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A 3 D Printable Polypropylene Composition And A Process For Preparing 3 D Printable Polypropylene Filament

Abstract: The process for preparing 3D printable polypropylene filament comprises melt-mixing 20-100wt% of Propylene ethylene block co-polymer, 30-40wt% of Propylene ethylene hetrophasic copolymer, 15-25wt% of Polypropylene Homopolymer, 20-30wt% of Calcium Carbonate M/B, 5-15wt% of Elastomer -G-MA, 0-2wt% of ZnO, 1-5wt% of PP -g – MA, 2-5wt% of Anhydride modified isotactic propylene based metallocene elastomer, 10-15wt% of Propylene-based olefinic elastomer, 5-10wt% of Glass Fiber, 0-1wt% of Phenolic antioxidants, Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and 0-1wt% of Tris(2,4-ditert-butylphenyl) phosphite with phenolic and phosphite antioxidants (1:2 ratio) along with reinforcement, polymer & compatibilizers; pelletizing the compounded materials and drying at 80°C in vacuum oven for overnight; preparing test specimen using injection molding machine of 80-ton capacity after compounding at a user defined process parameters; and converting the compound formulation into filament of 2.85mm diameter using a vertical extruded Filament Maker and performing 3D printing using the formulations through an Ultimaker 3D-printing machine.

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Notices, Deadlines & Correspondence

Patent Information

Application #
Filing Date
17 June 2023
Publication Number
51/2024
Publication Type
INA
Invention Field
POLYMER TECHNOLOGY
Status
Email
Parent Application

Applicants

HPCL-MITTAL ENERGY LTD.
CUSTOMER SERVICES & DEVELOPMENT CENTER, PLOT A27, SECTOR 65, GAUTAM BUDDHA NAGAR, NOIDA- 201301, UTTAR PRADESH, India

Inventors

1. PRIYANKA SINGH
CUSTOMER SERVICES & DEVELOPMENT CENTER, PLOT A27, SECTOR 65, GAUTAM BUDDHA NAGAR, NOIDA- 201301, UTTAR PRADESH, India
2. SAIKAT BANERJEE
CUSTOMER SERVICES & DEVELOPMENT CENTER, PLOT A27, SECTOR 65, GAUTAM BUDDHA NAGAR, NOIDA- 201301, UTTAR PRADESH, India
3. VINEET KUMAR GUPTA
CUSTOMER SERVICES & DEVELOPMENT CENTER, PLOT A27, SECTOR 65, GAUTAM BUDDHA NAGAR, NOIDA- 201301, UTTAR PRADESH, India

Specification

Description:FIELD OF THE INVENTION The present disclosure relates to development of 3D Printable Polypropylene Formulations. In more detail, a 3D printable polypropylene composition and a process for preparing 3D printable polypropylene filament. BACKGROUND OF THE INVENTION Fused deposition modelling (FDM) is one of the most evolved 3D printing processes globally. FDM method is the most accepted 3D printing technique for it’s simple and economic process considering both tools and material associated. It is also known as Fuse filament fabrication. This process prints any 3D printing objects layer by layer. Material deposits in each layer through a nozzle which is again fed in the form of filament. These filaments for 3D printing are made of different polymers. Common polymers for FDM based 3D printing process are PLA, Polyamide, Polycarbonate, ABS etc. Although polypropylene (PP) based material is in use, but there is scarcity of PP availability with good 3D printability. PP exhibits a number of advantages over other 3D printable materials like low moisture absorption, low density, excellent layer adhesion and excellent flexibility. In addition, PP requires low printing temperature (200 -230?) and low build plate temperature (60-80?). However, there are challenges associated with printability of polypropylene. The normal Bowden extruder & direct drive extruders face difficulties while pushing PP filament through nozzle due to uneven filament diameter. Polypropylene shows differential shrinkage leading to warpage in 3D printed part. The main reason behind difficulties faced during 3D printing of PP in FDM process is its inherent volumetric shrinkage behaviour. Volumetric shrinkage & warpage behaviour is shown by semicrystalline material like PP. The defect is strongly dependent on shape and size of printing object. The effect of warpage and shrinkage will be more for 3D printing object of bigger size and shape. For commercial suitability, cost of material also plays a very important role. Hence, to address these issues, in this present invention, PP is selected as a base material and further modified to increase the atactic content, reduce the shrinkage as well as the differential shrinkage induced warpage. Functional polymer is also introduced to enhance the compatibility between polypropylene and inorganic reinforcement. In the view of the forgoing discussion, it is clearly portrayed that there is a need to have a 3D printable polypropylene composition and a process for preparing 3D printable polypropylene filament. SUMMARY OF THE INVENTION The present disclosure seeks to provide an economical process for preparing 3D printable polypropylene filament using a 3D printable polypropylene composition for printing 3D designs. In an embodiment, a 3D printable polypropylene composition is disclosed. The composition includes 20-100 wt% of Propylene ethylene block co-polymer; 30-40 wt% of Propylene ethylene hetrophasic copolymer; 15-25 wt% of Polypropylene Homopolymer; 20-30 wt% of Calcium Carbonate M/B; 5-15 wt% of Elastomer -G-MA; 0-2 wt% of ZnO; 1-5 wt% of PP -g – MA; 2-5 wt% of Anhydride modified isotactic propylene based metallocene elastomer; 10-15 wt% of Propylene-based olefinic elastomer; 5-10 wt% of Glass Fiber; 0-1 wt% of Phenolic antioxidants, Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate; and 0-1 wt% of Tris(2,4-ditert-butylphenyl) phosphite. In another embodiment, a process for preparing 3D printable polypropylene filament is disclosed. The process includes melt-mixing 20-100 wt% of Propylene ethylene block co-polymer, 30-40 wt% of Propylene ethylene hetrophasic copolymer, 15-25 wt% of Polypropylene Homopolymer, 20-30 wt% of Calcium Carbonate M/B, 5-15 wt% of Elastomer -G-MA, 0-2 wt% of ZnO, 1-5 wt% of PP -g – MA, 2-5 wt% of Anhydride modified isotactic propylene based metallocene elastomer, 10-15 wt% of Propylene-based olefinic elastomer, 5-10 wt% of Glass Fiber, 0-1 wt% of Phenolic antioxidants, Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and 0-1 wt% of Tris(2,4-ditert-butylphenyl) phosphite with phenolic and phosphite antioxidants (1:2 ratio) along with reinforcement, polymer & compatibilizers. The process further includes pelletizing the compounded materials and drying at 80°C in vacuum oven for overnight. The process further includes preparing test specimen using injection molding machine of 80-ton capacity after compounding at a user defined process parameters. The process further includes converting the compound formulation into filament of 2.85 mm diameter using a vertical extruded Filament Maker and performing 3D printing using the formulations through an Ultimaker 3D printing machine using a process parameter. An object of the present disclosure is to develop 3D Printable Polypropylene Formulations. Another object of the present disclosure is to make cost effective 3D printable polypropylene grades for different application like biomedical, automotive, prototyping and the like. Yet another object of the present invention is to deliver an expeditious and cost-effective process for preparing 3D printable polypropylene filament. To further clarify advantages and features of the present disclosure, a more particular description of the invention will be rendered by reference to specific embodiments thereof, which is illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail with the accompanying drawings. BRIEF DESCRIPTION OF FIGURES These and other features, aspects, and advantages of the present disclosure will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein: Figure 1 illustrates a flow chart of a process for preparing 3D printable polypropylene filament in accordance with an embodiment of the present disclosure; Figure 2 illustrates Table 1 depicts sample description of PP formulations in accordance with an embodiment of the present disclosure; Figure 3 illustrates Table 2 depicts chemicals and materials used in accordance with an embodiment of the present disclosure; Figure 4 illustrates Table 3 depicts process parameters of Injection Moulding in accordance with an embodiment of the present disclosure; Figure 5 illustrates a graph of tensile properties of developed PP formulations in accordance with an embodiment of the present disclosure; Figure 6 illustrates a graph of flexural properties of developed PP formulations in accordance with an embodiment of the present disclosure; Figure 7 illustrates a graph of impact properties of developed PP formulations in accordance with an embodiment of the present disclosure; Figure 8 illustrates Table 4 depicts process parameters of 3D printing in accordance with an embodiment of the present disclosure; Figure 9 illustrates differential shrinkage of PP formulations in accordance with an embodiment of the present disclosure; Figure 10 illustrates Table 5 depicts 3D printability of PP compositionsin accordance with an embodiment of the present disclosure; Figure 11 illustrates a graph of Differential shrinkage of PP compositions in accordance with an embodiment of the present disclosure; and Figure 12 illustrates exemplary profiles of 3D moulding in accordance with an embodiment of the present disclosure. Further, skilled artisans will appreciate that elements in the drawings are illustrated for simplicity and may not have necessarily been drawn to scale. For example, the flow charts illustrate the method in terms of the most prominent steps involved to help to improve understanding of aspects of the present disclosure. Furthermore, in terms of the construction of the device, one or more components of the device may have been represented in the drawings by conventional symbols, and the drawings may show only those specific details that are pertinent to understanding the embodiments of the present disclosure so as not to obscure the drawings with details that will be readily apparent to those of ordinary skill in the art having benefit of the description herein. DETAILED DESCRIPTION: For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated system, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates. It will be understood by those skilled in the art that the foregoing general description and the following detailed description are exemplary and explanatory of the invention and are not intended to be restrictive thereof. Reference throughout this specification to “an aspect”, “another aspect” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Thus, appearances of the phrase “in an embodiment”, “in another embodiment” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment. The terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process or method that comprises a list of steps does not include only those steps but may include other steps not expressly listed or inherent to such process or method. Similarly, one or more devices or sub-systems or elements or structures or components proceeded by "comprises...a" does not, without more constraints, preclude the existence of other devices or other sub-systems or other elements or other structures or other components or additional devices or additional sub-systems or additional elements or additional structures or additional components. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The system, methods, and examples provided herein are illustrative only and not intended to be limiting. Embodiments of the present disclosure will be described below in detail with reference to the accompanying drawings. In an embodiment, a 3D printable polypropylene composition is disclosed. The composition includes 20-100 wt% of Propylene ethylene block co-polymer; 30-40 wt% of Propylene ethylene hetrophasic copolymer; 15-25 wt% of Polypropylene Homopolymer; 20-30 wt% of Calcium Carbonate M/B; 5-15 wt% of Elastomer -G-MA; 0-2 wt% of ZnO; 1-5 wt% of PP -g – MA; 2-5 wt% of Anhydride modified isotactic propylene based metallocene elastomer; 10-15 wt% of Propylene-based olefinic elastomer; 5-10 wt% of Glass Fiber; 0-1 wt% of Phenolic antioxidants, Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate; and 0-1 wt% of Tris(2,4-ditert-butylphenyl) phosphite. In one embodiment, the composition includes RICCPOE, RCCMZN, RCCVN, RGFM, and R, wherein the weight percentage of the RICCPOE includes Propylene ethylene block co-polymer, Propylene ethylene hetrophasic copolymer, Calcium Carbonate M/B, Elastomer -G-MA, Phenolic antioxidants Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and Tris(2,4-ditert-butylphenyl) phosphite is, 29.7%, 35%, 25%, 10%, 0.1%, and 0.2%, respectively. In one embodiment, the weight percentage of the RCCMZN includes Propylene ethylene block co-polymer, Calcium Carbonate M/B, ZnO, PP -g – MA, Phenolic antioxidants Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and Tris(2,4-ditert-butylphenyl) phosphite is, 71.7%, 25%, 1%, 2%, 0.1%, and 0.2%, respectively, wherein the weight percentage of the RCCVN includes Propylene ethylene block co-polymer, Calcium Carbonate M/B, Anhydride modified isotactic propylene based metallocene elastomer, Propylene-based olefinic elastomer, Phenolic antioxidants Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and Tris(2,4-ditert-butylphenyl) phosphite is, 59.7%, 25%, 3%, 12%, 0.1%, and 0.2%, respectively. In one embodiment, the weight percentage of the RGFM includes Propylene ethylene block co-polymer, Polypropylene Homopolymer, PP -g – MA, Glass Fiber, Phenolic antioxidants Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and Tris(2,4-ditert-butylphenyl) phosphite is, 69.7%, 20%, 3%, 7%, 0.1%, and 0.2%, respectively, wherein the weight percentage of the R includes Propylene ethylene block co-polymer, Phenolic antioxidants, Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and Tris(2,4-ditert-butylphenyl) phosphite is, 99.7%, 0.1%, and 0.2%, respectively. Referring to Figure 1, a flow chart of a process for preparing 3D printable polypropylene filament is illustrated in accordance with an embodiment of the present disclosure. At step 102, process 100 includes melt-mixing 20-100 wt% of Propylene ethylene block co-polymer, 30-40 wt% of Propylene ethylene hetrophasic copolymer, 15-25 wt% of Polypropylene Homopolymer, 20-30 wt% of Calcium Carbonate M/B, 5-15 wt% of Elastomer -G-MA, 0-2 wt% of ZnO, 1-5 wt% of PP -g – MA, 2-5 wt% of Anhydride modified isotactic propylene based metallocene elastomer, 10-15 wt% of Propylene-based olefinic elastomer, 5-10 wt% of Glass Fiber, 0-1 wt% of Phenolic antioxidants, Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate, and 0-1 wt% of Tris(2,4-ditert-butylphenyl) phosphite with phenolic and phosphite antioxidants (1:2 ratio) along with reinforcement, polymer & compatibilizers. At step 104, process 100 includes pelletizing the compounded materials and drying at 80°C in vacuum oven for overnight;. At step 106, process 100 includes preparing test specimen using injection molding machine of 80-ton capacity after compounding at a user defined process parameter. At step 108, process 100 includes converting the compound formulation into filament of 2.85 mm diameter using a vertical extruded Filament Maker and performing 3D printing using the formulations through an Ultimaker 3D printing machine using a process parameter. In another embodiment, the melt mixing is performed in co-rotating twin screw extruder, with a screw diameter of 25mm and L/D ratio of 32, wherein temperature profile during extrusion is kept at 180-210°C with 15 kg/h throughput and screw speed of 300 rpm which results 61-64% of torque. In another embodiment, the PP random copolymer is used as base resin with high atactic content in comparison to PP homopolymer to minimize the effect of crystallization, and random copolymer is chosen to promote further layer by layer adhesion and reduce overall volumetric shrinkage related issues, and Calcium carbonate is chosen as inorganic filler to reinforce the base matrix and reduce the differential shrinkage related issue and increase the mechanical properties of the polymer, and Maleic anhydride grafted polypropylene is used as a compatibilizer to improve interaction between base resin and the inorganic filler for better dispersion. In another embodiment, the user defined process parameters are selected from 190-220oC temperature profile, 65 bar injection pressure, 30mm/s injection speed, 18s injection time, 50s total cycle time, 65 bar hold on pressure, 18s holding time, and 28mm/s holding speed. In another embodiment, the temperature profile for different zones of filament maker is selected from Z1 -150°C, Z2 -185°C, Z3 -195°C, Z4 -185°C, Z5 -175°C and Screw Speed of the filament maker is kept at 8 rpm with fan cooling with ambient air. In another embodiment, the process parameter is selected from 150 µm Layer Resolution, 100% Infill percentage, Triangle Infill pattern, Polypropylene Material Profile, 215? Printing Temperature, 95? Build Plate Temperature, Magigoo PP Build Plate adhesion, Glass bed Surface Build Plate adhesion, 35 mm/s Printing Speed, 20% Cooling Fan Speed, 0.4 mm Nozzle Diameter, Ultimaker S5 3D printer, and ASTM D638 Type-V Printing orientation. Isotactic PP, being a semicrystalline material, faces issues like shrinkage and warpage of the filament and 3D printed part while cooling. Hence, to minimize the effect of crystallization, PP random copolymer is used as base resin with high atactic content in comparison to PP homopolymer. Random copolymer is also chosen to promote further layer by layer adhesion and reduce overall volumetric shrinkage related issues. Calcium carbonate is chosen as inorganic filler to reinforce the base matrix and reduce the differential shrinkage related issue as well as increase the mechanical properties of the polymer. Maleic anhydride grafted polypropylene is used as a compatibilizer to improve interaction between base resin and the inorganic filler for better dispersion. Figure 2 illustrates Table 1 depicts sample description of PP formulations in accordance with an embodiment of the present disclosure. To improve 3D printability of polypropylene, different approaches has been established. In this invention, a cost effect novel approach has been introduced based on reinforced and compatibilized PP random copolymer. Five different formulations have been made and summarized in Table 1. Figure 3 illustrates Table 2 depicts chemicals and materials used in accordance with an embodiment of the present disclosure. Compounding: All the formulations are melted mixed with phenolic and phosphite antioxidants (1:2 ratio) along with reinforcement, polymer & compatibilizers. Melt mixing is performed in co-rotating twin screw extruder, with a screw diameter of 25mm and L/D ratio of 32. Temperature profile during extrusion is kept at 180-210°C with 15 kg/h throughput and screw speed of 300 rpm which results 61-64% of torque. The compounded materials is pelletized. Figure 4 illustrates Table 3 depicts process parameters of Injection Moulding in accordance with an embodiment of the present disclosure. Test specimens are prepared using injection moulding machine of 80-ton capacity after compounding. Before moulding, the compounded polypropylene pellets are dried at 80°C in vacuum oven for overnight. Injection moulding is performed using parameters as summarized in Table 3. Figure 5 illustrates a graph of tensile properties of developed PP formulations in accordance with an embodiment of the present disclosure. All specimens are conditioned as per ASTM D618 at 23±2°C and 50±10% RH for at least 40 h prior to testing. All formulations are tested for tensile, flexural and impact properties. Heat deflection temperature (HDT) of all the specimens is evaluated. RGFM which is glass filled formulation shows high strength i.e., 35 MPa and 1519 MPa flexural modulus (stiffness) along with low elongation. Formulations like RICCPOE, RCCMZN and RCCVN shows tensile strength around 20 to 28 MPa while composition R which is a stabilized random copolymer, shows tensile strength more than 30 MPa. All the formulations have elongation higher than 250%. Formulation RCCVN shows highest elongation more than 500% which indicates good stretchability. RICCPOE, RCCMZN and RCCVN exhibits relatively lower flexural modulus (stiffness) and higher impact & elongation, which indicates improved softness, toughness and stretchability of those formulations which is a prerequisite for 3D printability. Figure 6 illustrates a graph of flexural properties of developed PP formulations in accordance with an embodiment of the present disclosure. Figure 7 illustrates a graph of impact properties of developed PP formulations in accordance with an embodiment of the present disclosure. Preparation of Filament: All the compounded formulation are converted to filament of 2.85 mm diameter using vertical extruded VFX 3030 PRO-Lab 3D Filament Maker. Process parameters used in VFX 3D Filament Maker to Make 3D Filament(Lab scale trial). Temperature profile for different zones of filament maker is as below: Zone Temperature: Z1 -150°C, Z2 -185°C, Z3 -195°C, Z4 -185°C, Z5 -175°C Screw Speed of the filament maker is kept at 8 rpm with fan cooling with ambient air. Figure 8 illustrates Table 4 depicts process parameters of 3D printing in accordance with an embodiment of the present disclosure. 3D Printing using the Filament: 3D printing of all the developed formulations is carried out with Ultimaker 3D printing machine. Tensile specimen as per ASTM D638, Type-V is prepared from injection moulding as well as 3D printing for a comparative study to evaluate the performance of the developed formulations. Process Parameter for 3D printing is mentioned in Table 4. Figure 9 illustrates differential shrinkage of PP formulations in accordance with an embodiment of the present disclosure. During 3D printing, the Brim is not removed in the specimens as retaining the brim around the specimen helps in analysing part warpage visually. Although, the brim is removed before tensile testing. Visual Warpage is accessed by maximum contact on surface. Order of warpage performance as below. Left side is lower warpage and right side is higher warpage. RCCVN

Documents

Application Documents

# Name Date
1 202311041326-STATEMENT OF UNDERTAKING (FORM 3) [17-06-2023(online)].pdf 2023-06-17
2 202311041326-FORM 1 [17-06-2023(online)].pdf 2023-06-17
3 202311041326-FIGURE OF ABSTRACT [17-06-2023(online)].pdf 2023-06-17
4 202311041326-DRAWINGS [17-06-2023(online)].pdf 2023-06-17
5 202311041326-DECLARATION OF INVENTORSHIP (FORM 5) [17-06-2023(online)].pdf 2023-06-17
6 202311041326-COMPLETE SPECIFICATION [17-06-2023(online)].pdf 2023-06-17
7 202311041326-Proof of Right [20-07-2023(online)].pdf 2023-07-20
8 202311041326-FORM-26 [26-07-2023(online)].pdf 2023-07-26
9 202311041326-FORM 18 [04-08-2023(online)].pdf 2023-08-04
10 202311041326-FORM-8 [22-03-2025(online)].pdf 2025-03-22