Title of Invention

INFLUENCING SPECIFIC MECHANICAL PROPERTIES OF THREE-DIMENSIONAL OBJECTS MANUFACTURED BY A SELECTIVE SINTERING BY MEANS OF ELECTROMAGNETIC RADIATION FROM A POWDER COMPRISING AT LEAST ONE POLYMER OR COPOLYMER

Abstract A three-dimensional object is manufactured from a powder of polymer material by selective sintering process by means of electromagnetic radiation of the powder, wherein the powder comprises a preselected polymer or copolymer and is subjected to selective sintering such that the manufactured three-dimensional object has a final crystallinity which is in such a range that the balance of properties, in particular mechanical properties including Young"s modulus, tensile strength and elongation at break, is improved.
Full Text Influencing specific mechanical properties of three-dimensional objects manufactured
by a selective sintering by means of electromagnetic radiation from a powder
comprising at least one polymer or copolymer
The present invention .elates to a process for manufacturing a three-dimensional object
from a powder by selective sintering by means of electromagnetic radiation of the powder,
wherein the powder comprises at least one polymer material and wherein the manufactured
three-dimensional object has an advantageously decreased crystallinity compared to
conventional selective entering by means of electromagnetic radiation. Furthermore, the
present invention relat :s to a three-dimensional object obtained by said process, an
apparatus for said process and a use of a preselected polymer powder in said process.
As known from DE 44 10 046, a process for manufacturing a three-dimensional object by a
selective sintering by means of electromagnetic radiation may be carried out layer-wise
with a source for electromagnetic radiation. In such a process, three-dimensional objects are
manufactured in a layer-wise manner by applying layers of a powder and bonding them to
each other by a selective solidification of the powders at positions in the layers
corresponding to cross-sections of the objects.
Fig. 1 shows as an example of a laser sintering device by means of which a process for a
layer-wise manufacturing of a three-dimensional object may be performed. As is apparent
from Fig. 1, the device comprises a container 1. This container is open to the top and is
limited at the bottom by a support 4 for supporting an object 3 to be formed. By the upper
edge 2 of the container (or by its sidewalls) a work plane 6 is defined. The object is located
on the top side of the support 4 and is formed from a plurality of layers of a building

material in powder form that can be solidified by means of electromagnetic radiation,
wherein the layers are in parallel to the top side of the support 4. The support may be
moved in a vertical direction, i.e. in parallel to the sidewall of the container 1, via a height
adjustment device. Thereby the position of the support 4 relative to the work plane 6 can be
adjusted.
Above the container 1, or rather the work plane 6, an application device 10 is provided for
applying the powder material 11 to be solidified onto the support surface 5 or a previously
solidified layer. Also, an irradiation device in the form of a laser 7, which emits a directed
light beam 8, is arranged above the work plane 6. This light beam 8 is directed as deflected
beam 8' towards the work plane 6 by a deflection device 9 such as a rotating mirror. A
control unit 40 allows to control the support 4, the application device 10 and the deflection
device 9. The items 1 to 6, 10 and 11 are located within a machine frame 100.
When the three-dimensional object 3 is manufactured, the powder material 11 is applied
layer-wise onto the support 4 or a previously solidified layer and is solidified at the
positions of each powder layer that correspond to the object by means of the laser beam 8'.
After each selective solidification of a layer the support is lowered by the thickness of the
powder layer to be subsequently applied.
Many modifications of processes and devices for manufacturing a three-dimensional object
by a selective sintering by means of electromagnetic radiation compared to the system
described above exist and can be used. For example, instead of using a laser and/or a light
beam, other systems to selectively deliver electromagnetic radiation could be used, such as,
e.g., mask exposure systems or the like.
However, in previous processes for selective sintering by means of electromagnetic
radiation of polymer powders, insufficient attention was paid to mechanical properties of
the manufactured objects.
Therefore, the object of the present invention is to provide an improvement of a process for
manufacturing a three-dimensional object by selective sintering by means of

electromagnetic radiation of polymer powders, which leads to improved mechanical
properties of the manufactured objects.
According to the present invention, it has been surprisingly found that when observing that
the manufactured three-dimensional objects have a specific range of crystallinity, a marked
improvement of certain, very advantageous mechanical properties including, but not limited
to high stiffness, high compression strength, high impact strength, high maximal tensile-
and bending strength as well as high elongation at break and high heat deflection
temperature are obtained, while on the other hand opposing or trade-off properties such as
good chemical resistance and low post shrinkage by post crystallisation are well balanced.
Furthermore, it has been surprisingly found that particular process conditions, especially
regarding the cooling period after sintering, and particular selection criteria concerning
preselected polymer materials, respectively alone or in combination, contribute to
significant enhancements of the aforementioned mechanical properties and balancing
characteristics. Moreover, a markedly improved combination of both controlled
crystallinity and low porosity in the manufactured three-dimensional object can be
achieved, which provides for a further improvement of the above mentioned properties. The
advantages of the invention are particularly feasible when polyaryletherketone polymer or a
polyaryletherketone copolymer, or when a polyamide polymer or a polyamide copolymer is
appropriately used as a polymer material of the polymer powder. Furthermore, the
advantages of the invention are also feasible for composites, wherein the crystallinity value
relates to the polymer matrix of the composite. Such' composites comprise one or more
filler(s) and/or additive(s) besides a matrix of the respective polymer, copolymer or blend.
As a preferred alternative to classical polymer processing technologies involving pressure
processing of polymers, like e.g. injection molding, the process according to the present
invention can be carried out layer-wise in an additive process, wherein successive layers of
the object to be formed from solidifiable powder material are subsequently solidified by the
electromagnetic radiation at positions corresponding to the cross-section of the object.
Various aspects, advantageous features and preferred embodiments of the present invention
as summarized in the following items, respectively alone or in combination, contribute to
solving the object of the invention:

(1) A process for manufacturing a three-dimensional object from a powder by selective
sintering by means of electromagnetic radiation of the powder, wherein the powder
comprises a preselected polymer or copolymer and is subjected to selective sintering such
that the manufactured three-dimensional object has a final crystallinity which is in such a
range that the balance of the overall mechanical properties of Young's modulus, tensile
strength and elongation at break is improved.
The Young's modulus of the polymer or copolymer is preferably at least 500 MPa, more
preferably at least 1000 MPa and particularly at least 2000 MPa, tensile strength is
preferably at least 20 MPa, more preferably at least 30 MPa and particularly at least 40
MPa and elongation at break is preferably at least 1 %, more preferably at least 2%, still
more preferably at least 5%. and particularly at least 20%.
To provide more specific values, for example, for polyaryletherketone polymer and
polyaryletherketone copolymers , the Young's modulus is preferably at least 3000MPa,
more preferably at least 3500MPa and particularly at least 4000MPa, tensile strength is
preferably at least 50MPa, more preferably at least 70MPa and particularly at least 90MPa
and elongation at break is preferably at least 1,5%, more preferably at least 2%, still more
preferably at least 3%. and particularly at least 5%, and for polyamide polymer and
polyamide copolymers, Young's modulus is preferably at least lOOOMPa, more preferably
at least 1500MPa, still more preferably at least 2500MPa, tensile strength is preferably at
least 35MPa, more preferably at least 45MPa and particularly at least 70MPa and
elongation at break is preferably at least 5%, more preferably at least 20%, still more
preferably at least 40% and particularly at least 60%.
(2) A process for manufacturing a three-dimensional object from a powder by selective
sintering by means of electromagnetic radiation of the powder, alone or in combination
with (1) above, wherein the powder comprises a preselected polymer or copolymer and is
subjected to selective sintering such that the manufactured three-dimensional object has a
final crystallinity of 80% or less, preferably 50% or less, especially 5-70%, more preferably
15-50% and particularly 15-35%.

(3) The process according to (1) or (2), in which process layers of the object to be
formed from solidifiable powder material are successively solidified at positions
corresponding to the cross-section of the object.
(4) The process according to any one of the preceding items, in which process the
electromagnetic radiation is provided by a laser.
(5) The process according to any one of the preceding items, which comprises a
predefined and/or controlled cooling step after completion of the sintering step.
(6) The process according to any one of the preceding items, wherein the manufactured
three-dimensional object has a porosity of less than 10%, preferably 5%, more preferably
3% and most preferably less than 2%.
(7) The process according to any one of the preceding items, wherein the powder
comprising a polymer or a copolymer has a melting point Tm in a range of 100°C to 450°C,
preferably 15.0°C to 400°C and more preferably 250°C to 400QC.
(8) The process according to any one of the preceding items, wherein the polymer or
copolymer has a molecular weight Mn of at least 10,000, preferably 20,000 to 200,000,
more preferably 20,000 to 100,000 or Mw of at least 20,000, preferably 30,000 to 500,000,
more preferably 30,000-200,000.
( 9) The process according to any one of the preceding items, wherein the polymer or
copolymer has a polymerisation degree of preferably 10 to 10,000, more preferably 20 to
5,000 and particularly 50 to 1,000.
(10) The process according to any one of the preceding items, wherein the polymer or
copolymer comprises at least one aromatic group in the backbone chain, preferably in at
least one of the repeating units of the backbone chain.

(11) The process according to item (10), wherein the aromatic groups independently
from each other denote unsubstituted or substituted, monocyclic or polycyclic aromatic
hydrocarbons.
(12) The process according to item (10) or (11), wherein the aromatic groups are
respectively and independently selected from the group consisting of 1,4-phenylene, 4,4'-
biphenylene, 4,4'-isopropylidendiphenylene, 4,4'-diphenylsulfone, 1,4-, 1,5- and 2,6-
naphthalene, 4,4'-terphenylene and 2,2-di-(4-phenylen)-propane.
(13) The process according to items (10) to (12), wherein the aromatic groups are
substituted with one or more side chains.
(14) The process according to items (10) to (13), wherein the side chains are respectively
and independently selected from the group of CI to C6 straight chain or branched chain or
cyclic alkyl and alkoxy groups, and aryl groups.
(15) The process according to items (13) or (14), wherein the side chains are respectively
and independently selected from methyl, isopropyl, t-butyl or phenyl.
(16) The process according to any of the preceding items, wherein the end groups of the
backbone chain of the polymer or copolymer are modified.
(17) The process according to any of the preceding items, wherein a blend of at least two
different polymers or copolymers is used.
(18) The process according to (17), wherein one component of the blend reduces the
final crystallinity of the manufactured object.
(19) The process according to any of the preceding items, wherein the polymer or
copolymer is selected from the group consisting of polyamide (PA), polyaryletherketone
(PAEK), Polyarylethersulfone (PAES), polyester, polyether, polyolefme, polystyrene,
polyphenylenesulfide, polyvinylidenfluoride, polyphenylenoxid, polyimide and copolymers
and blends comprising at least one of the aforementioned polymers.

(20) The process according to any of the preceding items, wherein the polymer or
copolymer is selected from the group consisting of polyamide, polyaryletherketone, and
copolymers and blends comprising at least one of the aforementioned polymers.
(21) The process according to any of the preceding items, wherein the polymer or
copolymer is a polyaryletherketone (PAEK) selected from the group consisting of
polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketone (PEK),
polyetheretherketoneketone (PEEKK) and polyetherketoneetherketoneketone (PEKEKK)
and Polyetheretheretherketone (PEEEK) and copolymers and blends comprising at least
one of the aforementioned polymers.
(22) The process according to any of the preceding items, wherein the polymer or
copolymer is a polyaryletherketone (PAEK) selected from the group of PEEK, PEK,
PEKEKK, and copolymers and blends comprising at least one of the aforementioned
polymers.
(23) The process according to any of the preceding items, wherein the copolymer is a
polyaryletherketone (PAEK)/polyarylethersulfone(PAES)-copolymer.
(24) The process according to (23), wherein the ratio between the amount of sulfone
groups to the amount of keto groups in the PAEK/PAES-copolymer is in a range of 50:50
to 10:90.
(25) The process according to (23) or (24), wherein the
polyaryletherketone(PAEK)/polyarylethersulfone(PAES)-copolymer is selected from the
group consisting of polyaryletherketone(PAEK)/polyarylethersulfon(PAES)-diblock-
copolymers or PAEK/PAES/PAEK-triblock-copolymers, preferably from the group
consisting of (PEK)/(PES)-diblock-copolymers and PEK/PES/PEK-triblock-copolymers.
(26) The process according to any one of (19) to (25), wherein the polyaryletherketone
(PAEK) polymer or copolymer has a molecular weight Mn of at least 9,000, preferably'
10,000 to 100,000, more preferably 15,000 to 50,000 and most preferably 20,000 to 35,000

or Mw of 20,000 to 500,000 preferably 40,000 to 200,000 and more preferably 50,000 to
125,000.
(27 ) The process according to any one of (20) to (26), wherein the polyaryletherketone
(PAEK) polymer or copolymer has a melt viscosity in a range of 0.05 - 1 0 kN*s/m2,
preferably 0.15 - 0.6 kN*s/m2, and particularly 0.2-0.45 kN*s/m2.
(28) The process according to (19), wherein the polyaryletherketone (PAEK) polymer or
copolymer has a polymerisation degree n of preferably 10 to 1,000, more preferably 20 to
500 and particularly 40 to 250.
(29) The process according to any one of (19) to (28), wherein the polymer or copolymer
is polyaryletherketone(PAEK) and wherein the manufactured three-dimensional object has
a final crystallinity of 5 to 45%, preferably 10 to 40%, more preferably 15 to 35%, even
more preferably 15 to 30% and most preferably 20 to 25%.
(30) The process according to any one of (19) to (29), wherein the polymer or copolymer
is polyaryletherketone(PAEK) and wherein the manufactured three-dimensional object has
a density of at least 1.24 g/cm , more preferably 1.26 g/cm , even more preferably 1.28
g/cm3 and most preferably > 1.30 g/cm3.
(31) The process according to (19), wherein the polymer or copolymer is polyamide (PA)
and wherein the manufactured three-dimensional object has a final crystallinity of 10 to
50%, more preferably 15 to 40%, even more preferably 15 to 35% and most preferably 20
to 30%.
(32) The process according to (31), wherein the polyamide (PA) polymer or copolymer
has at least one repeating unit of the backbone chain wherein the length of at least one
aliphatic chain is in the range of preferably C4 to C18, more preferably C6 to C12 and
particularly C10 to C12.

(33) The process according to (32), wherein the polymer or copolymer is polyamide (PA)
and wherein the manufactured three-dimensional object has a density of at least 0.90 g/cm3,
more preferably 0.95 g/cm3 and particularly 1.00 g/cm3.
(34) The process according to any one of the preceding items, comprising a step of
cooling the object from a temperature which is 1-50°C, more preferably 1-30°C, even more
preferably 1-20°C and most preferably 1-10°C lower than Tm of the polymer or copolymer
comprised by the powder down to Tg of the polymer or copolymer comprised by the
powder at a cooling rate of 0.01-10°C/min, preferably 0.1-5°C/min, more preferably 1-
5°C/min, after completion of the object, wherein Tm is the melting temperature and Tg is the
glass transition temperature of the polymer or copolymer comprised by the powder,
respectively.
(35) A process for manufacturing a three-dimensional object from a powder by a step of
selective sintering by means of electromagnetic radiation of the powder, wherein the
powder comprises at least one polymer or copolymer material, wherein the process
comprises a predefined and/or controlled cooling step after completion of the sintering step.
(36) The process according to (34) or (35), wherein the cooling step is predefined and/or
controlled such that the manufactured three-dimensional object has a final crystallinity
which is in such a range that the balance of the overall mechanical properties of Young's
modulus, tensile strength and elongation at break is improved. The Young's modulus of the
polymer or copolymer is preferably at least 500 MPa, more preferably at least 1000 MPa
and particularly at least 2000 MPa, tensile strength is preferably at least 20 MPa, more
preferably at least 30 MPa and particularly at least 40 MPa and elongation at break is
preferably at least 1 %, more preferably at least 2%, still more preferably at least 5%. and
particularly at least 20%. To provide more specific values, for example for
polyaryletherketone polymer and polyaryletherketone copolymers , the Young's modulus is
preferably at least 3000MPa, more preferably at least 3500MPa and particularly at least
4000MPa, tensile strength is preferably at least 50MPa, more preferably at least 70MPa and
particularly at least 90MPa and elongation at break is preferably at least 1,5%, more
preferably at least 2%, still more preferably at least 3%. and particularly at least 5%, and

for polyamide polymer and polyamide copolymers, Young's modulus is preferably at least
1000MPa, more preferably at least 1500MPa, still more preferably at least 2500MPa,
tensile strength is preferably at least 35MPa, more preferably at least 45MPa and
particularly at least 70MPa and elongation at break is preferably at least 5%, more
preferably at least 20%, still more preferably at least 40% end particularly at least 60%.
(37) The process according to (35) or (36), wherein the final crystallinity of the
manufactured object is 80% or less, preferably 50% or less, especially 5-70%, more
preferably 15-50% and particularly 15-35%.
(38) The process according to any one of (35) to (37), wherein the cooling step cools the
object from a temperature which is 1-50°C, more preferably 1-30°C and most preferably 1-
10°C lower than Tm of the polymer or copolymer comprised by the powder down to Tg of
the polymer or copolymer comprised by the powder at a cooling rate of 0.01-10°C/min,
preferably 0.1-5°C/min, more preferably l-5°C/min, after completion of the object, wherein
Tm is the melting temperature and Tg is the glass transition temperature of the polymer or
copolymer comprised by the powder, respectively.
(39) The process according to any one of (35) to (3 8), whereby the polymer or
copolymer is as defined in (7) to (33).
(40) A three-dimensional object obtained by a selective sintering of a polymer, a
copolymer or a blend of polymers in powder form by means of electromagnetic radiation,
wherein the final crystallinity is in such a range that the balance of the overall mechanical
properties of Young's modulus, tensile strength and elongation at break is improved. The
Young's modulus of the polymer or copolymer is preferably at least 500 MPa, more
preferably at least 1000 MPa and particularly at least 2000 MPa, tensile strength is
preferably at least 20 MPa, more preferably at least 30 MPa and particularly at least 40
MPa, and elongation at break is preferably at least 1 %, more preferably at least 2%, still
more preferably at least 5%. and particularly at least 20%. To provide more specific values,
for example for polyaryletherketone polymer and polyaryletherketone copolymers , the
Young's modulus is preferably at least 3000MPa, more preferably at least 3500MPaand
particularly at least 4000MPa, tensile strength is preferably at least 50MPa, more preferably

at least 70MPa and particularly at least 90MPa and elongation at break is preferably at least
1,5%, more preferably at least 2%, still more preferably at least 3%. and particularly at least
5%, and for polyamide polymer and polyamide copolymers, Young's modulus is preferably
at least 1000MPa, more preferably at least 1500MPa, still more preferably at least
2500MPa, tensile strength is preferably at least 35MPa, more preferably at least 45MPa and
particularly at least 70MPa and elongation at break is preferably at least 5%, more
preferably at least 20%, still more preferably at least 40% and particularly at least 60%.A
three-dimensional object, alone or in combination with (40), obtained by a selective
sintering of a polymer, a copolymer or a blend of polymers in powder form by means of
electromagnetic radiation, wherein the final crystallinity is 80% or less, preferably 50% or
less, especially 5-70%, more preferably 15-50%> and particularly 15-35%.
(41) The three-dimensional object according to (40) to (41), whereby the polymer or
copolymer is as defined in (7) to (33).
(42) An apparatus for manufacturing a three-dimensional object from a powder by
selective sintering by means of electromagnetic radiation of the powder, comprising a
temperature control device for a predefined cooling of the object after completion of
manufacturing the object.
(43) The apparatus according to (43), wherein the temperature control device is set
depending on the powder material.
(44) The apparatus according to (43) or (44), wherein the temperature control device is
set depending on a type of polymer, copolymer or polymer blend comprised by the powder
material.
(45) A use of a polymer powder in the manufacture of a three-dimensional object by
means of selective electromagnetic irradiation sintering, wherein the polymer is preselected
for lowering the final crystallinity of the manufactured object.
(46) The use according to (46), wherein the crystallinity is lowered such that the balance
of the overall mechanical properties of Young's modulus, tensile strength and elongation at

break is improved. The Young's modulus of the polymer or copolymer is preferably at least
500 MPa, more preferably at least 1000 MPa and particularly at least 2000 MPa, tensile
strength is preferably at least 20 MPa. more preferably at least 30 MPa and particularly at
least 40 MPa and elongation at break is preferably at least 1 %. more preferably at least 2%,
still more preferably at least 5%. and particularly at least 20%.
To provide more specific values, for example for polyaryletherketone polymer and
polyaryletherketone copolymers , the Young's modulus is preferably at least 3000MPa,
more preferably at least 3500MPa and particularly at least 4000MPa, tensile strength is
preferably at least 50MPa, more preferably at least 70MPa and particularly at least 90MPa
and elongation at break is preferably at least 1,5%, more preferably at least 2%, still more
preferably at least 3%. and particularly at least 5%, and for polyamide polymer and
polyamide copolymers, Young's modulus is preferably at least 1000MPa, more preferably
at least 1500MPa, still more preferably at least 2500MPa, tensile strength is preferably at
least 35MPa, more preferably at least 45MPa and particularly at least 70MPa and
elongation at break is preferably at least 5%, more preferably at least 20%, still more
preferably at least 40% and particularly at least 60%.
(47) The use according to (46) or (47), wherein the crystallinity is lowered such that the
final crystallinity is 80% or less, preferably 50% or less, especially 5-70%, more preferably
15-50% and particularly 15-35%.
(48) The use according to any one of (46) to (48), whereby the preselected polymer is as
defined in (7) to (33).
(49) The use according to any one of (45) to (48), wherein the polymer is further
preselected for lowering the porosity of the manufactured three-dimensional object.
Fig. 1 shows a laser sintering device for a layer-wise manufacturing of a three-
dimensional object.
In order to improve a process for manufacturing a three-dimensional object from a powder
by selective sintering by means of electromagnetic radiation of the powder comprising at
least one polymer or copolymer, extensive test series were carried out by the inventors to

find critical factors that are particularly suited to manufacture three-dimensional objects
having improved mechanical properties.
Thereby it was found that certain mechanical properties of the three-dimensional object
manufactured-by selective. sintering of polymer powder materials are -significantly
improved when limiting the crystallinity of the manufactured object, and in particular when
adjusting the obtained crystallinity within a specific range. Surprisingly, this resulted in a
marked improvement of certain, very advantageous mechanical properties including, but
not limited to high stiffness, high compression strength, high impact strength, high maximal
tensile- and bending strength as well as high elongation at break and high heat deflection
temperature, while on the other hand trade-off properties such as good chemical resistance
and low post shrinkage by post crystallisation are well balanced. Furthermore, a decrease of
the porosity of the manufactured object became feasible, which additionally contributes to
the improvement of the mechanical properties of the manufactured object.
Objects manufactured by selective sintering by means of electromagnetic radiation of a
powder comprising at least one polymer, typically have crystallinity values substantially
higher than objects manufactured by classical polymer processing technologies like e.g.
injection molding. That is, in a process for manufacturing a three-dimensional object from a
powder by selective sintering by means of electromagnetic radiation of the powder
comprising at least one polymer, for example of a type as it is illustrated in Fig. 1,
crystallinity values in the manufactured object tend to become predominant without the
crystallinity adjustment according to the present invention. Specifically, in the layer-wise
building process, a high powder bed temperature lying at about 1-50°C, preferably 1-30°C,
even more preferably 1-20°C and most preferably 1-10°C below the melting point Tm of the
polymer is generally used. The object is typically exposed to relatively high processing
temperatures for a substantial period of time and still passes a usually very long cooling
period. To prevent or minimize curling of the part during the building process, the
processing temperature should be kept close to the melting point of the polymer powder in
order to provide for a good connection between succesive layers and minimizes the
formation of pores due to an inadequately melting of the powder particles. Consequently,
the temperature of the powder bed is kept during the whole building process above the
crystallization temperature Tc of the polymer. The generated object itself may be exposed

for a long time to temperatures above Tc. At the end of the building process, when all
heating sources of the sintering machine are switched off, the cooling through Tc of the
object starts due to natural heat loss to the environment. Because of the low heat
conductivity of the polymer powder and the large powder bed, this may take hours to days,
depending on the polymer powder used and the processing conditions, i.e. without
predefining a proper cooling rate - which would further amplify crystallization of the
polymer object, eventually during the cooling process. Without proper control, even post-
crystallization of the laser sintered polymer object may occur. As a consequence, relatively
high and partly extremely high crystallinities are obtained in the manufactured object
without properly observing crystallinity characteristics according to the present invention.
In turn, without properly limiting crystallinity, relevant mechanical properties of the object
may be worsened.
On the other hand, in the selective sintering process according to the present invention, the
crystallinity in the manufactured object may be beneficially adjusted still high enough to
also provide for positive influences on high chemical resistance, low post shrinkage at
temperatures above Tg or high stiffness of the manufactured object. Thus, an excellent
balance of properties can be achieved by the present invention.
When the crystallinity of the object manufactured from polymer powder materials is
properly limited and preferably adjusted within a particular range, a marked improvement
of certain, very advantageous mechanical properties like tensile strength, Young's modulus
and elongation at break can be attained. 1) Preselecting an appropriate type of polymer
material, 2) tailoring of the structural characteristics and/or modifications of the polymer
comprised in the preselected powder, and/or 3) paying attention to a predefined and/or
controlled cooling step after completion of the sintering process of the object are
particularly effective and preferred means to limit and adjust the crystallinity values of the
manufactured object.
Thus, according to a preferred embodiment of the present invention, a predefined and/or
controlled cooling step after completion of the object after the sintering is preferably
applied to the object. The predefined and/or controlled cooling step may be realized by
predefined slow cooling, possibly slower than native (passive) cooling, or by active cooling

in order to provide fast cooling. As the conditions of the predefined and/or controlled
cooling step mainly depend on the type and specification of the polymer, copolymer or
polymer blend used, useful settings for said cooling step can be experimentally tested with
the proviso that the final crystallinity is preferably 80% or less, preferably 50% or less,
especially 5-70%, more preferably 15-50.% and particularly. 15-35%.
As for example, illustrated when using PAEK materials as representative examples and
seeking to prevent curling, PEEK (polyetheretherketone) rather need a well defined low
cooling rate after the sintering/building process of the object, while other PAEK materials
like PEK (polyetherketone) are preferably cooled down with a fast cooling rate after the
sintering/building process. Preferred cooling rates for PAEKs after the sintering/building
process are: When the manufactured object is cooled from the processing temperature
which is preferably at a temperature being 1-10°C lower than the melting point of the
powder, to Tg of the used PAEK, the cooling rate is preferably 0.01-10°C/min and more
preferably between 0.1-5°C/min and most preferably between l-5°C/min, in order to
minimize and ensure low post-crystallization and low curling of the parts. For example,
preselecting PEK powder and appropriately applying a cooling rate of e.g. 0.3°C/min, a low
crystallinity of e.g. 36% is attained, which provides improved mechanical properties like a
tensile strength of 79 MPa (see Example 5). Further limiting crystallinity down to 31%, for
example by applying a faster cooling rate of e.g. more than 0.3°C/min provides a
surprisingly further improved tensile strength of 88 MPa (Example 6).
However, the cooling rate after completion of the object may also affect the curling and
thus the dimensional stability of the object. It has been surprisingly found that the cooling
rate can be predefined such that the three-dimensional object has not only a specific range
of crystallinity and thereby provides the above mentioned advantageous mechanical
properties, but also a high dimensional stability, that is, it does not curl.
As for example illustratively demonstrated by using PAEK polymers, it was found that a
PEEK powder, rather needs a relatively slow cooling rate, e.g. about 0.1-0.3°C/min,
compared to a PEK powder in order to attain both low crystallinity and high dimensional
stability (avoiding curling) (cf. Examples 2 and 3). At a higher cooling rate, this material
would tend to curling phenomena .

In the following, some significant structural characteristics or modifications of a polymer or
copolymer material, which are appropriate for a preselection to be subjected to a selective
sintering process by electromagnetic radiation, are exemplarily described for PAEK
polymers and copolymers. It will become apparent for the person skilled in the art that the
below described structural characteristics or modifications likewise apply to other kinds of
polymers.
Particularly suitable alternative polymer materials other than PEAK polymers and
copolymers include, but are not limited to polyamides, polyesters, polyethers, polyolefines,
polystyrenes, polyphenylensulfides, polyvinylidenfluorides, polyphenylenoxides,
polyimides, and copolymers thereof. Suitable polyamide polymers or copolymers may be
selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide
12, polyamide 612, polyamide 610, polyamide1010, polyamidel212 and copolymers
comprising at least one of the aforementioned polymers, and polyamide elastomers such as
polyether block amide, e.g. PEBAX®-based materials. Suitable polyester polymers or
copolymers may be selelected from the group consisting of polyalkylentherephthalates (e.g.
PET, PBT) and their copolymers with 1,4-cyclohexanedimethylol. Suitable polyolefine
polymers or copolymers may be selected from the group consisting of polyethylene and
polypropylen. Suitable polystyrene polymers or copolymers may be selected from the
group consisting of syndiotactic- and isotactic polystyrene.
Assuming a given molecular weight of a selected polymer such as PAEK as a reference, it
was found by the inventors that already a relatively slight increase in molecular weight of
the polymer comprised in the powder readily leads to a surprisingly marked decrease of the
crystallinity in the manufactured object, which in turn transforms into a significant
improvement of certain, very advantageous mechanical properties of the manufactured
object. For example, preselecting a PEEK polymer material having a relatively higher
molecular weight of typically Mn=32,000 and Mw=99,000 rather than having a molecular
weight of typically Mn=23,000 and Mw=68,000 assists in lowering crystallinity of the
manufactured object to below 50% (see, e.g. Examples 1 and 2 showing a lowering from
52% to 45%). While an increase in molecular weight might lower the density and thus
increase porosity, it substantially contributes to increasing the tensile strength and

elongation at break (see, e.g. Examples 1 and 2 showing a considerable increase in tensile
strength from 44 MPa to 71 MPa and an increase in elongation at break from -1% to -2%).
However, above a specific molecular weight, a saturation effect occurs. No considerable
decrease of crystallinity and increase of mechanical properties is possible anymore (cf.
Example 3). Therefore, the molecular-weight Mn is preferably adjusted to at least 9,000,
preferably 10,000 to 100,000, more preferably 15,000 to 50,000 and most preferably 20,000
to 35,000 or Mw is preferably adjusted to 20,000 to 500,000, preferably 40,000 to 200,000
and more preferably 50,000 to 125,000.
Analogous explanations as stated above for the molecular weight also apply for the melt
viscosity of the polymer or copolymer. The melt viscosity correlates with the molecular
weight of the polymer or copolymer as follows: the higher the molecular weight of a
polymer or copolymer, the higher is also its melt viscosity. Therefore, for PAEK polymers
or copolymers, melt viscosities in a range of 0.05 - 1.0 kN*s/m , more preferably 0.15 -
0.6 kN*s/m2 and particularly 0.2-0.45 kN*s/m2 are preferred.
The formula shown below shows a general structure for PAEK or PAES polymers and
copolymers that are preferred to built up laser sintered objects, wherein structural
peculiarities will be further described below to obtain desirably low crystallinities:

Ar1, Ar2 and Ar3 independently from each other denote unsubstituted or substituted,
monocyclic or polycyclic aromatic hydrocarbons, wherein optional substituents may be
selected from:
Rf1, Rf2, Rf3 = denote independently from each other C1 to C6 straight chain or branched
chain or cyclic alkyl and alkoxy groups, and aryl groups, preferably Me, i-Pr, t-Bu, Ph,
wherein each Ar1, Ar2 and Ar3 may have one or more Rf1, Rf2, Rf3 substituent(s)
respectively

X = 0 and/or S
Y = CO and/or SO2
Z = SO2, CO, O and/or S
a is a low integer which is more than 0, preferably lower than 12, more preferably 1 to 6
and particularly 1 to 3
b is a low integer which is more than 0, preferably lower than 12, more preferably 1 to 6
and particularly 1 to 3
c is 0 or a low integer, preferably lower than 12, more preferably 1 to 6 and particularly 1
to 3
n denotes the degree of polymerisation
In the above general formula, the indices a, b and c denote the number of the respective
units in squared brackets in the repeating unit of the polymer or the repeating units of the
copolymer respectively, wherein one or more unit(s) of the same kind, e.g. the unit indexed
with a, may be located between units of a different kind, e.g. the unit indexed with b and/or
c. The location of the respective units within the repeating unit may be derived from the
abbreviation of the PAEK derivative.
For example, for PEK, the repeating unit comprises Ar1 being unsubstituted phenylene, X
being O and a = 1, Ar2 being unsubstituted phenylene, Y being CO and b =1 and c = 0.
Thus, PEK has a structure of the following formula

, wherein n denotes the degree of polymerisation. As another example, for PEEK, the
repeating unit comprises An being unsubstituted phenylene, X being 0 and a = 2, Ar2
being unsubstituted phenylene, Y being CO and b =1 and c = 0. Concerning the location of
the respective ester and ketone units, the abbreviation PEEK indicates that two ester (E)
units are followed by one ketone (K) unit, thus PEEK has a structure of the following
formula


, wherein n denotes the degree of polymerisation. As a further example, for PEKEKK, the
repeating unit comprises Ar1 being unsubstituted phenylene, X being O and a = 2, Ar1
being unsubstituted phenylene, Y being CO and b =3 and c = 0. Concerning the location of
the respective ester and ketone units, the abbreviation PEKEKK indicates that one ester (E)
unit is followed by one ketone (K) unit, then one ether unit follows which is followed by 2
ketone units, thus PEKEKK has a structure of the following formula

, wherein n denotes the degree of polymerisation.
For PAEK polymers and copolymers, the degree of polymerisation n is preferably 10 to
1.000, more preferably 20 to 500 and particularly 40 to 250.
The larger the required space of the aromatic hydrocarbon group Ar1, Ar2 and Ar3, the more
the aromatic hydrocarbon group behaves like a rigid rod segment and the lower is the final
crystallinity of the manufactured object. Hence, it is preferred that the aromatic
hydrocarbon groups Ar1, Ar2 and Ar3 are respectively and independently selected from the
group consisting of 1,4-phenylene, 4,4'-biphenylene, 4,4'-isopropylidendiphenylene, 4,4'-
diphenylsulfone, 1,4-, 1,5- and 2,6-naphthalene, 4,4'-terphenylene and alpha-di(4-
phenylene)phtalide.
Side chains Rf1, Rf2, Rf3 at the aromatic hydrocarbons in the backbone chain affect the
mobility of the polymer chains in the melt and thus preferably allow to beneficially
influence, hence lower the final crystallinity of the manufactured object.
Moreover, the ratio between the amount of keto groups Y and the amount of ether- or
thioether groups X is preferably 1:4 to 4:1. Within this ratio range, the crystallinity can be

considerably lowered. For example, when comparing the use of PEK (ratio 1:1) and PEEK
(ratio 2:1) having similar typical molecular weights (cf. examples 1 and 4). PEK is
preferred over PEEK in terms of achieving lower crystallinity. On the other hand, a
similarly controlled crystallinity can be achieved also when using PEEK by making use of
other compensation control; e.g. by using PEEK of correspondingly higher molecular
weight, or by appropriately predefining cooling after sintering at a high cooling rate.
A further possibility for tailoring the polymer to achieve the desirably limited final
crystallinity of the manufactured object after the selective sintering process is to use an
appropriate copolymer. For PAEKs, a copolymer with polyarylethersulfone (PAES) is
preferable, in particular a polyaryletherketone(PAEK)/polyarylethersulfone(PAES)-
diblock-copolymer or PAEK/PAES/PAEK-triblock-copolymer, more particular a
polyetherketone(PEK)/poIyethersulfone(PES)-diblock-copolymer or PEK/PES/PEK-
triblock-copolymer. It was found that the higher the amount of the polyarylethersulfone-
component, the lower the crystallinity of the manufactured object. Thus, in particular, the
ratio of the amount of sulfone groups Z to the amount of keto groups Y is preferably
between 50:50 and 10:90. Within this ratio range, a glass transition temperature (Tg) and a
melting point (Tm) of the polymer material can be adjusted which are suitable for
processing the polymer in an apparatus for manufacturing a three-dimensional object by a
selective sintering by means of electromagnetic radiation. In order to provide suitable
processing temperatures for the selective sintering process, said PEK/PES-copolymers
preferably have a Tg higher than 180°C and a melting temperature Tm of 300 to 430°C.
It was further found that the end groups of the backbone chain of the polymer or copolymer
may act as a crystallisation seed during the crystallisation. Therefore, the end groups of the
polymer or copolymer may be derivatised in order to interfere with crystallisation, and thus
to limit the crystallinity of the manufactured object.
The end groups may also be chosen such that they lead to an elongation of the poiymei- or
copolymer chain by a chemical reaction, preferably at temperatures above Tm of the
polymer, between the end group, e.g. by polycondensation, elektrophilic or nucleophilic
aromatic substitution, coupling reactions or the like. This results in a decrease of the
crystallinity of the manufactured object due to an increased molecular mass

The end groups of the backbone chain of the polymer or copolymer depend on the kinds of
monomers used for synthesis and on the kind of polymerisation. In the following, two
different kinds of PAEK synthesis schemes resulting in different kinds of PAEKs with
different end groups are shown.
PAEKs can be normally synthesized in two ways, namely by electrophilic aromatic
substitution (Friedel-Crafts-Acylation) or nucleophilic aromatic substitution. For example,
in the nucleophilic synthesis of a PAEK, a 1,4-bishydroxy-benzene is polymerized with an
4,4' dihalogenated benzophenone component:
xHO-Ph-OH + (y+1) Hal-Ph-CO-Ph-Hal → Hal-Ph-CO-Ph-[0-Ph-O]x[Ph-CO-Ph]y-Hal
, wherein Hal is F, Cl, Br and x and y denote the number of monomers incorporated in the
polymer.
As a result , the PAEK backbone chain, in the above example PEEK may be terminated
with a residual halogen group after the polymerization, most suitably with fluorine,
optionally alternatively with chlorine or bromine, at none or one end (not shown) or at both
ends (shown) of the backbone chain. The same applies for the synthesis of PAEK or
polyethersulfone (PAES) copolymers, wherein the dihalogenated ketone unit may be
substituted partly by a dihalogenated aromatic sulfone. The aromatic bishydroxy-
component may likewise be partly or fully substituted by a bisthiol component.
For example, the halogen substituted ends of the polymer may be derivatized by a
termination reaction with phenol:
2Ph-OH + Hal-Ph-CO-Ph-[O-Ph-O]x[Ph-CO-Ph]y-Hal →
Ph-O-Ph-CO-Ph-[O-Ph-O]x[Ph-CO-Ph]y-O-Ph
Preferably, Hal in the formulae above is F.
In the case of synthesis of PAEK polymers or copolymers by electrophilic aromatic
substitution reaction, diacylaromates, e.g. aromatic diacids or preferably aromatic diacid
chlorides or aromatic diacid anhydrides, are polymerized with a bisaromatic ether or

thioether component. For example, for PEKK, this may result in PEKK polymers or
copolymers with phenyl groups at none or one end (not shown) or both ends (shown) of the
backbone chain:
x RAOC-Ph-CORA + (y+1) PhrO-Ph → Ph-O-Ph-[OC-Ph-CO]x[Ph-O-Ph]y-H -
, wherein RA is Cl or -OH and x and y denote the number of monomers incorporated in the
polymer.
Alternatively, a synthesis by a single monomer route using, for example, an aromatic
mono-acid chloride may be applied.
For example, the phenyl groups at the ends of the polymer may be derivatized by a
termination reaction with benzoic acid chloride:
2Ph-COCl + Ph-O-Ph-[OC-Ph-CO]x[Ph-O-Ph]y-H →
Ph-CO-Ph-O-Ph-[OC-Ph-CO]x[Ph-O-Ph]y-OC-Ph
Irrespective if a nucleophilic or aromatic substitution reaction is chosen, to slow down
crystallization of the polymer, the end groups may be preferably substituted, e.g. such that a
PAEK polymer has the following formula:
RT-U-[PAEK]- U-RT
, wherein U is a linking moiety, for example NH, O, CO, CO-O-, SO, a single bond, -
(CH2)k wherein k is 1-6, or the like; and the left hand and right hand structural moieties RT
may be the same or different structural groups, usually the structural moieties RT are the
same. Preferably, RT is selected from the group of unsubstituted or substituted aliphatic or
aromatic hydrocarbon residues. U may be formed by direct reaction with the ends of the
polymer or copolymer, for example a monofunctional hydroxy compound may form 0 as
U, or it may be introduced as a substituent of the termination reagent, e.g. HO-Ph-COO-
tert-butyl may form COO as U.

Furthermore, if it is necessary to increase the crystallization rate in order to adjust the
crystallinity of the manufactured three-dimensional object appropriately, the
polyaryletherketones with a halogenated end group can be terminated with ionic end groups
like e.g. phenate salts like NaOPhSO3Na or NaOPhCOPhOPhS03Na. Subsequent
acidification of the phenate salts with e.g. HC1 leads to -SO3H end groups that show a
slightly reduced nucleation effect.
The polymer or copolymer may be blended with an alloying component in a blend, wherein
a blend of at least two different polymers or copolymers is used. It is preferred that in such
a blend, at least one component of the blend reduces the final crystallinity of the
manufactured object.
Similar structural characteristics or modifications explained for PAEK can likewise be
applied to alternative polymer or copolymer materials mentioned above.
Furthermore, the powder may be a composite powder which comprises one or more filler(s)
and/or additive(s) besides a matrix of the respective polymer, copolymer or blend. Fillers
may be used to further improve the mechanical properties of the manufactured object. For
example, fillers such as fibers, including but not limited to carbon fibers, glass fibers,
Kevlar fibers, carbon nano fibers, or fillers having a low aspect ratio (glass beads,
aluminum grit, etc.) or mineral fillers such as titane dioxide may be incorporated in the
powder comprising at least one polymer or copolymer. Furthermore, process additives
which improve the proccesability of the powder, e.g. free flowing agents such as the ones
from the Aerosil series (e.g. Aerosil R974, Aerosil 200), or other functional additives, like
heat stabilizers, oxidation stabilizers, color pigments (carbon black, graphite, etc.)) may be
used.
From the findings of the present invention it can be inferred generally that the following
structural characteristics or modifications of polymers or copolymers favour limited
crystallinity characteristics and thus are particularly preferred when a preselection of
specific type of polymer or copolymer is made, e.g. among polyamide (PA),
polyaryletherketone (PAEK), polyester, polyether, polyolefine, polystyrene,

polyphenylensulfide. poiyvinylidenfiuoride, polyphenylenoxid, polyimide and copolymers
thereof:
(i) selecting relatively high Mn or Mw or melt viscosities,
(ii) using long chain lengths or high polymerization degrees n
(iii) introducing aromatic groups in the backbone chain, which independently
from each other denote unsubstituted or substituted, monocyclic or
polycyclic aromatic hydrocarbons; preferably, the aromatic groups are
respectively and independently selected from the group consisting of 1,4-
phenylene, 4,4'-biphenylene, 4,4'-isopropylidendiphenylene, 4,4'-
diphenylsulfone, 1,4-, 1,5- and 2,6-naphthalene, 4,4'-terphenylene and alpha-
di(4-phenylene)phtalide,
(iv) substitution of the aromatic groups with one or more side chains, wherein
the side chains are respectively and independently selected from the group of
C1 to C6 straight chain or branched chain or cyclic alkyl and alkoxy groups,
and aryl groups, preferably the side chains are respectively and
independently selected from methyl, isopropyl, t-butyl or phenyl,
(v) modification of the end groups of the backbone chain of the polymer or
copolymer, preferably by aliphatic or aromatic end groups, and
(vi) blending or alloying by blending at least two different polymers or
copolymers.
EXAMPLES
The crystallinity of the manufactured object can be determined by various methods that are
well known to the person skilled in the art. The crystallinity can be determined based on
Differential Scanning Calorimetry (DSC) according to DIN 53765 which is used as a
reference method according to the present invention. With the value of a theoretically 100%
crystalline polymer which can be found in scientific publications, e.g. 130J/g for PEEK and
160J/g for PEK (P C Dawson and D J Blundell, Polymer 1980,21, 577-578) it is possible to
calculate the final crystallinity by the following formula:


In case of objects manufactured from composite powders, i.e. a powder comprising one or
more filler(s) or additive(s) besides of a polymer, a copolymer or a blend of polymers, the
crystallinity value relates to the polymer matrix of the composite which can also be
calculated as defined above.
The crystallinity can also be determined by Wide Angle X-ray Scattering (WAXS)
measurement. The procedure is well known by the person skilled in the art.
As a reference method for the present invention, crystallinity was determined in the
following Examples based on DSC measurements performed on a Mettler-Toledo DSC 823
according to DIN 53765. The DSC sample was prepared from the middle of an ASTM
D638 tensile bar that was built in x,y direction at least 5 cm from the edge of the
exchangable frame on the laser sinter machine. Crystallinity was then determined by using
the above shown formula.
The density was measured according to ISO 1183 on a Kern 770-60 balance with a Satorius
Density Determination Set YDK 01.
Porosity is then calculated by the following formula:


The density values for theoretically 100% crystalline PEEK (d100%=1-40 g/cmJ) and PEK
(d100%=1-43 g/cmJ), as well as amorphous PEEK (d0%=1.265 g/cm3) and PEK (d00%o=1.272
g/cm3) are well known in literature (P C Dawson and D J Blundell, Polymer 1980,21. 577-
578)
If the theoretical density values for the polymer is not known, the porosity can also be
determined by micro-computerthomographie. A useful device is e.g. the U-CT40 supplied
by SCANCO Medical AG, Briittisellen, Switzerland. The procedure is well known by the
person skilled in the art.
In the Examples, melt viscosity are determined according to US-Patent 2006/0251878 Al
in a capillary viscosimeter with a wolfram-carbid nozzle at 400°C and a shear rate of 1000
s-1.
The following examples are merely illustrative of the present invention and they should not
be considered as limiting the scope of the invention in any way. The examples and
modifications or other equivalents thereof will become apparent to those versed in the art in
the light of the present entire disclosure.
Example 1 (not according to the invention)
A powder made of PEEK (supplied by Victrex Plc, Thornton Cleveleys, Lancashire FY5
4QD, Great Britain) with a mean particle size distribution of 48 urn, wherein the PEEK
polymer has a molecular mass of Mn = 23,000 and Mw = 65,000 and a melt viscosity of
0.15 kN*s/m2, is thermally treated above glass transition temperature in an oven.
The PEEK powder with a bulk density of 0.45 g/cm3 was processed on a laser sintering
machine of the type P700, that was modified by EOS for high temperature applications.
The temperature of the process chamber was 335°C.
After the laser sinter process was finished, the cooling rate was controlled by post-heating
between 335°C and Tg of PEEK (145°C). The cooling rate showed a maximum average of
0.3°C/min

The parts showed the following properties:
density = 1.316 g/ cm3
porosity (calculated by density/crystallinity) = 1,4%
crystallinity (by DSC) = 52%
Tensile test (ASTM D638, Type I):
Young's modulus = 4500 MPa
Tensile strength = 44 MPa
Elongation at break = 1.04%
Example 2 (according to the invention)
A powder made of PEEK (supplied by Victrex Pic, Thornton Cleveleys, Lancashire FY5
4QD, Great Britain) with a mean particle size distribution of 48 urn, wherein the PEEK
polymer has a molecular mass of Mn = 32,000 and Mw = 65,000' and a melt viscosity of
0.45 kN*s/m2, is thermally treated above glass transition temperature in an oven.
The PEEK powder with a bulk density of 0.40 g/cm3 was processed on a laser sintering
machine of the type P700, that was modified by EOS for high temperature applications.
The temperature of the process chamber was 335°C.
After the laser sinter process was finished, the cooling rate was controlled by post-heating
between 335°C and Tg of PEEK (145°C) . The cooling rate showed a maximum average of
0.3°C/min
The parts showed the following properties:
density = 1.303 g/cm3
porosity (calculated by density/crystallinity) = 1.6%
crystallinity = 45%
Tensile test (ASTM D638, Type I):
Young's modulus = 4200 MPa
Tensile strength = 71 MPa
Elongation at break = 1.9%

Example 3 (according to the invention)
A powder made of PEEK (supplied by Victrex Plc. Thornton Cleveleys, Lancashire FYS
4QD, Great Britain) with a mean particle size distribution of 48 urn, wherein the PEEK
polymer has a melt viscosity of 0.54 kN*s/m2, is thermally treated above glass transition
temperature in an oven.
The PEEK powder was processed on a laser sintering machine of the type P700, that was
modified by EOS for high temperature applications. The temperature of the process
chamber was 335°C.
After the laser sinter process was finished, the cooling rate was controlled by post-heating
between 335°C and Tg of PEEK (145°C). The cooling rate showed a maximum average of
0.3°C/min
The parts showed the following properties:
density = 1.300 g/cm3
crystallinity = 42%
porosity (calculated by density/crystallinity) = 1.6%
Tensile test (ASTM D638, Type I):
Young's modulus =3800 MPa
Tensile strength = 74 MPa
Elongation at break = 2.2%
Example 4 (according to the invention)
A powder made of PEK (supplied by Victrex Pic, Thornton Cleveleys, Lancashire FY5
4QD, Great Britain) with a mean particle size distribution of 48 µm, wherein the PEK
polymer has a molecular mass of Mn = 23,000 and Mw = 65,000 and a melt viscosity of
0.22 kN*s/m2, is thermally treated above glass transition temperature in an oven.

The PEK powder was processed on a laser sintering machine of the type P700, that was
modified by EOS for high temperature applications. The temperature of the process
chamber was 365°C.
After the laser sinter process was finished, the cooling rate was controlled by post-heating
between 365°C and Tg of PEK (157°C). The cooling rate showed a maximum average of
0.3°C/min
The parts showed the following properties:
density =1.310 g/cm3
crystallinity = 39%
porosity (calculated by density/crystallinity) = 1.8%
Tensile test (ASTM D638, Type I):
Young's modulus = 4220 MPa
Tensile strength =80 MPa
Elongation at break = 2.2%
Example 5 (according to the invention)
A powder made of PEK (supplied by Victrex Plc, Thornton Cleveleys, Lancashire FY5
4QD, Great Britain) with a mean particle size distribution of 48 urn, wherein the PEK
polymer has a melt viscosity of 0.45 kN*s/m2, is thermally treated above glass transition
temperature in an oven.
The PEK powder was processed on a laser sintering machine of the type P700, that was
modified by EOS for high temperature applications. The temperature of the process
chamber was 365°C.
After the laser sinter process was finished, the cooling rate was controlled by post-heating
between 365°C and Tg of PEK (157°C). The cooling rate showed a maximum average of
0.3°C/min.

The parts showed the following properties:
density = 1.277 g/cm3
crystallinity = 36%
porosity (calculated by density/crystallinity) = 3.9%
Tensile test (ASTM D638. Type I):
Young's modulus =3820MPa
Tensile strength = 79 MPa
Elongation at break = 2.5%
Example 6 (according to the invention)
A powder made of PEK (supplied by Victrex Plc, Thornton Cleveleys, Lancashire FY5
4QD, Great Britain) with a mean particle size distribution of 48 urn, wherein the PEK
polymer has a melt viscosity of 0.45 kN*s/m , is thermally treated above glass transition
temperature in an oven.
The PEK powder was processed on a laser sintering machine of the type P700, that was
modified by EOS for high temperature applications, as described in example 4.
After the laser sinter process was finished, all heatings of the laser sintermachine were
turned off. The average of the cooling rate was > 0.3°C/min.
The parts showed the following properties:
density = 1.285 g/cm3
porosity (calculated by density/crystallinity) = 2.8%
crystallinity = 31%
Tensile test (ASTM D638, Type I):
Young's modulus = 3950 MPa
Tensile strength =88 MPa
Elongation at break =2.8%

Claims
1. A process for manufacturing a three-dimensional object from a powder by selective
sintering by means of electromagnetic radiation of the powder, wherein the powder
comprises a polyaryletherketone polymer or a polyaryletherketone copolymer, and wherein
the manufactured three-dimensional object has a final crystallinity of 5 to 45%.
2. The process according to claim 1, wherein the manufactured three-dimensional
object has a porosity of lower than 5%, preferably lower than 3%.
3. The process according to any one of the preceding claims, wherein the powder
comprising a polyaryletherketone polymer or a polyaryletherketone copolymer has a
melting point Tm in a range of 280 to 450°C.
4. A process for manufacturing a three-dimensional object from a powder by selective
sintering by means of electromagnetic radiation of the powder, wherein the powder
comprises a polyamide polymer or a polyamide copolymer, and wherein the manufactured
three-dimensional object has a final crystallinity of 10 to 50%
5. The process according to claim 4, wherein the manufactured three-dimensional
object has a porosity lower than 10%, preferably lower than 5% and more preferably lower
than 3%.
6. A process for manufacturing a three-dimensional object from a powder by a step of
selective sintering by means of electromagnetic radiation of the powder, wherein the
powder comprises at least one polymer or copolymer material, the process being
characterized by a predefined and/or controlled cooling step after completion of the
sintering step.

7. The process according to claim 6, wherein a powder having a melting point Tm in a
range of 100 to 450°C is used, preferably 150 to 400°C and more preferably 250 to 400°C.
8. A three-dimensional object obtained by a selective sintering of a polymer, a
copolymer or a blend of polyaryletherketone in powder form by means of electromagnetic
radiation, wherein the final crystallinity is 5 to 45%.
9. The three-dimensional object according to claim 8, wherein the porosity is lower
than 5%, preferably lower than 2%.
10. The three-dimensional object according to claim 8, wherein the density is at least
1.24 g/cm3, more preferably 1.26 g/cm3, even more preferably 1.28 g/cm3 and most
preferably > 1.30 g/cm3.
11. A three-dimensional object obtained by a selective sintering of a polymer, a
copolymer or a blend of polyamide in powder form by means of electromagnetic radiation,
wherein the final crystallinity is 10 to 50%.
12. The three-dimensional object according to claim 11, wherein the porosity is lower
than 10%, preferably lower than 5% and more preferably lower than 3%..
13. An apparatus for manufacturing a three-dimensional object from a powder by
selective sintering by means of electromagnetic radiation of the powder, comprising a
temperature control device for a predefined cooling of the object after completion of the
object.
14. A use of a polymer in powder form in the manufacture of a three-dimensional object
by means of selective electromagnetic irradiation sintering, wherein the polymer is
preselected for lowering the crystallinity of the manufactured three-dimensional object.
15. The use according to claim 14, wherein the preselection is made of a type of
polymer or copolymer of polyamide (PA), polyaryletherketone (PAEK),
Polyarylethersulfone (PAES), polyester, polyether, polyolefine, polystyrene,

polyphenylenesulfide, polyvinylidenfluoride, polyphenylenoxid, polyimide and copolymers
comprising at least one of the aforementioned polymers, preferably a polymer or copolymer
of polyaryletherketone or polyamide, more preferably
polyaryletherketone(PAEK)/polyarylethersulfon(PAES)-diblock-copolymers or
PAEK/PAES/PAEK-triblock-copolymers and in particular polyetherketone
(PEK)/polyethersulfone(PES)-diblock-copolymers or PEK/PES/PEK-triblock-copolymers.
16. The use according to claim 14 or 15, wherein the polymer is further preselected for
lowering the porosity of the manufactured three-dimensional object.

A three-dimensional object is manufactured from a powder of polymer material by selective sintering process by means of electromagnetic radiation of the powder, wherein the powder comprises a preselected polymer or copolymer and is subjected to selective sintering such that the manufactured three-dimensional object has a final crystallinity which is in such a range that the balance of properties, in particular mechanical properties including Young's modulus, tensile strength and elongation at break, is improved.

Documents:

761-KOL-2009-(23-05-2014)-CORRESPONDENCE.pdf

761-KOL-2009-(30-04-2014)-ABSTRACT.pdf

761-KOL-2009-(30-04-2014)-ANNEXURE TO FORM 3.pdf

761-KOL-2009-(30-04-2014)-CLAIMS.pdf

761-KOL-2009-(30-04-2014)-CORRESPONDENCE.pdf

761-KOL-2009-(30-04-2014)-DESCRIPTION (COMPLETE).pdf

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761-KOL-2009-(30-04-2014)-PETITION UNDER RULE 137.pdf

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Patent Number 262630
Indian Patent Application Number 761/KOL/2009
PG Journal Number 36/2014
Publication Date 05-Sep-2014
Grant Date 01-Sep-2014
Date of Filing 19-May-2009
Name of Patentee EOS GMBH ELECTRO OPTICAL SYSTEMS
Applicant Address ROBERT-STIRLING-RING 1, 82152 KRAILLING
Inventors:
# Inventor's Name Inventor's Address
1 LEUTERER, MARTIN KARL-THEODOR-STR. 1, 82140 OLCHING
2 MÜLLER, FRANK ENZIANSTR. 4, 82256 FURSTENFELDBRUCK
3 WOOD, ALAN LAUREL HOUSE, MULBURN, PENRITH, CUMBRIA CA10 1TW
4 WILSON, BRIAN 1 WHITE LEA, CABUS, GARSTANG, LANCASHIRE PR3 1JG
5 SANDNER, HORST TAUNUSBLICK 1, 65529 WALDEMS
6 PFISTER, ANDREAS KEMPTENER STR. 63, 81475 MÜNCHEN
PCT International Classification Number B01J19/12; C08J3/28; B01J19/12
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 61/188,958 2008-08-14 EUROPEAN UNION
2 08 009 274.5 2008-05-20 EUROPEAN UNION