic binder including a first polymer strand and a second
polymer strand. The first polymer strand includes a first functional group and the second polymer strand
includes a second functional group, and the first and second functional groups non-covalently couple at
least a portion of the second polymer strand with at least a portion of the first polymer strand, and the
binder solution is substantially free of a surfactant.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] These and other features, aspects, and advantages of the present invention will become better
understood when the following detailed description is read with reference to the accompanying drawings
in which like characters represent like parts throughout the drawings, wherein:

[0007] FIG. 1 is a flow diagram of an embodiment of a method of manufacturing a metal part via a
binder jet printing process that uses a linkable thermoplastic binder;

[0008] FIG. 2 is a schematic diagram of an embodiment of a layer of material from which the metal
part is printed resulting from the acts of the method of FIG. 1;

[0009] FIG. 3 is a block diagram of an embodiment of a binder jet printer used to print the metal part
in accordance with the method of FIG. 1;

[0010] FIG. 4 is a cross-sectional view of an embodiment of a printed layer having particles of the
material coated with the linkable thermoplastic binder in accordance with the method of FIG. 1;
[0011] FIG. 5 is a top view of an embodiment of the printed layer of FIG. 4 having the linkable
thermoplastic binder selectively deposited in a pattern representative of a structure of the metal part in
accordance with the method of FIG. 1;

[0012] FIG. 6 is a schematic diagram illustrating linking between polymer strands in an embodiment
of the linkable thermoplastic binder via non-covalent forces; and

[0013] FIG. 7 is a bar graph illustrating a comparison between the green strength of a green body part
printed using an embodiment of the linkable thermoplastic binder and the green strength of a green body
part printed using a non-linkable binder.

DETAILED DESCRIPTION

[0014] One or more specific embodiments will be described below. In an effort to provide a concise
description of these embodiments, all features of an actual implementation may not be described in the
specification. It should be appreciated that in the development of any such actual implementation, as in
any engineering or design project, numerous implementation-specific decisions must be made to achieve
the developers' specific goals, such as compliance with system-related and business-related constraints,
which may vary from one implementation to another. Moreover, it should be appreciated that such a
development effort might be complex and time consuming, but would nevertheless be a routine
undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this
disclosure.

[0015] When introducing elements of various embodiments of the present invention, the articles "a,"
"an," "the," and "said" are intended to mean that there are one or more of the elements. The terms
"comprising," "including," and "having" are intended to be inclusive and mean that there may be
additional elements other than the listed elements. Furthermore, any numerical examples in the
following discussion are intended to be non-limiting, and thus additional numerical values, ranges, and
percentages are within the scope of the disclosed embodiments.

[0016] As used herein, a "linkable thermoplastic binder" is intended to denote a chemical binder that
includes a first and a second thermoplastic polymer having functional groups that interact with one
another via weak non-covalent forces (e.g., interactions, bonds) to link, or otherwise couple, strands of
each respective thermoplastic polymer. As used herein, "weak non-covalent forces" are intended to
denote hydrogen bonding, ionic bonding, Van der Waals forces, and the like. As defined herein, "green
body metal part" and "green body part" is intended to denote a printed part that has not undergone heat
treatment to remove the chemical binder. As defined herein, "brown body metal part" and "brown body
part" is intended to denote a printed part that has undergone heat treatment to remove the chemical
binder. As defined herein, a metal part is intended to denote a part having metallic materials. While the
present embodiments are primarily described in the context of metal parts, the linkable thermoplastic
binders described herein may be applicable to a number of other 3D printed parts, including ceramic
parts.

[0017] There are several techniques for manufacturing articles, such as ceramic parts and/or metal
parts used in a variety of machinery. For example, molding techniques such as sand molding, cast
molding, and/or injection molding, among others, may be used to manufacture parts for machinery
applications. As noted above, other techniques that may be used to manufacture parts include additive
manufacturing. For example, additive manufacturing techniques include, but are not limited to, laser
melting, laser sintering, and binder jetting. Additive manufacturing may be advantageous for fabricating
parts compared to molding techniques due, in part, to the flexibility of materials that may be used, the
ability to manufacture more complex articles, and lower manufacturing costs.

[0018] Unlike laser melting and laser sintering additive manufacturing techniques, which heat the
material to consolidate and build layers of the material to form a part, binder jetting uses a chemical
binder to bond particles of the material into layers that form a green body the part. The green body part
may be further processed (e.g., sintered) to consolidate the layers and form the final metal part.
Chemical binders have been used in sand molding techniques to bond sand particles and form a sand
mold that can be used to fabricate other parts. Similar to sand molding, in binder jet printing, the
chemical binder is successively deposited into layers of powder (e.g., ceramic and/or metal powder) to
print the part. For example, the chemical binder (e.g., a polymeric adhesive) may be selectively
deposited onto a powder bed in a pattern representative of a layer of the part being printed. Each printed
layer may be cured (e.g., via heat, light, moisture, solvent evaporation, etc.) after printing to bond the
particles of each layer together to form the green body part. After the green body part is fully formed,
the chemical binder is removed during post-printing processes (e.g., debinding and sintering). It may be
appreciated that such debinding and sintering steps are not part of sand molding processes, in which the
chemical binder remains an integral part of the sand mold, even as the sand mold is subsequently used to
form a molded metal part. However, in binder jet 3D printing of direct metal and/or ceramic
components, the chemical binder is an integral part of the green body part (e.g., the chemical binder is
disposed within and in between each layer of the printed part), and is subsequently removed during
debinding and/or sintering to form a completed 3D printed metal part. It may also be noted that binder
jet printing enables the manufacture of metal and/or ceramic parts having complex, 3D geometries that
are impossible or impractical to manufacture using a sand molding manufacturing process.

[0019] As discussed above, the green body part undergoes additional processing (e.g., debinding and
sintering) to consolidate the layers and form the completed 3D printed metal part. Accordingly, it is
desirable for the green body part to have a suitable green strength for handling (e.g., transferring,
inspecting, depowdering) during the post printing processes. However, chemical binders previously
available for binder jet 3D printing tend to produce char residue within the consolidated metal part. For
example, a process for removing the chemical binders from a brown body part may be performed in an
oxygen (O2) containing environment. The O 2 may drive complete decomposition of the chemical binder
to carbon dioxide (CO2) and water (H2O), among other decomposition by-products. However, these
debinding conditions (e.g., Ch-containing environment) may also result in formation of metal oxides in
the consolidated metal part. Accordingly, certain properties (e.g., mechanical properties) of the
consolidated metal part may be undesirable and the part may be unsuitable for use in the desired
machinery.

[0020] For example, in Nickel alloys, during debinding (e.g., at temperatures between approximately
400 °Celsius (°C) and approximately 450 °C) the chemical binder from the green part is burned out
leaving a brown part that is mostly a metal powder bound by trace amounts of the chemical binder.
Next the part is subjected to different phases of sintering during which time the metal powder particles
starts to neck during sintering at temperatures in excess of 1000 degrees Celsius (°C), depending on the
metal powder used to fabricate the printed metal part. Additionally, diffusion takes over during long
incubation times of sintering, which is typically between approximately 1280 °C and approximately
1300 °C for between approximately 6 hours and approximately 24 hours to close out most of the
porosity in the metal part and produce parts between approximately 94% and approximately 99%
density. At these debinding and sintering temperatures, when oxygen is present, oxidation of the metal
particles may occur in the metal part, resulting in metal oxide formation on surfaces and in between
layers of the metal part. Both char residue and oxidation of the metal particles can affect certain
properties of the metal part (e.g., microstructure, mechanical properties) that may result in undesirable
effects (e.g., stress fractures, corrosion, etc.) when the metal part is in use. As such, it is presently
recognized that there is a need to develop chemical binders that can be used for binder jet 3D printing
that provide sufficient bond strength to maintain the integrity of the green body metal part, after printing
and before debinding, and that are cleanly removed during debinding and/or sintering such that the
consolidated metal part is substantially free of char and any other undesirable decomposition products of
the chemical binder.

[0021] Chemical binders, such as thermoset binders, generally provide a green strength that is
suitable for handling of the green body metal part during post printing processes. In thermoset binders,
polymer strands are highly crosslinked (i.e., via covalent interactions and bonds) and result in a desirable
green strength for handling the green body metal part. However, it is presently recognized thermoset
binders are difficult to remove in inert and vacuum conditions due to strong covalent bonding between
the crosslinked polymer strands. As such, thermoset binders are generally removed in the presence of
air (oxygen), which may result in an undesirable amount of byproducts (e.g., char, metal oxides) that
affect the overall properties of the completed 3D printed metal part. For example, in the presence of air,
the thermoset binder may decompose in a manner that increases the oxide content within (e.g., between
the particles of the metal powder) the metal part during removal. These oxides may induce metal oxide
formation during sintering of the printed metal part. The metal oxide on the consolidated metal part
generated after sintering the printed metal part may affect mechanical properties of the consolidated
metal part resulting in mechanical property debits. On the contrary if the thermosets are burned in inert
atmospheres a lot of residual char formation will occur due to the inefficient burning. This char residue
may end up as metal carbides due to sintering. Both the char and oxide content that effectively turn into
metal carbides and metal oxides respectively lead to mechanical property debits especially in certain
alloys. It is presently recognized that thermoplastic binders may be more suitable for 3D printing metal
parts due, in part, to the absence of covalent crosslinking between thermoplastic polymer strands. The
absence of covalent crosslinking between the thermoplastic polymer strands enables clean removal of
the thermoplastic binder in inert, vacuum, or air conditions. That is, the thermoplastic binder is removed
from the printed metal part in a manner that does not generate char residue and/or metal oxides. As
such, a consolidated metal part formed from a binder jet printed green body metal part with
thermoplastic binders may have properties that are similar to the properties of the metal used to
manufacture the consolidated metal part.

[0022] However, while thermoplastic binders are cleanly removed during debinding and sintering
processes, it is presently recognized that green body metal parts printed using thermoplastic binders may
not have a suitable green strength for handling during post printing processes (in particular during
depowdering processes). This is due, in part, to the absence of covalent crosslinking between the
polymer strands of the thermoplastic binder. It is presently recognized that by using a linkable
thermoplastic binder that enables linking between thermoplastic polymer strands via weak non-covalent
forces, the green strength and stability of the green body metal part may be improved compared to a
green body metal part printed using non-linkable thermoplastic binders. Additionally, similar to non-
linkable thermoplastic binders, the linkable thermoplastic binders may be readily removed during
debinding under inert and vacuum conditions. The weak non-covalent forces linking the polymer
strands of the linkable thermoplastic polymer can be easily broken under inert and vacuum conditions to
unlink the polymer strands and allow removal of the unlinked thermoplastic polymers. Therefore,
unlike thermoset binders that are generally removed in the presence of O2, the linkable thermoplastic
binders disclosed herein can be mostly removed in the absence of O2. Moreover, in the presence of O2,
the linkable thermoplastic binders can be removed at temperatures that do not generate char residue or
induce metal oxide formation. Accordingly, decomposition of the linkable thermoplastic binder results
in a green body metal part having a green strength comparable to a green body metal part printed using
thermoset binders, and without the undesirable char residue associated with removal of the thermoset
binders. Disclosed herein are chemical binders (i.e., linkable thermoplastic binders) that may be used
for binder jet 3D printing, that yield a suitable green strength for handling of the green body metal part,
and that are readily and cleanly removed from the metal part during heat treatment (e.g., debinding
and/or sintering).

[0023] With the foregoing in mind, FIG. 1 is a block diagram depicting an embodiment of a method
10 for manufacturing an article (e.g., a consolidated metal part) via binder jet 3D printing using a
linkable thermoplastic binder. The linkable thermoplastic binder may include or consist of a two-
component thermoplastic polymer that, once cured, bonds particles and layers of a metal powder used to
print the article. Additionally, at least one component of the two-component thermoplastic polymer
includes one or more functional groups that enable coupling (e.g., linking) of polymer strands within the
linkable thermoplastic binder via weak non-covalent forces (e.g., hydrogen bonding, ionic bonding, Van
der Waals forces). By way of non-limiting example, the one or more functional groups may include a
hydroxyl (-OH), carboxylate (-COOH), amine (NH3), thiol (-SH), amide (-CONR2), or any other
suitable functional group that enables linking of polymer strands via weak non-covalent forces, and
combinations thereof. By linking the polymer strands of the components in the linkable thermoplastic
binder via weak non-covalent interactions after binder jetting and curing, the linkable thermoplastic
binder provides a desired green strength for the green body metal part. Additionally, the linkable
thermoplastic binder may be readily removed from the printed metal part in a manner that produces a
consolidated metal part that is substantially free of char residue associated with the decomposition of the
chemical binders used to manufacture the printed metal part and suitable for use in machinery.
Additionally, the conditions by which the linkable thermoplastic binder undergoes decomposition in
inert atmospheres, mitigates formation of metal oxides within the consolidated metal part resulting from
a reaction between the metal of the green body metal part and water (H2O) and/or oxygen (O2) during
debinding/ sintering.

[0024] To facilitate discussion of aspects of the method 10 illustrated in FIG. 1, reference is made to
FIGS. 2-5, which generally correspond to certain steps of the illustrated method 10. The method 10 of
FIG. 1 begins with depositing a layer of a metal powder that is used to manufacture an article of interest
(block 12). For example, FIG. 2 is a cross-sectional view of a layer 16 of a metal powder 18 (e.g., a
powder bed) on a working surface of a binder jet printer. In certain embodiments, the layer 16 may have
a thickness 20 of between approximately 10 microns ( µιη) and approximately 200 µιη . However, in
other embodiments, the thickness 20 of the layer 16 may be any suitable value.

[0025] The article to be printed may include a variety of metal parts having complex, 3D shapes,
such as, but not limited to, fuel tips, fuel nozzles, shrouds, micro mixers, turbine blades, or any other
suitable metal part. Therefore, the metal powder 18 used to print the metal part may vary depending on
the type of article and the end use of the article (e.g., gas turbine engines, gasification systems, etc.). By
way of non-limiting example, the metal powder 18 may include nickel alloys (e.g., Inconel 625, Inconel
718, Rene 108, Rene ' 80, Rene ' 142, Rene ' 195, and Rene ' M2, Marm-247); cobalt alloys (e.g., Hans 188
and L605); cobalt-chromium alloys, cast alloys: (e.g., X40, X45, and FSX414), titanium alloys,
aluminum-based materials, tungsten, stainless steel, or any other suitable material and combinations
thereof. In certain embodiments, the metal powder 18 may have particles having a particle size
distribution (e.g., dso) that is between approximately 1 micron ( m) and 75 m . However, the metal
powder 1 may have any other suitable particle size distribution.

[0026] Returning to FIG. 1, following deposition of the layer of metal powder 16, the method 10
continues with selectively depositing a linkable thermoplastic binder into portions of the layer 16
according to a pattern (block 24). For example, the linkable thermoplastic binder may be selectively
printed into the layer of metal powder 16 using a print head that is operated by a controller based on a
CAD design that includes representation of the layer of the article being printed.

[0027] For example, FIG. 3 is a block diagram of an embodiment of a binder jet printer 26 that may
be used to selectively deposit the linkable thermoplastic binder into the layer 16, according to the acts of
block 24 (FIG. 1). In the illustrated embodiment, the binder jet printer 26 includes a working surface 28
that supports the layer of metal powder 16, a reservoir 30 that stores a binder solution 34, and a printer
head 42 that is fluidly coupled to the reservoir 30. The binder solution 34 includes a linkable
thermoplastic binder 36 that includes a first thermoplastic polymer strand 3 and a second thermoplastic
polymer strand 40. The printer head 42 selectively deposits the binder solution 34 into the layer of
metal powder 16 to print the linkable thermoplastic binder 36 onto and into the layer 16 in a pattern that
is representative of the layer of the metal part being printed. The illustrated binder jet printer 26
includes a control system 46 for controlling operation of the binder jet printer 26. The control system 46
may include a distributed control system (DCS) or any computer-based workstation that is fully or
partially automated. For example, the control system 46 can be any suitable device employing a general
purpose computer or an application-specific device, which may generally include memory circuitry 48
storing one or more instructions for controlling operation of the binder jet printer 26. The memory 48
may store CAD designs representative of a structure of the article being printed. The processor may
include one or more processing devices (e.g., microprocessor 50), and the memory circuitry 48 may
include one or more tangible, non-transitory, machine-readable media collectively storing instructions
executable by the processor to control actions described herein.

[0028] As discussed above, the binder solution 34 is selectively deposited into the layer of metal
powder 16 in a pattern representative of the structure of the metal part being printed. FIG. 4 is a cross-
sectional schematic view of the layer of metal powder 16 after deposition of the linkable thermoplastic
binder 36. As illustrated, the linkable thermoplastic binder 36 coats an outer surface 54 of metal powder
particles 56, thereby generating binder-coated particles 58. The linkable thermoplastic binder 36 bonds
the binder-coated particles 58 according to the pattern of binder solution 34 printed into the layer of
metal powder 16 to form a layer of the green body metal part after curing (e.g., heat treatment at
approximately 200 °C). For example, FIG. 5 is a top view of a printed layer 60 of a green body metal
part 62 having the binder-coated particles 58 bonded to one another in a pattern 64 that is representative
of the layer of the metal part being printed.
[0029] Returning to FIG. 1, the method 10 may repeat the acts of blocks 1 and 24 to continue
building up the article in a layer-by-layer manner until a desired number of layers have been printed to
generate the green body metal part. The linkable thermoplastic binder 36 bonds each successive layer
60 and provides a certain degree of strength (e.g., green strength) to the printed article such that the
integrity of the structure of the printed green body metal part is not affected during post-printing
processes (e.g., debinding, sintering, depowdering, etc.). That is, the green strength provided by the
linkable thermoplastic binder 36 maintains bonding between the particles of metal powder within the
layers 60 and blocks (e.g., resists, prevents) delamination of the layers 60 during handling and post-
printing processing of the green body metal part.

[0030] The linkable thermoplastic binder 36 disclosed herein facilitates manufacturing of a 3D

printed article that is substantially free of char residue that may be formed during debinding and
sintering of the 3D printed article. Accordingly, the linkable thermoplastic binder 36 may be selected
from a class of thermoplastic polymers that generally decompose into carbon dioxide (CO2) and water
(H2O), without requiring the presence of O2, which are cleanly and readily removed during sintering, to
generate a consolidated metal part that is substantially free of the linkable thermoplastic binder 36 and
decomposition products (e.g., char and metal oxides) that may be generated during heat treatment of the
printed metal part. As discussed above, the linkable thermoplastic binder 36 includes the first
thermoplastic polymer strand 3 and the second thermoplastic polymer strand 40. The first
thermoplastic polymer strand 38 may include functional groups such as hydrogen bond donors,
hydrogen bond acceptors, negatively charged groups, positively charged groups, or combinations thereof
that complement a functional group of the second thermoplastic polymer strand 40 to facilitate non-
covalently linking the polymer strands 38, 40. By way of non-limiting example, the functional groups
of the first thermoplastic polymer strand 3 include hydroxyl groups, carboxylate groups, amine, thiol,
amide, or any other suitable functional group that enables coupling of polymer strands 38, 40 via weak
non-covalent forces, and combinations thereof. The first thermoplastic polymer strand 38 may include
polymers such as, but not limited to, polyvinyl alcohol (PVA), polyamides, polyacryl amide, derivatives
thereof, or any other suitable thermoplastic polymer that accepts coupling with the second thermoplastic
polymer strand 40 via the weak non-covalent forces, and combinations thereof. The first thermoplastic
polymer strand 8 may have an average molecular weight of between approximately 5K and 150K. For
example, in certain embodiments, the primary thermoplastic polymer 38 may have a molecular weight
between approximately 5-10K+/- 2K, approximately 10-25K+/- 2K, approximately 30-50K+/- 2K ,
approximately 75-100K+/- 3K , or approximately 100-150K +/- 5K.

[0031] As discussed above, the linkable thermoplastic binder improves the green strength to the
green body metal part to allow handling and stability of the metal part during post printing processes
(e.g., depowdering). Accordingly, the linkable thermoplastic binder includes the second thermoplastic
polymer strand 40 to enable coupling (e.g., non-covalent crosslinking) between polymer strands 38, 40
to increase the green strength in the green body metal part. Therefore, the second thermoplastic polymer
strand 40 includes functional groups that enable the polymer strands to interact with first thermoplastic
polymer strands 38 to link the respective polymer strands via weak non-covalent forces 70, as shown in
FIG. 6 . For example, the second thermoplastic polymer strand 40 may include functional groups that
are complementary to the functional groups on the first thermoplastic polymer strand 38. That is, the
second thermoplastic polymer strand 40 may include functional groups that such as hydrogen bond
donors, hydrogen bond acceptors, negatively charged groups, positively charged groups, or
combinations thereof that complement the functional groups of the first thermoplastic polymer strand 3
to facilitate non-covalently linking the polymer strands 38, 40. By way of non-limiting example, the
functional groups of the second thermoplastic polymer strand 40 include hydroxyl groups, carboxylate
groups, amine, thiol, amide, or any other suitable functional group that enables coupling of polymers 38,
40 via weak non-covalent forces, and combinations thereof.

[0032] In one embodiment, the polymer strands 38, 40 are the same thermoplastic polymer. In this
particular embodiment, the first thermoplastic polymer strand 38 is a portion of the thermoplastic
polymer that includes the first functional group and the second thermoplastic polymer strand 40 is
another portion of the thermoplastic polymer that includes the second functional groups. That is, the
first and second polymer strands 38, 40 are portions of a strand of the thermoplastic polymer. Because
each polymer strand of the thermoplastic polymer includes both the first and second functional group,
homocoupling between the functional group on the first polymer strand 3 portion and the functional
group on the second polymer strand 40 portion of may occur. That is, the first functional group in the
polymer strand 38, 40 may couple with the corresponding second functional group of the polymer strand
38, 40, thereby decreasing the degree of coupling between separate strands of the thermoplastic
polymer. To mitigate homocoupling between the first and second function groups in each respective
portion of the polymer strand 38, 40, the binder solution 36 may include primers (e.g., small polymers)
that may block coupling between the first and second functional groups of the polymer strand 38, 40.
Additionally, a concentration of the polymer strands 38, 40 may be controlled and/or the pH of the
binder solution 36 may be adjusted to block homocoupling between the functional groups in the polymer
strands 38, 40.

[0033] In other embodiments, the first thermoplastic polymer strand 38 is a first thermoplastic
polymer and the second thermoplastic polymer strand 40 is a second thermoplastic polymer that is
different than the first thermoplastic polymer. Accordingly, homocoupling between the functional
groups in the polymer strands 38, 40 is not a concern when the first thermoplastic polymer strand 38 is a
first thermoplastic polymer and the second thermoplastic polymer strand 40 is a second thermoplastic
polymer that is different from the first thermoplastic polymer. By way of non-limiting example, the
second thermoplastic polymer strand 40 may include polyacrylic acid (PAA), polyvinyl pyrrolidone
(PVP), polymethyl methacrylate (PMMA), derivatives thereof, or any other suitable polymer having
functional groups that enable non-covalent interactions, and combinations thereof. In certain
embodiments, the binder solution 34 is substantially free of any surfactants. By omitting the surfactant,
the formulation of the binder solution 34 can be simplified and manufacturing costs can be decreased
compared to formulations that include the surfactant. Additionally, as discussed in further detail below,
binder solution formulations that are substantially free of surfactants may enable printing of green body
metal parts having a green strength that is higher than the green strength of green body metal parts
printed with binder solution formulations that include a surfactant.

[0034] In certain embodiments, the second thermoplastic polymer strand 40 may include a protected
polyanhydride. For example, the second thermoplastic polymer strand 40 may include polyvinyl methyl
ether-maleic anhydride (PVME-MA). Upon exposure to moisture (e.g., water), the maleic anhydride is
hydrolyzed to expose carboxylate functional groups that may interact with the first thermoplastic
polymer strand 38 to link the respective polymer strands via the weak non-covalent forces. In certain
embodiments, the second polymer strand 40 may include ammonium (- H 3+) or amine (-NH2). The
ammonium links the polymer strands of the respective polymer strands 38, 40 via ionic intramolecular
forces. By way of non-limiting example, the second polymer strand 40 may include
poly(ethyleneimine), poly(allylamine), polyacrylate copolymer containing 2-(diethylamino)ethyl
methacrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl acrylate, derivatives thereof,
and combinations thereof. The second thermoplastic polymer strand 40 may have an average molecular
weight between approximately 1.5K and 160K.
[0035] As discussed above, the binder solution 34 includes a mixture of the first thermoplastic
polymer strand 38 and the second thermoplastic polymer strand 40. The binder solution 34 may include
any suitable ratio of the first thermoplastic polymer strand 38 to the second thermoplastic polymer
strand 40. The ratio of the first thermoplastic polymer strand 38 and the second thermoplastic polymer
strand 40 in the binder solution 34 is such that a suitable degree of linking between the polymer strands
38, 40 is achieved to yield a green body metal part having a desirable green strength suitable for
handling during post printing processes, and that allows clean removal of the linkable thermoplastic
binder 36. In addition to the degree of linking between the polymer strands 38, 40, it is also recognized
that the combination of the first thermoplastic polymer strand 3 and the second thermoplastic polymer
strand 40 can achieve a viscosity that is suitable for 3D binder jet printing (e.g., a viscosity between
approximately 2 centipoise (cP) and approximately 200 cP). By way of non-limiting example, the ratio
of the first thermoplastic polymer strand 3 to the second thermoplastic polymer strand 40 may be 1:1,
2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 9:1, 10:1, or any other suitable ratio.

[0036] As discussed above with reference to FIG. 3, the printer head 42 receives the binder solution
34 (e.g., ink) having the linkable thermoplastic binder 36 and prints the linkable thermoplastic binder 36
into the layer of metal powder 16. Accordingly, the binder solution 34 may have certain properties that
facilitate binder jet printing via the printer head 42. The binder solution 34 may include additives that
may facilitate deposition of the linkable thermoplastic binder 26 into the layer 16. For example, in
certain embodiments, the binder solution 34 may include one or more additives such as surfactants,
diluents, viscosity modifiers, dispersants, stablizers, or any other additive that facilitates jettability of the
binder solution 34 and deposition of the linkable thermoplastic binder 36 into the layer 16. The
surfactants may be ionic (e.g., zwitterionic, cationic, anionic) or non-ionic depending on the properties
of the linkable thermoplastic binder 36 and/or the metal powder 18. By way of non-limiting example,
the surfactant may be polypropoxy diethyl methylammonium chloride (e.g., VARIQUAT® CC-42NS),
oligomers of hexanoic acid (e.g., HYPERMER® KD1), alkylene oxide copolymer (HYPERMER®
KD2), alkylene esters of fatty acids and alkylamines (HYPERMER® KD3), and combinations thereof.

[0037] The one or more additives may improve the wettability of the metal powder 18 to facilitate
coating the particles of the metal powder 18 with the linkable thermoplastic binder 36. The one or more
additives may also change (e.g., modify) the surface tension of the binder solution 34 to facilitate
jettability of the binder solution 34. For example, in certain embodiments, the binder solution 34 is
generally considered jettable if the Ohnesorge number (e.g., the ratio of viscous forces to inertial and
surface tension forces) is between approximately 0.1 and approximately 1.

[0038] In certain embodiments, the one or more additives may also include a solvent that dissolves
the linkable thermoplastic binder 36. The solvent may be aqueous or non-aqueous, depending on the
selected polymer strands 38, 40 and other additives that may be in the binder solution 34. The solvent is
generally non-reactive (e.g., inert) such that it does not react with the metal powder 18, the linkable
thermoplastic binder 36, or any other additives that may be in the binder solution 34. Additionally, the
solvent should readily evaporate after selective deposition of the linkable thermoplastic binder 36 into
the layer of metal powder 16 to facilitate bonding of the binder-coated particles 58 and the printed layers
60. Example solvents that may be used in the binder solution include, but are not limited to, water,
methylene chloride (CH2CI2), chloroform (CHCb), toluene, xylenes, mesitylene, anisole, 2-methoxy
ethanol, butanol, diethylene glycol, tetrahydrofuran (THF), methyl ethyl ketone (MEK),
trichloroethylene (TCE), or any other suitable solvent.

[0039] The linkable thermoplastic binder 36 in the binder solution 34 may be in the form of pr e
formed, dissolved polymer strands 38, 40. The linkable thermoplastic binder 36 may be solubilized in a
suitable solvent to facilitate linking of the polymer strands 38, 40, j ettability, and deposition into the
layer of metal powder 16. Following deposition of the binder solution 34 into the layer of metal powder
16, the solvent may evaporate and the linkable thermoplastic binder 36 may coalesce and bond the
binder-coated particles 8 and the printed layers 60 to form the green body metal part.

[0040] Following deposition of the layer 16 and printing of the linkable thermoplastic binder 36, as
set forth in blocks 12 and 24 of FIG. 1, the method 10 continues with curing the linkable thermoplastic
binder to form a layer of the green body metal part (block 74). For example, as discussed above, the
binder solution 36 may be a mixture of the linkable thermoplastic binder 36 (e.g., polymer strands 38,
40) and a solvent. While a portion of the solvent in the binder solution 36 may be evaporated during
deposition (e.g., printing) of the linkable thermoplastic binder 36, a certain amount of the solvent may
remain within the layer of metal powder 16. Therefore, in certain embodiments, the green body metal
part may be thermally cured (in a subsequent, post-print step (e.g., block 74 of FIG. 1)) at a temperature
that is suitable for evaporating the solvent remaining in the printed layer 60 and allowing efficient
bonding of the printed layers 60 of the green body metal part (e.g., approximately 200 °C). Excess
material 18 (e.g., the metal powder 18 that is not bonded by the linkable thermoplastic binder 36) may
be removed after curing to prepare the green body for debinding and sintering processing. After curing,
the green body metal part may undergo a drying step to remove any residual solvent and/or other
volatile materials that may remain in the metal part. For example, the green body metal part may be
dried in a vacuum, under an inert atmosphere (e.g., nitrogen (N2), argon (Ar)), or air at slightly elevated
or room temperatures.

[0041] As discussed above, the linkable thermoplastic binder used to form the green body metal part
in binder jetting applications may be removed in a manner that mitigates both formation of char residue
and metal oxide formation during sintering processes. Accordingly, the method 10 includes removing
(e.g., debinding) a portion of the linkable thermoplastic binder 36 from the green body metal part to
generate a brown body metal part (block 78). As discussed above, the binders used in binder jetting
applications provide strength (e.g., green strength) to the printed article. Therefore, it is desirable to
remove only a portion (i.e., not all) of the linkable thermoplastic binder during debinding of the green
body metal part to improve the handling strength of the resulting brown body metal part before
sintering.

[0042] As mentioned above, certain thermoplastic binders used in binder jet 3D printing may not
yield a green strength suitable for handling the green body metal part in post printing processes (e.g.,
depowdering and debinding). However, it is now recognized that by using the linkable thermoplastic
binder 36, the green strength of the printed article may be increased compared to an article that is printed
using non-linkable thermoset binders. Additionally, the linkable thermoplastic binder 36 can be easily
removed in the absence of O2, which may result, in a consolidated article that is substantially free of
char residue after debinding and sintering. In this way, certain properties of the consolidated metal part
(e.g., level of oxidation) may be similar or identical to the properties of the metal powder 18 used to
print the article.

[0043] A table of example binder solutions, along with data for the green strength of a green body
printed using the binder solutions is shown below, in accordance with embodiments of the present
technique. The green body metal part was prepared by placing a metal powder of Rene' 108 ( d o of
approximately 16 µ ) in a 1.43" plastic petri dish, and tapping the petri dish approximately 50 times to
pack the metal powder. Approximately 2 milliliters (mL) of the binder solution (e.g., polyvinyl alcohol
(PVA)), the linkable thermoplastic polymer 36 (e.g., PVA:polyacrylic acid (PAA), PVA:polyvinyl
pyrrolidone; PVA:poly(methyl vinyl ether-alt-maleic) anhydride, or a commercial binder) was added
dropwise to the metal powder until the metal powder was saturated with the binder solution. The petri
dish was tapped simultaneously along with the addition of each drop of the binder solution to allow the
binder solution to be absorbed into the packed metal powder. The saturated metal powder was allowed
to dry at ambient conditions for approximately 1 hour. Following drying, the saturated metal powder
was cured at approximately 85 °C overnight to yield the green body metal part. The green body metal
part was subject to 3-point flexural testing with a 500 Newton (N) loaded cell applied until the green
body metal part broke. The green strength for each green body metal part prepared according to the
above method is reported in Table 1 below.

TABLE 1 GREEN STRENGTH FOR GREEN BODIES PRINTED USING VARIOUS BINDER
SOLUTION FORMULATIONS
 PVA:PAA 3:1 31-50K; 1.8K KD2 217 48.7

PVA:PAA 2:1 31-50K; 1.8K KD2 291 65.0

PVA:PAA 5:1 80-125K; 1.8K KD2 186 41.8

PVA:PAA 5:1 80-125K; 1.8K KD2 265 59.5

PVA:PAA 2:1 80-125K; 1.8K KD2 187 42.0

PVApolyvinyl
pyrrolidone 5:1 31-50K; 155K KD2 278 62.5

PVA:Poly (methyl vinyl

ether-alt-maleic 5:1 31-50K; 216K — 333 74.8
anhydride)

PVA:Poly (methyl vinyl

ether-alt-maleic 5:1 31-50K; 216K KD2 177 39.7
anhydride)

Commercial binder — — — 283 63.6

[0044] FIG. 7 is a bar graph 80 of green strength associated with embodiments of green body metal
parts printed using various binder solution formulations listed in Table 1 above. For example, bar graph
80 illustrates green strength 82 in pounds force (IbF) for green body metal parts 84 and 86 printed with a
linkable thermoplastic binder having a 5:1 ratio of either PVA (3 1-50K):PAA or PVA (13-23K):PAA,
respectively. The bar graph 80 also illustrates the green strength for green body metal parts 90 and 94
printed using non-linkable thermoplastic binder formulation having a surfactant and either PVA (31-
50K) or PVA (13-23K), respectively, and the green strength for a green body metal part 96
printed using a commercial binder formulation. As shown in FIG. 7, the green strength of green body
metal parts 84, 86 have a higher green strength 82 compared to the green body metal part 90, 94,
respectively. For example, the green strength for the green body metal parts 84, 86 have between
approximately 20% and % more than the green strength of the green body metal parts 90, 94 printed
with the non-linkable thermoplastic binder formulation. Additionally, certain formulations of the
linkable thermoplastic binders disclosed herein demonstrate between 20% and 46% greater green
strength compared to existing state of the art binders (e.g., the commercial binder).

[0045] Moreover, surprisingly and unexpectedly, it is presently recognized that the linkable
thermoplastic binder formulations disclosed herein that do not include a surfactant result in a higher
green strength compared to linkable thermoplastic binder formulations that include the surfactant, as
shown in Table 1 above. In certain binder formulations, the surfactant may facilitate coating of the
metal powder 18 with the binder by enhancing surface properties (e.g., wettability) of the metal powder.
However, when using certain linkable thermoplastic binder formulations, the surfactant may hinder
molecular interactions between strands of the polymer strands 38, 40, decreasing or blocking coupling
between the functional group of the polymer strand 40 with the polymer strand 38 via weak non-
covalent forces. As such, the linkable thermoplastic binder 36 may not have sufficient linking between
the polymer strands 38, 40 to yield a suitable green strength for handling the printed and cured green
body metal part during post printing processes. Therefore, depending on the functional groups of the
polymer strand 40 and the type of weak non-covalent forces linking the polymer strands 38, 40, it may
be desirable to omit the surfactant from the linkable thermoplastic binder formulation to enable
formation of weak non-covalent forces between the polymer strands 38, 40. Alternatively, in certain
embodiments, a surfactant that does not substantially interact (e.g., is substantially inert) with the
polymer strands 38, 40 may be used in the linkable thermoplastic binder formulation.

[0046] During the partial removal of the linkable thermoplastic binder 36 during debinding, the green
body metal part may be heated to separate the linked polymer strands 38, 40 and break down a portion
of the polymer strands 38, 40. For example, the green body metal part may be heated to a temperature
that is approximately 500 °C or less, such as between approximately 250 °C and approximately 450 °C,
during the debinding step of block 78. The conditions to which the green body metal part is exposed
during debinding decomposes the polymer strands 38, 40 and generates the brown body metal part
having a substantial portion (e.g., approximately 95%, approximately 96%, approximately 97%,
approximately 98%) of the linkable thermoplastic binder 36 removed. The remaining carbon residues of
the polymer strand 38, 40 in the brown body metal part after debinding may continue to bond the printed
layers in the brown body metal part and provide a brown strength that maintains the structure of the
brown body metal part during handling.
[0047] In certain embodiments, between approximately 98% and approximately 99 .95% of the
linkable thermoplastic binder 36 may be removed during debinding by partial decomposition of the
linkable thermoplastic binder 36. Many of the small molecules that form during the partial
decomposition of the linkable thermoplastic binder may be gaseous at room temperature or at the
debinding temperature. The portion of the linkable thermoplastic binder 36 (e.g., oligomers) that remain
in the brown body metal part after debinding continue to bond the layers of metal powder of the brown
body metal part and enable a suitable amount of brown strength. In one embodiment, the portion of the
oligomers that remain in the brown body is between approximately 0.05% and approximately 2%. In
other embodiments, the portion of the oligomers that remain in the brown body is between
approximately 0.1% and approximately 1%.

[0048] In certain embodiments, debinding of the linkable thermoplastic binder 36 may include
heating the green body metal part to a desired temperature (e.g., between approximately 250 °C and
approximately 450 °C) in an oxygen-free environment (e.g., in a vacuum chamber under inert
atmosphere). For example, debinding may be performed under nitrogen (N2), argon (Ar), or another
substantially inert gas. However, in certain embodiments, the debinding may be performed in air. Due,
in part, to the weak non-covalent forces linking the polymer strands 38, 40 of the linkable thermoplastic
binder 36, debinding in air may be done at temperatures less than approximately 450 °C, which blocks
oxidation of the metal powder 18. As such, the overall properties of the consolidated metal part printed
using the linkable thermoplastic binder 36 may be similar to the properties of the metal powder 18 used
to manufacture the 3D printed metal part.

[0049] Following debinding of the linkable thermoplastic binder 36, as set forth in block 78, the
method 10 of FIG. 1 continues with pre-sintering the brown body metal part to remove the remaining
portion of the linkable thermoplastic binder (e.g., oligomers formed during debinding) in the brown
body metal part (block 100). For example, as discussed above, the linkable thermoplastic binder 36 may
partially decompose to form oligomers that provide sufficient strength to the brown body metal part
formed from the green body metal part after partially debinding the linkable thermoplastic binder 36,
according to the acts of block 78. During pre-sintering, the brown body metal part may be heated to pre-
sintering temperatures that are between approximately 500 °C and approximately 800 °C. The heat
applied to the brown body metal part during pre-sintering decomposes the remaining oligomers into
small molecules that quickly volatilize and escape from the brown body metal part. The oligomers
decompose cleanly into the smaller molecules, which may evaporate through the porous structure of the
brown body, leaving substantially no residue. As such, when the brown body metal part is subsequently
sintered, the resulting consolidated metal part may be substantially free of char. Accordingly, the
consolidated metal part may have properties similar to those of the metal powder 18 used to print the
metal part.

[0050] Finally, the method 10 illustrated in FIG. 1 concludes with sintering the brown body metal
part to consolidate the particles of metal powder without generating a metal oxides (block 104). During
sintering, the brown body metal part may be exposed to a concentrated source of energy (e.g., a laser,
electron beam, or any other suitable energy source) that heats the brown body metal part and
consolidates the printed layers 60 of the brown body to form a substantially solid metal part (e.g., the
consolidated metal part) having a density that is greater than the density of the corresponding brown
body metal part. Sintering imparts strength and integrity to the brown body metal part such that the
consolidated metal part is suitable for use in machinery. Sintering temperatures may be in excess of
1000 °C, depending on the metal powder 18 used to print the part. For example, in certain
embodiments, the sintering temperature may be between approximately 1200 °C and approximately
1300 °C. Therefore, any organic compounds, such as the binders generally used in binder jetting, that
may be present in the brown body metal part may form metal carbides/oxides during sintering.

[0051] As discussed above, the char may affect certain characteristics of the consolidated article (e.g.,
microstructure and/or mechanical properties), which may affect the performance of the consolidated
metal part when used in machinery. The production of char during debinding and sintering of the metal
part to generate the consolidated article may be mitigated by using thermoplastic polymers, which may
be easily removed in inert, vacuum, and air atmospheres. However, thermoplastic binders may not
provide sufficient green strength to handle the printed green body in post printing processes (e.g.,
depowdering). It is now recognized that, by mixing the polymer strand 3 with the polymer strand 40
having functional groups that interact with the polymer strand 38 to generate the linkable thermoplastic
binder 36 disclosed herein, the printed green body metal part may have sufficient handling strength for
post printing processes, and the consolidated metal part may be substantially free of char residue.
Therefore, the properties of the consolidated metal part may be similar to the properties of the metal
powder 18, and may be comparable to properties of metal parts manufactured via molding techniques.
The consolidated metal part manufactured via binder jet 3D printing using the linkable thermoplastic
binder 36 disclosed herein may have a carbon content and an oxygen content that is equal to or less than
a carbon content and oxygen content of the metal powder 1 used to print the metal part.
[0052] State of the art chemical binders used for 3-D binder jet metal printing generally produce
green body metal parts having a green strength that is lower than the green strength of green body metal
parts printed the linkable thermoplastic binder disclosed herein. Additionally, state of the art chemical
binders used for 3-D binder jet metal printing generally produce consolidated metal articles having char
residues that yield carbon (C) and oxygen (O) (e.g., metal oxides or oxygen-containing binder
decomposition products) content that is greater than the C and O levels of the metal powder used to print
the metal part. However, the linkable thermoplastic binders disclosed herein, improve the green strength
of the printed green body that enables handling of the green body metal part during depowdering and
debinding processes compared to state of the art chemical binders. Additionally, surprisingly and
unexpectedly, certain linkable thermoplastic binder formulations that do not include a surfactant result in
an increased green strength compared to linkable thermoplastic binder and non-linkable thermoplastic
formulations that include a surfactant.

[0053] As discussed above, the linkable thermoplastic binders disclosed herein may be used in binder
jetting additive manufacturing to print an article, such as a metal machine part. The disclosed linkable
thermoplastic binders may include thermoplastic polymers that interact via weak non-covalent forces to
link (e.g., non-covalently cross-link) the respective polymer strands of the thermoplastic polymers in the
linkable thermoplastic binder. In this way, the green strength of the printed green body metal part may
be increased compared to a green body printed with non-linkable thermoplastic binders. Moreover, the
disclosed linkable binders improve the green strength of the green body metal body without the use of
surfactants that facilitate interactions between the linkable thermoplastic binder and the particles of
metal powder used to print the metal part. Additionally, when heated above a decomposition
temperature of the binder, the thermoplastic polymers in the linkable thermoplastic binder form
decomposition products (e.g., oligomers) that are relatively stable at a lower debinding temperature, and
are readily removed from the metal part at higher (e.g., pre-sintering, sintering) temperatures. The
decomposition products may include oligomers that remain in the article after debinding and improve
the strength of the brown body metal part. In this way, the integrity of the brown body metal part may
be maintained until the article is sintered. Additionally, the oligomers are readily and cleanly
decomposed in a pre-sintering step without charring. In this way, the consolidated metal part may be
substantially free of char residue, which may deleteriously affect the material properties of the
consolidated metal part.
[0054] This written description uses examples to disclose the invention, including the best mode, and
also to enable any person skilled in the art to practice the invention, including making and using any
devices or systems and performing any incorporated methods. The patentable scope of the invention is
defined by the claims, and may include other examples that occur to those skilled in the art. Such other
examples are intended to be within the scope of the claims if they have structural elements that do not
differ from the literal language of the claims, or if they include equivalent structural elements with
insubstantial differences from the literal languages of the claims.
CLAIMS:

1. A method of binder j et printing a part comprising:

depositing a layer of a powder on a working surface of a binder jet printer;

selectively printing a binder solution comprising a linkable thermoplastic binder into the
layer of powder in a pattern to the generate a printed layer, wherein the pattern is representative of a
structure of a layer of the part, wherein the linkable thermoplastic binder comprises a first polymer strand
and a second polymer strand, wherein the first polymer strand comprises a first functional group and the
second polymer strand comprises a second functional group different from the first functional group, and
wherein the first and second functional groups are configured to non-covalently couple the first polymer
strand with the second polymer strand;

curing the linkable thermoplastic binder in the printed layer to generate a layer of a green
body part;

heating the green body part above a first temperature to remove at least a portion of the
linkable thermoplastic binder and generate a brown body part; and

heating the brown body part above a second temperature to sinter the metal powder to
generate the part, wherein the part is substantially free of char residue.

2. The method of binder jet printing the part of claim 1, wherein the binder solution comprises
a mixture of the linkable thermoplastic binder and a solvent without a surfactant, and wherein curing the
printed layer comprises evaporating the solvent.

3. The method of binder jet printing the part of claim 1, wherein the binder solution comprises
a mixture of the linkable thermoplastic binder, a solvent, and a surfactant, and wherein curing the printed
layer comprises evaporating the solvent.

4. The method of binder jet printing the part of claim 1, wherein a molecular weight of the
first polymer strand is between approximately 5K and 150K.

5. The method of binder jet printing the part of claim 1, wherein the molecular weight of the
second polymer strand is between approximately 1.5K and 160K.
 6. The method of binder jet printing the part of claim 1, wherein the first functional group is
a hydrogen bonding acceptor or negatively charged, and the second functional group is a hydrogen
bonding donor or positively charged.

7. The method of binder jet printing the part of claim 1, wherein the first and second
functional groups comprise a carboxylate group, a hydroxyl group, amine, amide, thiol, or a combination
thereof.

8. The method of binder jet printing the part of claim 1, wherein the first polymer strand is
polyvinyl alcohol (PVA), polyamides, polyacryl amide, derivatives thereof , and combinations thereof,
and wherein the second polymer strand is polyacrylic acid (PAA), polyvinyl pyrrolidone (PVP),
polymethyl methacrylate (PMMA), polyvinyl methyl ether-maleic anhydride (PVME-MA), derivatives
thereof, and combinations thereof.

9. The method of binder jet printing the part of claim 1, wherein the first polymer strand is a
first thermoplastic polymer and the second polymer strand is a second thermoplastic polymer, and wherein
the first thermoplastic polymer is different from the second thermoplastic polymer.

10. The method of binder jet printing the part of claim 9, wherein a ratio of the first
thermoplastic polymer to the second thermoplastic polymer is 5:1.

11. The method of binder jet printing the part of claim 1, wherein the powder comprises a
nickel alloy, titanium alloy, cobalt alloy, aluminum-based material, tungsten, stainless steel, ceramic, or a
combination thereof.

12. The method of binder jet printing the part of claim 1, wherein the layer of metal powder
has a thickness of between approximately 10 microns and approximately 200 microns.

13. The method of binder jet printing the part of claim 1, wherein selectively printing
comprises selectively printing the binder solution with a print head of the binder jet printer.

14. The method of binder jet printing the part of claim 1, comprising drying the green body
part before heating the green body part to the first temperature to remove residual solvent used in the
binder solution from the green body part.

15. A part manufactured via a binder jet printing process comprising the steps of:

depositing a layer of a powder on a working surface of a binder jet printer;

 selectively printing a binder solution comprising a linkable thermoplastic binder into the
layer of powder in a pattern to generate a printed layer, wherein the pattern is representative of a structure
of a layer of the part, wherein the linkable thermoplastic binder comprises a first polymer strand and a
second polymer strand, wherein the first polymer strand comprises a first functional group and the second
polymer strand comprises a second functional group, and wherein the first and second functional groups
are configured to non-covalently couple the first polymer strand with the second polymer strand;

curing the linkable thermoplastic binder in the printed layer to generate a layer of a green
body part;

heating the green body part above a first temperature to remove at least a portion of the
linkable thermoplastic binder and generate a brown body part; and

heating the brown body part above a second temperature to sinter the powder to generate
the part, wherein the part is substantially free of char residue.

16. The part of claim 15, wherein the green body part comprises a strength of between
approximately 40 and approximately 118 pounds force (lbF).

17. The part of claim 15, wherein a carbon content of the part is substantially the same or less
than a carbon content of the metal powder.

18. The part of claim 15, wherein an oxygen content of the part is substantially the same or
less than an oxygen content of the metal powder.

19. A binder solution configured for use in binder jet printing, comprising:

a binder solution comprising a linkable thermoplastic binder comprising a first polymer

strand and a second polymer strand, wherein the first polymer strand comprises a first functional group
and the second thermoplastic polymer strand comprises a second functional group, and wherein the first
and second functional groups are configured to non-covalently couple at least a portion of the second
polymer strand with at least a portion of the first polymer strand, wherein the binder solution is
substantially free of a surfactant.

20. The binder solution of claim 19, wherein the first polymer strand is polyvinyl alcohol
(PVA), polyamides, polyacryl amide, derivatives thereof , and combinations thereof, and wherein the
second polymer strand is polyacrylic acid (PAA), polyvinyl pyrrolidone (PVP), polymethyl methacrylate
(PMMA), polyvinyl methyl ether-maleic anhydride (PVME-MA), derivatives thereof, and combinations
thereof.

21. The binder solution of claim 19, wherein a molecular weight of the first polymer strand is
between approximately 5K and approximately 150K.

22. The binder solution of claim 19, wherein the molecular weight of the second polymer
strand is between approximately 1.5K and approximately 160K.

23. The binder solution of claim 19, wherein the first functional group is a hydrogen bonding
acceptor or negatively charged, and the second functional group is a hydrogen bonding donor or positively
charged.

24. The binder solution of claim 19, wherein the first and second functional groups comprise
a carboxylate group, a hydroxyl group, amide, amine, thiol, or a combination thereof.

25. The binder solution of claim 19, wherein the first polymer strand is a first thermoplastic
polymer and the second polymer strand is a second thermoplastic polymer, and wherein the first
thermoplastic polymer is different from the second thermoplastic polymer.

26. The binder solution of claim 25, wherein a ratio of the first thermoplastic polymer to the
second thermoplastic polymer is approximately 5:1.

27. The binder solution of claim 19, wherein the first polymer strand and the second polymer
strand are both polymer strands of the same thermoplastic polymer, and wherein the first polymer strand
further comprises the second functional group and the second polymer strand further comprises the first
functional group.

28. The binder solution of claim 19, wherein a viscosity of the binder solution is between
approximately 2 centipoise (cP) and 200 cP.
 A. CLASSIFICATION OF SUBJECT MATTER
B29C 64/209(2017.01)i, B29C 64/165(2017.01)i, B22F 3/105(2006.01)i, B33Y 70/00(2015.01)i, B33Y 30/00(2015.01)i

According to International Patent Classification (IPC) or to both national classification and IPC
B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
B29C 64/209; B22F 1/00; B22F 3/105; B22F 3/26; B22K 3/12; B24B 3/28; B24D 18/00; B29C 35/08; C08F 2/46; B29C 64/165; B33Y
70/00; B33Y 30/00

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched
Korean utility models and applications for utility models
Japanese utility models and applications for utility models

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)
eKOMPASS(KIPO internal) & keywords: binder jet printing, powder, binder solution, thermoplastic binder, pattern, printed layer, first
functional group, second functional group, non-covalently couple, green body part

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category' Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 6508980 Bl (SACHS, E . M . e t al.) 21 January 2003 1-18

See column 12, lines 22-31; column 19, line 66-column 20, line 5 ; and claims
1, 4 , 8.
19-28

WO 2017-029657 A l (STRATASYS LTD.) 23 February 2017 19-28

See page 34, lines 25-26; page 35, lines 8-9; and claims 1 , 2 , 6 , 15, 18, 28
, 29.
1-18

US 5976457 A (AMAYA, H . E . e t al.) 02 November 1999 1-28

See the whole document.

WO 2017-018984 A l (HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.) 02 February 20 1-28

17
See the whole document.

WO 2017-127221 A l (APPLIED MATERIALS, INC.) 27 July 1-28

See the whole document.

I IFurther documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents: "T" later document published after the international filing date or priority
"A" document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand
to b e of particular relevance the principle or theory underlying the invention
"E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot b e
filing date considered novel or cannot be considered to involve an inventive
"L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone
cited to establish the publication date of another citation or other "Y" document of particular relevance; the claimed invention cannot b e
special reason (as specified) considered to involve an inventive step when the document is
"O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents,such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later "&" document member of the same patent family
than the priority date claimed

Date of the actual completion of the international search Date of mailing of the international search report
14 November 2018 (14. 11.2018) 15 November 2018 (15.11.2018)
Name and mailing address of the ISA/KR Authorized officer ·· -·· „
International Application Division

.
Korean Intellectual Property Office
189 Cheongsa-ro, Seo-gu, Daejeon, 35208, Republic of Korea
KWON, Yong Kyong | f ¾¾ ¾
Facsimile No. +82-42-481-8578 Telephone No. +82-42-481-3371 "

Form PCT/ISA/210 (second sheet) (January 2015)

 Information on patent family members
PCT/US2018/040983

Patent document Publication Patent family Publication

cited in search report date member(s) date

US 6508980 Bl 21/01/2003 CA 2304339 Al 01/04/1999

CA 2304339 C 03/04/2007
DE 69827844 T2 08/12/2005
EP 1039980 Al 04/10/2000
EP 1039980 A4 08/01/2003
EP 1039980 Bl 24/11/2004
JP 2001-517732 A 09/10/2001
JP 2006-517732 A5 05/01/2006
JP 4314396 B2 12/08/2009
WO 99-15293 Al 01/04/1999

WO 2017-029657 Al 23/02/2017 CN 107921703 A 17/04/2018

CN 108136677 A 08/06/2018
EP 3334582 Al 20/06/2018
EP 3334590 Al 20/06/2018
JP 2018-525473 A 06/09/2018
JP 2018-526481 A 13/09/2018
R 10-2018-0031802 A 28/03/2018
R 10-2018-0042303 A 25/04/2018
US 2018-0230246 Al 16/08/2018
us 2018-0236717 Al 23/08/2018
wo 2017-029658 Al 23/02/2017

US 5976457 A 02/11/1999 wo 01-32332 Al 10/05/2001

WO 2017-018984 Al 02/02/2017 CN 108025359 A 11/05/2018

EP 3325191 Al 30/05/2018
US 2018-0178447 Al 28/06/2018

WO 2017-127221 Al 27/07/2017 CN 106716604 A 24/05/2017

CN 107078048 A 18/08/2017
CN 107107305 A 29/08/2017
CN 107107306 A 29/08/2017
EP 3207560 Al 23/08/2017
EP 3362224 Al 22/08/2018
JP 2017-533585 A 09/11/2017
JP 2017-533586 A 09/11/2017
JP 2017-533832 A 16/11/2017
KR 10-2017-0068534 A 19/06/2017
KR 10-2017-0070210 A 21/06/2017
KR 10-2017-0071558 A 23/06/2017
KR 10-2017-0071559 A 23/06/2017
KR 10-2018-0056786 A 29/05/2018
KR 10-2018-0097759 A 31/08/2018
SG 11201703112 A 29/06/2017
SG 11201703113 A 29/06/2017
SG 11201703114 A 29/06/2017
TW 201614730 A 16/04/2016
TW 201615341 A 01/05/2016

Form PCT/ISA/2 10 (patent family annex) (January 20 15)

 Information on patent family members
PCT/US2018/040983

Patent document Publication Patent family Publication

cited in search report date member(s) date

TW 201622972 A 01/07/2016
TW 201725091 A 16/07/2017
TW 201726325 A 01/08/2017
us 2016-0101500 Al 14/04/2016
us 2016-0107287 Al 21/04/2016
us 2016-0107290 Al 21/04/2016
us 2016-0107295 Al 21/04/2016
us 2016-0114458 Al 28/04/2016
us 2016-0136787 Al 19/05/2016
us 2017-0100817 Al 13/04/2017
us 2017-0136603 Al 18/05/2017
us 2017-0203406 Al 20/07/2017
us 2017-0203408 Al 20/07/2017
us 9873180 B2 23/01/2018
wo 2016-057075 Al 14/04/2016
wo 2016-060712 Al 21/04/2016
wo 2016-061544 Al 21/04/2016
wo 2016-061585 Al 21/04/2016
wo 2017-066077 Al 20/04/2017

Form PCT/ISA/2 10 (patent family annex) (January 20 15)