Modified nylon alloy material for 3D printing and application thereof

Abstract

The present application relates to a kind of modified nylon alloy material and preparation method thereof for 3D printing.The modified nylon alloy material is composed of the following components by mass percentage: nylon resin 30.0-65.0 %, amorphous resin 5.0-40.0 %, carbon fiber 10.0-25.0 %, compatibilizer 3.0-7.0 %, inorganic mineral filler 10.0-25.0 %, antioxidant 0.2-0.5 %, lubricant 0.5-1.0 %, and other processing aids 0.2-1.0 %; the sum of the above-mentioned component mass percentages is 100%.The present application is prepared by melt extrusion molding to produce a modified nylon alloy material for 3D printing, which can be applied to 3D printing, including fused deposition (FDM) and laser sintering (SLS), and can be machined to size according to product requirements, which can be used for customized tools, household appliance accessories and other applications.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer composite materials, specifically relating to a modified nylon alloy material that can be used for 3D printing and its applications. Background Technology

[0002] 3D printing technology, or additive manufacturing technology, integrates multiple disciplines such as computer software, mathematics, mechanical automation, materials science, and design. 3D printing boasts advantages such as low cost, a wide variety of formable shapes, energy efficiency, environmental friendliness, and short production cycles, making it significant for the development of manufacturing, aerospace, automotive, and robotics industries. However, printing consumables are one of the major issues limiting the development of 3D printing. Compared to traditional metals and inorganic non-metallic materials, polymer materials offer advantages such as light weight, low cost, ease of processing and molding, superior performance, and ease of adjustment, making them of great research and application value in the field of 3D printing.

[0003] Polyamide (PA), commonly known as nylon, is obtained by the condensation polymerization of diacids and diamines or amino acids. It possesses excellent mechanical properties, resistance to high and low temperatures, chemical resistance, abrasion resistance, and processability, and is widely used in electronics, office supplies, sporting goods, textile accessories, home appliances, and automobiles. Nylon's good processing fluidity and rigidity also enable its application in 3D printing.

[0004] Due to its high crystallinity, nylon exhibits significant shrinkage during molding, leading to warping after molding. This is typically mitigated by adding low-anisotropic fillers or combining it with amorphous materials. For example, Chinese patent CN106433108A discloses a high-temperature resistant nylon filament for 3D printing. This filament is prepared by intercalating organically modified montmorillonite with nylon resin using a melt-blending intercalation method, enhancing the material's mechanical properties and heat distortion temperature. Furthermore, adjusting the formulation improves shrinkage and molding accuracy. The resulting high-temperature resistant nylon filament is suitable for general functional parts, meeting the requirements of fused deposition modeling. Another example is Chinese patent CN109880358A, which utilizes PETG and compatibilizers in synergistic action with inorganic fillers to significantly reduce the warping of PA materials in FDM 3D printing, preparing a low-warping reinforced PA material. However, these methods can reduce the material's mechanical properties, and many applications, especially 3D printing, require materials with excellent overall performance to suit diverse application scenarios. Therefore, developing a modified nylon material with excellent physical and mechanical properties, low warpage, low shrinkage, and other functionalities has significant technological value and application prospects. Summary of the Invention

[0005] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide a modified nylon alloy material suitable for 3D printing. This material not only possesses excellent physical and mechanical properties, good dimensional stability, low warpage, and low density, but also exhibits excellent wear resistance and antistatic properties. This invention utilizes an amorphous second substrate (amorphous resin) blended with nylon resin to reduce the molding shrinkage rate and achieve low warpage, and further enhances the overall performance of the material by adding compatibilizers, carbon fibers, inorganic minerals, and other additives. A second objective of this invention is to provide applications for the aforementioned modified nylon alloy material suitable for 3D printing.

[0006] The primary objective of this invention is achieved through the following technical solution:

[0007] A modified nylon alloy material suitable for 3D printing, comprising the following components by mass percentage:

[0008] Nylon resin 30.0–65.0%

[0009] Amorphous resin 5.0–40.0%

[0010] Carbon fiber 10.0–25.0%

[0011] Compatibilizer 3.0–7.0%

[0012] Inorganic mineral fillers 10.0–25.0%

[0013] Antioxidant 0.2-0.5%

[0014] Lubricant 0.5-1.0%

[0015] Other processing aids: 0.2–1.0%;

[0016] The sum of the mass percentages of the above components is 100%.

[0017] Preferably, the nylon resin of the present invention is at least two of nylon 6, nylon 66, nylon 12, nylon 612, nylon 1010, and nylon 1012, and the relative viscosity of the nylon resin is 2.0-3.2.

[0018] Preferably, the amorphous resin of the present invention is at least one of acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polycarbonate (PC), or polyethylene terephthalate-1,4-cyclohexanediethanol ester (PETG).

[0019] Preferably, the amorphous resin is acrylonitrile-butadiene-styrene copolymer (ABS), which is a high-strength, tough, and easily processed thermoplastic polymer. ABS retains the excellent electrical properties and easy processing of styrene, while also improving elasticity, strength (characteristics of butadiene), heat resistance, and corrosion resistance (excellent properties of acrylonitrile). It also has high surface hardness and good chemical resistance. Furthermore, as an amorphous material, it has low molding shrinkage, making it a commonly used material for 3D printing. The PA / ABS alloy obtained by blending it with nylon combines the advantages of both PA and ABS, and can reduce the warpage of the alloy material.

[0020] Preferably, the carbon fiber of the present invention is treated with a coupling agent and has a single filament diameter in the range of 5-10 μm.

[0021] Preferably, the compatibilizer of the present invention is at least one selected from acrylonitrile-butadiene-styrene copolymer grafted with maleic anhydride (ABS-g-MAH), polypropylene grafted with maleic anhydride (PP-g-MAH), polyethylene grafted with maleic anhydride (PE-g-MAH), acrylonitrile-styrene-methacrylic acid copolymer (ASM), and polyolefin elastomer grafted with maleic anhydride (POE-g-MAH).

[0022] Preferably, the compatibilizer is an acrylonitrile-butadiene-styrene copolymer grafted with maleic anhydride (ABS-g-MAH) and an acrylonitrile-styrene-methacrylic acid copolymer (ASM).

[0023] Preferably, the inorganic mineral filler of the present invention is at least one of calcium carbonate, precipitated barium sulfate, talc, hollow glass microspheres, mica, wollastonite, montmorillonite, or kaolin.

[0024] Preferably, the inorganic mineral filler is at least one of hollow glass microspheres, wollastonite, or talc.

[0025] Preferably, the antioxidant of the present invention is at least one of hindered phenolic antioxidants, thioester antioxidants, phosphite antioxidants, and ester antioxidants.

[0026] Preferably, the lubricant of the present invention is at least one of low molecular weight polymer wax and silicone masterbatch.

[0027] Preferably, the other processing aids described in this invention are any aids suitable for nylon, such as nucleating agents, processing flow aids, etc.

[0028] Preferably, the preparation method of the modified nylon alloy material for 3D printing according to the present invention includes the following steps:

[0029] (1) Add nylon resin, amorphous resin, compatibilizer, antioxidant, lubricant and processing aid to a mixer in proportion and mix them evenly to prepare a mixture;

[0030] (2) The mixture obtained in step (1) is added from the main feed port of the twin-screw extruder and melt-extruded into granules. The temperature of each section of the twin-screw extruder is set to 180℃, 230℃, 250℃, 250℃, 260℃, 250℃, 230℃, 220℃, 220℃, the die head temperature is 260℃, and the screw speed is 300-600 rpm.

[0031] (3) Carbon fiber and inorganic mineral filler are added from both sides of the feed port for extrusion melt blending. The side feed ports are set in the third and fifth sections of the extruder barrel, respectively, and the feed is metered according to the ratio.

[0032] (4) The raw materials of the formulation system are melted, extruded, cooled, air-dried, pelletized, vibrated and sieved, and homogenized to prepare modified nylon alloy materials that can be used for 3D printing.

[0033] In step (1), the mixing refers to high-speed mixing at 800-1500 rpm for 2-5 minutes, with the temperature of the mixer at 55-65℃.

[0034] The second objective of this invention is achieved through the following technical solution:

[0035] Application of a modified nylon alloy material for 3D printing in fused deposition modeling (FDM) and laser sintering (SLS).

[0036] Specifically, the modified nylon alloy material that can be used for 3D printing is applied in customized tools and household appliance accessories.

[0037] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0038] (1) This invention uses alloying of amorphous resin and nylon resin and inorganic mineral filler to effectively reduce warpage, enabling nylon alloys to be used in 3D printing, including fused deposition modeling (FDM) and laser sintering (SLS).

[0039] (2) The addition of compatibilizer can effectively increase the compatibility of nylon alloy components, thereby ensuring the improvement of the performance of nylon alloy materials;

[0040] (3) The addition of carbon fiber can effectively improve the wear resistance and antistatic properties of nylon alloy materials, and make the material lightweight while maintaining its mechanical properties, making it suitable for applications such as tools and household appliance accessories that require customization. Detailed Implementation

[0041] The present invention will be further described in detail below with reference to embodiments, but the embodiments of the present invention are not limited thereto. All raw materials involved in the present invention can be purchased directly from the market. For process parameters not specifically specified, conventional techniques can be referred to.

[0042] The raw materials used in Examples 1 to 7 and Comparative Examples 1 to 3 of the present invention are as follows:

[0043] Nylon resin: PA6, M2400, Xinhui Meida Company;

[0044] Amorphous resin: ABS, 0215A, Jilin Petrochemical Jieyang Production Base;

[0045] Carbon fiber, CFUW-MC C-6, Toray Industries, Japan;

[0046] Compatibilizer-1: ASM, S601N, UMG Japan;

[0047] Compatibilizer-2: ABS-g-MAH, KT-2, Shenyang Ketong Plastics Co., Ltd.;

[0048] Inorganic mineral filler-1: Hollow glass microspheres, HS20-HS60, Zhongke Yali Technology Co., Ltd.;

[0049] Inorganic mineral filler-2: Wollastonite, SW-18, Southern Wollastonite;

[0050] Inorganic mineral filler-3: Talc, 92-20-A, Longsheng Huamei;

[0051] Antioxidant: The main antioxidant is 1098 (N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine), Ciba, Switzerland;

[0052] Lubricant-1: Silicone powder, LYSI-100A, Chengdu Silike Technology Co., Ltd.;

[0053] Lubricant-2: Low molecular weight polymer wax, AC540-A, Honeywell;

[0054] Nucleating agents: rice bran wax, RBW330, Clariant;

[0055] Processing aid: NF-01, hyperbranched compound.

[0056] The present invention weighs the raw materials according to the formulas described in Table 1, and then prepares modified nylon alloy materials. The main experimental steps are as follows:

[0057] (1) Add nylon resin, amorphous resin, compatibilizer, antioxidant, lubricant and processing aid to a mixer in proportion and mix them evenly to obtain a mixture;

[0058] (2) The mixture obtained in step (1) is added from the main feed port of the twin-screw extruder and melt-extruded into granules. The temperature of each section of the twin-screw extruder is set to 180℃, 230℃, 250℃, 250℃, 260℃, 250℃, 230℃, 220℃, 220℃, the die head temperature is 260℃, and the screw speed is 300-600 rpm.

[0059] (3) Carbon fiber and inorganic mineral filler are added from both sides of the feed port for extrusion melt blending. The side feed ports are set in the third and fifth sections of the extruder barrel, respectively, and the feed is metered according to the ratio.

[0060] (4) The raw materials of the formulation system are melted, extruded, cooled, air-dried, granulated, vibrated and sieved, and homogenized.

[0061] The mixing in step (1) refers to high-speed mixing at 800-1500 rpm for 2-5 minutes, with the temperature of the high-speed mixer controlled at 55-65℃.

[0062] Examples 1 to 7 and Comparative Examples 1 to 3 all follow the above preparation steps with slight modifications. Those skilled in the art can obtain the corresponding operating methods by combining conventional knowledge.

[0063] Table 1 Experimental Formula Table

[0064]

[0065] Table 2 Experimental Data

[0066]

[0067] Note: Density is tested according to ISO 1183-1 standard; Warpage test: Injection mold a 150 mm*150 mm*1.5 mm square plate, place the plate on a horizontal surface, press down one corner of the plate with a heavy object, and use calipers to measure the distance of the highest point from the horizontal surface; Melt flow index is tested according to GB / T 3682.2-2018 standard; Tensile, bending and impact tests are conducted according to GB / T 1040.2-2022, GB / T 9341-2008 and GB / T 1043.1 respectively.

[0068] As shown in Examples 1 to 7, the modified nylon alloy of the present invention possesses excellent mechanical properties, meeting the requirements of engineering plastics. It also exhibits excellent warpage resistance (warpage less than 0.6 mm) and suitable flowability (melt index between 7.0 and 10.0 g / 10 min), making it suitable for 3D printing and applicable to various fields such as household appliance parts and customized tools.

[0069] In Comparative Example 1, no amorphous resin was added, and in Comparative Example 2, no inorganic mineral filler was added. The warpage of the resulting nylon alloy material was significantly higher than that of Examples 1 to 4. In Comparative Example 3, neither amorphous resin nor inorganic minerals were added. Although the mechanical properties were the best, the warpage was further increased. Comparing Examples 1, 3, and 4, it can be seen that the addition of hollow glass microspheres resulted in a lower density of the nylon alloy material, meeting the requirements for lightweighting. In Example 6, nucleating agents and processing aids were added. Compared with Example 1, the fluidity was improved, but the warpage was also increased due to the improved crystallinity.

[0070] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A modified nylon alloy material that can be used for 3D printing, characterized in that, It consists of the following components by mass percentage: Nylon resin 30.0–65.0% Amorphous resin 5.0–40.0% Carbon fiber 10.0–25.0% Compatibilizer 3.0–7.0% Inorganic mineral fillers 10.0–25.0% Antioxidant 0.2-0.5% Lubricant 0.5-1.0% Other processing aids: 0.2–1.0%; The sum of the mass percentages of the above components is 100%.

2. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The nylon resin is at least two of nylon 6, nylon 66, nylon 12, nylon 612, nylon 1010, and nylon 1012, and the relative viscosity of the nylon resin is 2.0-3.

2.

3. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The amorphous resin is at least one of acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, polycarbonate, or polyethylene terephthalate-1,4-cyclohexanediol ester.

4. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The compatibilizer is at least one of acrylonitrile-butadiene-styrene copolymer grafted with maleic anhydride, polypropylene grafted with maleic anhydride, polyethylene grafted with maleic anhydride, acrylonitrile-styrene-methacrylic acid copolymer, and polyolefin elastomer grafted with maleic anhydride.

5. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The inorganic mineral filler is at least one of calcium carbonate, precipitated barium sulfate, talc, hollow glass microspheres, mica, wollastonite, montmorillonite, or kaolin.

6. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The inorganic mineral filler is at least one of hollow glass microspheres, wollastonite, or talc.

7. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The antioxidant is at least one of hindered phenolic antioxidants, thioester antioxidants, phosphite antioxidants, and ester antioxidants.

8. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The lubricant is at least one of low molecular weight polymer wax and silicone masterbatch.

9. The modified nylon alloy material for 3D printing according to claim 1, characterized in that, The method for preparing the modified nylon alloy material that can be used for 3D printing includes the following steps: (1) Add nylon resin, amorphous resin, compatibilizer, antioxidant, lubricant and processing aid to a mixer in proportion and mix them evenly to prepare a mixture; (2) The mixture obtained in step (1) is added from the main feed port of the twin-screw extruder and melt-extruded into granules. The temperature of each section of the twin-screw extruder is set to 180℃, 230℃, 250℃, 250℃, 260℃, 250℃, 230℃, 220℃, 220℃, the die head temperature is 260℃, and the screw speed is 300-600 rpm. (3) Carbon fiber and inorganic mineral filler are added from both sides of the feed port for extrusion melt blending. The side feed ports are set in the third and fifth sections of the extruder barrel, respectively, and the feed is metered according to the ratio. (4) The raw materials of the formulation system are melted, extruded, cooled, air-dried, pelletized, vibrated and sieved, and homogenized to prepare modified nylon alloy materials that can be used for 3D printing. In step (1), the mixing refers to high-speed mixing at 800-1500 rpm for 2-5 minutes, with the temperature of the mixer at 55-65℃.

10. The application of a modified nylon alloy material for 3D printing according to any one of claims 1 to 9 in 3D printing fused deposition modeling and laser sintering.

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