AMORPHOUS POLYARYLETHERKETONE AND BLENDS THEREOF FOR USE IN ADDITIVE MANUFACTURING

Abstract

A material for use with a 3D printer comprises a polyaryletherketone (PAEK) having an amorphous morphology. In some embodiments, the material also includes one or more further compounds having an amorphous morphology. In some further embodiments, the material includes, in addition to an amorphous PAEK, a compound having a semi-crystalline morphology.

Description

CROSS-REFERENCE

The present application is a continuation of International Application No. PCT/US2016/055505, filed Oct. 5, 2016, which is a continuation of U.S. patent application Ser. No. 14/874,963, filed Oct. 5, 2015, each of which is entirely incorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to compositions for use in additive manufacturing, more commonly known as “3D printing.”

BACKGROUND OF THE INVENTION

The additive manufacturing process is widely known as the three-dimensional (“3D”) printing of objects. There are a variety of 3D-printing processes, VAT polymerization, material jetting, binder jetting, material extrusion, powder bed fusion, sheet lamination, and directed energy deposition.

Extrusion-based 3D printing involves the deposition of thermoplastic materials. This process fabricates a three-dimensional object from a mathematical model of the object using materials such as thermoplastics and metals that are typically in the form of a filament. In the case of a thermoplastic material, the object is built by feeding a thermoplastic filament into a heated extrusion head. The thermoplastic is heated past its glass transition temperature and then deposited by the extrusion head as a series of beads in a continuous motion. After deposition, the bead quickly solidifies and fuses with the beads next to and below it. The nozzle of the extrusion head follows a tool-path controlled by a computer-aided manufacturing (CAM) software package, and the object is built from the bottom up, one layer at a time.

Prototyping is currently the most common application for extrusion-based printing, using materials such as acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), methyl methacrylate acrylonitrile butadiene styrene copolymer (ABSi), and polycarbonate (PC), among others.

Toward the end of printing production-suitable parts, higher-end engineering semi-crystalline and amorphous polymers, as well as metals and ceramics with greater mechanical, chemical, thermal, and electrical properties are being used. Examples of semi-crystalline polymers include, among others, semi-crystalline polyaryletherketones (PAEK), polyetheretherketone (PEEK), and polyetherketoneketone (PEKK). Examples of amorphous engineering polymers include polyphenylsulphone (PPSU) and polyetherimide (PEI), among others.

Amorphous polymers are relatively easy to process via material extrusion. Unfortunately, these polymers tend to have relatively poor chemical resistance, poor heat resistance, and inferior mechanical properties such that the parts formed therefrom using material extrusion are often not suitable for production (as opposed to prototyping) applications.

Semi-crystalline thermoplastic PEEK, mentioned above, has exceptionally high tensile and flexural strength compared to other polymers and can perform under load at high temperatures. Its chemical resistance and tolerance to steam and hot water have enabled its use in high-strength applications in the medical and oil & gas industries.

Although parts formed from PEEK have been printed using material extrusion, this polymer introduces challenges to the 3D-printing process due to its semi-crystalline morphology. In particular, more advanced build platforms and enclosures are required to manage the high ambient temperature during printing. Furthermore, this semi-crystalline polymer has a longer cooling time compared to lower temperature amorphous materials, which increases the minimum layer time and requires the use of cooling to speed up solidification. PEEK parts printed via material extrusion also experience more significant shrinkage and warpage compared to parts printed from amorphous materials. This leads to decreased dimensional accuracy and larger tolerances for PEEK parts printed in this fashion. The increased warpage can also result in part separation from the build surface unless high build-chamber temperatures (c.a. 280 to 310° Celsius) are used. Additionally, PEEK has higher melt flows requiring higher pressures during extrusion and printing compared to amorphous materials.

To overcome the problems associated with printing via material extrusion using PEEK, the present inventors have blended PEEK with other amorphous thermoplastics, as disclosed in U.S. patent application Ser. No. 14/297,185. These compositions have been optimized for a materials extrusion printing process allowing large, complex production parts to be formed. Although easier to process than neat semi-crystalline PEEK, these PEEK blends do not exhibit the superior mechanical, thermal, and chemical resistivity properties of neat PEEK.

A need therefore remains for materials for use in 3D printing, via material extrusion as well as other 3D printing techniques, that are relatively easy to process and will result in printed parts that exhibit high chemical resistance, high heat resistance, and high strength such that the parts can be used as a production/working part in relatively demanding applications, such as arises in the aerospace, healthcare, and oil & gas industries.

SUMMARY

The present invention provides a material for use in 3D printing that avoids some of the drawbacks of the prior art.

In accordance with the present teachings, a resin comprising an amorphous form of a (normally semi-crystalline) polyaryletherketone (PAEK) is used for forming production parts via 3D-printing techniques. PAEK thermoplastics useful in conjunction with embodiments of the invention include, without limitation, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and polyetherketoneetherketoneketone (PEKEKK).

In the illustrative embodiment, the PAEK is amorphous PEEK. To the extent this Detailed Description references PEEK or any other specific PAEK, such as those mentioned above, it is to be understood that these teachings apply generally to any PAEK compound unless otherwise specified. In various embodiments, the resin comprises:

• • one amorphous PAEK compound (e.g., PEEK, etc.);
  • one type of amorphous PAEK (e.g., PEEK, etc.) but at least two versions thereof, each having a different measure of amorphousness (i.e., one relatively less amorphous, one relatively more amorphous) from the other;
  • two or more different amorphous PAEKs (e.g., PEEK and PEKK, etc.);
  • at least one PAEK compound in amorphous form and at least one amorphous compound that is not a PAEK compound;
  • at least one amorphous PAEK and at least one semi-crystalline PAEK, wherein the PAEK compound is the same (e.g., amorphous PEEK and semi-crystalline PEEK, etc.);
  • at least one amorphous PAEK and at least one semi-crystalline PAEK, wherein each PAEK compound is different (e.g., amorphous PEEK and semi-crystalline PEKK, etc.);
  • at least one amorphous PAEK and at least one semi-crystalline compound that is not a PAEK compound;
  • combinations of the foregoing.

Semi-crystalline PAEK has a relatively high viscosity and melt flow and therefore requires relatively high pressure to force it through an extrusion head of a 3D printer during printing. On the other hand, amorphous PAEK and blends thereof in accordance with the present teachings exhibit the relatively more desirable rheological properties of a higher melt mass-flow rate that is characteristic of a lower temperature, common amorphous polymer. In other words, the use of amorphous PEEK orotheramorphous forms of other PAEK compounds decreases the viscosity sufficiently to reduce the pressure required to print the polymer blend via a material extrusion technique.

Furthermore, semi-crystalline PAEK has an increased shrinkage and warpage compared to amorphous polymers, requiring the use of high-temperature heating beds, a slower print speed, and/or the use of cooling to maintain geometrical accuracy around critical object features and to prevent the part from pulling off the build plate. The use of amorphous PAEK or blends thereof in accordance with the present teachings exhibit less warpage or shrinkage given its lower coefficient of thermal expansion and contraction. In other words, the use of amorphous PAEK allows the material to adhere better to the build surface and may produce tighter geometrical tolerances.

The addition of amorphous PAEK to semi-crystalline PAEK can increase the heat resistance and maximum operating temperature compared to conventional materials used for 3D printing.

As previously noted, after it is prepared, the resin can be used to print parts via material-extrusion 3D-printing techniques. However, in some other embodiments, parts are printed from the resin using other 3D-printing techniques, such as, for example, directed energy deposition, sheet lamination, powder bed fusion, binder jetting, and material jetting. With respect to its use with powder bed fusion, binder jetting, and material jetting techniques, the resin must be ground to an appropriate particle size. In embodiments in which the resin comprises more than a single compound, melt blending is used to blend the compounds. Melt blending for extrusion is specific to material extrusion and directed energy deposition 3D-printing techniques. However, for powder bed fusion, binder jetting, and material jetting techniques, melt blending is used to form the blend prior to grinding to form a powder.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a flow diagram of a first method for preparing a blend of polymers, including at least one amorphous PAEK compound, in accordance with an illustrative embodiment of the present invention.

FIG. 2 depicts a flow diagram of a second method for preparing a blend of polymers, including at least one amorphous PAEK compound, in accordance with an illustrative embodiment of the present invention.

DETAILED DESCRIPTION

Although the illustrative embodiment is directed to the use of amorphous PEEK and blends thereof, any polyaryletherketone (PAEK) that can be synthesized to exhibit an amorphous morphology as disclosed herein, can be used either alone or in a blend to print production-quality parts.

The crystallization of polymers is a process associated with partial alignment of their molecular chains. The fraction of the ordered molecules in a polymer is characterized by the degree of crystallinity, which typically ranges between 10% and 80%, inclusive. For this reason, crystallized polymers are often called “semi-crystalline. A polymer with less than 10% crystallinity is considered to be “amorphous.” The degree of amorphousness is the inverse of degree of crystallinity. For example, a polymer with a crystallinity of 5% has a greater degree of amorphousness than a polymer having a crystallinity of 9%.

The degree of crystallinity is estimated by the different analytical methods' such as density measurement, differentia-scanning calorimetry (DSC), infrared spectroscopy, nuclear magnetic resonance (NMR), and X,-ray diffraction (XRD). In addition, the distribution of crystalline and amorphous regions (and hence degree of crystallinity) can be visualized with microscopic techniques, such as polarized light microscopy and transmission electron microscopy. The numbers for (degree of) crystallinity provided herein are based on DSC, unless otherwise indicated.

PAEK compounds are characterized by phenylene rings that are linked via oxygen bridges (ether and carbonyl groups (ketone)). The ether-to-ketone ratio and the sequence thereof in the PAEK compound affects the compound's glass transition temperature and melting point. This ratio and sequence also affects the heat resistance and processing temperature of the PAEK. The higher the ratio of ketones, the more rigid the polymer chain, which results in a higher glass transition temperature and melting point. The processing temperatures can range from about 350 to 430° C.

PEEK is commercially manufactured as a semi-crystalline thermoplastic using step-growth polymerization of bisphenolate salts. PEEK is usually manufactured with a degree of crystallinity in the range of about 25 to 35%

In accordance with the illustrative embodiment and unlike conventional practice, PEEK is manufactured to exhibit an amorphous morphology (i.e., lower degree of crystallinity) by altering the process conditions during polymerization.

One method to achieve amorphous PEEK is to continue the step-growth polymerization, creating very high molecular weight grades. The polymerization processing conditions must be carefully controlled to enable the polymerization process to continue. For example, the amount of initial monomers added must be limited and precisely measured. An excess of one type of monomeric reagent over another can limit the molecular weight. The reactants must have a high purity to prevent the occurrence of side reactions from contaminates. The viscosity of the polymerization medium must be controlled to promote continued step reactions. Finally, solid-state polycondensation can be used as a post-processing step to further increase the molecular weight.

Furthermore, incorporating certain additives during polymerization can prevent or restrict the organization of crystalline chains. For example, reactants containing bulky side groups (e.g., multiple benzene rings, etc.) can be added to the ends of the polymer chains. These bulky side groups prevent the polymer from organizing into a crystalline morphology. Amorphous PEEK exhibits a higher toughness and ductility compared to semi-crystalline PEEK, but generally has a lower tensile strength and chemical resistivity.

In light of the present disclosure, those skilled in the art will be able to apply the foregoing techniques and others to suitably control the polymerization process to produce amorphous PEEK and other amorphous PAEK compounds.

The amorphous PAEK compound can be extruded into filament for use in a material extrusion 3D-printing process. In some embodiments, a semi-crystalline PAEK compound and an amorphous PAEK compound are blended together to improve the mechanical performance (i.e., tensile strength and Young's modulus) and increase the chemical resistance (as measured, for example, via ASTM D543) of the resulting printed part, as compared to using an amorphous PAEK compound alone.

Semi-crystalline thermoplastics other than semi-crystalline PAEK compounds can be blended with the amorphous PEEK to achieve specific material properties or processing properties. For example and without limitation, semi-crystalline resins such as polyimide, polyethylene, nylon, polyphenylene sulfide, and polyphthalamide can be used.

Also, amorphous compounds other than amorphous PAEK compounds can be blended with one or more amorphous PAEK compounds to achieve specific material properties or processing properties. For example and without limitation, amorphous resins such as polyetherimide (PEI commonly known as Ultem®), polyethersulfone (PES), Polysulfone (PSU commonly known as Udel®), polyphenyl sulfone (PPSU commonly known as Radel®), polyphenylene oxides (PPOs), acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyglycolic acid (PGA), polyamide-imide (PAl commonly known as Torlon®), polystyrene (PS), polyamide (PA), polybutylene terephthalate (PBT), poly(p-phenylene sulfide) (PPS), polyethersulfone (PESU), polyethylene ether (commonly known as PrimoSpire®), and polycarbonate (PC) can suitably be used.

Thus, in various embodiments, a resin for a 3D-printing process includes:

• • (i) One type of amorphous PAEK (e.g., PEEK, etc.);
  • (ii) One type of amorphous PAEK (e.g., PEEK, etc.) but at least two versions thereof with differing degrees of amorphousness (i.e., one relatively less amorphous, one relatively more amorphous);
  • (iii) Two or more different amorphous PAEKs (e.g., PEEK and PEKK, etc.);
  • (iv) At least one amorphous PAEK and at least one amorphous compound that is not a PAEK compound;
  • (v) At least one amorphous PAEK and at least one semi-crystalline PAEK, wherein the PAEK compound(s) is the same (e.g., amorphous PEEK and semi-crystalline PEEK, etc.);
  • (vi) At least one amorphous PAEK and at least one semi-crystalline PAEK, wherein the PAEK compound is the different (e.g., amorphous PEEK and semi-crystalline PEKK, etc.);
  • (vii) At least one amorphous PAEK and at least one semi-crystalline compound that is not a PAEK compound; and
  • (viii) Any combinations of (i) through (vii). For example and without limitation, variations on (v) or (vi) with (ii), wherein multiple versions of the amorphous PEAK(s) with differing degrees of amorphousness and/or multiple versions of the semi-crystalline PAEK(s) with different semi-crystallinity; etc.

In some embodiments, the mixing or compounding of the blend of amorphous and semi-crystalline thermoplastic polymers (e.g., PEEK, etc.) takes place before filament extrusion (for material extrusion and directed energy deposition techniques). In such embodiments, the polymers are heated above their processing temperatures and are well mixed. The resulting resin is a homogenous blend of multiple polymers.

In some other embodiments, the mixing or compounding of the blend of amorphous and semi-crystalline thermoplastic polymers (e.g., PEEK, etc.) occurs through melt blending during filament extrusion (for material extrusion and directed energy deposition techniques). In such embodiments, the pellets of the polymers are mixed and then added to the hopper of the filament extruder. The materials are then melted in the barrel and mixed as the extruder screw rotates. Although this method is more cost-effective and requires one less step than pre-compounding, it may not yield a completely homogenous polymer blend.

In some embodiments, the weight ratio of (total) amorphous PAEK to (total) semi-crystalline PAEK is in a range of about 50:50 to about 95:5, inclusive. The ratio selected for any particular application may vary primarily as a function of the materials used and the properties desired for the printed object.

The blend of amorphous PEEK with semi-crystalline PEEK can result in miscible, immiscible, or compatible polymer blends. If the polymers are miscible, the blend will have one glass transition temperature modeled by the Fox Equation:

$\frac{1}{T_g}=\frac{w_1}{T_{g·1}}+\frac{w_2}{T_{g·2}}$

• • where: T_g is the glass transition temperature

Considering a specific example, if PEEK (T_g=143° C.) is blended with polyethylene ether (T_g=168° C.) with in a ratio of 40 to 60% respectively, the resulting T_g would be 157° C. If the polymers are immiscible or compatible, the blend will have two or more glass transition temperatures characteristic of the individual polymers.

As described in prior art, both miscible and immiscible blends have demonstrated an increase in mechanical properties compared to the properties of each polymer in the blend assuming the appropriate mixing technique is used (Ibrahim & Kadum, 2010). With the use of amorphous PEEK in a polymer blend, extremely high-strength polymer blends for 3D printing result.

In another embodiment, the blended material may include two or more thermoplastic materials. In embodiments in which multiple materials are used to form the blended material, the total amount of each type of material should fall within the ratio guidelines provided above.

In yet another embodiment, a solid non-polymer filler material having a higher melting temperature than the thermoplastic polymer material(s) is added to the blend to improve mechanical properties of the printed objects. The amount of the filler material by weight is up to about 60%, and more preferably between 5% and 20% of the total blend. The filler material can include, without limitation, chopped carbon fibers, chopped glass fibers, chopped aramid/Kevlar fibers, continuous carbon fiber, continuous glass fiber, continuous polyethylene fiber, milled carbon, milled glass, graphite, graphene, carbon nanotubes, and graphene nanoplatelets. Preferably, the fibers are suspended and mixed in the blend during its fabrication. In an exemplary embodiment, the fibers are treated or sized for the specific resin of choice and then encapsulated or coated with resin to ensure sufficient wetting with the polymer.

Blending. If a blend of polymers (e.g., multiple amorphous polymers, amorphous and semi-crystalline polymers, etc.) is being prepared, it can be prepared in accordance with method 100 depicted in FIG. 1. The materials to be blended are typically provided in pellet or powder form.

In step 101, the materials are dried in a dryer to remove moisture in order to prevent hydrolysis of the polymer, which can reduce polymer chain length resulting in poorer properties. In step 102, the dried materials in powder form are physically and thoroughly mixed in a mixing device. In step 103, the mix is then fed to a hopper of an extruder. In some embodiments, a single-screw or a twin-screw extruder is used to melt blend the materials and then extrude the blended material into a strand.

In embodiments in which a filler material is used, it can be added during steps 102 or 103 or in step 201, discussed later herein. In the extruder, the mixed materials are “melted” (step 104). In accordance with one embodiment, the melt blending is performed at a temperature that is:

• • (a) above the glass transition temperature of the amorphous polymer materials, preferably at a temperature at which the polymer is fluid;
  • (b) above the melting point of semi-crystalline polymer materials (if present); and
  • (c) below the polymer degradation temperature of all amorphous and semi-crystalline materials.

A typical melt blend temperature for the various PAEK polymers will be in the range of about 360 to about 370° C.

In embodiments in which more than one amorphous polymer material is used in the blend, the melt blending is performed at a temperature that is above the glass transition temperature of all the amorphous polymer materials, at which the polymers behave like a fluid. Likewise, in embodiments in which more than one semi-crystalline polymer material is used, the melt blending is performed at a temperature that is above the melting point of all the semi-crystalline polymer materials that are used in the blend.

In step 105, the melted material passes through a die of an extruder (e.g., a single-screw extruder, a twin-screw extruder, etc.) and is extruded. In some embodiments, the resulting extrudate is formed into a strand, which is typically about 6 to 13 millimeters (¼-½ inch) in diameter. The melt processing temperature (i.e., the temperature of the material as it is extruded through an extrusion head) will typically be near the temperature at which the materials are melt blended.

Of course, the melt processing temperature for the blended material will be dictated by the highest melting temperature or highest glass transition temperature of all the amorphous and semi-crystalline materials in the blend, whichever is higher.

After extrusion, in step 106, the strand is cooled, such as in a water bath. In some embodiments, the size of the extrusion die is such that the strand is in a form of a filament having a diameter of 1-2 mm. In step 107A, the filament is wound as a roll of filament, which can be fed directly to a 3D printer (based on material extrusion or directed energy deposition processing).

Alternatively, in step 107B, the strand is cut into small pellets for storage. In this case, the pellets are reprocessed into a filament of 1-2 mm in diameter, which is adapted for direct feeding into a 3D printer (based on material extrusion or directed energy deposition processing) as illustrated in FIG. 2.

In step 201, the pellets containing the blended materials from step 107B are fed into a hopper of an extruder, such as a single or twin-screw extruder. If the filler material is to be added, it can be added in this step instead of step 102 or 103. In step 202, the blended pellets are “melted” in the extruder. Similar to step 104, the melting is performed at a temperature that is:

• • (a) above the glass transition temperature of the amorphous polymer materials, preferably at a temperature at which the polymer is fluid;
  • (b) above the melting point of semi-crystalline polymer materials (to the extent present); and
  • (c) below the polymer degradation temperature of all amorphous and semi-crystalline materials.
    The temperature in the extruder will typically be about 370 to about 380° C.

In step 203, the melted material passes through a die of the extruder and is extruded into a filament, which is typically 1 to 2 mm in diameter. After extrusion, in step 204, the filament is cooled, such as in a water bath and is rolled onto a roll as a final product in step 205, which is suitable to be fed directly into a 3D printer (based on material extrusion or directed energy deposition processing).

To print a 3D object, the filament from the filament roll of the heat-blended material is fed to the 3D printer (based on material extrusion or directed energy deposition processing). The filament is then heated (e.g., by a heater block of the 3D printer to a temperature that is above the glass transition temperature of the amorphous material and the melting point of the semi-crystalline material (if present). Typical printing temperature for amorphous PAEK and blends in accordance with the present teachings will be in the range of about 350 to about 370° C. The 3D printer then deposits the heated material in a selected pattern layer-by-layer in accordance with a mathematical model of the 3D object in order to fabricate the object.

Claims

1-53. (canceled)

54. A composition for use with a three-dimensional (3D) printer, comprising a first compound and a second compound different than the first compound, wherein the first compound is a polyaryletherketone (PAEK), and wherein the composition is amorphous.

55. The composition of claim 54, wherein the second compound comprises an additional PAEK.

56. The composition of claim 55, wherein the PAEK is more amorphous than the additional PAEK.

57. The composition of claim 54, wherein the second compound does not include a PAEK.

58. The composition of claim 54, wherein the PAEK is polyetherketone, polyetherketoneketone, polyetheretherketoneketone, or polyetherketoneetherketoneketone.

59. The composition of claim 58, wherein the PAEK is polyetherketone.

60. The composition of claim 58, wherein the PAEK is polyetheretherketone.

61. The composition of claim 58, wherein the PAEK is polyetheretherketoneketone.

62. The composition of claim 54, further comprising a filler material having a melting temperature that is greater than a glass transition temperature of the PAEK.

63. The composition of claim 62, wherein the filler material comprises one or more members selected from the group consisting of chopped carbon fibers, chopped glass fibers, chopped aramid fibers, continuous carbon fiber, continuous glass fiber, continuous polyethylene fiber, milled carbon, milled glass, graphite, graphene, carbon nanotubes, and graphene nanoplatelets.

64. The composition of claim 63, wherein the filler material comprises carbon nanotubes.

65. The composition of claim 63, wherein the filler material comprises continuous carbon fiber.

66. The composition of claim 62, wherein the filler material is encapsulated within the PAEK.

67. The composition of claim 54, wherein a weight ratio of the first compound to the second compound is at least 1:1.

68. The composition of claim 67, wherein the weight ratio is from about 1:1 to 19:1.

69. The composition of claim 54, wherein the composition is included in a filament.

70. The composition of claim 69, wherein a diameter of the filament is from about 6 millimeters (mm) to 13 mm.

71. The composition of claim 69, wherein a diameter of the filament is from about 1 mm to 2 mm.

72. The composition of claim 54, wherein the composition is included in a pellet.

73. The composition of claim 54, wherein the composition is included in a material roll.