Poly(aryl-ether-ketone) (PAEK) powder suitable for multiple use in sintering methods

Abstract

Provided is a poly(aryl-ether-ketone) (PAEK) powder suitable for use in a method for building objects layer-by-layer by electromagnetic radiation-generated sintering, which is obtained from a thermal pretreatment at a temperature between 260° C. and 290° C. and which has a melting temperature which is stable, at the build temperature, and below or equal to 330° C.

Claims

1. A method for building a three-dimensional object layer-by-layer by electromagnetic radiation-generated sintering of powder, wherein the powder is a poly(aryl-ether-ketone) (PAEK) powder, the powder being obtained from thermal pretreatment at a temperature between 260° C. and 290° C. and having a melting temperature which is stable at the build temperature and which is below or equal to 330° C., wherein the powder comprises a mixture of recycled and non-recycled powders, wherein parameters of the sintering machine include laser power and powder bed temperature, wherein the sintering is conducted in a sintering machine and wherein at least two successive sinterings are carried out while keeping the laser power of the sintering machine and the bed temperature unchanged, and wherein the second sintering of the at least two successive sinterings uses the unsintered powder from the first sintering of the at least two successive sinterings as recycled powder.

2. The method according to claim 1, wherein the thermal pretreatment is carried out for a period between 5 min and 120 min.

3. The method according to claim 1, wherein the powder comprises a mixture of several polymers belonging to the PAEK family, the melting temperature Tm of which is below or equal to 330° C.

4. The method according to claim 1, wherein the powder comprises at least one poly(ether-ketone-ketone) (PEKK) powder which represents more than 60% by weight, bounds included.

5. The method according to claim 1, wherein the powder is a poly(ether-ketone-ketone) (PEKK) powder.

6. The method according to claim 4, wherein the PEKK powder has a percentage by weight of terephthalic units relative to the sum of terephthalic and isophthalic units comprised between 55% and 65%.

7. The method according to claim 1, wherein molecular weight of the powder remains stable during sintering.

8. The method according to claim 1, wherein melting temperature of the powder does not increase by more than 2° C. after each sintering run.

9. The method according to claim 1, wherein melting temperature of the powder does not increase by more than 1° C. after each sintering run.

10. A method for building a three-dimensional object layer-by-layer by electromagnetic radiation-generated sintering of powder, wherein the powder is a poly(aryl-ether-ketone) (PAEK) powder, the powder being obtained from thermal pretreatment at a temperature between 260° C. and 290° C. and having a melting temperature which is stable at the build temperature and which is below or equal to 330° C., wherein the powder comprises a mixture of recycled and non-recycled powders, the recycled powders having been used in an identical and/or a different number of cycles, wherein parameters of the sintering machine include laser power and powder bed temperature, wherein the sintering is conducted in a sintering machine and wherein successive sintering is carried out while keeping the bed temperature unchanged, wherein the bed temperature is the same bed temperature as the one which would be used for sintering a totally non-recycled powder of the PAEK.

11. The method according to claim 10, wherein the bed temperature is the same bed temperature as the one which would be used for sintering a totally non-recycled powder of the PAEK, and the laser power is the same laser power as the one which would be used for sintering a totally non-recycled powder of the PAEK.

12. A method for building a three-dimensional object layer-by-layer by electromagnetic radiation-generated sintering of powder, wherein the powder is a poly(aryl-ether-ketone) (PAEK) powder, the powder being obtained from thermal pretreatment at a temperature between 260° C. and 290° C. and having a melting temperature which is stable at the build temperature and which is below or equal to 330° C., wherein the powder comprises a mixture of recycled and non-recycled powders, the recycled powders having been used in an identical and/or a different number of cycles, wherein parameters of the sintering machine include laser power and powder bed temperature, wherein the sintering is conducted in a sintering machine and wherein successive sintering is carried out while keeping laser power of the sintering machine, the bed temperature unchanged, wherein the laser power is the same laser power as the one which would be used for sintering a totally non-recycled powder of said PAEK.

13. The method according to claim 12, wherein the bed temperature is the same bed temperature as the one which would be used for sintering a totally non-recycled powder of the PAEK, and the laser power is the same laser power as the one which would be used for sintering a totally non-recycled powder of the PAEK.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) By way of preamble, it is specified that the expression “comprised between” used within the context of this description must be understood as including the cited bounds.

(2) The term “build temperature” refers to the temperature at which the powder bed, of a constituent layer of a three-dimensional object being built, is heated during the layer-by-layer sintering method of the powder. This build temperature is below the melting temperature of the powder by 40° C., preferably by 30° C., more preferably by 20° C.

(3) Poly(aryl-ether-ketone)s (PAEKs) consist of units having the following formulae:
(—Ar—X—) and (—Ar.sub.1—Y—)
wherein: Ar and Ar.sub.1 each denote a divalent aromatic radical; Ar and Ar.sub.1 may be preferably selected from 1,3-phenylene, 1,4-phenylene, 4,4′-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2,6-naphthylene; X designates an electron-withdrawing group; it may preferably be selected from the carbonyl group and the sulphonyl group; Y denotes a group selected from an oxygen atom, a sulphur atom, an alkylene group, such as —CH.sub.2— and isopropylidene.

(4) In these units X and Y, at least 50%, preferably at least 70%, and more particularly at least 80% of the groups X are a carbonyl group, and at least 50%, preferably at least 70%, and more particularly at least 80% of the groups Y represent an oxygen atom. According to a preferred embodiment, 100% of the groups X denote a carbonyl group and 100% of the groups Y represent an oxygen atom.

(5) More preferentially, the poly(arylene-ether-ketone) (PAEK) may be selected from: a poly(ether-ketone-ketone), also called PEKK, comprising units of formula I A, formula I B and a mixture thereof:

(6) ##STR00001## a poly(ether-ether-ketone), also called PEEK, comprising units of formula II:

(7) ##STR00002##
The sequences can be totally para (formula II). Similarly, meta sequences can be introduced, partially or totally, into these structures at the ethers and the ketones according to the two examples of formulae III and IV below:

(8) ##STR00003##
Or ortho sequences according to formula V:

(9) ##STR00004## a poly(ether-ketone), also called PEK, comprising units of formula VI:

(10) ##STR00005##
Similarly, the sequence may be totally para, but meta sequences can also be partially or totally introduced (formulae VII and VIII):

(11) ##STR00006## a poly(ether-ether-ketone-ketone), also called PEEKK, comprising units of formula IX:

(12) ##STR00007##
Similarly, meta sequences can be introduced into these structures at the ethers and the ketones. a poly(ether-ether-ether-ketone), also called PEEEK, comprising units of formula X:

(13) ##STR00008##
Similarly, meta sequences can be introduced into these structures at the ethers and the ketones, but also biphenol sequences according to formula XI:

(14) ##STR00009##

(15) Other arrangements of the carbonyl group and the oxygen atom are also possible.

(16) Among the PAEKs described above, some have a melting temperature Tm above 330° C. However, it is well known to persons skilled in the art that the melting temperature can be lowered by introducing co-monomers into the formulae. One example is a PEEK-based copolymer with addition of biphenol-type co-monomers (formula XI).

(17) Preferably, the PAEKs used in the invention are selected from PEKKs, PEEK-based copolymers, and PEK-based copolymers.

(18) Advantageously, the PAEK powder of the invention suitable for use in a method for additive building of objects, layer-by-layer, by electromagnetic radiation-generated sintering of powder is obtained from a thermal pretreatment carried out at a temperature comprised between 260° C. and 290° C., preferably between 280° C. and 290° C.

(19) The PAEK polymer is indeed not used as it is, directly after synthesis, in a layer-by-layer sintering fabrication method. It is first transformed into a powder, by milling, to modify the particle size distribution of the polymer so as to obtain a powder having a suitable particle size distribution, known to persons skilled in the art, compatible with the laser sintering fabrication method. This milling step can be preceded or followed by other treatments, such as for example one or more additions of additive(s), filler(s) or fibres in the powder.

(20) Advantageously, the thermal treatment prior to the sintering step, carried out after the milling step, makes it possible to modify the thermal signature of the polymer, without modifying its particle size distribution. In the PEKK, the polymer material constituting the initial powder, obtained directly after synthesis, has two melting peaks, called the high-temperature and low-temperature melting peaks. Thermal pretreatment makes it possible to eliminate the low-temperature melting peak and to stabilise the crystalline morphology of the polymer, without modifying its high melting temperature.

(21) Thanks to this thermal pretreatment, the powder of the invention has a stable melting temperature, at the build temperature. Within the meaning of the invention, a stable melting temperature Tm means that the melting temperature does not increase by more than 3° C. after each laser sintering run, and preferably it does not increase by more than 2° C., and more preferably it does not increase by more than 1° C. Preferably, the melting temperature of the polymer powder is below or equal to 330° C., more preferably below or equal to 320° C., and even more preferably below or equal to 310° C.

(22) Such a powder has the advantage of being thermally stable during a sintering fabrication method and does not change. Its molecular weight notably remains stable and the phenomenon of viscosity rise due to increased molecular weight, which has been observed heretofore, appears little if at all.

(23) Preferably, the thermal pretreatment of the powder is carried out for a period comprised between 5 min and 120 min, preferably between 5 min and 60 min, and more preferably between 5 min and 30 min.

(24) The layer-by-layer fabrication method by sintering the powder by means of electromagnetic radiation is then carried out at a build temperature of the same order of magnitude as that of the thermal pretreatment. This build temperature is below the melting temperature of the powder by 40° C., preferably by 30° C. and more preferably by 20° C. Preferably, the build temperature is below 290° C.

(25) The PAEK powder can comprise a mixture of several polymers belonging to the PAEK family, the melting temperature Tm of which is below 330° C., preferably below or equal to 320° C., and more preferably below or equal to 310° C.

(26) Preferably, the PAEK powder comprises at least one poly(ether-ketone-ketone) (PEKK) powder which represents more than 60%, preferably more than 70% by weight of the powder, bounds included. The remaining 30% to 40% by weight may for example be constituted either by other polymers belonging to the PAEK family, the melting temperature of which is below or equal to 330° C., and/or by fillers and/or by fibres, such as carbon fibres, glass fibres for example, by glass beads, by mineral fillers, or by carbon blacks, graphites, graphenes, carbon nanotubes.

(27) More preferably, the PAEK powder is a PEKK powder. Advantageously, this PEKK powder has a percentage by weight of terephthalic units relative to the sum of terephthalic and isophthalic units comprised between 55% and 65%, and preferably this ratio is 60%.

(28) Due to this thermal stability of the powder, it can be used a large number of times in successive layer-by-layer object fabrication methods, by sintering powder by means of laser radiation, for example.

(29) Moreover, due to this stability of the powder, the parameters of the sintering fabrication machine, such as laser power and/or powder bed temperature, remain unchanged regardless of the number of times the powder is subsequently used. As a result, the fabrication of objects by laser sintering is more productive. Since the recyclability of the powder is improved, the sintering of PAEK powder becomes economically attractive and industrially possible.

(30) Finally, because the sintering parameters remain unchanged, it becomes possible and easy to use a powder comprising a mixture of different recycled or non-recycled powders, said recycled powders possibly having been used an identical and/or different number of cycles.

(31) The powder of the invention is thus very attractive economically since it can be recycled several times in a sintering method, while guaranteeing the same fabrication machine settings.

(32) Finally, the invention relates to a three-dimensional article obtained by sintering the powder which has just been described, layer-by-layer, using electromagnetic radiation, such as laser radiation for example. The object obtained has satisfactory and constant mechanical properties regardless of the number of times the powder has been used.

EXAMPLES

(33) 1. Changes in PAEK Powders after Initial Sintering

(34) Two PEKK powders are compared: a reference PEKK powder, comprising 60% terephthalic units and 40% isophthalic units and not having undergone thermal pretreatment, and a PEKK powder of the invention, comprising 60% terephthalic units and 40% isophthalic units.

(35) After synthesis of the two PEKK polymers, they are milled into powder. Only the powder of the invention undergoes a thermal pretreatment of 120 minutes at 285° C.

(36) The solution viscosity in 96% sulphuric acid of the reference powder is then measured at 0.87 dL/g. The solution viscosity in 96% sulphuric acid of the powder of the invention is measured at 0.85 dL/g. The viscosities are measured at 25° C. using an Ubbelohde tube-type viscometer.

(37) The two powders are then each placed in a tube under nitrogen sweeping and heated to 285° C. for 24 hours. Each powder is then re-analysed in terms of solution viscosity, and a viscosity of 0.90 dL/g is found for the reference powder and a viscosity of 0.85 dL/g for the powder of the invention. Consequently, the viscosity of the reference powder increases by more than 3% after 24 hours at 285° C., whereas the viscosity of the powder of the invention remains constant. The measurement uncertainty corresponds to 0.01 dL/g.

(38) TABLE-US-00001 TABLE I Inherent Inherent viscosity viscosity at t0 after 24 h at 285° C. Change in inherent (in dL/g) (in dL/g) viscosity Reference 0.87 0.90 +3.4% PEKK PEKK of the 0.85 0.85 approx. 0% or <1% invention

(39) The PEKK powder of the invention has an inherent viscosity which does not change significantly (change between 0% and 1%, corresponding to the measurement uncertainty), unlike the reference powder whose inherent viscosity increases significantly by more than 3%.

(40) 2. Recyclability after Sintering at a Build Temperature Equal to Tm−15° C.

(41) The two powders of Example 1 and a PEEK powder marketed by the company EOS under the name HP3 were compared after an initial sintering at a temperature 15° C. below their respective melting temperatures, and their recyclability at the conclusion of this sintering was evaluated.

(42) PEEK powder HP3 has a melting temperature of 372° C. The reference PEKK powder has, before the initial sintering, a melting temperature Tm.sub.1 of 300° C., but this temperature changes and increases after the initial sintering, by about 15 degrees. The PEKK powder of the invention, in turn, has an average melting temperature of 300° C., which remains constant after the sintering method. This is referred to here as the “average melting temperature” because, even if it does not change, it may be slightly different depending on the batches of powder and varies between 297° C. and 303° C.

(43) The melting temperature is measured by differential scanning calorimetry (DSC) according to standard ISO11357-3.

(44) The skilled person knows that, for a PAEK powder, it is usual to heat the fabrication chamber to a build temperature 10° C. to 20° C. (typically 15° C.) below the melting temperature of the polymer material constituting the powder in order to be able to produce a three-dimensional object by laser sintering with good performance in terms of sintering and of mechanical properties of the final object obtained.

(45) Laser sintering tests were carried out on a DTM Sinterstation 2500 modified to work at high temperatures (i.e., up to 300° C.). The powder not subjected to the laser beam, and thus not sintered, remaining in the fabrication compartment, also called “powder to be recycled”, was recovered.

(46) The initial powder—i.e., before its initial use in the laser sintering machine—and the powder to be recycled were compared in solution. To this end, about 30 mg of powder is dissolved in 1 mL of 4-chlorophenol at 150° C. for 24 h. After cooling the solution to room temperature, 14 mL of hexafluoroisopropanol (HFIP) is added. The solution is filtered on an Acrodisc syringe filter with a polytetrafluoroethylene (PTFE) membrane with a 25-mm diameter and a 0.2-μm pore size.

(47) TABLE-US-00002 TABLE II PEKK of the HP3 Reference PEKK invention Tm of the initial 372° C. Tm.sub.1 (300° C.) 300° C. powder Solubility of the Soluble Soluble Soluble initial powder Tm of the powder 386° C. Tm.sub.2 > Tm.sub.1 by 300° C. to be recycled about 15° C. Solubility of the Insoluble (>99% Soluble (<5% Soluble (<5% powder to be insolubles) insolubles) insolubles) recycled

(48) The results, summarised in Table II above, show that when the build temperature is set 15° C. below the melting temperature, PEEK powder HP3, once used, becomes insoluble with more than 99% by weight insoluble particles, which means that it has cross-linked, its molecular weight has increased, and the polymer has changed structure.

(49) The other two PEKK powders are soluble, with less than 5% by weight insoluble particles, which means that they can be reused.

(50) However, the reference PEKK powder, after the initial sintering, has a second melting temperature Tm.sub.2 higher than the first by about 15 degrees. The effect of this increase in the melting temperature, in terms of being able to recycle the powder again in a laser sintering method, is to modify the sintering parameters, and in particular the build temperature, but also the laser beam power.

(51) The PEKK powder of the invention has a constant melting temperature during the laser sintering method. It thus makes it possible to obtain one or more other sintered parts without changing the parameters of the sintering apparatus.

(52) 3. Sinterability at Constant Build Temperature

(53) The three powders-HP3, reference PEKK, and PEKK of the invention—are again compared for their sinterability at a fixed, constant build temperature, regardless of the number of sintering cycles.

(54) To be able to recycle the powder, the experiment was conducted by setting the build temperature at 285° C., in order to avoid thermal degradation of the powder and to be able to recycle it in subsequent laser sintering runs. Sintering is carried out under the same experimental conditions, in particular at a fixed build temperature and for a suitable and constant laser power.

(55) The initial powder—i.e., before the initial sintering—was compared with the powder recovered from the fabrication compartment after sintering (i.e., the powder to be recycled) and with a powder recycled once. For each of these powders, the mechanical properties of the sintered specimens were measured and compared, in particular tensile modulus and elongation at break.

(56) The results of these comparisons are summarised in Table III below.

(57) TABLE-US-00003 TABLE III PEKK of Reference the HP3 PEKK invention Mechanical properties of the object inadequate good good obtained after the 1.sup.st sintering Powder can be recycled a first time YES YES YES Mechanical properties of the object inadequate inadequate good obtained after the 2.sup.nd sintering Powder can be recycled a second YES YES YES time

(58) It turns out that at the build temperature of 285° C., which is much below the melting temperature of 372° C. of PEEK powder HP3, said powder HP3 is not degraded and can be recycled. On the other hand, at this temperature, the powder is not sintered properly and the three-dimensional object obtained does not have good mechanical properties; it does not pass the tests.

(59) The reference PEKK is also recyclable and the object obtained after the first sintering has good mechanical properties. On the other hand, if the same build temperature is left at 285° C. for a second test then, in this case, the powder is again recyclable but the three-dimensional object obtained has mechanical properties whose performance is significantly reduced.

(60) In this case, only the PEKK powder of the invention makes it possible to obtain sintered specimens with good mechanical properties, regardless of the number of sintering cycles and without changing the sintering parameters of both build temperature and laser beam power.

(61) 4. Successive Sintering Tests of Various Powders Under Conventional Sintering Conditions

(62) Table IV below summarises the parameters of the laser sintering machine, within the context of successive runs, carried out under conventional conditions, with the three powders—HP3, reference PEKK, and PEKK of the invention—making it possible to obtain sintered parts having satisfactory mechanical properties. The number of builds (tests) indicated in the table is 4, but, for the powder of the invention, sintered parts could be obtained with recycled powder a greater number of times without observing a significant decrease in mechanical properties.

(63) TABLE-US-00004 TABLE IV Laser power (W) Build temperature (° C.) PEKK PEKK Reference of the Reference of the HP3 PEKK invention HP3 PEKK invention Test 1 30 30 30 357 285 285 Test 2 — 39 30 — 300 285 Test 3 — 42 30 — 300 285 Test 4 — — 30 — — 285

(64) This table shows that the PEKK powder of the invention, used several times consecutively to produce three-dimensional objects layer-by-layer, by laser sintering of the powder, makes it possible to obtain objects having satisfactory and stable mechanical properties regardless of the number of times the powder is recycled. Moreover, the build parameters of the laser sintering machine remain unchanged regardless of the number of times the powder is recycled.

(65) It was observed, with the reference PEKK powder of the prior art, that the mechanical properties of the three-dimensional object obtained after 2 cycles are affected and begin to decrease. It thus becomes very difficult to recycle this powder in sintering methods beyond 3 or 4 cycles.

(66) The PAEK powder of the invention which has just been described, with a stable melting temperature below 330° C. and preferably below or equal to 310° C., has improved recyclability, so that it becomes very economically attractive. It makes it possible to build three-dimensional objects by sintering, without changing the parameters of the sintering method, thus significantly improving productivity. Finally, the three-dimensional objects obtained have satisfactory and constant mechanical properties regardless of the number of cycles.