Method for modifying a 3D printed object

Patent metadata

Field	Value
Publication number	US-12337533-B2
Application number	US-202017760816-A
Country	US
Kind code	B2
Filing date	Sep 25, 2020
Priority date	Sep 30, 2019
Publication date	Jun 24, 2025
Grant date	Jun 24, 2025

Abstract

The invention relates to a method for modifying an object comprising the step of: I) providing an object which is made at least partially of a construction material comprising a thermoplastic polyurethane. The method also comprises the following steps: II) contacting, at least in part, the construction material, for a first predetermined period of time, with a first liquid comprising ≥80% by weight, based on the total weight of the first liquid, of a polar aprotic solvent; III) contacting, for a second predetermined period of time, the areas of the construction material that were in contact with the liquid in step II) with a second liquid comprising ≥80% by weight, based on the total weight of the second liquid, of a polar protic solvent. Preferably, the first liquid is DMSO or acetone and the second liquid is water.

First claim

The invention claimed is:

1. A process for modifying an article comprising:
I) providing an article which is at least partially constructed from a build material comprising a thermoplastic polyurethane;
II) at least partially contacting the build material for a first predetermined duration with a first liquid including >80% by weight of a polar aprotic solvent based on a total weight of the first liquid;
III) contacting for a second predetermined duration regions of the build material contacted with the first liquid in step II) with a second liquid including >80% by weight of a polar protic solvent based on a total weight of the second liquid;
wherein a section of the article modified by the process has a higher tensile strength according to DIN 53504 or a higher breaking elongation according to DIN 53504 than a corresponding section on an unmodified but otherwise identical article.

2. The process as claimed in claim 1 , wherein the polar aprotic solvent in the first liquid comprises acetone, methyl ethyl ketone, dimethyl sulfoxide, or a mixture thereof.

3. The process as claimed in claim 1 , wherein the first liquid further includes water, a polyisocyanate, a polyol, or a mixture of at least two of the preceding liquids.

4. The process as claimed in claim 1 , wherein the polar protic solvent in the second liquid includes water, methanol, ethanol, n-propanol, isopropanol, or a mixture of at least two of the preceding liquids.

5. The process as claimed in claim 1 , wherein in step II) the first predetermined duration is >1 second to ≤120 seconds and/or wherein in step III) the second predetermined duration is ≥1 second to ≤120 seconds.

6. The process as claimed in claim 1 , further comprising heating the article to a temperature of ≥50° C. for a predetermined duration after step III).

7. The process as claimed in claim 1 , wherein the regions of the build material contacted with the solvent in step II) have a porosity Φ of ≥0.01 to ≤0.6 and the porosity Φ is expressed as:
Φ=1−(ρ/ρ 0 )

wherein ρ represents the density of the volume assigned to the regions of the article that are contacted with the solvent and po represents the true density of the build material.

8. The process as claimed in claim 1 , wherein the article is at least partially produced by means of an additive manufacturing process using the build material.

9. The process as claimed in claim 8 , wherein the additive manufacturing process comprises the steps of:
applying a layer of particles comprising the build material to a target surface;
energizing a selected portion of the layer corresponding to a cross section of the article to join the particles in the selected portion;
repeating the steps of applying and energizing for a plurality of layers so that the selected portions of adjacent layers become joined to form the article.

10. The process as claimed in claim 9 , wherein the energizing comprises:
irradiating the selected portion of the layer with an energy beam to join the particles in the selected portion.

11. The process as claimed in claim 9 , wherein the energizing comprises:
applying a liquid to the selected portion of the layer, wherein the liquid increases absorption of energy in regions of the layer contacted by the liquid relative to regions of the layer not contacted by the liquid;
irradiating the layer so that the particles in regions of the layer contacted by the liquid are joined to one another and the particles in regions of the layer not contacted by the liquid are not joined to one another.

12. The process as claimed in claim 8 , wherein the additive manufacturing process comprises the steps of:
applying a filament of the at least partially molten build material to a carrier, such that a layer of the build material is obtained, corresponding to a first selected cross section of the article;
applying a filament of the at least partially molten build material onto a previously applied layer of the build material to obtain a further layer of the build material which corresponds to a further selected cross section of the article and which is joined to the previously applied layer;
repeating the step of applying a filament of the at least partially molten build material onto a previously applied layer of the build material until the article has been formed.

13. The process as claimed in claim 1 , wherein the build material comprises a thermoplastic polyurethane elastomer which has a melting range (DSC, differential scanning calorimetry; second heating at a heating rate of 5 K/min) of ≥20° C. to ≤240° C.,
has a Shore A hardness according to DIN ISO 7619-1 of >40 A to ≤85 D, has a melt volume rate (MVR) according to ISO 1133 (10 kg) at a temperature T of 5 to 15 cm 3 /10 min, and exhibits a change in the melt volume rate (10 kg) at an increase of temperature T by 20° C. of ≤90 cm 3 /10 min.

14. The process as claimed in claim 1 , wherein in step II) the first predetermined duration is ≥5 seconds to ≤90 seconds and/or wherein in step III) the second predetermined duration is >5 seconds to ≤90 seconds.

15. The process as claimed in claim 1 , wherein in step II) the first predetermined duration is ≥30 seconds to ≤60 seconds and/or wherein in step III) the second predetermined duration is ≥30 seconds to ≤60 seconds.

16. The process as claimed in claim 1 , wherein the build material comprises an ester-based thermoplastic polyurethane elastomer which has a Shore D hardness according to DIN ISO 7619-1 of 59.

17. The process as claimed in claim 1 , wherein the build material comprises an ester-based thermoplastic polyurethane elastomer which has a Shore A hardness according to DIN ISO 7619-1 of 88.

18. The process as claimed in claim 1 , wherein the build material comprises an ether-based thermoplastic polyurethane elastomer which has a Shore A hardness according to DIN ISO 7619-1 of 72.

19. The process as claimed in claim 1 , wherein the build material comprises an ester-based thermoplastic polyurethane elastomer which has a Shore D hardness according to DIN ISO 7619-1 of 65.

20. The process as claimed in claim 1 , wherein the process results in an increase in the tensile strength of the section of the article by at least 10%, as determined by a tensile test according to DIN 53504 or an increase in the breaking elongation of the section of the article by at least 10%, as determined by a tensile test according to DIN 53504.

Assignees

• Stratasys Inc

Inventors

• Achten Dirk
• Mettmann Bettina
• Buesgen Thomas
• Kessler Michael

Classifications

• B29K2995/0077

  Yield strength; Tensile strength · CPC title

• B29K2995/007

  Hardness · CPC title

• B29K2105/0058

  Liquid or visquous · CPC title

• B29K2075/00

  Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material · CPC title

• B29C64/268

  using laser beams; using electron beams [EB] · CPC title