Method for processing PAEK and articles manufactured from the same

Abstract

A process for manufacturing a three-dimensional object from a powder by selective sintering the powder using electromagnetic radiation. The powder includes recycled PAEK. In one embodiment, the powder includes recycled PEKK. In one embodiment, the powder includes first recycle PEKK and second recycle PEKK. In one embodiment, the powder consists essentially of recycled PEKK. The process may include the step of maintaining a bed of a selective laser sintering machine at approximately 300 degrees Celsius and applying a layer of the powder to the bed. The average in-plane tensile strength of the three-dimensional object is greater than that of a three-dimension object manufactured by selective sintering using a powder including an unused PEKK powder.

Claims

1. A three dimensional object obtained from a powder by selective laser sintering by applying a layer of the powder on a bed of a laser sintering machine, solidifying selected points of the applied layer of powder by irradiation, successively repeating the step of applying the powder and the step of solidifying the applied layer of powder until all cross sections of the three-dimensional object are solidified, wherein the powder has the following structural characteristics: the powder comprises recycled polyetherketoneketone (PEKK), wherein the recycled PEKK is a PEKK powder that has been previously used in an SLS process having a bed temperature between a melting point temperature of the PEKK powder before the SLS process (T.sub.M1) and 20 degrees Celsius less than the T.sub.M1 and having a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2); a melting point temperature of the recycled PEKK (T.sub.M2) is greater than T.sub.M1.

2. The three-dimensional object according to claim 1, wherein a bed temperature of the powder comprising the recycled PEKK (T.sub.Bed) is greater than a bed temperature for an unused PEKK; wherein the unused PEKK is a PEKK powder that has not been used in a selective laser sintering (SLS) process.

3. The three-dimensional object according to claim 2, wherein T.sub.Bed is approximately 285 degrees Celsius or greater.

4. The three-dimensional object according to claim 2, wherein T.sub.Bed is approximately 300 degrees Celsius or greater.

5. The three-dimensional object according to claim 2, wherein a laser power of the powder comprising the recycled PEKK is greater than laser power for an unused PEKK.

6. The three-dimensional object according to claim 1, wherein the SLS process used to manufacture the three-dimensional object has a bed temperature between T.sub.M2 and 20 degrees Celsius less than the T.sub.M2 and has a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2).

7. The three-dimensional object according to claim 5 wherein an average in-plane tensile strength of the three-dimensional object is greater than an average in-plane tensile strength of a three-dimensional object manufactured by selective sintering using electromagnetic radiation from a powder consisting essentially of unused PEKK powder, wherein the SLS process used to manufacture the three-dimensional object consisting essentially of the unused PEKK powder has a bed temperature between the melting point temperature of the unused PEKK powder and 20 degrees Celsius less than the melting point temperature of the unused PEKK and has a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2).

8. The three-dimensional object according to claim 1, wherein the powder further comprises an unused PEKK; wherein the unused PEKK is a PEKK powder that has not been used in a selective laser sintering (SLS) process.

9. The three-dimensional object according to claim 8, wherein the SLS process used to manufacture the three-dimensional object has a bed temperature between T.sub.M2 and 20 degrees Celsius less than the T.sub.M2 and has a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2).

10. The three-dimensional object according to claim 9, wherein an average in-plane tensile strength of the three-dimensional object is greater than an average in-plane tensile strength of a three-dimensional object manufactured by selective sintering using electromagnetic radiation from a powder consisting essentially of unused PEKK powder, wherein the SLS process used to manufacture the three-dimensional object consisting essentially of the unused PEKK powder has a bed temperature between the melting point temperature of the unused PEKK powder and 20 degrees Celsius less than the melting point temperature of the unused PEKK and has a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2).

11. The three-dimensional object according to claim 7 wherein an average in-plane tensile strength of the three-dimensional object is greater than 10 ksi.

12. The three-dimensional object according to claim 1, wherein the recycled PEKK comprises of first recycle PEKK; wherein the first recycle PEKK is recycled PEKK that has been used previously in only one SLS process.

13. The three-dimensional object according to claim 1, wherein the recycled PEKK comprises of second recycle PEKK; wherein the second recycle PEKK is recycled PEKK that has been used previously in two SLS processes.

14. The three-dimensional object according to claim 1, wherein the powder consists essentially of recycled PEKK.

15. The three-dimensional object according to claim 8, wherein the recycled PEKK powder is at least 50% of the powder by weight.

16. A three-dimensional object made by a process comprising the following steps: applying a layer of a powder on a bed of a laser sintering machine, the powder comprising recycled polyetherketoneketone (PEKK); solidifying selected points of the applied layer of powder by irradiation; successively repeating the step of applying the powder and the step of solidifying the applied layer of powder until all cross sections of a three-dimensional object are solidified; wherein the recycled PEKK is a PEKK powder that has been previously used in an SLS process having a bed temperature between a melting point temperature of the PEKK powder before the SLS process (T.sub.M1) and 20 degrees Celsius less than the T.sub.M1 and having a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2); wherein a melting point temperature of the recycled PEKK (T.sub.M2) is greater than T.sub.M1/; wherein a bed temperature of the powder comprising the recycled PEKK (T.sub.Bed) is greater than a bed temperature for a powder consisting of a PEKK powder that has not been used in a selective laser sintering (SLS) process.

17. The object of claim 16, wherein the SLS process used to manufacture the three-dimensional object has a bed temperature between T.sub.M2 and 20 degrees Celsius less than the T.sub.M2 and has a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2); wherein an average in-plane tensile strength of the three-dimensional object is greater than an average in-plane tensile strength of a three-dimensional object manufactured by selective sintering using electromagnetic radiation from a powder consisting essentially of an unused PEKK powder, wherein the SLS process used to manufacture the three-dimensional object consisting essentially of the unused PEKK powder has a bed temperature between the melting point temperature of the unused PEKK powder and 20 degrees Celsius less than the melting point temperature of the unused PEKK and has a laser with a power between 2 and 50 (W*s/mm{circumflex over ( )}2).

18. The three-dimensional object according to claim 17 wherein the average in-plane tensile strength of the three-dimensional object is greater than 10 ksi.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a chart illustrating a comparison between an SLS process using essentially unused PEKK, an SLS process using essentially first recycle PEKK, and an SLS process using essentially second recycle PEKK.

DETAILED DESCRIPTION

(2) An SLS process performed on unused PEKK powders is generally as follows. First, an operator verifies that the unused powder is adequately dry. The unused powder is loaded into an SLS machine. Typically, the unused powder is loaded into a hopper, or the like, from which the SLS machine can distribute sequential layers of powder on to a bed of the SLS machine for sintering. It should be understood that there are different types of PEKK powder blends. Unlike other PAEK materials, PEKK is a copolymer (AB type EKK/EKK). The examples described herein pertain to the 60/40 PEKK blend unless otherwise noted. It should be understood, however, that the present invention is not limited to any specific blend of PEKK resin, and that different blends may be used.

(3) Next, the part geometrics, also referred to as the build definition, is loaded into a computer associated with the SLS machine. It should be understood that the present disclosure is not limited to the specific sequence of steps described herein and that many different sequences of the disclosed steps may be apparent and used by a person of ordinary skill in the art. After the unused PEKK powder is loaded, the SLS machined is preheated according to known methods. The bed temperature is set to a temperature as specified by the vendor of the PEKK powder. The laser power is also set to a power specified by the vendor and/or to a power determined from earlier runs of the SLS process.

(4) Using the above described PEKK, the bed temp is set to approximately 285 degrees Celsius and the laser power is set to approximately 30 (W*S/mm{circumflex over ( )}2). A powder layer thickness of 125 microns is typical. After the layer-wise build is performed, the powder cake is allowed to cool at controlled rates. For example, for PEKK, the cake is typically cooled at between 1 and 100 degrees Celsius per hour. It should be appreciated by a person of ordinary skill in the art that the rate of cooling depends on the dimensions of the cake, with deeper beds typically requiring more time to cool.

(5) When the cake has achieved near room temperature throughout, the built parts are removed therefrom. Typically, the mass yield from an SLS build using unused PEKK powder is less than 20% of the PEKK material required to form the cake bed in the initial build. In other words, the built parts account for approximately 20% of the PEKK material used in the build. The remaining PEKK material, approximately 80%, is not built into any part.

(6) After the parts are removed from the cake bed, the remaining PEKK material is referred to as used PEKK material or recycled PEKK material. This material is referred to as used or recycled because it has been used at least once in the SLS process. In other words, this material has been raised to the bed temperature and added to the bed in a layer-wise fashion. Material adjacent to the used material was sintered in the initial SLS process.

(7) After the parts are removed from the cake, the PEKK powder forming the cake is recycled for subsequent use in the SLS process. Sieving of the cake is performed to restore common size to the recovered cake structure, which is typically lumpy. The sieve size may be similar to the original powder or the sieve size may be different than the original powder. In the process described, it is preferred that the sieve size falls in the 20-200 micron range. It is possible to blend batches of used sieved PEKK powder. However, it is preferred that batches of used sieved PEKK powder that are blended have similar thermodynamic properties. The use of DSC, FTIR, and other analytical methods may be used to determine which batches of used sieved PEKK powder can be mixed. A test build can be used to validate analytical results.

(8) The SLS process for recycled PEKK is described below. The correct bed temperature and laser power must be determined. In performing the SLS process using non-PAEK polymers, the same bed temperature and laser power are typically used on unused non-PAEK polymer and recycled non-PAEK polymer. Unlike the non-PAEK polymers, it has been discovered that the melting point of recycled PEKK is significantly higher than the melting point of unused PEKK. As a result, a different bed temperature is typically determined and used for recycled PEKK as compared to unused PEKK. Similarly, a different laser temperature is typically determined and used for recycled PEKK as compared to unused PEKK.

(9) To determine the correct bed temperature for the recycled PEKK lot, the bed is set approximately 15 degrees Celsius below the melting temperature of unused PEKK material, as specified by the vendor. The temperature of the bed is increased in increments of one or two degrees Celsius while the SLS machine lays down a PEKK powder layer with each incremental temperature change. At some point, the bed provides a visual cue that indicates that under the current temperature the layers of PEKK powder are trying to fuse into a single block. For example the color of the bed and the texture of the bed shift, indicating that the layers of PEKK are trying to fuse into a single block. The bed temperature for a build using the recycled PEKK powder is usually 5 to 7 degrees Celsius below the temperature at which the layers of PEKK powder begin to fuse.

(10) Next, the correct laser power for the recycled PEKK is determined. Different laser powers are searched to determine correct power. The laser power for a specific lot is determined by trying different powers to determine which power works best. Tests of dimensional accuracy and mechanical behavior on the sintered material are known and are common to establish the preferred laser settings for unused PEKK. After the bed temperature and laser power are determined for the recycled PEKK product, the SLS process is established and the desired objects are built using the process.

(11) The inventor has discovered that the bed temperature and laser power for the recycled PEKK may be significantly higher than the known bed temperature and laser power for unused PEKK. For example, in an SLS process using essentially first recycle PEKK, the preferred bed temperature is approximately 300 degrees Celsius and the laser power is approximately 39 (W*S/mm{circumflex over ( )}2). This compares to a bed temperature of approximately 285 degrees Celsius and a laser power of approximately 30 (W*S/mm{circumflex over ( )}2) for an SLS process using a lot including essentially unused PEKK. It should be understood that the term first recycle PEKK refers to a batch of PEKK that has been previously used one time in the SLS process. The term second recycle PEKK, as used herein below, accordingly refers to a batch of PEKK powder that has previously been used twice. Although the disclosure refers to lots consisting of unused PEKK (also referred to as virgin PEKK), first recycle PEKK, and second recycle PEKK, the present invention is not so limited and many different blends may be used.

(12) In an SLS process using a lot including essentially second recycle PEKK, the preferred bed temperature is approximately 300 degrees Celsius and the laser power is approximately 42 (W*S/mm{circumflex over ( )}2).

(13) Recycling of PEKK powders in SLS processes is achieved by using 100% used, unfused cake material. It is preferred to segregate used unfused SLS powders until appropriate mixing parameters are determined as described earlier.

(14) It has been discovered that the parts made from the SLS process using recycled PEKK may be substantially more durable than parts made from the SLS processing using unused PEKK. For example, one test that is used to determine the strength of parts formed using the SLS process is the ASTM D638, which tests the tensile strength of the formed part. For example, in the case of an SLS process using a lot including essentially first recycle PEKK, the average in-plane tensile strength by ASTM D638 was 14.0 ksi with elongation to fail of ˜3.4%. This compares to an in-plane tensile strength by ASTM D638 of 13.5 ksi with elongation to fail ˜3.25% for a part formed using the SLS process with essentially unused PEKK.

(15) In reference to FIG. 1, a chart 100 illustrates a comparison between an SLS process using essentially unused PEKK 110, an SLS process using essentially first recycle PEKK 120, and an SLS process using essentially second recycle PEKK 130. The layer thickness was approximately 125 microns in each case. The data in the chart represents approximate averages based on approximately 120 different test runs.

(16) Although the present invention has been illustrated using recycled PEKK material, the present invention is not so limited and may be employed to perform the SLS process on any recycled PAEK material. In particular, the process disclosed herein may be used to perform the SLS process on materiel from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketone (PEK), polyetheretherketoneketone (PEEKK) or polyetherketoneetherketoneketone (PEKEKK).

(17) Although the present invention has been illustrated with lots consisting essentially of 100% unused PAEK material, 100% first recycle PAEK material, or 100% second recycle material, the present invention is not so limited. It is possible to blend a recycled PAEK material with an unused PAEK material, or, for example, it is possible to blend a first recycled material with a second recycled material. It should be understood that the number of recycles can be greater than two.

(18) Although the present invention has been disclosed and described with reference to certain embodiments thereof, it should be noted that other variations and modifications may be made, and it is intended that the following claims cover the variations and modifications within the true scope of the invention.