CN110105763B - Composite material for 3D printing and preparation method thereof - Google Patents
Composite material for 3D printing and preparation method thereof Download PDFInfo
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- CN110105763B CN110105763B CN201910433618.XA CN201910433618A CN110105763B CN 110105763 B CN110105763 B CN 110105763B CN 201910433618 A CN201910433618 A CN 201910433618A CN 110105763 B CN110105763 B CN 110105763B
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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Abstract
The invention provides a composite material for 3D printing, which comprises: 100 parts by weight of polyphenylsulfone resin; 32-35 parts by weight of polycarbonate; 1-3 parts of glass fiber; 0.5-2 parts by weight of organic modified clay. Compared with the prior art, the invention takes the polyphenylsulfone resin and the polycarbonate as resin raw materials, improves the physical and mechanical properties of the composite material by adding the glass fiber, and simultaneously reduces the water absorption of the composite material by adding the organic modified clay, so that the obtained composite material has higher mechanical properties and lower water absorption.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a composite material for 3D printing and a preparation method thereof.
Background
The additive technology (3D printing) is a radical technological innovation, and is now widely used in industry, and not only in the future, but also in the present day. The market for additive technology is growing rapidly, at approximately a quarter of a year. As for future developments, the potential of layered synthesis technology is infinite. Although composites for additive technology are widely used in the scientific and technical fields, they still suffer from a number of drawbacks, which developers and researchers of 3D printed polymer materials have been working on to remove.
German patent No. 1998513345 discloses a thermoplastic composite material comprising at least one poly (arylene ether), a filler or reinforcing material, and a modified carboxyl-containing poly (arylene ether) having repeating structural elements, which composite material has improved melt stability and mechanical properties, but does not indicate whether the composite material can be used in additive technology.
US patent No. US6495615 discloses thermoplastic polymer materials with improved impact toughness comprising thermoplastic polyether sulfone polymers with glass fibers processed with polyolefin waxes, which polymer materials have a high modulus of elasticity and improved impact toughness.
U.S. Pat. No. 5, 8703862, 2 discloses a composite material comprising at least one poly (arylene ether) containing on average not more than 0.1 phenolic end groups per polymer chain in an amount of 20 to 92% by weight, and another poly (arylene ether) containing on average 1.5 phenolic end groups per polymer chain in an amount of 3 to 20% by weight, and a fibrous or dispersed filler in an amount of 5 to 60% by weight, and further additives and/or process additives in an amount of 0 to 40% by weight. The composite materials are distinguished by a significantly improved melt stability and good mechanical properties.
The main disadvantage of these composites is however that there is no complete information about the material properties, i.e. no information about moisture absorption, which is a very important feature of the produced polymer material, and that none of these composites can be applied for 3D printing.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a composite material for 3D printing with high mechanical properties and low hygroscopicity, and a preparation method thereof.
The invention provides a composite material for 3D printing, which comprises:
preferably, the organic modified clay is urea modified montmorillonite; the urea-modified montmorillonite is prepared according to the following steps: mixing urea and montmorillonite in water to obtain urea modified montmorillonite.
Preferably, the mass of the urea is 2-10% of the mass of the montmorillonite.
Preferably, the mass of the urea is 5% of the mass of the montmorillonite.
Preferably, the polyphenylsulfone resin is Radel R-5100.
Preferably, the glass fibers are chopped glass fiber filaments.
Preferably, the length of the chopped glass fiber yarns is 1-5 mm.
The invention also provides a preparation method of the composite material for 3D printing, which comprises the following steps:
mixing and heating 100 parts by weight of polyphenylsulfone resin, 32-35 parts by weight of polycarbonate, 1-3 parts by weight of glass fiber and 0.5-2 parts by weight of organic modified clay to obtain the composite material for 3D printing.
Preferably, the temperature of the mixing and heating is 140-160 ℃.
The invention provides a composite material for 3D printing, which comprises: 100 parts by weight of polyphenylsulfone resin; 32-35 parts by weight of polycarbonate; 1-3 parts of glass fiber; 0.5-2 parts by weight of organic modified clay. Compared with the prior art, the invention takes the polyphenylsulfone resin and the polycarbonate as resin raw materials, improves the physical and mechanical properties of the composite material by adding the glass fiber, and simultaneously reduces the water absorption of the composite material by adding the organic modified clay, so that the obtained composite material has higher mechanical properties and lower water absorption.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a composite material for 3D printing, which comprises:
the present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
The invention takes the polyphenylene sulfone resin (PPSU) as a base material, and the polyphenylene sulfone resin has the preferred melt flow rate of 10-30 g/10min, more preferably 12-25 g/10min, and still more preferably 14-20 g/10 min; in the present invention, the polyphenylsulfone resin is most preferably Radel R-5100.
The content of the polycarbonate is preferably 33 to 35 parts by weight, and more preferably 34 to 35 parts by weight; the polycarbonate is preferably a granulate of the brand Carbomix, which is prepared according to technical Specification 2226-.
The content of the glass fiber is preferably 1-2.5 parts by weight; in some embodiments provided herein, the glass fibers are preferably present in an amount of 1 part by weight; in some embodiments provided herein, the glass fibers are preferably present in an amount of 1.2 parts by weight; in some embodiments provided herein, the glass fibers are preferably present in an amount of 2.4 parts by weight; in some embodiments provided herein, the glass fibers are preferably present in an amount of 2.5 parts by weight; in other embodiments provided herein, the glass fibers are preferably present in an amount of 3 parts by weight; the glass fiber is preferably chopped glass fiber yarn; the length of the chopped glass fiber filaments is preferably 1-5 mm, more preferably 2-4 mm, and further preferably 3 mm.
According to the invention, the content of the organic modified clay is preferably 1 to 2 parts by weight, more preferably 1.5 to 2 parts by weight; in some embodiments provided herein, the organically modified clay is preferably present in an amount of 0.5 parts by weight; in some embodiments provided herein, the organically modified clay is preferably present in an amount of 1 part by weight; in some embodiments provided herein, the organically modified clay is preferably present in an amount of 1.5 parts by weight; in other embodiments provided herein, the organically modified clay is preferably present in an amount of 2 parts by weight; the organically modified clay is preferably organically modified montmorillonite, more preferably urea modified montmorillonite.
The clay-modified montmorillonite is preferably prepared according to the following method: mixing urea and montmorillonite in water to obtain urea modified montmorillonite; the cation exchange capacity of the montmorillonite is preferably 80-150 milliequivalent/100 g, more preferably 90-120 milliequivalent/100 g, further preferably 90-100 milliequivalent/100 g, and most preferably 95 milliequivalent/100 g; the mass of the urea is preferably 2 to 10 percent of the mass of the montmorillonite, more preferably 4 to 8 percent, still more preferably 4 to 6 percent and most preferably 5 percent; in the invention, preferably, the montmorillonite and the water are mixed and stirred firstly, and then the urea is added for continuous stirring; the mixing and stirring time is preferably 10-40 min, more preferably 20-40 min, and further preferably 30 min; the continuous stirring time is preferably 1-4 h, and more preferably 2-3 h; the steps are preferably carried out at room temperature; after the stirring is finished, preferably repeatedly decanting with water for many times, and drying at room temperature to obtain urea modified montmorillonite; the time for drying at room temperature is preferably 20-30 h, more preferably 22-28 h, and still more preferably 24-26 h.
The invention takes the polyphenylsulfone resin and the polycarbonate as resin raw materials, improves the physical and mechanical properties of the composite material by adding the glass fiber, and simultaneously reduces the water absorption of the composite material by adding the organic modified clay, so that the obtained composite material has higher mechanical properties and lower water absorption.
The invention also provides a preparation method of the composite material for 3D printing, which comprises the following steps: mixing and heating 100 parts by weight of polyphenylsulfone resin, 32-35 parts by weight of polycarbonate, 1-3 parts by weight of glass fiber and 0.5-2 parts by weight of organic modified clay to obtain the composite material for 3D printing.
Wherein, the polyphenylsulfone resin, the polycarbonate, the glass fiber and the organic modified clay are shown in the same way, and are not described again.
Mixing and heating the polyphenylsulfone resin, the polycarbonate, the glass fiber and the organic modified clay to obtain a composite material for 3D printing; the mixing and heating temperature is preferably 140-160 ℃, and more preferably 146-160 ℃; the mixing and heating are preferably carried out in an extruder; the temperatures of the four heating zones of the extruder are preferably 146 ℃, 149 ℃, 155 ℃ and 160 ℃ in this order.
In order to further illustrate the present invention, the following describes a composite material for 3D printing and a method for preparing the same in detail with reference to examples.
The reagents used in the following examples are all commercially available; the PPSU used in the examples was Radel R5100; polycarbonate is a particle of the brand Carbomix, prepared according to technical Specification 2226-; the glass fiber is chopped glass fiber filaments with the fiber length of 3 mm; the organic modified clay is urea modified montmorillonite, and the mass of the urea is 5% of that of the montmorillonite.
Examples 1 to 6
Sequentially loading the PPSU, the polycarbonate, the glass fiber and the organic modified clay into a working mixer according to the amount of the PPSU, the polycarbonate, the glass fiber and the organic modified clay specified in the formula (Table 1); and pouring the obtained powdery mixture into an extruder, and correspondingly processing the powdery mixture in areas I-IV, namely the temperature of 146 ℃, 149 ℃, 155 ℃ and 160 ℃ to obtain particles, namely the composite material for 3D printing.
The obtained particles were used to prepare polymer filaments having a diameter of 1.75 mm for subsequent use to obtain samples for 3D printing tests. Samples were obtained using a 3D printer RobozeOne + 400.
In the study of composite materials, the following criteria were used:
1. national standard 9550-81; plastic; a method of determining the modulus of elasticity in tension, compression, bending;
2. national Standard 4648-2014(ISO 178: 2010); plastic; static bending test method (revision);
3. 11262-80 (C.EPE. beta. 1199-78) of the national Standard of Perilla; plastic; tensile test method (N1 variation);
4. national Standard 4650-2014(ISO 62: 2008); plastic; method for determining water absorption.
The test results are shown in table 2.
Table 1 composition of composites of examples
Table 2 composite material performance test results
Claims (8)
1. A composite material for 3D printing, comprising:
the organic modified clay is urea modified montmorillonite;
the glass fiber is chopped glass fiber yarn.
2. The composite material for 3D printing according to claim 1, wherein the urea-modified montmorillonite is prepared according to the following steps: mixing urea and montmorillonite in water to obtain urea modified montmorillonite.
3. The composite material for 3D printing according to claim 2, wherein the mass of the urea is 2% to 10% of the mass of the montmorillonite.
4. The composite material for 3D printing according to claim 2, characterized in that the mass of urea is 5% of the mass of montmorillonite.
5. The composite for 3D printing according to claim 1, wherein the polyphenylsulfone resin is Radel R-5100.
6. The composite material for 3D printing according to claim 1, wherein the chopped glass fiber filaments have a length of 1 to 5 mm.
7. A method of preparing the composite material for 3D printing according to claim 1, comprising:
mixing and heating 100 parts by weight of polyphenylsulfone resin, 32-35 parts by weight of polycarbonate, 1-3 parts by weight of glass fiber and 0.5-2 parts by weight of organic modified clay to obtain the composite material for 3D printing.
8. The method of claim 7, wherein the temperature of the mixing and heating is 140 ℃ to 160 ℃.
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| CN201910433618.XA CN110105763B (en) | 2019-05-23 | 2019-05-23 | Composite material for 3D printing and preparation method thereof |
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| CN201910433618.XA CN110105763B (en) | 2019-05-23 | 2019-05-23 | Composite material for 3D printing and preparation method thereof |
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| CN110105763B true CN110105763B (en) | 2021-10-15 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1784295A (en) * | 2003-05-05 | 2006-06-07 | 斯特拉塔西斯公司 | Material and method for three-dimensional modeling |
| CN107141799A (en) * | 2017-06-19 | 2017-09-08 | 合肥斯科尔智能科技有限公司 | A kind of architectural engineering resistance to oxidation high intensity 3D printing material and preparation method thereof |
| WO2018101537A1 (en) * | 2016-11-29 | 2018-06-07 | 주식회사 삼양사 | Eco-friendly polycarbonate resin composition having excellent adhesion |
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2019
- 2019-05-23 CN CN201910433618.XA patent/CN110105763B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1784295A (en) * | 2003-05-05 | 2006-06-07 | 斯特拉塔西斯公司 | Material and method for three-dimensional modeling |
| WO2018101537A1 (en) * | 2016-11-29 | 2018-06-07 | 주식회사 삼양사 | Eco-friendly polycarbonate resin composition having excellent adhesion |
| CN107141799A (en) * | 2017-06-19 | 2017-09-08 | 合肥斯科尔智能科技有限公司 | A kind of architectural engineering resistance to oxidation high intensity 3D printing material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Development of composite material based on polyphenylene sulfone for 3D printing;A.L.Slonov et al;《Fibre Chemistry》;20181130;第50卷(第4期);第373-377页 * |
| 超细蒙脱石粉体的制备;陈剑;《中国优秀硕士学位论文全文数据库工程科技I辑》;20130415(第4期);第B020-249页 * |
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