阅读说明：本技术 使用电子束对增材制造部件进行后固化的方法 (Method for post-curing an additive manufactured part using an electron beam ) 是由 克里斯托弗·迈克尔·舒伯特 马克·爱德华·尼科尔斯 李正琪 于 2019-01-09 设计创作，主要内容包括：一种形成部件(50)的方法包括3D打印可光聚合树脂并且形成预成型部件,随后用电子束(127)对预成型部件(50)进行后固化。可以通过紫外线固化来固化预成型部件。用电子束后固化的预成型部件的一部分可以具有至少1.0厘米的厚度,例如具有至少2.0厘米或至少3.0厘米的厚度。对预成型部件进行后固化的电子束剂量可以在10千戈瑞(kGy)和100kGy之间。可以使用立体光刻(SLA)、数字光处理(DLP)和材料喷射(MJ)3D打印预成型部件,并且可光聚合树脂可以包括丙烯酸酯官能聚合物和甲基丙烯酸酯官能聚合物中的至少一种。在替代方案中,或除此之外,可光聚合树脂可以包括氨基甲酸酯、聚酯和聚醚中的至少一种。(A method of forming a part (50) includes 3D printing a photopolymerizable resin and forming a preform part, followed by post-curing the preform part (50) with an electron beam (127). The pre-formed part may be cured by ultraviolet curing. A portion of the pre-formed part that is post-cured with an electron beam may have a thickness of at least 1.0cm, for example at least 2.0cm or at least 3.0 cm. The electron beam dose to post cure the preform component may be between 10 kilograys (kGy) and 100 kGy. The preform component may be 3D printed using Stereolithography (SLA), Digital Light Processing (DLP), and Material Jetting (MJ), and the photopolymerizable resin may include at least one of an acrylate functional polymer and a methacrylate functional polymer. In the alternative, or in addition, the photopolymerizable resin may include at least one of urethane, polyester, and polyether.)

1. A method of forming a component, comprising:

3D printing a photopolymerizable resin and forming a preform component; and

the pre-formed part is subsequently post-cured with an electron beam.

2. The method of claim 1, wherein the preformed component is cured by ultraviolet curing.

3. The method of claim 1, wherein the portion of the pre-formed part post-cured with the electron beam comprises a thickness of at least 1.0 centimeter.

4. The method of claim 1, wherein the portion of the pre-formed part post-cured with the electron beam comprises a thickness of at least 2.0 centimeters.

5. The method of claim 1, wherein the portion of the pre-formed part post-cured with the electron beam comprises a thickness of at least 3.0 centimeters.

6. The method according to claim 1, wherein the preformed part is 3D printed by at least one of Stereolithography (SLA), Digital Light Processing (DLP) and Material Jetting (MJ).

7. The method of claim 1, wherein the preformed component comprises a plurality of portions and each of the plurality of portions has a thickness of at least 1.0 centimeter.

8. The method of claim 7, wherein the plurality of portions are oriented non-parallel to each other.

9. The method of claim 1, wherein during post-curing, the preform component rotates without electron beam movement.

10. The method of claim 1, wherein the photopolymerizable resin comprises at least one of an acrylate functional polymer and a methacrylate functional polymer.

11. The method of claim 1, wherein the photopolymerizable resin comprises at least one of urethane, polyester, and polyether.

12. The method of claim 11, wherein an electron beam dose of the electron beam for post-curing the pre-formed component is between 10kGy and 100 kGy.

13. The method of claim 1, further comprising passing the pre-formed component through an electron beam curing chamber in which the pre-formed component is post-cured with the electron beam.

14. The method of claim 1, wherein the pre-formed part is post-cured without external heating.

15. A method of post-curing a plurality of 3D printed preformed components, comprising:

3D printing a photopolymerizable resin and forming a plurality of preformed components; and

moving a plurality of the pre-formed components through an electron beam chamber containing an electron beam, wherein each of the plurality of pre-formed components is irradiated by the electron beam and post-cured.

16. The method of claim 15, wherein the plurality of preform components are uv cured during 3D printing of the photopolymerizable resin.

17. The method of claim 15, wherein each of the plurality of preformed components comprises a plurality of portions, and at least one of the plurality of portions has a thickness of at least 1.0 centimeter.

18. A method of post-curing a plurality of 3D printed preformed components, comprising:

3D printing a photopolymerizable resin, curing using ultraviolet light and forming a plurality of preform components, wherein a first subset of the plurality of preform components has a different shape than a second subset of the plurality of preform components, and each of the plurality of preform components comprises at least one portion having a dimension equal to or greater than 1.0 centimeter;

moving the plurality of pre-formed components through an electron beam curing chamber containing an electron beam; and

irradiating the first subset of preform components and the second subset of preform components with an electron beam as the plurality of preform components move through the electron beam curing chamber.

19. The method of claim 18, wherein each of the first subsets of preformed components is irradiated with the electron beam for a first period of time and each of the second subsets of preformed components is irradiated with the electron beam for a second period of time equal to the first period of time.

20. The method of claim 18 wherein each of said first subsets of preformed components is irradiated with said electron beam at a first dose and each of said second subsets of preformed components is irradiated with said electron beam at a second dose equal to said first dose.

Technical Field

The present invention relates to additive manufacturing and in particular to post-curing of components formed by additive manufacturing.

Background

The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.

Additive Manufacturing (AM) (also referred to herein as "3D printing") is a manufacturing technique for producing parts by sequential deposition and curing of materials such that the parts are gradually assembled in a given direction (often referred to as the "z-direction"). Ultraviolet (UV) curable resins are used to form polymeric AM components. The ultraviolet curable resin is polymerized by a radical reaction when exposed to ultraviolet light of a specific wavelength. In addition, curing of the resin stops once the ultraviolet light is removed, and post-treatment or post-curing is typically required to improve the "green strength" of the AM component. Post-cure techniques include additional uv curing and thermal curing. Additional uv curing requires AM parts to be thin enough so that light can penetrate the entire volume of the AM parts, while thermal curing requires the addition of expensive heat-activated crosslinking additives to the uv curable resin. Furthermore, thermal curing of thick sections (e.g.. gtoreq.1.0 cm) requires extended curing times (e.g.. gtoreq.1 hours) and may negatively impact the dimensional stability of AM parts if the glass transition temperature (Tg) of the final polymer approaches the post-curing temperature.

The present invention addresses the problems of post-cured AM components and other problems associated with AM using materials that require post-curing.

Disclosure of Invention

This section provides a general summary of the invention, and is not a comprehensive disclosure of its full scope or all of its features.

In one form of the invention, a method of forming a part includes 3D printing a photopolymerizable resin and forming a preform part, and subsequently post-curing the preform part with an electron beam. In some aspects of the invention, forming the preform component includes uv curing and curing with an electron beam a portion of the preform component having a thickness of at least 1.0cm, such as at least 2.0cm or at least 3.0 cm. The electron beam dose of the electron beam used to post cure the preform part is between 10 kilogray (kGy) and 100 kGy. The preform component may be 3D printed using Stereolithography (SLA), Digital Light Processing (DLP), and Material Jetting (MJ), and the photopolymerizable resin may include at least one of an acrylate functional polymer and a methacrylate functional polymer. In the alternative, or in addition, the photopolymerizable resin may include at least one of urethane, polyester, and polyether.

In some aspects of the invention, the preform component has a plurality of portions and each of the plurality of portions has a thickness of at least 1.0 centimeter. In such an aspect, the plurality of portions may be oriented non-parallel to one another. Further, the preform part may or may not rotate when irradiated by the electron beam.

In some aspects of the invention, the method includes passing the preform component through an electron beam curing chamber where the preform component is post-cured with an electron beam. Furthermore, the preformed part is post-cured with an electron beam without additional heating of the preformed part.

In another form of the invention, a method of post-curing a plurality of 3D printed preform parts includes 3D printing a photopolymerizable resin and forming a plurality of preform parts. A plurality of pre-formed components are moved through an electron beam chamber and post-cured by electron beam irradiation. In some aspects of the invention, the plurality of preform components have a plurality of portions and at least one of the plurality of portions has a thickness of at least 1.0 centimeter.

In yet another form of the present invention, a method of post-curing a plurality of 3D printed preform parts includes using 3D printing photopolymerizable resin, curing using ultraviolet light and forming a plurality of preform parts. The first subset of the plurality of preform components has a different shape than the second subset of the plurality of preform components. Moreover, each of the plurality of preformed components has at least one portion having a dimension equal to or greater than 1.0 centimeter. The plurality of preform components are moved through an electron beam curing chamber where a first subset of the preform components and a second subset of the preform components are irradiated with an electron beam. In some aspects of the invention, each first subset of the pre-formed parts is irradiated with an electron beam for a first time period, and each second subset of the pre-formed parts is irradiated with an electron beam for a second time period equal to the first time period. That is, the first subset of the preformed components and the second subset of the preformed components are irradiated with the electron beam for the same period of time. In such an aspect, the dose from the electron beam may be the same or different for the first subset of preformed components and the second set of preformed components. In other aspects of the invention, each first subset of the pre-formed parts is irradiated with an electron beam at a first dose and each second subset of the pre-formed parts is irradiated with an electron beam at a second dose equal to the first dose. That is, the first subset of the preform components and the second subset of the preform components are irradiated with the same dose. In these aspects, the irradiation time of the electron beam may be the same or different for the first subset of the preformed components and the second subset of the preformed components.

Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

Drawings

For a better understanding of the present invention, various forms thereof will now be described by way of example, with reference to the accompanying drawings, in which:

FIG. 1 schematically depicts a method for 3D printing and post-curing a pre-formed component according to the teachings of the present invention;

FIG. 2 schematically depicts a method for 3D printing and post-curing a plurality of preformed components according to the teachings of the present invention;

FIG. 3 schematically depicts a method for 3D printing and post-curing a plurality of preformed components according to the teachings of the present invention;

FIG. 4 schematically depicts an exemplary 3D printed part formed by a method according to the teachings of the present disclosure;

FIG. 5 schematically depicts another exemplary 3D printed component formed by a method according to the teachings of the present disclosure;

FIG. 6 is a flow chart of a method of 3D printing and post-curing a pre-formed component according to the teachings of the present invention; and

fig. 7 is a flow chart of a method of 3D printing and post-curing a plurality of pre-formed components according to the teachings of the present invention.

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

Detailed Description

The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. It should be understood that throughout the drawings, corresponding reference numerals indicate like or corresponding parts and features. Examples are provided to fully convey the scope of the invention to those skilled in the art. Numerous specific details are set forth such as specific components, devices, and types of methods to provide a thorough understanding of variations of the invention. It will be apparent to one skilled in the art that specific details need not be employed and that the examples provided herein may include alternative embodiments and are not intended to limit the scope of the invention. In some instances, well-known processes, well-known device structures, and well-known techniques are not described.

Referring now to fig. 1, a method 10 of 3D printing a pre-form part and post-curing the 3D printed pre-form part according to the teachings of the present invention is schematically depicted. The method 10 includes 3D printing a pre-formed part 50 (also referred to herein simply as "part 50") at a 3D printing station 100 that includes a 3D printer 102 and post-curing the part 50 at a post-curing station 120 to provide a post-cured part 60. In some aspects of the present invention, the post-cure component 60 is fully cured. As used herein, the phrase "fully cured" refers to sufficient cross-linking within the material used to form the part such that the post-cured part has predetermined properties (e.g., mechanical properties, vapor emission properties, solvent resistance properties, etc.) for a given application or use. In some aspects of the invention, the component 50 is formed from a photopolymerizable resin 51. In these aspects, the photopolymerizable resin 51 may be an ultraviolet curable resin 51 that is ultraviolet cured with ultraviolet light 104 during 3D printing of the part 50 at the 3D printing station 100.

Still referring to fig. 1, the component 50 is post-cured at the post-cure station 120 by an electron beam 127 generated and propagating from an electron beam source 126. An electron beam source 126 is within the chamber 122. It is to be understood that the electrons in the electron beam ionize molecules in the ultraviolet curable resin 51, thereby generating radicals that crosslink with other molecules (with radicals), causing additional curing of the part 50 and providing the post-cured part 60. It should also be understood that the penetration of the electron beam 127 into the part 50 is not limited by the opacity of the ultraviolet curable resin 51, and that thick portions of the part 50 may be post-cured with the electron beam 127. In some aspects of the present invention, portions of the component 50 having dimensions equal to or greater than 1.0 centimeter (cm) (i.e., h and/or w ≧ 1.0cm) can be post-cured with an electron beam. For example, the energy (MeV) of the electron beam 127 may be adjusted such that the electron beam penetrates into the 3D printed part such that portions having a size of greater than 2.0cm or greater than 3.0cm are capable of post-curing in accordance with the teachings of the present invention. In some aspects of the invention, one or more portions of the component 50 have a dimension of between 1.0cm and 2.0cm, between 2.0cm and 3.0cm, between 3.0cm and 4.0cm, or between 4.0cm and 5.0 cm. However, in other aspects of the invention, one or more portions of the component 50 have a dimension of less than 1.0cm, for example, between 1.0cm and 0.75cm, between 0.75cm and 0.50cm, between 0.50cm and 0.25cm, or between 0.25cm and 0.1 cm. It should be understood that although a portion having a thinner size (e.g., a size of less than 0.25cm) may be completely cured using ultraviolet radiation depending on the ultraviolet light resin 51 used to form the part 50, the electron beam 127 completely cures the ultraviolet light resin 51 for a shorter time than the ultraviolet light curing or the thermal curing. That is, electron beam curing of the part 50 reduces the time to fully cure the part 50 by at least 50%, for example, at least 60%, at least 70%, at least 80%, or at least 90%.

The chamber 122 has an interior 124 that may provide an inert atmosphere around the part 50 during post-curing. Alternatively, the interior 124 of the chamber 122 may provide an oxygen-containing atmosphere (e.g., air) during post-curing of the component 50. For example, ultraviolet curing of the part 50 at the 3D printing station 100 provides a generally non-porous surface 52 such that oxygen penetration into the part 52 is retarded. Therefore, ionization of oxygen that may change the properties of the ultraviolet curable resin 51 inside the part 50 or affect crosslinking of the ultraviolet curable resin 51 during post-curing is prevented and an inert atmosphere is not required.

In some aspects of the invention, the component 50 has a shape and size that is retained during and after post-curing of the component 50. For example and as schematically shown in fig. 1, the part 50 has a width 'w' and a height 'h', and the post-cure part 60 has the same width 'w' and height 'h'. In some aspects of the invention, the uv curing of the uv curable resin 51 at the 3D printing station 100 provides shape stability to the part 50 so that the part 50 can be moved to the post-curing station 120 without changing its shape and/or size, and the post-curing of the part 50 with the electron beam 127 at the post-curing station 120 provides structural and/or chemical stability to the post-cured part 60 so that the post-cured part 60 can be used for its intended purpose.

Referring now to fig. 2, a method 20 of 3D printing and post-curing a plurality of 3D printed components according to the teachings of the present invention is schematically depicted. Method 20 includes 3D printing a plurality of parts 50 at a 3D printing station 200 including a 3D printer 202 and post-curing the plurality of parts 50 at a post-curing station 220 to provide a plurality of post-cured parts 60. In some aspects of the present invention, the post-cure component 60 is fully cured. The part 50 may be formed of an ultraviolet curable resin 51, and the ultraviolet curable resin 51 is ultraviolet cured with ultraviolet light 204 during 3D printing of the part 50 at the 3D printing station 200.

Still referring to fig. 2, the component 50 is moved through the post-cure station 220 via the conveyor 210 at a constant speed (i.e., the conveyor 210 provides a constant linear speed) and post-cured at the post-cure station 220 by an electron beam 227 generated and propagated from an electron beam source 226. It should be understood that in some aspects of the present invention, the component 50 has a shape and size that is retained during and after post-curing of the component 50. For example, and as schematically shown, the part 50 has a width 'w' and a height 'h', and the post-cure part 60 has the same width 'w' and height 'h'. The chamber 222 has an interior 224 that can provide an inert atmosphere around (shield) the component 50 during post-curing. Alternatively, the interior 224 of the chamber 222 may provide an oxygen-containing atmosphere (e.g., air) during post-curing of the component 50.

In some aspects of the invention, the uv curing of the uv curable resin 51 at the 3D printing station 200 provides shape stability to the parts 50 so that the parts 50 can be moved to the post-curing station 220 without changing their shape and/or size, and the post-curing of the parts 50 with the electron beam 227 at the post-curing station 220 provides structural and/or chemical stability to the post-cured parts 60 so that the post-cured parts 60 can be used for their intended purpose.

Although fig. 2 schematically depicts components 50 having the same shape and size, it should be understood that 3D printed components having different shapes and sizes may be post-cured in accordance with the teachings of the present invention. For example, and referring to fig. 3, a method 30 of 3D printing and post-curing a plurality of 3D printed parts having different shapes and sizes in accordance with the teachings of the present invention is schematically depicted. Method 30 includes 3D printing a plurality of parts 52 having different shapes and sizes at 3D printing station 200 and post-curing the plurality of parts 52 at post-curing station 220 to provide a plurality of post-cured parts 62. In some aspects of the present invention, post-cure component 62 is fully cured. Also, the part 52 may be formed of the ultraviolet curable resin 51, and the ultraviolet curable resin 51 is ultraviolet cured with the ultraviolet light 204 during 3D printing of the part 52 at the 3D printing station 200.

In some aspects of the present invention, the part 52 is moved at a constant speed through the post-cure station 220 via the conveyor 210. In these aspects, the energy of the electron beam 227 and/or the dose provided by the electron beam 227 may or may not be constant during the post-curing of each component 52. For example, the energy of the electron beam 227 and/or the dose provided by the electron beam 227 may be adjusted as the part 52 moves through the post-cure station 220 at a constant linear speed. In the alternative, the energy of the electron beam 227 and/or the dose provided by the electron beam 227 may be constant as the part 52 moves through the post-cure station 220 at a constant linear speed. In other aspects of the invention, the energy of the electron beam 227 and/or the dose provided by the electron beam 227 is constant and the linear velocity is adjusted as the part 52 moves through the post-cure station 220 via the conveyor belt 210. For example, the linear speed of the conveyor belt 210 may be reduced as the part 52 having the relatively thick portion moves through the post-cure station 220.

Although fig. 2 and 3 schematically depict a single 3D printer 102, 202 forming multiple parts 50, 52 that are post-cured at post-curing stations 120, 220, respectively, it should be understood that more than one 3D printer may be used to form multiple parts that are post-cured at a single post-curing station. It should also be understood that more than one post-cure station may be used to post-cure multiple parts from a single 3D printer.

Referring now to fig. 4 and 5, non-limiting examples of 3D printed parts post-cured with an electron beam according to the teachings of the present invention are schematically depicted. In particular, a gear 60 is schematically depicted in fig. 4, and a polygonal support 70 is schematically depicted in fig. 5. Gear 60 (FIG. 4) has a thickness't ' and a radial thickness ' r_o'. In some aspects of the invention, the thickness t and/or the radial thickness r_oCan be between 1.0cm and 2.0cm, at 2.0cm andbetween 3.0cm, between 3.0cm and 4.0cm, or between 4.0cm and 5.0 cm. The polygonal bracket 70 has three portions, that is, a thickness of' t₁And has a width of' w₁First portion 71 of 'having a thickness of' t₂And has a width of' w₂'second portion 72, and a thickness of' t₃And has a width of' w₃The third portion 73 of'. Also, the second portion 72 is spaced apart from the first portion 71. In some aspects of the invention, t of the first portion 71₁And/or w₁T of the second portion 72₂And/or w₂And/or t3 and/or w3 of the third portion 73 may be between 1.0cm and 2.0cm, between 2.0cm and 3.0cm, between 3.0cm and 4.0cm, or between 4.0cm and 5.0 cm. However, the penetration of the electron beam 227 enables the post-cure chamber 220 to post-cure components such as the gear 60 and the polygonal support 70 in a few seconds as opposed to thermal curing of such components which requires a time period of minutes and hours. In particular, in some aspects of the invention, a preformed 3D printed part having a thick portion (i.e., a portion having a thickness between 1.0cm and 5.0 cm) is post-cured with an electron beam in less than 60 seconds, e.g., less than 45 seconds or less than 30 seconds, in accordance with the teachings of the present invention. In contrast, thermosetting a preformed 3D printed part having a thick portion takes one hour or more. Further, it should be understood that, depending on the ultraviolet resin used to form a particular part, while ultraviolet radiation may be used to fully cure a portion of a relatively thin size (e.g., less than 0.25cm in size), the electron beam takes less time to fully cure the ultraviolet resin than to either ultraviolet or thermal curing. That is, electron beam curing of the part, even for thin portions of the part (e.g., less than 0.25cm in thickness), reduces the time to fully cure the part 50 by at least 50%, such as at least 60%, at least 70%, at least 80%, or at least 90%.

As described above, in some aspects of the invention, the energy of the electron beam 227 and/or the dose provided by the electron beam 227 is constant and the rate of movement (i.e., linear velocity) of the component 52 through the chamber 222 is varied according to the shape and size of a given component 52. In other aspects of the invention, the rate of movement of the part 52 through the chamber 222 is constant and the energy of the electron beam 227 and/or the dose provided by the electron beam 227 is varied according to the shape and size of a given part 52. In other aspects, the size and shape of the part 52 is such that the energy of the electron beam 227 and/or the dose provided by the electron beam 227 provided to the post-cure part 62 is constant, and the rate of movement of the part 52 through the chamber 222 provided to the post-cure part 62 is constant.

Referring now to fig. 6, a flow diagram of a method of post-curing a 3D preform part is schematically depicted at 80. The method 80 includes providing a 3D printed preform part at step 82 and post-curing the 3D printed preform part with an electron beam at step 84.

Referring now to fig. 7, a flow diagram of a method of post-curing a plurality of 3D preform components is schematically depicted at reference numeral 90. The method 90 includes 3D printing a plurality of pre-form components from a photopolymerizable resin (e.g., an ultraviolet curable resin) at step 92 and moving the plurality of pre-form components through an electron beam chamber at step 94. At step 96, the plurality of preform components are irradiated with an electron beam in an electron chamber and post-cured.

Although the terms first, second, third, etc. may be used to describe various elements, components, regions, sections and/or periods, these elements, components, regions, sections and/or periods should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Terms such as "first," "second," and other numerical terms used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section could be termed a second element, component, region, layer or section without departing from the teachings of the example forms. Further, an element, component, region, layer or section may be referred to as a "second" element, component, region, layer or section without necessarily referring to the element, component, region, layer or section as a "first" element, component, region, layer or section.

As used herein, at least one of the phrases A, B and C should be construed to mean logical (a or B or C), use a non-exclusive logical or, and should not be construed to mean "at least one of a, at least one of B, and at least one of C.

Unless otherwise expressly stated, all numbers expressing mechanical/thermal properties, compositional percentages, dimensions and/or tolerances, or other characteristics are to be understood as being modified in describing the scope of "about" or "approximately" in this disclosure. Such modifications are desirable for a variety of reasons, including industrial practice, manufacturing techniques, and testing capabilities.

The terminology used herein is for the purpose of describing particular example forms only and is not intended to be limiting. The singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises" and "comprising," when used in this specification, are taken to specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features (integers, steps, operations, elements, components, and/or groups thereof). Unless specifically identified as an order of execution, the method steps, processes, and operations described herein are not to be construed as necessarily requiring their execution in the particular order discussed or illustrated. It should also be understood that additional or alternative steps may be employed.

The description of the invention is merely exemplary in nature and, thus, examples that do not depart from the gist of the invention are intended to be within the scope of the invention. Such examples are not to be construed as a departure from the spirit and scope of the invention. The broad teachings of the present invention can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent from the drawings, the specification, and the following claims.