AU2019206102A1 - Impact and ultraviolet aging-resistant PLA filament for 3D printing and method for making same - Google Patents

Impact and ultraviolet aging-resistant PLA filament for 3D printing and method for making same Download PDF

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AU2019206102A1
AU2019206102A1 AU2019206102A AU2019206102A AU2019206102A1 AU 2019206102 A1 AU2019206102 A1 AU 2019206102A1 AU 2019206102 A AU2019206102 A AU 2019206102A AU 2019206102 A AU2019206102 A AU 2019206102A AU 2019206102 A1 AU2019206102 A1 AU 2019206102A1
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pbs
pla
zno
screw extruder
twin
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AU2019206102B2 (en
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Ligui CHEN
Lei Fu
Shikui JIA
Zhong Wang
Yan Zhu
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Shaanxi University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

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Abstract

Disclosed is an impact and ultraviolet aging-resistant PLA filament for 3D printing, including a TiO2/PBS functional masterbatch resistant to impact and ultraviolet aging, a coupling agent and PLA. The PLA has a mass fraction of 60-89%; the TiO 2/PBS functional 5 masterbatch has a mass fraction of 10-35%; the coupling agent has a mass fraction of 1-5%; and the sum of the mass fractions of the above components is 100%. The present invention also discloses a method of producing the impact and ultraviolet aging-resistant PLA filament for 3D printing to solve the problem that the existing nano-TiO2 is difficult to be extruded and to disperse in the melting process, and this method improves the impact strength and 0 ultraviolet aging resistance of the PLA filament for 3D printing. TiO2 Silicon oil {High-speed mixing AC Highly-dispersed TiO2 powder High-speedmixing ZnO PBS Expandable Melt blending TiO2 powder+ ZnO/PBS Dryingblowing aid (Melt blending) TiO2/PBS functional masterbatch Melt-extrusion Impact and UV aging-resistant TiO2/PBS-modified PLA filament for 3D printing Performance test Application analysis

Description

IMPACT AND ULTRAVIOLET AGING-RESISTANT PLA FILAMENT FOR 3D PRINTING AND METHOD FOR MAKING SAME
TECHNICAL FIELD
The present invention relates to processing of 3D printing consumables, and more 5 particularly to an impact and ultraviolet aging-resistant polylactic acid (PLA) filament for 3D printing and a method for making the same.
BACKGROUND OF THE INVENTION
In recent years, 3D printing technology has received considerable attention and has been widely investigated around the world, especially in the western developed countries such as 0 Europe and the United States, which promotes the rapid development of the 3D printing equipment, material and technology. A great progress has also been made to the 3D printing technology in China. The development and research about the 3D equipment and technologies conducted by Xi'an Jiaotong University, Sichuan University and Beijing University of Chemical Technology have attracted extensive attention worldwide, and the related 3D 5 products have already been applied in the military and civilian fields and achieved initial success. Meanwhile, Chinese enterprises have also increased development of the 3D printing equipment, technology and material, for example, sales of Dongguan Silver Age Sci&Tech Co. Ltd., Shenzhen eSUN Industrial Co., Ltd. and Wuyi Sting 3d technology Co., Ltd. with regard to the 3D equipment and consumables have all exceeded 10 million yuan. The Academy of 20 Qianzhan industry research predicts that China's 3D printing market will reach 8 billion yuan in 2018.
Currently, most of the high-end functional 3D printing consumables in China are obtained by importation. Although some enterprises have increased the investment for the independent research and development of 3D printing consumables, there is still a large gap 25 between the products manufactured in China and those produced overseas in terms of strength,
2019206102 18 Jul 2019 precision and other functionalities, which seriously hindered the development of the China's 3D printing industry and industrial application. Meanwhile, the modem 3D printing technology raises higher requirements for the 3D printing consumables in versatility, mechanical properties, precision and processability, and the functionalization of the 3D 5 filament will also play a key role in the future development. Filament is a resin consumable used in fused deposition printing technology, and the commonly-used filament includes polylactic acid (PLA), acrylonitrile-butadiene-styrene copolymer (ABS) and polyamide (PA), where the PLA is the most widely used in the 3D printing due to degradability, good strength and workability. In addition, the PLA can also be biologically prepared. However, there are 0 also some defects in the PLA filament, such as poor impact resistance, easy breakage during the processing and easy degradation and aging. Meanwhile, it has not been reported on a PLA filament with impact and ultraviolet aging resistance.
So far, Chinese Patent Application CN 107793720A discloses a fully-biodegradable mulch film specific for peanut and a preparation method thereof, where a composite 5 anti-ultraviolet agent, a molecular weight modifier, a flexibility modifier and PLA are mixed by melt blending and then subjected to the film-blowing to produce a film with excellent hydrolysis resistance, excellent photo-aging resistance and good flexibility. But this patent not only fails to disclose the use of titanium dioxide (T1O2) with excellent ultraviolet barrier property and polybutylene succinate (PBS) with toughness and biodegradability in the 20 modification of PLA, but also fails to disclose the research on the impact and ultraviolet aging resistance of PLA filaments for 3D printing. In addition, another Chinese Patent Application CN 104817834A discloses a toughened PLA resin material and a preparation method thereof, where a toughener, a surfactant, a processing aid, an anti-heat aging agent, an antioxidant, a filler, a plasticizer and a lubricant are premixed to obtain a premix, and then the premix and 25 the PLA are sequentially extruded, stretched and cool-granulated by a parallel twin-screw extruder to obtain the toughened PLA resin material. But this patent fails to disclose the development of a foamed T1O2/PBS functional masterbatch and a preparation method of PLA filaments for 3D printing.
2019206102 18 Jul 2019
SUMMARY OF THE INVENTION
An object of the application is to provide an impact and ultraviolet aging-resistant PLA filament for 3D printing to overcome the defects of low impact strength and poor ultraviolet aging resistance in the prior art.
Another object of the invention is to provide a method of producing the above PLA filament for 3D printing.
In a first aspect, the present application discloses an impact and ultraviolet aging-resistant PLA filament for 3D printing, comprising a T1O2/PBS functional masterbatch resistant to impact and ultraviolet aging, a coupling agent and PLA, wherein the PLA has a 0 mass fraction of 60-89%, the T1O2/PBS functional masterbatch has a mass fraction of 10-35%, and the coupling agent has a mass fraction of 1-5%, the sum of the mass fractions of the PLA, the T1O2/PBS functional masterbatch and the coupling agent is 100%.
The T1O2/PBS functional masterbatch comprises an expandable T1O2 powder, blowing aids and PBS, wherein the expandable T1O2 powder has a mass fraction of 10-20%, the 5 blowing aids have a mass fraction of 1-10%, the PBS has a mass fraction of 70-89%, the sum of the mass fractions of the expandable T1O2 powder, the blowing aids and the PBS is 100%.
The expandable T1O2 powder comprises T1O2, azodicarbonamide (AC) and silicone oil, wherein the TiCbhas a mass fraction of 80-94%, the AC has a mass fraction of 5-15%, the silicone oil has a mass fraction of 1-5%, the sum of the mass fractions of the T1O2, the silicon 20 oil and the AC is 100%.
The blowing aid comprises nano zinc oxide (nano-ZnO) and the PBS, wherein the nano-ZnO has a mass fraction of 1-5%, the PBS has a mass fraction of 95-99%, the sum of the mass fractions of the nano-ZnO and the PBS is 100%.
In a second aspect, the present application discloses a method of producing an impact
2019206102 18 Jul 2019 and ultraviolet aging-resistant PLA filament for 3D printing, comprising:
(1) dispersing and mixing nano TiCh and azodicarbonamide (AC) using a high-speed mixer to obtain an expandable TiCh powder;
(2) preparing ZnO/PBS blowing aids by melt blending;
(3) mixing the expandable TiCh powder and the ZnO/PBS blowing aids by melt blending to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance; and (4) subjecting the T1O2/PBS functional masterbatch and PLA to melt extruding to prepare the PLA filament for 3D printing.
Further, the method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing will be described in detail.
The step (1) specifically comprises the following steps: mixing the nano T1O2 and silicone oil in the high-speed mixer at a rotation speed of 800 r/min-1500 r/min for 30-45 min, wherein the silicone oil is sprayed onto the nano T1O2 every 5-10 min; adding the AC to the .5 high-speed mixer followed by mixing at the same rotation speed for 30-45 minutes to obtain a T1O2/AC blend; and drying the T1O2/AC blend in a drying oven at 30°C-60°C for 1-4 h to obtain the highly-dispersed expandable T1O2 powder; wherein a mass ratio of the T1O2 to the silicone oil to AC is 8-9.4: 0.1-0.5: 0.5-1.5.
The step (2) specifically comprises the following steps: drying nano-ZnO and PBS in a 20 drying oven at 40°C-80°C for 6-12 h; premixing the dried nano-ZnO and PBS in the high-speed mixer, and subjecting the premixed product to melt blending and extruding granulation in a twin-screw machine followed by drying in the drying oven at 60°C-80°C for 4-8 h to obtain the ZnO/PBS blowing aids; wherein a mass ratio of the PBS to the nano-ZnO is 9.5-9.9:0.1-0.5; and an extrusion temperature of the twin-screw extruder is 120°C-160°C
2019206102 18 Jul 2019 and an extrusion speed of the twin-screw extruder is 30-60 r/min.
The step (3) specifically comprises the following steps: premixing the expandable T1O2 powder, the ZnO/PBS blowing aids and PBS in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in the twin-screw extruder 5 followed by drying in a drying oven at 60°C-80°C for 4-8 h to obtain the T1O2/PBS functional masterbatch; wherein a mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids to PBS is 1-2:0.1-1:7-8.9; and an extrusion temperature of the twin-screw extruder is 120°C-160°C and an extrusion speed of the twin-screw extruder is 30-60 r/min.
The step 4 specifically comprises the following steps:
(4-1) premixing the T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging-resistance, a coupling agent and a dried PLA in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in a twin-screw extruder followed by drying in a drying oven at 60°C-90°C for 4-8 h to obtain a granular composite T1O2/PBS/PLA material;
wherein a mass ratio of the PLA to the T1O2/PBS functional masterbatch to the coupling agent is 6-8.9: 1-3.5: 0.1-0.5; and an extrusion temperature of the twin-screw extruder is 150°C-180°C and an extrusion speed of the twin-screw extruder is 60-120 r/min;
(4.2) subjecting the composite T1O2/PBS/PLA material obtained in step (4.1) to extrusion 20 drawing in a single-screw extruder to obtain the PLA filament for 3D printing;
wherein an extrusion temperature of the twin-screw extruder is 50°C-180°C, an extrusion speed of the twin-screw extruder is 30-60 r/min and a die for the twin-screw extruder is 1.75 mm or 3 mm in diameter.
The present invention has the following beneficial effects.
2019206102 18 Jul 2019
In this invention, T1O2 with excellent ultraviolet-shielding property, silicone oil and high-performance blowing agent AC are subjected to high-dispersion mixing to prepare the expandable T1O2 powder; ZnO with a lowerable decomposition temperature is then melt-blended with PBS having impact resistance to prepare the ZnO/PBS blowing aids; and 5 the expandable T1O2 powder is fully melt-blended with the ZnO/PBS blowing aids by the twin-screw extruder to obtain the impact and ultraviolet aging-resistant T1O2/PBS functional masterbatch. The resulting masterbatch has high dispersibility, good toughness and ultraviolet aging resistance. The masterbatch is then melt-blended with PLA by a screw extruder to prepare a T1O2/PBS/PLA filament which has a high impact and ultraviolet aging resistance. 0 Therefore, this invention can further promote the development of the functionality of the PLA filament for 3D printing, expanding the application of the PLA filament.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart showing a method of the invention for producing an impact and ultraviolet aging-resistant PLA filament for 3D printing.
FIG. 2 is a scanning electron microscope (SEM) image showing an expandable T1O2 according to an embodiment.
FIG. 3 is a SEM image showing a T1O2/PBS functional masterbatch according to an embodiment.
FIG. 4 is a SEM image showing a T1O2/PBS/PLA filament according to an embodiment.
FIG. 5 shows the impact strength of a composite T1O2/PBS/PLA material according to an embodiment.
FIG. 6 shows the tensile strength of the composite T1O2/PBS/PLA material according to an embodiment.
DETAILED DESCRIPTION OF EMBODIMENTS
2019206102 18 Jul 2019
The invention will be described in detail with reference to the drawings and embodiments.
The invention discloses an impact and ultraviolet aging-resistant PLA filament for 3D printing, including a T1O2/PBS functional masterbatch with impact resistance and ultraviolet 5 aging resistance, a coupling agent and PLA, where the PLA has a mass fraction of 60-89%; the T1O2/PBS functional masterbatch has a mass fraction of 10-35%; the coupling agent has a mass fraction of 1-5%; and the sum of the mass fractions of the PLA, the T1O2/PBS functional masterbatch and the coupling agent is 100%.
The T1O2/PBS functional masterbatch includes an expandable T1O2 powder, blowing aids 0 and PBS, where the expandable T1O2 powder has a mass fraction of 10-20%, the blowing aids have a mass fraction of 1-10%, the PBS has a mass fraction of 78-89%, the sum of the mass fractions of the expandable T1O2 powder, the blowing aids and the PBS is 100%.
The expandable T1O2 powder includes T1O2, azodicarbonamide (AC) and silicone oil; where the T1O2 has a mass fraction of 80-94%, the silicon oil has a mass fraction of 1-5%, the 5 AC has a mass fraction of 5-15%, the sum of the mass fractions of the T1O2, the silicon oil and the AC is 100%.
The blowing aids include nano zinc oxide (nano-ZnO) and the PBS, where the PBS has a mass fraction of 95-99%, the nano-ZnO has a mass fraction of 1-5%, and the sum of the mass fractions of the nano-ZnO and the PBS is 100%.
A method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing according to the present invention, including:
(1) dispersing and mixing nano T1O2 and AC using a high-speed mixer to obtain an expandable T1O2 powder;
where the step (1) specifically includes the following steps: mixing the nano T1O2 and
2019206102 18 Jul 2019 silicon oil in the high-speed mixer at a rotation speed of 800 r/min-1500 r/min for 30-45 min, where the silicone oil is sprayed onto the nano T1O2 every 5-10 min; adding AC to the high-speed mixer followed by mixing at the same rotation speed for 30-45 min to obtain a T1O2/AC blend; and drying the T1O2/AC blend in a drying oven at 30°C-60°C for 1-4 h to 5 obtain the highly-dispersed expandable T1O2 powder;
where a mass ratio of the T1O2 to the silicone oil to the AC is 8-9.4:0.1-0.5: 0.5-1.5;
(2) preparing ZnO/PBS blowing aids by melt blending;
where the step (2) specifically includes the following steps: using a bio-derived and degradable PBS as a base material and nano-ZnO as auxiliary powder which can regulate the 0 decomposition temperature of a decomposable AC; drying the nano-ZnO and PBS in a drying oven at 40°C-80°C for 6-12 h; premixing the dried nano-ZnO and PBS in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in a twin-screw machine followed by drying in the drying oven at 60°C-80°C for 4-8 h to obtain the ZnO/PBS blowing aids;
where a mass ratio of PBS to the nano-ZnO is 9.5-9.9:0.1-0.5;
and an extrusion temperature of the twin-screw extruder is 120°C-160°C and an extrusion speed of the twin-screw extruder is 30-60 r/min;
(3) mixing the expandable T1O2 powder and the ZnO/PBS blowing aids by melt blending to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance;
where the step (3) specifically includes the following steps: premixing the expandable T1O2 powder, the ZnO/PBS blowing aids and PBS in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in a twin-screw extruder followed by drying in a drying oven at 60°C-80°C for 4-8 h to obtain the T1O2/PBS functional
2019206102 18 Jul 2019 masterbatch;
where a mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids to PBS is 1-2:0.1-1:7-8.9;
an extrusion temperature of the twin-screw extruder extrusion processing temperature is 5 120°C-160°C and an extrusion speed of the twin-screw extruder is 30-60 r/min;
(4) subjecting the T1O2/PBS functional masterbatch and PLA to melt extruding to prepare the PLA filament for 3D printing;
where the step (4) specifically includes the following steps:
(4.1) premixing the T1O2/PBS functional masterbatch with impact resistance and 0 ultraviolet aging resistance, a coupling agent and a dried PLA in the high-speed mixer, and subjecting the premixed product to melt blending and extruding granulation in a twin-screw extruder followed by drying in a drying oven at 60°C-90°C for 4-8 h to obtain a granular composite T1O2/PBS/PLA material;
where a mass ratio of the PLA to the T1O2/PBS functional masterbatch to the coupling A agent is 6-8.9: 1-3.5: 0.1-0.5; and an extrusion temperature of the twin-screw extruder is 150°C-180°C and an extrusion speed of the twin-screw extruder is 60-120 r/min;
(4.2) subjecting the composite T1O2/PBS/PLA material obtained in step (4.1) to extrusion drawing in a single-screw extruder to obtain the PLA filament for 3D printing;
where an extrusion temperature of the twin-screw extruder is 50°C-180°C; an extrusion speed of the twin-screw extruder is 30-60 r/min and a die of the twin-screw extruder has a diameter of 1.75 mm or 3 mm.
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2019206102 18 Jul 2019
Example 1
The invention discloses a method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing, which specifically includes the following steps.
(1) Nano-TiCb and azodicarbonamide (AC) were dispersed and mixed by a high-speed 5 mixer to produce an expandable TiCh powder.
The step (1) specifically included the following steps. The nano-TiCb was mixed with silicone oil in the high-speed mixer at 800 r/min for 30 min, where the silicone oil was sprayed onto the nano-TiCh every 5-10 min to reduce the surface energy of T1O2, thereby producing fine and highly-dispersed T1O2 powder which was not prone to agglomeration. 0 Then the T1O2 powder was added with AC and mixed at the same rotation speed for 10 min to obtain a T1O2/AC blend. The T1O2/AC blend was finally dried in a drying oven at 30°C for 4 h to obtain the highly-dispersed expandable T1O2 powder, of which the microscopic morphology was shown in FIG. 2.
Amass ratio of the T1O2 to the silicone oil to the AC was 8:0.5:1.5.
(2) ZnO/PBS blowing aids were prepared by melt blending, which was specifically described as follows.
The nano-ZnO and PBS were dried in the drying oven at 40°C for 10 h and then premixed in the high-speed mixer. The premixed product was subjected to melt blending and extruding granulation in a twin-screw machine. The resulting product was dried in the drying 20 oven at 60°C for 8 h to obtain the ZnO/PBS blowing aids.
Amass ratio of PBS to the nano-ZnO was 9.9: 0.1.
An extrusion temperature of the twin-screw extruder was 120°C, and an extrusion speed was 30 r/min.
2019206102 18 Jul 2019 (3) The expandable T1O2 powder was melt-blended with the ZnO/PBS blowing aids to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, which was specifically described as follows.
The expandable T1O2 powder, the ZnO/PBS blowing aids and PBS were premixed in the 5 high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 60°C for 8 h to obtain the T1O2/PBS functional masterbatch.
A mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids to PBS was 1:0.1:8.9.
An extrusion temperature of the twin-screw extruder was 120°C, and an extrusion speed was 30 r/min.
(4) The T1O2/PBS functional masterbatch and PLA were subjected to melt-extrusion to prepare the PLA filament for 3D printing, which was specifically described as follows.
(4.1) The T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging 5 resistance, the coupling agent and the dried PLA were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 60°C for 8 h to obtain a granular composite T1O2/PBS/PLA material.
A mass ratio of PLA to the T1O2/PBS functional masterbatch to the coupling agent was 20 8.9:1:0.1.
An extrusion temperature of the twin-screw extruder was 150°C, and an extrusion speed was 60 r/min.
(4.2) The composite T1O2/PBS/PLA material obtained in step (4.1) was subjected to extrusion drawing in a single-screw extruder to produce the PLA filament for 3D printing, of
2019206102 18 Jul 2019 which a SEM image was shown in FIG. 4.
An extrusion temperature of the single-screw extruder was 150°C, and an extrusion speed was 30 r/min. A die of the single-screw extruder had a diameter of 3 mm.
A series of the composite PBS/PLA or TiCh/PBS/PLA materials were tested for the 5 impact strength, and the results were shown in FIG. 5. Moreover, the tensile strengths of the composite TiCh/PBS/PLA material before and after ultraviolet aging were also tested, and the results were shown in FIG. 6. It was found that the impact strength of the PLA was significantly improved by the PBS, specifically, the impact strengths of the composite PBS/PLA and TiCh/PBS/PLA materials were respectively about 6 and 3 times that of the PLA 0 Meanwhile, the ultraviolet irradiation test of the pure PLA and the composite TiCh/PBS/PLA material was conducted under an intensity of 300 W/m2 respectively for 24 h, 48 h and 72 h, and the results showed that after irradiated for 72 h, the tensile strength of the pure PLA was reduced by 16.5% while the tensile strength of the composite TiCh/PBS/PLA material was only reduced by 5.1 %.
Example 2
The invention discloses a method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing, which specifically includes the following steps.
(1) Nano-TiCh and azodicarbonamide (AC) were dispersed and mixed by a high-speed mixer to produce an expandable TiCh powder.
The step (1) specifically included the following steps. The nano-TiCh was mixed with silicone oil in the high-speed mixer at 1000 r/min for 35 min, where the silicone oil was sprayed onto the nano-TiCh every 5 min to reduce the surface energy of T1O2, thereby producing fine and highly-dispersed T1O2 powder which was not prone to agglomeration. Then the T1O2 powder was added with AC and mixed at the same rotation speed for 15 min to 25 obtain a T1O2/AC blend. The T1O2/AC blend was finally dried in a drying oven at 40°C for 3 h
2019206102 18 Jul 2019 to obtain the highly-dispersed expandable T1O2 powder.
Amass ratio of the T1O2 to the silicone oil to the AC was 8.5: 0.4: 1.1.
(2) ZnO/PBS blowing aids were prepared by melt blending, which was specifically described as follows.
The nano-ZnO and PBS were dried in the drying oven at 50°C for 8 h and then premixed in the high-speed mixer. The premixed product was subjected to melt blending and extruding granulation in a twin-screw machine. The resulting product was dried in the drying oven at 70°C for 6 h to obtain the ZnO/PBS blowing aids.
A mass ratio of the PBS to the nano-ZnO was 9.8: 0.2;
An extrusion temperature of the twin-screw extruder was 130°C, and an extrusion speed was 40 r/min.
(3) The expandable T1O2 powder was melt-blended with the ZnO/PBS blowing aids to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, which was specifically described as follows.
The expandable T1O2 powder, the ZnO/PBS blowing aids and PBS were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 70°C for 6 h to obtain the T1O2/PBS functional masterbatch;
A mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids and the PBS 20 was 1.5:0.3:8.2.
An extrusion temperature of the twin-screw extruder was 130°C, and an extrusion speed was 40 r/min.
2019206102 18 Jul 2019 (4) The T1O2/PBS functional masterbatch and PLA were subjected to melt-extrusion to prepare the PLA filament for 3D printing, which was specifically described as follows.
(4.1) The T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, the coupling agent and the dried PLA were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 70°C for 6 h to obtain a granular composite T1O2/PBS/PLA material.
A mass ratio of PLA to the T1O2/PBS functional masterbatch to the coupling agent was 8.3: 1.5: 0.2.
An extrusion temperature of the twin-screw extruder was 160°C, and an extrusion speed was 60 r/min.
(4.2) The composite T1O2/PBS/PLA material obtained in step (4.1) was subjected to extrusion drawing in a single-screw extruder to produce the PLA filament for 3D printing.
An extrusion temperature of the single-screw extruder was 160°C, and an extrusion speed was 30 r/min. A die for the single-screw extruder was 3 mm in diameter.
Example 3
The invention discloses a method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing, which specifically includes the following steps.
(1) Nano-TiCfi and azodicarbonamide (AC) were dispersed and mixed by a high-speed 20 mixer to produce an expandable T1O2 powder.
The step (1) specifically included the following steps. The nano-TiCfi was mixed with silicone oil in the high-speed mixer at 1000 r/min for 40 min, where the silicone oil was sprayed onto the nano-TiCh every 6 min to reduce the surface energy of T1O2, thereby
2019206102 18 Jul 2019 producing fine and highly-dispersed T1O2 powder which was not prone to agglomeration. Then the T1O2 powder was added with AC and mixed at the same rotation speed for 20 min to obtain a T1O2/AC blend. The T1O2/AC blend was finally dried in a drying oven at 40°C for 3 h to obtain the highly-dispersed expandable T1O2 powder.
A mass ratio of the T1O2 to the silicone oil to the AC was 8.8: 0.3: 0.9;
(2) ZnO/PBS blowing aids were prepared by melt blending, which was specifically described as follows.
The nano-ZnO and PBS were dried in the drying oven at 60°C for 10 h and then premixed in the high-speed mixer. The premixed product was subjected to melt blending and 0 extruding granulation in a twin-screw machine. The resulting product was finally dried in the drying oven at 70°C for 6 h to obtain the ZnO/PBS blowing aids.
A mass ratio of the PBS to the nano-ZnO was 9.7: 0.3.
An extrusion temperature of the twin-screw extruder was 140°C, and an extrusion speed was 50 r/min.
.5 (3) The expandable T1O2 powder was melt-blended with the ZnO/PBS blowing aids to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, which was specifically described as follows.
The expandable T1O2 powder, the ZnO/PBS blowing aids and PBS were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the 20 twin-screw extruder. The resulting product was dried in the drying oven at 70°C for 6 h to obtain the T1O2/PBS functional masterbatch.
A mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids to PBS was 1.5:0.5:8.
2019206102 18 Jul 2019
An extrusion temperature of the twin-screw extruder was 140°C, and the extrusion speed was 50 r/min.
(4) The T1O2/PBS functional masterbatch and PLA were subjected to melt-extrusion to prepare the PLA filament for 3D printing, which was specifically described as follows.
(4.1) The T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, the coupling agent and the dried PLA were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 70°C for 6 h to obtain a granular composite T1O2/PBS/PLA material.
A mass ratio of PLA to the T1O2/PBS functional masterbatch to the coupling agent was 7.7:2: 0.3.
An extrusion temperature of the twin-screw extruder was 160°C, and an extrusion speed was 80 r/min.
(4.2) The composite T1O2/PBS/PLA material obtained in step (4.1) was subjected to 5 extrusion drawing in a single-screw extruder to produce the PLA filament for 3D printing.
An extrusion temperature of the single-screw extruder was 160°C, and an extrusion speed was 40 r/min. A die for the single-screw extruder was 3 mm in diameter.
Example 4
The invention discloses a method of producing an impact and ultraviolet aging-resistant 20 PLA filament for 3D printing, which specifically includes the following steps.
(1) Nano-TiCfi and azodicarbonamide (AC) were dispersed and mixed by a high-speed mixer to produce an expandable T1O2 powder.
2019206102 18 Jul 2019
The step (1) specifically included the following steps. The nano-TiCh was mixed with silicone oil in the high-speed mixer at 1200 r/min for 45 min, where the silicone oil was sprayed onto the nano-TiCh every 8 min to reduce the surface energy of T1O2, thereby producing fine and highly-dispersed T1O2 powder which was not prone to agglomeration.
Then the T1O2 powder was added with AC and mixed at the same rotation speed for 10 min to obtain a T1O2/AC blend. The T1O2/AC blend was finally dried in a drying oven at 50°C for 2 h to obtain the highly-dispersed expandable T1O2 powder.
A mass ratio of the T1O2 to the silicone oil to AC was 9: 0.4: 0.6.
(2) ZnO/PBS blowing aids were prepared by melt blending, which was specifically 0 described as follows.
The nano-ZnO and the PBS were dried in the drying oven at 80°C for 9 h and then premixed in the high-speed mixer. The premixed product was subjected to melt blending and extruding granulation in a twin-screw machine. The resulting product was dried in the drying oven at 80°C for 4 h to obtain the ZnO/PBS blowing aids.
Amass ratio of PBS to the nano-ZnO was 9.6: 0.4.
An extrusion temperature of the twin-screw extruder was 150°C, and an extrusion speed was 50 r/min.
(3) The expandable T1O2 powder was melt-blended with the ZnO/PBS blowing aids to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, which was specifically described as follows.
The expandable T1O2 powder, the ZnO/PBS blowing aids and PBS were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 80°C for 4 h to obtain the T1O2/PBS functional masterbatch.
2019206102 18 Jul 2019
A mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids to PBS was 2:0.7:7.3.
An extrusion temperature of the twin-screw extruder was 150°C, and an extrusion speed was 50 r/min.
(4) The T1O2/PBS functional masterbatch and PLA were subjected to melt-extrusion to prepare the PLA filament for 3D printing, which was specifically described as follows.
(4.1) The T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, the coupling agent and the dried PLA were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 80°C for 4 h to obtain a granular composite T1O2/PBS/PLA material.
A mass ratio of PLA to the T1O2/PBS functional masterbatch to the coupling agent was 7.1:2.5:0.4.
An extrusion temperature of the twin-screw extruder was 170°C, and an extrusion speed 5 was 80 r/min.
(4.2) The composite T1O2/PBS/PLA material obtained in step (4.1) was subjected to extrusion drawing in a single-screw extruder to produce the PLA filament for 3D printing.
An extrusion temperature of the single-screw extruder was 170°C, and an extrusion speed was 50 r/min. A die for the single-screw extruder was 1.75 mm in diameter.
Example 5
The invention discloses a method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing, which specifically includes the following steps.
2019206102 18 Jul 2019 (1) Nano-TiCh and azodicarbonamide (AC) were dispersed and mixed by a high-speed mixer to produce an expandable T1O2 powder.
The step (1) specifically included the following steps. The nano-TiCh was mixed with silicone oil in the high-speed mixer at 1500 r/min for 30-45 min, where the silicone oil was 5 sprayed onto the nano-TiCh every 10 min to reduce the surface energy of T1O2, thereby producing fine and highly-dispersed T1O2 powder which was not prone to agglomeration. Then the T1O2 powder was added with AC and mixed at the same rotation speed for 30 min to obtain a T1O2/AC blend. The T1O2/AC blend was finally dried in a drying oven at 60°C for 1 h to obtain the highly-dispersed expandable T1O2 powder.
A mass ratio of the T1O2 to the silicone oil to AC was 9.4: 0.1: 0.5.
(2) ZnO/PBS blowing aids were prepared by melt blending, which was specifically described as follows.
The nano-ZnO and PBS were dried in the drying oven at 80°C for 12 h and then premixed in the high-speed mixer. The premixed product was subjected to melt blending and 5 extruding granulation in a twin-screw machine. The resulting product was finally dried in the drying oven at 80°C for 4 h to obtain the ZnO/PBS blowing aids.
A mass ratio of the PBS to the nano-ZnO was 9.5: 0.5.
An extrusion temperature of the twin-screw extruder was 160°C, and an extrusion speed was 60 r/min.
(3) The expandable T1O2 powder was melt-blended with the ZnO/PBS blowing aids to prepare a T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance.
The expandable T1O2 powder, the ZnO/PBS blowing aids and PBS were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the
2019206102 18 Jul 2019 twin-screw extruder. The resulting product was dried in the drying oven at 80°C for 4 h to obtain the T1O2/PBS functional masterbatch.
A mass ratio of the expandable T1O2 powder to the ZnO/PBS blowing aids to PBS was 2:1: 7.
An extrusion temperature of the twin-screw extruder was 160°C, and the extrusion speed was 60 r/min.
(4) The T1O2/PBS functional masterbatch and PLA were subjected to melt-extrusion to prepare the PLA filament for 3D printing, which was specifically described as follows.
(4.1) The T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging 0 resistance, the coupling agent and the dried PLA were premixed in the high-speed mixer, and then subjected to melt-blending and extruding granulation in the twin-screw extruder. The resulting product was dried in the drying oven at 90°C for 4 h to obtain a granular composite T1O2/PBS/PLA material.
A mass ratio of PLA to the T1O2/PBS functional masterbatch to the coupling agent was 6: 5 3.5: 0.5.
An extrusion temperature of the twin-screw extruder was 180°C, and an extrusion speed was 90 r/min.
(4.2) The composite T1O2/PBS/PLA obtained in step (4.1) was subjected to extrusion drawing in a single-screw extruder to produce the PLA filament for 3D printing.
An extrusion temperature of the single-screw extruder was 80°C, and an extrusion speed was 60 r/min. A die for the single-screw extruder was 1.75 mm in diameter.
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general
2019206102 18 Jul 2019 knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive 5 sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Claims (5)

  1. (1) dispersing and mixing nano T1O2 and azodicarbonamide (AC) using a high-speed
    2019206102 18 Jul 2019 mixer to obtain an expandable T1O2 powder;
    1. An impact and ultraviolet aging-resistant polylactic acid (PLA) filament for 3D printing, comprising: a TiCh/PBS functional masterbatch resistant to impact and ultraviolet aging, a coupling agent and PLA;
    5 wherein the PLA has a mass fraction of 60-89%; the TiCL/PBS functional masterbatch has a mass fraction of 10-35%; the coupling agent has a mass fraction of 1-5%; and the sum of the mass fractions of the PLA, the TiCh/PBS functional masterbatch and the coupling agent is 100%.
  2. (2) preparing ZnO/PBS blowing aids by melt blending;
    2. The PLA filament according to claim 1, characterized in that the TiCL/PBS functional 0 masterbatch comprises an expandable TiCL powder, blowing aids and PBS; wherein the expandable T1O2 powder has a mass fraction of 10-20%; the blowing aids have a mass fraction of 1-10%; the PBS has a mass fraction of 70-89%; and the sum of the mass fractions of the expandable T1O2 powder, the blowing aids and the PBS is 100%.
  3. (3) mixing the expandable T1O2 powder and the ZnO/PBS blowing aids by melt blending to prepare a T1O2/PBS functional masterbatch resistant to impact and ultraviolet aging; and
    5 (4) subjecting the T1O2/PBS functional masterbatch and PLA to melt extruding to prepare the PLA filament for 3D printing.
    6. The method according to claim 5, characterized in that the step (1) comprises the following steps:
    mixing the nano T1O2 and silicone oil in the high-speed mixer at a rotation speed of 800 0 r/min-1500 r/min for 30-45 min, wherein the silicone oil is sprayed onto the nano T1O2 every
    5-10 min; adding AC into the high-speed mixer followed by mixing at the same rotation speed for 30-45 min to obtain a T1O2/AC blend; and drying the T1O2/AC blend in a drying oven at 30°C-60°C for 1-4 h to obtain a highly-dispersed expandable T1O2 powder; wherein a mass ratio of T1O2 to the silicone oil to the AC is 8-9.4: 0.1-0.5: 0.5-1.5.
    .5 7. The method according to claim 5, characterized in that the step (2) comprises the following steps:
    drying nano-ZnO and PBS in a drying oven at 40°C-80°C for 6-12 h; premixing the dried nano-ZnO and PBS in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in a twin-screw machine followed by drying in a drying 20 oven at 60°C-80°C for 4-8 h to obtain the ZnO/PBS blowing aids; wherein a mass ratio of PBS to the nano-ZnO is 9.5-9.9:0.1-0.5; and an extrusion temperature of the twin-screw extruder is 120°C-160°C and an extrusion speed of the twin-screw extruder is 30-60 r/min.
    8. The method according to claim 5, characterized in that the step (3) comprises the following steps:
    2019206102 18 Jul 2019 premixing the expandable T1O2 powder, the ZnO/PBS blowing aids and PBS in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in a twin-screw extruder followed by drying in a drying oven at 60°C-80°C for 4-8 h to obtain the T1O2/PBS functional masterbatch; wherein a mass ratio of the expandable
    5 T1O2 powder to the ZnO/PBS blowing aids to PBS is 1-2:0.1-1:7-8.9; and an extrusion temperature of the twin-screw extruder is 120°C-160°C and an extrusion speed of the twin-screw extruder is 30-60 r/min.
    9. The method according to claim 5, characterized in that the step (4) comprises the following steps:
    0 (4.1) premixing the T1O2/PBS functional masterbatch with impact resistance and ultraviolet aging resistance, a coupling agent and a dried PLA in the high-speed mixer; and subjecting the premixed product to melt blending and extruding granulation in a twin-screw extruder followed by drying in a drying oven at 60°C-90°C for 4-8 h to obtain a granular composite T1O2/PBS/PLA material;
    3. The PLA filament according to claim 2, characterized in that the expandable T1O2 5 powder comprises T1O2, AC and silicon oil; wherein the T1O2 has a mass fraction of 80-94%;
    the silicon oil has a mass fraction of 1-5%; the AC has a mass fraction of 5-15%; and the sum of the mass fractions of the T1O2, the silicon oil and the AC is 100%.
  4. 4. The PLA filament according to claim 2, characterized in that the blowing aids comprise nano-ZnO and PBS; wherein the PBS has a mass fraction of 95-99%; the nano-ZnO
    20 has a mass fraction of 1-5%; and the sum of the mass fractions of the nano-ZnO and the PBS is 100%.
    5. A method of producing an impact and ultraviolet aging-resistant PLA filament for 3D printing, comprising:
  5. 5 wherein a mass ratio of PLA to the T1O2/PBS functional masterbatch to the coupling agent is 6-8.9: 1-3.5: 0.1-0.5; and an extrusion temperature of the twin-screw extruder is 150°C-180°C and an extrusion speed of the twin-screw extruder is 60-120 r/min; and (4.2) subjecting the composite T1O2/PBS/PLA material obtained in step (4.1) to extrusion 20 drawing in a single-screw extruder to obtain the PLA filament for 3D printing;
    wherein an extrusion temperature of the twin-screw extruder is 50°C-180°C; an extrusion speed of the twin-screw extruder is 30-60 r/min and a die for the twin-screw extruder is 1.75 mm or 3 mm in diameter.
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