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3-d printed semi-crystalline and amorphous polymer articles
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A technology of semi-crystalline polymers and amorphous polymers, applied in 3D object support structures, single-component synthetic polymer rayon, additive manufacturing, etc., can solve poor Z-direction performance, poor layer adhesion, Poor material fluidity and other issues
Active Publication Date: 2021-07-30
ARKEMA FRANCE SA
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[0008] A common problem in 3D printing is that printed parts are much weaker mechanically than traditional injection molded parts
For example, most polyamide materials have poor material flow when cooled - hardening rapidly, resulting in poor interpenetrating layers, exhibiting poor layer adhesion and poor Z-direction performance
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Embodiment 1
[0105] PEBA (invention and comparative example) and polyamide (comparative example) with different amounts of hard blocks and soft blocks were selected as silk materials. Stretch strips of each material are printed in XY and Z directions.
[0106] PA = polyamide block
[0107] PTMG = poly(1,4-butylene glycol) block
[0108] The ratio is the weight ratio of polyamide blocks to polyether blocks.
[0109] Mn was determined by GPC.
[0110] G' / G" refers to the junction temperature (hardening temperature) in °C. This is determined by oscillatory rheology at 2π radians / second (2πrad / s) (low shear) from the printing temperature to approximately 50°C .
[0111] IM yield strength is the yield strength of injection molded parts measured by tensile testing.
[0112] The 3D yield stress in XY and Z directions was measured according to ASTM D638 by tensile bars (Type 1, longitudinally reduced to 50%) printed in XY or Z direction.
[0113] "PA12+PTMG" denotes a polyether block amide h...
Embodiment 2
[0120] The TWLT and haze of the samples of Example 1 were measured using ASTM D1003. The results are shown in Table 2 below.
[0121] Table 2
[0122] sample TWLT Haze 2 72 93 4 78 69 5 75 93
[0123] figure 1 Enlarged pictures of 3D printed sample blocks (approximately 3 mm thick with a layer height of 0.1 mm) for samples 2, 4, and 5 are shown, respectively. Note the reduction in interlayer lines in Sample 4, resulting in reduced haze and increased transmittance.
[0124] figure 2 is a graph showing the layer strength (elongation at break of z-layer / elongation at break of injection molding) versus interface temperature for various amorphous and semi-crystalline materials. Note that a junction temperature of less than 140°C, preferably 130°C, more preferably less than 120°C has a significant effect.
[0125] image 3 A plot of the rheological curves G' and G" of Sample 7 is shown as the temperature decreases. Note that the junction ...
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Abstract
The invention relates to 3D printed parts made with thermoplastic polymers having a low stiffening temperature. 3D printed parts of the invention have very good Z layer adhesion, have a high elongation at break in the Z direction, preferably of more than 50 percent, and have at least an 80 percent ratio of Z to XY stress at yield or at break. The resulting part may be nearly isotropic, having similar mechanical properties in the XY and Z print directions. The excellent layer adhesion makes the resultant printed part more robust to withstand many cycles of use. Certain polymers of the invention produce printed parts that have a very low haze, and are nearly transparent.
Description
[0001] field of invention [0002] The present invention relates to 3D printed parts made of thermoplastic polymers with a low hardening temperature. The 3D printed parts of the present invention have very good Z-layer adhesion, high elongation at break in the Z direction, preferably greater than 50%, and a ratio of Z to XY stress at yield or fracture of at least 80%. The resulting parts can be nearly isotropic—having similar mechanical properties in the XY and Z printing directions. Excellent layer adhesion makes the resulting printed parts stronger - able to withstand many cycles of use. Certain polymers of the invention produce very low haze and nearly transparent printed parts. [0003] Background of the invention [0004] Advances in equipment and falling prices have made 3D printing widely used in homes, schools, and industry as an easy and often inexpensive shortcut to prototyping and manufacturing customer end-use parts. Specifically, material extrusion 3D printing (...
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