WARPAGE FREE 3D PRINTING OF POLYMERS

Abstract

A composition contains a blend of a primary polymer and a secondary polymer, an additive and an adhesive. The secondary polymer is less crystalline than the primary polymer, and the additive increases the melt viscosity of the blend. The composition can be used in 3D printing to result in reduced warping of polymers during 3D printing, especially when using lower polymers, such as, HDPE and LLDPE.

Claims

1. A composition for warpage-free 3D printing comprising a blend of: i. 98 to 99.8 parts of a semi-crystalline polymer and; ii. 0.2 to 2 parts of a nanofibrillar network forming additive.

2. The composition as claimed in claim 1, wherein the nanofibrillar network forming additive used is a sorbitol derivative, which dissolves into the semi-crystalline polymer above the melt temperature of the semi-crystalline polymer to form a nanofibrillar network.

3. The composition as claimed in claim 2, wherein the sorbitol derivative is selected from the group consisting of dimethyldibenzylidene sorbitol (DMDBS) and 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol sorbitol (NX 8000).

4. The composition as claimed in claim 1, wherein the semi-crystalline polymer is selected from the group consisting of High-Density Polyethylene (HDPE), Medium-Density Polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Polyoxymethylene (POM), isotactic Polypropylene (PP), a copolymer of Polypropylene (CP-PP), and an impact copolymer of polypropylene (IC-PP), either alone or combination thereof.

5. A process for warpage-free 3D printing comprising: preparing a blend of 98-99.8 parts of a semi-crystalline polymer and 0.2-2 parts of a nanofibrillar network forming additive; compounding the blend as obtained in step (a) above the melting temperature of the semi-crystalline polymer to obtain a uniform composition; extruding the composition as obtained in step (b) to obtain a constant diameter filament; using the filament as obtained in step (c) for the warpage-free 3D printing.

6. A warpage-free 3D printing system comprising: a blend of 98 to 99.8 parts of semi-crystalline polymer and 0.2-2.0 parts of a nanofibrillar network forming additive; and a 3D printer.

7. The warpage-free 3D printing system as claimed in claim 6, wherein the semi-crystalline polymer used comprises a combination of 5-15 parts of linear low density polyethylene (LLDPE) in High-Density Polyethylene (HDPE).

8. The warpage-free 3D printing system as claimed in claim 6, wherein the semi-crystalline polymer used is selected from the group consisting of Medium-Density Polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Polyoxymethylene (POM), isotactic Polypropylene (PP), copolymer of Polypropylene (CP-PP), and impact copolymer of polypropylene (IC-PP) either alone or combination thereof.

9. The warpage-free 3D printing system as claimed in claim 6, wherein the nanofibrillar network forming additive is a sorbitol derivative, wherein said sorbitol derivative dissolves into said polymer above the melt temperature of said polymer to form a nanofibrillar network.

10. The warpage-free 3D printing system as claimed in claim 9, wherein said sorbitol derivative is selected from the group consisting of dimethyldibenzylidene sorbitol (DMDBS) and 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol sorbitol (NX 8000).

11. (canceled)

Description

BRIEF DESCRIPTION OF DRAWINGS

[0026] FIG. 1 represents the change in complex viscosity of the polymer composition comprising HDPE and 0.4%, 0.8% and 1.6% dimethyldibenzylidene sorbitol respectively is cooled from 240 C.

[0027] FIG. 2(a) and FIG. 2(b) represents the final 3D print of objects using a polymer composition comprising 89.6% HDPE, 0.4% dimethyldibenzylidene sorbitol and 10% LLDPE, as described in Example 1.

[0028] FIG. 3 represents the change in complex viscosity as a polymer composition comprising 89.2% HDPE, 0.8% Millad NX 8000 and 10% LLDPE is cooled from 200 C. to 120 C.

[0029] FIG. 4 represents the final 3D print of a bar using a polymer composition comprising 89.2% HDPE, 0.8% Millad NX 8000 sorbitol and 10% LLDPE, as described in Example 2.

DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention discloses composition comprising a polymer with an additive that increases the melt viscosity of the polymer melt as it cools after it is extruded and before it can crystallize Further, in order to reduce the gap in modulus between melt and solid states of the polymer, the primary polymer is, optionally, blended with a secondary polymer. Furthermore, an adhesive is applied on a print substrate.

[0031] The polymer is a semicrystalline polyolefin selected from the group consisting of HDPE, LLDPE, Polypropylene (PP), Polyethylene (PE), and blends thereof.

[0032] Secondary polymer is less crystalline than the primary polymer.

[0033] The additive is selected from derivatives of sorbitol or nanofillers.

[0034] The nanofillers is selected from the group consisting of nanoclay, graphene, carbon nanotubes or any other such material.

[0035] The additive is preferably derivatives of sorbitol.

[0036] The additive is dimethyldibenzylidene sorbitol.

[0037] In one of the aspect, the polymer composition may be in the form of filament.

[0038] The polymer composition comprises a primary polymer present in an amount of 98-99.8%, and an additive present in an amount of 0.2-2%.

[0039] Present invention discloses a polymer composition that prevents warping in a 3D object printed by FDM technique, comprises a polymer and an additive that increases the melt viscosity of the polymer melt before crystallization.

[0040] The polymer composition comprises of a polymer and an additive, such that the additive is capable of forming a nanofibrillar network.

[0041] The polymer could be a single polymer or a combination of polymers. Said one or more polymer(s) could be selected from High-Density Polyethylene (HDPE), Medium-Density Polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Polyoxymethylene (POM), isotactic Polypropylene (PP), copolymer of Polypropylene (CP-PP) or impact copolymer of polypropylene (IC-PP).

[0042] The polymer could be a combination of a primary semi-crystalline polymer and a secondary semi-crystalline polymer such that, the secondary polymer has preferably less crystallinity than the primary polymer. For the purpose of this embodiment, the primary polymer forms majority component of the blend, constituting about 85-100 parts of the blend, while the secondary polymer constitutes a minority components of blend being present in range of 0-15 parts.

[0043] The primary semi-crystalline polymer is selected from High-Density Polyethylene (HDPE), Medium-Density Polyethylene (MDPE), or isotactic polypropylene and the secondary semi-crystalline polymer is selected from atactic polypropylene copolymer of Polypropylene (CP-PP) or Low density polyethylene (LDPE), Linear Low density polyethylene (LLDPE). Preferably the primary semi-crystalline polymer is High-Density Polyethylene (HDPE) and the secondary semi-crystalline polymer is Linear Low density polyethylene (LLDPE).

[0044] The additive of the composition of the present invention is selected from derivatives of sorbitol. Preferably, said sorbitol derivatives dissolve into the polymer melt at elevated temperature, typically above 190 C. and that precipitate to form a nanofibrillar network on cooling, at temperatures where the polymer is still molten. The nanofibrillar network formed by the additive increased the stiffness of the polymer thereby eliminating warping.

[0045] The additive is dimethyldibenzylidene sorbitol (DMDBS) which is a derivative of sorbitol. The said derivative of sorbitol increases the melt viscosity of the polymer melt before crystallization. This decreases the gap in modulus between the melt and solid states. The sorbitol derivative undergoes phase change from dissolved phase in polymer melt to a solid nanofibre network as the melt cools. This phase change of the additive helps in reducing warpage by increasing the modulus of the polymer melt.

[0046] Alternatively, the additive is 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol sorbitol (NX 8000), marketed as Millad NX 8000 by Milliken & Company. The NX 8000 increases the complex viscosity at about 160 C., above the polyethylene crystallization temperature. This increase is attributed to the formation of a reinforcing network of the Millad NX 8000 in the polyethylene melt. This reduced warpage in the printed material.

[0047] The composition of the invention further comprises of an adhesive. The adhesive, preferably, is a resin based adhesive, sold under brand name Fevistik by Pidilite Industries Ltd or any acrylic based adhesive. The adhesive maintains registry during the printing operation by adhering the printed part to the substrate and preventing it from moving.

[0048] The method of preparation of polymer composition of the invention comprises of: [0049] i. Preparing a mixture of a primary polymer, an additive, and, optionally, a secondary polymer; [0050] ii. Compounding in the DSM co-rotating twin screw microcompounder at a temperature above the polymer melting point, with screw speed of 100 rpm; [0051] iii. Mixing the composition for certain time; [0052] iv. Extruding the composition so as to obtain a constant diameter filament.

EXAMPLES

[0053] Following examples are given by way of illustration and therefore should not be construed to limit the scope of the invention.

[0054] The example below demonstrates the effectiveness of the polymer composition of the instant invention, wherein the primary polymer is HDPE, the secondary polymer is LLDPE and the additive is Dimethyldibenzylidene sorbitol. For the purpose of demonstration, HDPE of the polymer composition may be obtained from waste plastic bottle, such as brand Harpic bottle and Dimethyldibenzylidene sorbitol may be obtained from product called Millad 3988 by its tradename, manufactured by Milliken.

[0055] FIG. 1 illustrates the complex viscosity of HDPE containing 0.4%, 0.8% and 1.6% of dimethyldibenzylidene sorbitol (DMDBS), as a function of temperature. The viscosity does not increase at high temperature above that of the polyethylene melt, above 195 C., and increases only on cooling to lower temperatures.

Example 1

[0056] The polymer composition comprising HDPE present in amount of 89.6%, dimethyldibenzylidene sorbitol in amount of 0.4% and LLDPE present in amount of 10% was prepared. HDPE of the instant composition has MFI of 1, and with a DSC melting point of approximately 140 C. The composition was compounded in the DSM co-rotating twin screw microcompounder at 190 C. with screw speed of 100 rpm. The composition is mixed for 5 min to allow for efficient mixing and extruded thereafter in the form of strands which are pelletized manually.

[0057] With extrusion of the pelletized material, a filament with diameter 1.70 (0.05) mm is prepared at 190 C. through Gttfert Capillary Rheometer at a fixed speed which is optimised to provide a filament with a constant diameter of 1.75 mm (+/0.05 mm). The filament obtained in the said manner is wound on a spool which may be connected to the 3D printer.

[0058] The filament is loaded in Julia, an FDM based 3D printer of Fractal Works, and printed with following print parameters:

[0059] 1) Nozzle Diameter=0.4 mm

[0060] 2) Nozzle Temperature=190 C.

[0061] 3) Bed Temperature=60 C.

[0062] 4) Bottom Layer Thickness=0.3 mm

[0063] 5) Print Speed=45 mm/s

[0064] 6) Fill Density=20%

[0065] 7) Adhesion Assist: Thin layer of glue from a glue stick is applied on the bed for improved adhesion.

[0066] 8) Adhesion Assist: Brim=15 Lines

[0067] 9) Cooling Fan: Enabled at full after 0.5 mm

[0068] 3D objects printed with the instant invention, demonstrated in FIG. 2(a) & FIG. 2(b), are warpage-free.

[0069] The warpage is calculated using following formula:

[00001]$\mathrm{Warpage}=100-\frac{\mathrm{Lay}.Math..Math.\mathrm{flat}.Math..Math.\mathrm{Height}}{\mathrm{Thickness}}100$

[0070] A higher value indicates higher warping. A long, solid bar, having dimensions of x=50 mm, y=15 mm, z=10 mm is selected as the standard test part for the calculations of warpings. In the case of our test part (the long solid bar, that is most prone to warpage), the features which warp the most are the corners of the bar. Therefore, warping is calculated at the corner and that value is assigned to the part.

[0071] Warpage of standard test part printed with different compositions:

TABLE-US-00001 Neat 0.4% (DMDBS) + 0.4% (DMDBS) + 10% HDPE 99.6% HDPE LLDPE + 89.6% HDPE Warpage 9 6.3 0 Parameter

Example 2

[0072] A polymer composition comprising HDPE present in amount of 89.2%, commercial sorbitol derivative Millad NX 8000 in amount of 0.8% and LLDPE present in amount of 10% was prepared. HDPE of the instant composition has MFI of 1, and with a DSC melting point of approximately 140 C. The composition was compounded in the DSM co-rotating twin screw microcompounder at 190 C. with screw speed of 100 rpm. The composition is mixed for 5 min to allow for efficient mixing and extruded thereafter in the form of strands which are pelletized manually. A disk of 1 diameter is compression molded and is mounted in the rheometer (TA ARES-G2). Dynamic mechanical rheology is performed on this sample (1 rad/s at a strain amplitude of 1%) as the sample is cooled from the melt state (200 C.). The complex viscosity of the sample is recorded as a function of temperature. We observe that there is an increase in the complex viscosity at about 160 C., above the polyethylene crystallization temperature (FIG. 3). This increase is attributed to the formation of a reinforcing network of the Millad NX 8000 in the polyethylene melt.

[0073] With extrusion of the pelletized material, a filament with diameter 1.70 (0.05 mm) is prepared at 190 C. through Gttfert Capillary Rheometer at a fixed speed which is optimised to provide a filament with a constant diameter of 1.75 mm (0.05 mm). The filament obtained in the said manner is wound on a spool which may be connected to the 3D printer.

[0074] The filament is loaded in Julia, an FDM based 3D printer of Fractal Works, and printed with following print parameters:

[0075] 1) Nozzle Diameter=0.4 mm

[0076] 2) Nozzle Temperature=190 C.

[0077] 3) Bed Temperature=60 C.

[0078] 4) Bottom Layer Thickness=0.3 mm

[0079] 5) Print Speed=45 mm/s

[0080] 6) Fill Density=20%

[0081] 7) Adhesion Assist: Thin layer of PVA based glue is applied on the bed for improved adhesion.

[0082] 8) Adhesion Assist: Brim=15 Lines

[0083] 9) Cooling Fan: Enabled at full after 0.5 mm

[0084] 3D objects printed with the instant invention, demonstrated in FIG. 4, are warpage-free.

[0085] The warpage is calculated using following formula:

[00002]$\mathrm{Warpage}=100-\frac{\mathrm{Lay}.Math..Math.\mathrm{flat}.Math..Math.\mathrm{Height}}{\mathrm{Thickness}}100$

[0086] A higher value indicates higher warping. A long, solid bar, having dimensions of x=50 mm, y=15 mm, z=10 mm is selected as the standard test part for the calculations of warpings. In the case of our test part (the long solid bar, that is most prone to warpage), the features which warp the most are the corners of the bar. Therefore, warping is calculated at the corner and that value is assigned to the part. For this part, the warpage calculated is 0.

Example 3

[0087] The polymer composition comprising PP (grade name: 4481WZ obtained from Total) present in amount of 99.2% and dimethyldibenzylidene sorbitol in amount of 0.8% was prepared. PP of the instant composition has MFI of 4, and with a DSC melting point of approximately 160 C. The composition was compounded in the DSM co-rotating twin screw microcompounder at 230 C. with screw speed of 100 rpm. The composition is mixed for 5 min to allow for efficient mixing and extruded thereafter in the form of strands which are pelletized manually.

[0088] With extrusion of the pelletized material, a filament with diameter 1.70 (0.05) mm is prepared at 190 C. through Gttfert Capillary Rheometer at a fixed speed which is optimised to provide a filament with a constant diameter of 1.75 mm (+/ 0.05 mm). The filament obtained in the said manner is wound on a spool which may be connected to the 3D printer.

[0089] The filament is loaded in Julia, an FDM based 3D printer of Fractal Works, and printed with following print parameters:

[0090] 1) Nozzle Diameter=0.4 mm

[0091] 2) Nozzle Temperature=230 C.

[0092] 3) Bed Temperature=60 C.

[0093] 4) Bottom Layer Thickness=0.3 mm

[0094] 5) Print Speed=40 mm/s

[0095] 6) Fill Density=20%

[0096] 7) Adhesion Assist: Thin layer of glue from a glue stick is applied on the bed for improved adhesion.

[0097] 8) Adhesion Assist: Brim=15 Lines

[0098] 9) Cooling Fan: Enabled at full after 0.5 mm

[0099] Warpage is calculated using following formula:

[00003]$\mathrm{Warpage}=100-\frac{\mathrm{Lay}.Math..Math.\mathrm{flat}.Math..Math.\mathrm{Height}}{\mathrm{Thickness}}100$

[0100] A higher value indicates higher warping. A long, solid bar, having dimensions of x=50 mm, y=15 mm, z=10 mm is selected as the standard test part for the calculations of warping. In the case of our test part (the long solid bar, that is most prone to warpage), the features which warp the most are the corners of the bar. Therefore, warping is calculated at the corner and that value is assigned to the part.

[0101] Warpage of standard test part printed with above composition:

TABLE-US-00002 0.8% (DMDBS) + 99.2% PP (4481WZ) Warpage Parameter 0.8

Example 4

[0102] The polymer composition comprising HDPE present in amount of 89.6%, calcium hexahydrophthalic acid (HPN 20E) in amount of 0.4% and LLDPE present in amount of 10% was prepared. HDPE of the instant composition has MFI of 1, and with a DSC melting point of approximately 140 C. The composition was compounded in the DSM co-rotating twin screw micro-compounder at 190 C. with screw speed of 100 rpm. The composition is mixed for 5 min to allow for efficient mixing and extruded thereafter in the form of strands which are pelletized manually.

[0103] With extrusion of the pelletized material, a filament with diameter 1.70 (0.05) mm is prepared at 190 C. through Gttfert Capillary Rheometer at a fixed speed which is optimised to provide a filament with a constant diameter of 1.75 mm (+/0.05 mm). The filament obtained in the said manner is wound on a spool which may be connected to the 3D printer.

[0104] The filament is loaded in Julia, an FDM based 3D printer of Fractal Works, and printed with following print parameters:

[0105] 1) Nozzle Diameter=0.6 mm

[0106] 2) Nozzle Temperature=230 C.

[0107] 3) Bed Temperature=60 C.

[0108] 4) Bottom Layer Thickness=0.3 mm

[0109] 5) Print Speed=30 mm/s

[0110] 6) Fill Density=20%

[0111] 7) Adhesion Assist: Thin layer of glue from a glue stick is applied on the bed for improved adhesion.

[0112] 8) Adhesion Assist: Brim=15 Lines

[0113] 9) Cooling Fan: Enabled at full after 0.5 mm

[0114] The warpage is calculated using following formula:

[00004]$\mathrm{Warpage}=100-\frac{\mathrm{Lay}.Math..Math.\mathrm{flat}.Math..Math.\mathrm{Height}}{\mathrm{Thickness}}100$

[0115] A higher value indicates higher warping. A long, solid bar, having dimensions of x=50 mm, y=15 mm, z=10 mm is selected as the standard test part for the calculations of warping. In the case of our test part (the long solid bar, that is most prone to warpage), the features which warp the most are the corners of the bar. Therefore, warping is calculated at the corner and that value is assigned to the part.

[0116] Warpage of standard test part printed with different compositions:

TABLE-US-00003 Neat 0.4% (HPN 20E) + 10% HDPE LLDPE + 89.6% HDPE Warpage Parameter 9 7.2

[0117] This can be contrasted to the case of the composition containing 0.4% Millad 3988 (dimethyldibenzylidene sorbitol), 10% LLDPE and 89.6% HDPE. The warpage parameter during 3D printing of the standard test part was 0. In general, we define low warpage as systems where printing of the standard test part yields a warpage parameter less than 1.

Advantages of the Invention

[0118] Warp-free 3D printing of semicrystalline polymer objects.