WO2022057298A1

WO2022057298A1 - Long basalt fiber thermoplastic consumable for 3d printing, preparation method therefor and preparation device therefor

Info

Publication number: WO2022057298A1
Application number: PCT/CN2021/095083
Authority: WO
Inventors: 石钱华; 田娅玲; 唐家文
Original assignee: 四川谦宜复合材料有限公司
Priority date: 2020-09-21
Filing date: 2021-05-21
Publication date: 2022-03-24
Also published as: CN112063167B; CN112063167A

Abstract

A long basalt fiber thermoplastic consumable for 3D printing belongs to the technical field of 3D printing, and is a continuous wire material prepared by impregnating and wrapping long basalt fiber bundle yarns with a thermoplastic resin. Said continuous wire material comprises the following components in parts by weight: 5 to 50 parts of a basalt fiber, 50 to 95 parts of a thermoplastic resin, and 1 to 5 parts of a coupling agent. The long basalt fiber bundle yarn is composed of 1 to 500 basalt fiber monofilaments having a diameter of 3 to 11 μm. Said consumable has advantages of high strength, high modulus, good electrical performance, impact resistance, high temperature resistance, etc. Further provided are a preparation method and a preparation device for the described long basalt fiber thermoplastic consumable for 3D printing, which can efficiently and continuously prepare high-quality continuous wire material.

Description

Long basalt fiber thermoplastic consumable for 3D printing, its preparation method and preparation device

technical field

The present application relates to the technical field of 3D printing, and in particular, to a long basalt fiber thermoplastic consumable for 3D printing, a preparation method and a preparation device thereof.

Background technique

3D printing is a kind of rapid prototyping technology. It appeared very early. The early masonry houses were the prototype of 3D printing. Since the first continuous carbon fiber 3D printer was launched in the United States in 2014, the technology is developing rapidly and has achieved success in the aviation field. application. With the gradual maturity and large-scale application of the technology, this technology may subvert the existing production mode of composite UAVs and low-cost composite aviation structures.

The design process of 3D printing is as follows: first modeling by computer modeling software, and then "partitioning" the built 3D model into layer-by-layer sections, that is, slices, so as to guide the printer to print layer by layer. 3D printing often uses laser technology. The needle of the printer moves to the place where it needs to be formed. The laser melts the solid material (the liquid is heated or illuminated to solidify and harden), and the melt is plastically printed and formed. Then the needle moves to the next point to print and completes step by step. print job.

With the expansion of 3D printing application fields, people's requirements for the strength and other properties of 3D printing blanks continue to increase. The core of 3D printing lies in the molding material. In some fields, traditional 3D printing materials cannot meet the strength requirements of the product well. Various research institutions at home and abroad have studied the use of fibers as reinforcements to composite ordinary 3D printing consumables for 3D printing, and chopped fiber reinforced thermoplastic resin matrix composite 3D printing filaments have been successfully prepared and successfully commercialized. The defects of the fiber itself, its addition amount, fiber length, etc. are always limited, and the reinforcement effect on the substrate is limited, and it still cannot meet the performance requirements of the application.

The Chinese patent with publication number CN108407300A discloses a continuous fiber reinforced resin-based composite material 3D printing filament preparation method and device, selecting dry fiber tows and thermosetting resin prepolymers that are solid at room temperature and their initiators, thermoplastic resins Or the mixed resin system is used as the preparation raw material, and the fiber tow is subjected to multiple yarn spreading, yarn splitting, pre-impregnated hot-melt resin, and yarn combination treatment in turn to obtain continuous fiber reinforced resin-based composite material 3D printing filaments, which greatly improves the performance of 3D printing. the properties of the molded components.

When the dry fiber tow is pre-impregnated with hot-melt resin, the pre-impregnation effect is poor, the distribution between the fiber and the resin is uneven, and the selected fiber itself has poor performance, so that the mechanical properties of the prepared filament still cannot be meet actual needs.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a long basalt fiber thermoplastic consumable material for 3D printing, which has the advantages of high strength, high modulus, good electrical properties, impact resistance, high temperature resistance and the like.

Another object of the present invention is to provide the above-mentioned preparation method of long basalt fiber thermoplastic consumables for 3D printing, which can effectively prepare high-quality long basalt fiber reinforced thermoplastic resin wires.

The third object of the present invention is to provide a preparation device for the above-mentioned long basalt fiber thermoplastic consumable material for 3D printing, and realize the efficient and continuous preparation of long basalt fiber reinforced thermoplastic resin wire through the preparation device of the present invention.

The present invention is achieved through the following technical solutions:

The invention provides a long basalt fiber thermoplastic consumable material for 3D printing, which is a continuous wire prepared by impregnating and wrapping thermoplastic resin with long basalt fiber bundles; the continuous wire comprises the following components by weight: 5-50 parts of basalt fibers , 50-95 parts of thermoplastic resin, and 1-5 parts of coupling agent; the long basalt fiber bundle yarn is composed of 1-500 basalt fiber monofilaments with a diameter of 3-11 μm.

The present invention selects basalt fiber as resin reinforcing fiber. Basalt fiber has high strength, high modulus, good high temperature resistance, oxidation resistance, radiation resistance, heat insulation and sound insulation, good filterability, high compressive strength and shear strength, and is suitable for various The composite material obtained by adding it to the thermoplastic resin has excellent properties of various properties.

The long basalt fiber bundle yarn of the present invention is impregnated with thermoplastic resin. Due to the high surface smoothness of the basalt fiber, the contact between the fiber and the resin is uniform during the impregnation process, so that the resin can fully infiltrate the fiber monofilament. The long basalt fiber bundles composed of basalt fiber monofilaments of 3-11 μm are impregnated with thermoplastic resin, preferably 200-300. If the number of monofilaments increases, the impregnation will be uneven and the impregnation effect will be poor.

The coupling agent of the present invention is selected from a silane coupling agent or a titanate coupling agent. The coupling agent is added to the thermoplastic resin. During the impregnation process, the coupling agent can increase the adhesion between the basalt fiber and the thermoplastic resin. It can effectively improve the performance of the final formed wire.

Preferably, the roll weight of the long basalt fiber bundle yarn is 3-10 kg.

The winding weight of the fiber bundle determines the length of the final continuous wire. The longer the wire is, the more convenient it is to apply and the better the printing effect.

Preferably, the thermoplastic resin is selected from at least one of polypropylene, polyethylene, polystyrene, nylon, polyvinyl chloride, and polyether ether ketone.

The present invention also provides a method for preparing long basalt fiber thermoplastic consumables for 3D printing, comprising the following steps: pulling long basalt fiber bundles, so that the long basalt fiber bundles are sequentially preheated, impregnated with thermoplastic resin, cooled, and finally Curl into continuous wire. Preferably, the preheating temperature is 170-230°C, the dipping temperature is 180-240°C, and the cooling temperature is 15-28°C.

In the preparation method of the present invention, the fiber bundle yarn is preheated first, so that the temperature of the fiber bundle yarn is similar to the melting temperature of the impregnating resin. It is found that the temperature of the two is similar, which can make the impregnation effect the best. Specifically, when the temperature is similar, the thermoplastic resin melt of the present invention has strong uniformity with the basalt fiber, and the thermoplastic resin melt has strong fluidity on the surface of the fiber, and it is easier to evenly wrap the surface of the fiber; The temperature of the two is similar, so that the bonding force of the two increases under the action of the coupling agent, and the bonding between the two is more stable.

The invention also provides a preparation device for long basalt fiber thermoplastic consumables for 3D printing, including a yarn feeding system, a preheating system, a dipping system, a cooling system, a detection system, a tensioning system and a winding system arranged in sequence.

Preferably, the yarn feeding system includes a forced unwinding device, a tension sensor and a rotating gauge knob device, an ultrasonic fiber bundle yarn positioning device, and a fiber bundle yarn C-type Uss evenness meter and a spectrometer device.

Preferably, the preheating system includes a carbon fiber heating element and a preheating temperature controller electrically connected to the carbon fiber heating element.

Preferably, the impregnation system includes a molten resin heating tank, a molten resin constant temperature tank and a constant temperature dipping tank connected in sequence; the molten resin heating tank is equipped with a heating temperature controller and a melt flow rate meter; the constant temperature dipping tank Equipped with constant pressure filter constant measuring device and digital display dial indicator.

Preferably, the cooling system includes a water cooling temperature controller and a water quantity controller.

Preferably, the detection system includes an on-line defect detection device and an NF series wire length tester device.

Preferably, the winding system includes a winding reel, a reel device and an on-line reel device.

The beneficial effects of the present invention are:

1. The present invention prepares a continuous wire that can be used for 3D printing by dipping thermoplastic resin on the surface of long basalt fibers, and the continuous wire is impregnated and wrapped with thermoplastic resin on the surface of long basalt fibers, so that the amount of fiber added can reach a higher level; and , the long basalt fiber of the present invention is a basalt fiber monofilament with a diameter of 3-11 μm, and its own performance is excellent; in addition, the surface of the basalt fiber is smooth, and the contact surface between the monofilament fiber and the resin is large and uniform. Therefore, the prepared wire has the advantages of high strength, high modulus, good electrical properties, impact resistance, high temperature resistance and the like.

2. The 3D printing consumables of the present invention are continuous wires that can be continuously supplied to the 3D printing head, and only need to cut off the wires when a cavity needs to be printed.

3. In the preparation method of the present invention, the fibers are preheated before re-impregnation, so that the temperature of the fibers and the resin melt is close, which can make the wrapping of the fibers more uniform and stable; the continuous impregnation method is adopted, so that continuous wires can be produced, The whole preparation process can be carried out continuously, the production method is simple, and the preparation efficiency is high.

4. The preparation device of the present invention has high intelligence, can ensure stable and orderly production, and can ensure the precision requirements of the prepared products.

Description of drawings

FIG. 1 is a schematic structural diagram of a device for preparing long basalt fiber thermoplastic consumables for 3D printing according to an embodiment of the present invention.

icon:

10- Yarn feeding system, 20- Preheating system, 21- Preheating box, 22- Carbon fiber heating element, 23- Preheating temperature detection probe, 24- Preheating temperature control panel, 30- Impregnation system, 31- Impregnation tank, 40-cooling system, 50-tensioning system, 51-fixed pulley, 52-moving pulley, 60-winding system, 61-winding reel.

detailed description

In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below.

Example 1

As shown in FIG. 1 , this embodiment provides a preparation device for long basalt fiber thermoplastic consumables for 3D printing, including a yarn feeding system 10 , a preheating system 20 , an impregnation system 30 , a cooling system 40 , and a detection system arranged in sequence. , tensioning system 50 and winding system 60 .

The yarn feeding system 10 includes a yarn feeding system including a forced unwinding device, a tension sensor and a rotating gauge knob device, an ultrasonic fiber bundle yarn positioning device, and a fiber bundle yarn C-type Usus evenness and spectrometer device. Specifically, the forced unwinding device includes a yarn unwinding roller 11, a tension sensor and a rotating stitch length knob device to control the tension of the fiber bundle to realize constant tension conveyance.

The preheating system 20 of this embodiment includes a preheating box 21, a carbon fiber heating body 22 disposed in the preheating box 21, and a preheating temperature controller electrically connected to the carbon fiber heating body 22. Further, the preheating controller includes a device The preheating temperature detection probe 23 in the preheating box 21 and the preheating temperature control panel 24 provided outside the preheating box 21 .

The dipping system 30 includes a molten resin heating tank, a molten resin constant temperature tank and a constant temperature dipping tank which are connected in sequence; the molten resin heating tank is equipped with a heating temperature controller and a melt flow rate meter; the constant temperature dipping tank is equipped with a constant pressure filter constant measuring device and Digital display dial indicator. When in use, the resin is heated in the molten resin heating tank with a temperature higher than the melting temperature of the melt, and then the heated and molten resin is introduced into the molten resin thermostatic tank for heat preservation, and the heat preservation temperature is 170-230 ° C. A heating device is provided to keep the temperature in the dipping tank 31 at 180-240°C. As the pre-dipping progresses, the molten resin in the dipping tank 31 will be consumed, and the molten resin thermostatic tank will continue to feed the dipping tank at a constant rate. Molten resin is supplied in 31 to maintain proper liquid level in dip tank 31 at all times.

The wire rod enters the cooling system 40 after being pre-impregnated by the impregnation system 30. The cooling system 40 in this embodiment includes a cooling temperature controller and a water quantity controller. The cooling temperature controller and the water volume controller are used to detect and regulate the temperature and water volume of the cooling liquid in the cooling box.

After passing through the cooling system 40, the wire also needs to be tested by a detection system. The detection system of this embodiment includes an online defect detection device and an NF series wire length tester device, which respectively detect the surface of the wire and the length of the wire.

The tensioning system 50 of this embodiment includes several fixed pulleys 51 and several movable pulleys 52 . The wire is wound on the fixed pulley 51 and the movable pulley 52 in turn, which can adjust the speed, delay the length, and adjust the tension.

After passing through the tensioning system 50, the wire enters the winding system 60 and is wound on the winding reel 61. The winding system 60 in this embodiment includes the winding reel 61, a take-up device and a reel device. Both the cylinder removal device and the cylinder loading device are manipulators, and the operation is simple and quick.

To sum up, the preparation device of the long basalt fiber thermoplastic consumable for 3D printing in this embodiment has a good degree of automation, and can intelligently control the process parameters of each stage, so as to ensure the smooth progress of the production and preparation process.

Example 2

This embodiment provides a method for preparing long basalt fiber thermoplastic consumables for 3D printing, including the following steps: pulling long basalt fiber bundles, so that the long basalt fiber bundles are sequentially preheated, impregnated with thermoplastic resin, cooled, and finally Curl into continuous wire. The preheating temperature was 170°C, the impregnation temperature was 240°C, and the cooling temperature was 20°C.

Example 3

This embodiment provides a method for preparing long basalt fiber thermoplastic consumables for 3D printing, including the following steps: pulling long basalt fiber bundles, so that the long basalt fiber bundles are sequentially preheated, impregnated with thermoplastic resin, cooled, and finally Curl into continuous wire. The preheating temperature was 180°C, the impregnation temperature was 230°C, and the cooling temperature was 20°C.

Example 4

This embodiment provides a method for preparing long basalt fiber thermoplastic consumables for 3D printing, including the following steps: pulling long basalt fiber bundles, so that the long basalt fiber bundles are sequentially preheated, impregnated with thermoplastic resin, cooled, and finally Curl into continuous wire. The preheating temperature was 180°C, the impregnation temperature was 190°C, and the cooling temperature was 20°C.

Example 5

This embodiment provides a long basalt fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with long basalt fiber bundles; the continuous wire includes the following components by weight: 5 parts of basalt fiber, 95 parts of PA6 , 3 parts of silane coupling agent; the long basalt fiber bundle yarn is composed of 10 basalt fiber monofilaments with a diameter of 11 μm, and the roll weight of the long basalt fiber bundle yarn is 3kg.

The long basalt fiber thermoplastic consumable material for 3D printing in this example was prepared on the preparation device of Example 1 according to the preparation method of Example 4.

Example 6

This embodiment provides a long basalt fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with long basalt fiber bundles; the continuous wire includes the following components by weight: 20 parts of basalt fiber and 80 parts of PA6 , 3 parts of silane coupling agent; the long basalt fiber bundle yarn is composed of 100 basalt fiber monofilaments with a diameter of 6 μm, and the roll weight of the long basalt fiber bundle yarn is 6kg.

The long basalt fiber thermoplastic consumable material for 3D printing in this example was prepared on the preparation device of Example 1 according to the preparation method of Example 2.

Example 7

The long basalt fiber thermoplastic consumable material for 3D printing in this example was prepared on the preparation device of Example 1 according to the preparation method of Example 3.

Example 8

Example 9

This embodiment provides a long basalt fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with long basalt fiber bundles; the continuous wire includes the following components by weight: 40 parts of basalt fiber and 60 parts of PA6 , 3 parts of silane coupling agent; the long basalt fiber bundle yarn is composed of 300 basalt fiber monofilaments with a diameter of 9 μm, and the roll weight of the long basalt fiber bundle yarn is 10kg.

Example 10

This embodiment provides a long basalt fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with long basalt fiber bundles; the continuous wire includes the following components by weight: 50 parts of basalt fiber, 50 parts of PA6 , 3 parts of silane coupling agent; the long basalt fiber bundle yarn is composed of 500 basalt fiber monofilaments with a diameter of 4 μm, and the roll weight of the long basalt fiber bundle yarn is 9kg.

Comparative Example 1

This comparative example provides a glass fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with glass fiber bundles; the continuous wire includes the following components by weight: 20 parts of glass fiber, 80 parts of PA6, silane 3 parts of coupling agent; the glass fiber bundle yarn is composed of 300 basalt fiber monofilaments with a diameter of 9 μm, and the roll weight of the glass fiber bundle yarn is 10 kg.

The glass fiber thermoplastic consumable for 3D printing of this comparative example was prepared on the preparation device of Example 1 according to the preparation method of Example 4.

Comparative Example 2

This embodiment provides a long basalt fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with long basalt fiber bundles; the continuous wire includes the following components by weight: 20 parts of basalt fiber and 80 parts of PA6 , 3 parts of silane coupling agent; the long basalt fiber bundle yarn is composed of 800 basalt fiber monofilaments with a diameter of 9 μm, and the roll weight of the long basalt fiber bundle yarn is 15kg.

The long basalt fiber thermoplastic consumable material for 3D printing in this comparative example was prepared on the preparation device of Example 1 according to the preparation method of Example 4.

Comparative Example 3

This embodiment provides a long basalt fiber thermoplastic consumable for 3D printing, which is a continuous wire prepared by impregnating and wrapping PA6 with long basalt fiber bundles; the continuous wire includes the following components by weight: 20 parts of basalt fiber and 80 parts of PA6 , 3 parts of silane coupling agent; the long basalt fiber bundle yarn is composed of 300 basalt fiber monofilaments with a diameter of 9 μm, and the roll weight of the long basalt fiber bundle yarn is 10kg.

The difference between the preparation method of the long basalt fiber thermoplastic consumable material for 3D printing in this example and Example 8 is that no preheating treatment is performed before the fiber is impregnated.

Experimental example

In this experimental example, the continuous wires prepared by the above-mentioned Examples 5-10 and Comparative Examples 1-3 were used to print samples of the same size with the same 3D printing equipment under the same parameter conditions, and the performance parameters of each sample were measured. As shown in Table 1:

Table 1 Performance parameters of each embodiment and comparative sample

试样sample	弯曲强度(MPa)Bending strength (MPa)	拉伸强度(MPa)Tensile strength (MPa)	层间剪切强度(MPa)Interlaminar Shear Strength (MPa)
实施例5Example 5	503503	375375	2525
实施例6Example 6	725725	449449	3939
实施例7Example 7	833833	552552	4545
实施例8Example 8	920920	623623	5353
实施例9Example 9	976976	682682	6161
实施例10Example 10	16241624	803803	7575
对比例1Comparative Example 1	665665	412412	3333
对比例2Comparative Example 2	621621	418418	2525

Comparative Example 3

625

389

30

From the experimental results in Table 1, it can be known that the mechanical properties of the long basalt fiber thermoplastic consumables for 3D printing prepared by the preparation method of the present invention are far superior to the prior art, and the number of fibers contained in the impregnated fiber bundle yarn is higher. less, the better the impregnation effect, and the better the mechanical properties of the obtained continuous wire; preheating the fiber before impregnation can significantly improve the impregnation effect of the fiber, and the closer the preheating temperature is to the impregnation temperature, the better the obtained wire The mechanical properties of the printed samples are better.

To sum up, the properties of the long basalt fiber thermoplastic consumable for 3D printing of the present invention are significantly improved, and it can be suitable for printing profiles of various structures, expand its application range, and develop the application of 3D printing in aerospace materials.

The above are only preferred embodiments of the present application, and are not intended to limit the present application. For those skilled in the art, the present application may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of this application shall be included within the protection scope of this application.

Claims

A long basalt fiber thermoplastic consumable for 3D printing, characterized in that it is a continuous wire prepared by impregnating and wrapping thermoplastic resin with long basalt fiber bundles; the continuous wire comprises the following components by weight: 5-50 parts of basalt fibers , 50-95 parts of thermoplastic resin, and 1-5 parts of coupling agent; the long basalt fiber bundle yarn is composed of 1-500 basalt fiber monofilaments with a diameter of 3-11 μm.
The long basalt fiber thermoplastic consumable material for 3D printing according to claim 1, wherein the roll weight of the long basalt fiber bundle yarn is 6-10 kg.
The long basalt fiber thermoplastic consumable material for 3D printing according to claim 1, wherein the thermoplastic resin is selected from at least one of polypropylene, polyethylene, polystyrene, nylon, polyvinyl chloride, and polyether ether ketone kind.
A method for preparing long basalt fiber thermoplastic consumables for 3D printing according to any one of claims 1-3, characterized in that it comprises the steps of: pulling long basalt fiber bundles, so that the long basalt fiber bundles are preheated in sequence , impregnated with thermoplastic resin, cooled, and finally wound into a continuous wire.
The method for preparing long basalt fiber thermoplastic consumables for 3D printing according to claim 4, wherein the preheating temperature is 170-230°C, and the impregnation temperature is 180-240°C.
A device for preparing long basalt fiber thermoplastic consumables for 3D printing according to any of claims 1-3, characterized in that it comprises a yarn feeding system, a preheating system, a dipping system, a cooling system, a detection system, a tensioning system, and a yarn feeding system arranged in sequence. systems and winding systems.
The device for preparing long basalt fiber thermoplastic consumables for 3D printing according to claim 6, wherein the yarn feeding system comprises a forced unwinding device, a tension sensor and a rotary stitch length knob device, and an ultrasonic fiber bundle yarn positioning device, And fiber bundle yarn C-type Uss evenness evenness meter and spectrometer device.
The device for preparing long basalt fiber thermoplastic consumables for 3D printing according to claim 6, wherein the preheating system comprises a carbon fiber heating element and a preheating temperature controller electrically connected to the carbon fiber heating element.
The device for preparing long basalt fiber thermoplastic consumables for 3D printing according to claim 6, wherein the impregnation system comprises a molten resin heating tank, a molten resin constant temperature tank and a constant temperature dipping tank connected in sequence; the molten resin heating The tank is equipped with a heating temperature controller and a melt flow rate meter; the constant temperature dipping tank is equipped with a constant pressure filter constant measuring device and a digital display dial gauge.
The device for preparing long basalt fiber thermoplastic consumables for 3D printing according to claim 6, wherein the detection system comprises an online defect detection device and an NF series line length tester device.