阅读说明：本技术 一种适用于3d打印的低温材料及其制备方法 (Low-temperature material suitable for 3D printing and preparation method thereof ) 是由 钟云腾 贺礼 白崇庆 王尘 吴立夫 于 2021-08-26 设计创作，主要内容包括：本申请提供了一种适用于3D打印的低温材料及其制备方法,所述3D打印的低温材料包括石蜡、增粘剂、增韧剂和松香,通过各组分间在特定条件下的相互作用制备得到呈液体状态的适用于3D打印的低温材料,该适用于3D打印的低温材料有效地提高了打印过程中材料的传输速度,提高3D打印的速度,同时液体形态的适用于3D打印的低温材料能够有效克服现有的3D打印材料存在的线材不能弯曲太大,材料和导料管内壁的摩擦力过大,线材韧性差、打印层面出现断层等的缺陷。此外,本发明采用石蜡作为基本材料,根据石蜡的性质在进行3D打印之后能够实现回收重复利用,大大降低了3D打印的成本。(The application provides a low temperature material suitable for 3D prints and preparation method thereof, the low temperature material that 3D printed includes paraffin, tackifier, toughening agent and rosin, the interact preparation under specific conditions through each component obtains the low temperature material that is applicable to 3D printing that is the liquid state, this low temperature material suitable for 3D printing has improved the transmission rate of printing in-process material effectively, improve the speed that 3D printed, the low temperature material that is applicable to 3D printing of liquid form can effectively overcome the wire rod that current 3D printed the material and exists and can not bend too big simultaneously, the frictional force of material and stock guide pipe inner wall is too big, wire rod toughness is poor, the printing aspect appears the defect of fault etc.. In addition, the paraffin is used as a basic material, and can be recycled after 3D printing according to the property of the paraffin, so that the cost of 3D printing is greatly reduced.)

1. The low-temperature material suitable for 3D printing is characterized by comprising the following raw materials in parts by mass: 40-60 parts of paraffin, 10-50 parts of tackifier, 10-30 parts of flexibilizer and 5-15 parts of rosin.

2. The low-temperature material suitable for 3D printing as claimed in claim 1, wherein the tackifier is one or more of phenolic resin, polyethylene terephthalate and hydrogenated styrene-butadiene block copolymer.

3. The low-temperature material suitable for 3D printing as claimed in claim 1, wherein the toughening agent is one or more of polyethylene, polypropylene and polystyrene.

4. The low-temperature material suitable for 3D printing as claimed in claim 1, wherein the mass ratio of the toughening agent, the tackifier and the rosin is (3-7): 1-2): 1.

5. The low-temperature material suitable for 3D printing as claimed in claim 1, wherein the particle diameter of the tackifier is 2.0-4.0 mm, and the viscosity is 100-800 mpa.s.

6. The low-temperature material suitable for 3D printing as claimed in claim 1, wherein the softening point of the rosin is 70-80 ℃, and the acid value of the rosin is 150-170 mgKOH/g.

7. The preparation method of the low-temperature material suitable for 3D printing as claimed in any one of claims 1-6, characterized by comprising the following steps in sequence:

s1, firstly, placing the paraffin with the formula amount into a container to be heated to be liquid, heating while stirring, firstly stirring at a low speed, after the temperature of the paraffin rises to 200-250 ℃, increasing the stirring speed, then slowly adding the tackifier particles with the formula amount of 1/10 into the high-temperature liquid paraffin, stirring until the tackifier particles are completely melted, adding the tackifier with the residual formula amount, and waiting for complete liquefaction to obtain an intermediate liquid A;

and S2, continuously stirring the intermediate liquid A obtained in the step S1, slowly adding a toughening agent in a formula amount, heating and stirring until the toughening agent is completely liquefied, finally adding rosin in a formula amount, stirring until the rosin is completely liquefied, standing and cooling to obtain the low-temperature material suitable for 3D printing.

8. The method of claim 7, wherein the stirring speed of the slow stirring in step S1 is 150r/min, and the stirring speed after the lifting is 240 r/min.

9. The method according to claim 7, wherein the intermediate liquid A in the step S2 is continuously stirred for 10-20 min.

10. The method according to claim 7, wherein the temperature of the mixture obtained in step S2 is 70 to 90 ℃.

Technical Field

The invention belongs to the field of 3D printing materials, and particularly relates to a low-temperature material suitable for 3D printing and a preparation method thereof.

Background

The 3D printing technology, as an emerging rapid prototyping technology, is mainly applied to the fields of product prototyping, mold manufacturing, artistic creation, jewelry making, and the like, and is used to replace some conventional finishing processes in these fields. In addition, the 3D printing technology is gradually applied to the fields of medicine, bioengineering, construction, clothing and the like, and a wide space is opened for innovation. At present, the 3D printing and forming method mainly includes Fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), Stereolithography (SLA), and Layered Object Manufacturing (LOM), wherein FDM is the fastest developing technology.

FDM means that the filiform thermoplastic material is fed into a spray head by a wire feeder, heated to a molten state in the spray head and extruded through a nozzle. And extruding the molten filamentous material, solidifying and molding at a specified position according to a path controlled by layered data of three-dimensional software, depositing and solidifying layer by layer, and finally forming the whole three-dimensional product. Traditional FDM's 3D print head department will draw a long wire rod, and the wire rod will extrude the shower nozzle through the extruder, so the wire rod can not have too big bending, and big bending can increase the frictional force of material and passage inner wall, and too big bending, wire rod will break, can lead to the not enough or fault of printer shower nozzle ejection of compact like this, causes 3D to print the model and prints the fault phenomenon that appears. FDM adopts melt extrusion, and extrusion speed is limited, has greatly restricted 3D printer's printing speed. Therefore, a 3D printing material with better mechanical properties, better printing performance and faster printing speed needs to be developed.

Patent document CN107189423A discloses an antifriction material printed based on FDM3D, a preparation method thereof and a method for enhancing antifriction performance of the material product, wherein the preparation method comprises the following steps: 1) mixing the components of the composition; the mixing mode is preferably fully mixed for 5-30 minutes by a high-speed mixer; 2) melting and plasticizing the mixture obtained after mixing in the step 1) through a double-screw extruder, and granulating through a granulator; the method for enhancing the antifriction performance of the antifriction material part based on FDM3D printing comprises the following steps: 1) preparing a 3D printed article from the friction reducing material printed based on FDM 3D; 2) putting the 3D printed part obtained in the step 1) into an electromagnetic induction heating furnace, and melting the babbitt metal to fill the gaps in the part. The friction reducing material for FDM3D printing has friction reducing characteristics, but the mechanical property of a product obtained by printing is poor.

Patent document CN105778423A discloses a novel thermosetting 3D printing material, which uses thermosetting resin as a matrix material and consists of A, B two components; the component A consists of liquid matrix resin, a diluent, a toughening agent, a filler, a defoaming agent and a pigment, and the component B consists of a curing agent or a crosslinking agent, a defoaming agent and a filler; respectively materializing the component A and the component B into fine fog drops, then achieving a fog mixing effect, and finally settling to a printing layer to realize thin-layer printing; due to rapid curing, the ink can be piled layer by layer without flowing during printing; the final product can be subjected to medium-temperature post-curing, so that the strength is improved. The product printed by the thermosetting 3D printing material has smooth surface and high strength, but has poor printing performance.

Disclosure of Invention

The invention aims to provide a low-temperature material suitable for 3D printing, a liquid-form 3D printing material is prepared through interaction among raw material components, the transmission speed of the material in the printing process is effectively improved, and meanwhile, the liquid-form low-temperature material suitable for 3D printing can effectively overcome the defects that a wire cannot be bent too much, the friction force between the material and the inner wall of a guide pipe is too large, the toughness of the wire is poor, a printing layer surface has faults and the like in the conventional 3D printing material.

In order to achieve the purpose, the invention adopts the following technical scheme: the low-temperature material suitable for 3D printing comprises the following raw materials in parts by mass: 40-60 parts of paraffin, 10-50 parts of tackifier, 10-30 parts of flexibilizer and 5-15 parts of rosin.

Preferably, the tackifier is one or more of phenolic resin, polyethylene terephthalate and hydrogenated styrene-butadiene block copolymer.

Preferably, the toughening agent is one or more of polyethylene, polypropylene and polystyrene.

Preferably, the mass ratio of the toughening agent to the tackifier to the rosin is (3-7): 1-2): 1.

Preferably, the particle diameter of the tackifier is 2.0-4.0 mm, and the viscosity is 100-800 mpa.s.

Preferably, the softening point of the rosin is 70-80 ℃, and the acid value of the rosin is 150-170 mgKOH/g.

In addition, the invention also provides a preparation method of the low-temperature material suitable for 3D printing, which comprises the following steps of:

s1, firstly, placing the paraffin with the formula amount into a container to be heated to be liquid, heating while stirring, firstly stirring at a low speed, after the temperature of the paraffin rises to 200-250 ℃, increasing the stirring speed, then slowly adding the tackifier particles with the formula amount of 1/10 into the high-temperature liquid paraffin, stirring until the tackifier particles are completely melted, adding the tackifier with the residual formula amount, and waiting for complete liquefaction to obtain an intermediate liquid A;

s2, continuously stirring the intermediate liquid A obtained in the step S1, slowly adding a toughening agent in a formula amount, heating and stirring until the toughening agent is completely liquefied, finally adding rosin in a formula amount, stirring until the rosin is completely liquefied, standing and cooling to obtain the low-temperature material suitable for 3D printing.

Preferably, the stirring speed of the slow stirring in the step S1 is 150r/min, and the stirring speed after the lifting is 240 r/min.

Preferably, the continuous stirring time of the intermediate liquid A in the step S2 is 10-20 min.

Preferably, the standing and cooling step S2 is to a temperature of 70-90 ℃.

In the invention, paraffin is used as a base material, and a tackifier and a flexibilizer are added on the basis, so that the viscosity and toughness of the material are effectively enhanced through the combined action of the raw material components, and the material can be drawn at a small distance in the printing process; the rosin is added into the raw material components for reaction, so that the hardness of the material can be effectively enhanced, the final printing model has better mechanical property, and the use requirement is met. In addition, the low-temperature material which is prepared according to the specific steps and is suitable for 3D printing exists in a liquid state, so that the transmission speed of the material in the material guide pipe of the 3D printer is effectively improved, and the printing performance can be kept better in the printing process.

Compared with the prior art, the invention has the following beneficial effects:

(1) the prepared low-temperature material suitable for 3D printing is in a liquid state, the transmission speed of the material in a material guide pipe of a 3D printer can be effectively improved in the FDM3D printing process, the printing speed of the FDM3D printer is greatly improved, and the defects that a wire cannot be bent too much, the friction force between the material and the inner wall of the material guide pipe is too large, the toughness of the wire is poor, a printing layer surface has faults and the like in the conventional FDM3D printing material can be effectively overcome.

(2) The low-temperature material suitable for 3D printing prepared by the invention has liquid property due to the fact that paraffin is used as a basic raw material, so that a feeding guide pipe can be arranged on any shaft of X or Y in the 3D printing process, and can be bent at any angle, and convenience in consumable transmission is further improved.

(3) The low-temperature material suitable for 3D printing provided by the invention adopts paraffin as a basic material, and can be recycled and reused after 3D printing according to the physical property that the paraffin is heated and melted into a liquid state, so that the cost of 3D printing is greatly reduced.

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.

Embodiment 1, a low-temperature material suitable for 3D printing and a preparation method thereof

The formula is as follows: 400g of paraffin, 350g of polyethylene, 50g of phenolic resin and 50g of rosin.

The preparation method comprises the following steps: s1, firstly, putting the formula amount of paraffin into a container to be heated to be liquid, heating while stirring, firstly stirring at the speed of 150r/min, after the temperature of the paraffin rises to 200 ℃, increasing the stirring speed to 240r/min, then slowly adding 1/10 formula amount of phenolic resin into the high-temperature liquid paraffin, stirring until the paraffin is completely melted, adding the rest formula amount of phenolic resin, and waiting for complete liquefaction to obtain intermediate liquid A;

s2, continuously stirring the intermediate liquid A obtained in the step S1 for 10min, slowly adding polyethylene according to the formula amount, heating and stirring until the mixture is completely liquefied, finally adding rosin according to the formula amount, stirring until the mixture is completely liquefied, standing and cooling to 70 ℃ to obtain the low-temperature material suitable for 3D printing.

Embodiment 2, low-temperature material suitable for 3D printing and preparation method thereof

The formula is as follows: 500g of paraffin wax, 300g of polypropylene, 200g of polyethylene terephthalate and 100g of rosin.

The preparation method comprises the following steps: s1, firstly, putting the formula amount of paraffin into a container to be heated to be liquid, heating while stirring, firstly stirring at the speed of 150r/min, after the temperature of the paraffin rises to 230 ℃, increasing the stirring speed to 240r/min, then slowly adding 1/10 formula amount of polyethylene terephthalate into the high-temperature liquid paraffin, stirring until the mixture is completely melted, adding the rest formula amount of polyethylene terephthalate, and waiting for complete liquefaction to obtain intermediate liquid A;

s2, continuously stirring the intermediate liquid A obtained in the step S1 for 15min, slowly adding the formula amount of polypropylene, heating and stirring until the mixture is completely liquefied, finally adding the formula amount of rosin, stirring until the mixture is completely liquefied, standing and cooling to 80 ℃, and thus obtaining the low-temperature material suitable for 3D printing.

Embodiment 3, low-temperature material suitable for 3D printing and preparation method thereof

The formula is as follows: 600g of paraffin wax, 500g of polystyrene, 200g of hydrogenated styrene-butadiene block copolymer and 100g of rosin.

The preparation method comprises the following steps: s1, firstly, putting the formula amount of paraffin into a container to be heated to be liquid, heating while stirring, firstly stirring at the speed of 150r/min, after the temperature of the paraffin rises to 250 ℃, increasing the stirring speed to 240r/min, then slowly adding 1/10 formula amount of polyethylene terephthalate into the high-temperature liquid paraffin, stirring until the mixture is completely melted, adding the rest formula amount of polyethylene terephthalate, and waiting for complete liquefaction to obtain intermediate liquid A;

s2, continuously stirring the intermediate liquid A obtained in the step S1 for 30min, slowly adding the formula amount of polypropylene, heating and stirring until the mixture is completely liquefied, finally adding the formula amount of rosin, stirring until the mixture is completely liquefied, standing and cooling to 90 ℃, and thus obtaining the low-temperature material suitable for 3D printing.

Embodiment 4, a low-temperature material suitable for 3D printing and a preparation method thereof

The formula is as follows: 500g of paraffin wax, 300g of polystyrene, 200g of polyethylene terephthalate and 100g of rosin.

The preparation method comprises the following steps: s1, firstly, putting the formula amount of paraffin into a container to be heated to be liquid, heating while stirring, firstly stirring at the speed of 150r/min, after the temperature of the paraffin rises to 230 ℃, increasing the stirring speed to 240r/min, then slowly adding 1/10 formula amount of polyethylene terephthalate into the high-temperature liquid paraffin, stirring until the mixture is completely melted, adding the rest formula amount of polyethylene terephthalate, and waiting for complete liquefaction to obtain intermediate liquid A;

s2, continuously stirring the intermediate liquid A obtained in the step S1 for 15min, slowly adding the polystyrene according to the formula amount, heating and stirring until the polystyrene is completely liquefied, finally adding the rosin according to the formula amount, stirring until the rosin is completely liquefied, standing and cooling to 80 ℃ to obtain the low-temperature material suitable for 3D printing.

Comparative example 1, 3D printing material and preparation method thereof

The comparative example differs from example 2 only in that: polypropylene and rosin are not contained.

The preparation method is the same as example 2.

Comparative example 2, 3D printing material and preparation method thereof

The comparative example differs from example 2 only in that: polypropylene is not included.

The preparation method is the same as example 2.

Comparative example 3, 3D printing material and preparation method thereof

The comparative example differs from example 2 only in that: does not contain rosin.

The preparation method is the same as example 2.

Comparative example 4, 3D printing material and preparation method thereof

The comparative example differs from example 2 only in that: the paraffin temperature was 150 ℃ when polyethylene terephthalate was added.

The preparation method is the same as example 2.

Comparative example 5, 3D printing material and preparation method thereof

The comparative example differs from example 2 only in that: the toughening agent, the tackifier and the rosin are added simultaneously.

The formula is as follows: 500g of paraffin wax, 300g of polypropylene, 200g of polyethylene terephthalate and 100g of rosin.

The preparation method comprises the following steps: firstly, putting the formula amount of paraffin into a container to be heated to liquid state, heating while stirring, firstly stirring at the speed of 150r/min, after the temperature of the paraffin rises to 230 ℃, increasing the stirring speed to 240r/min, then simultaneously adding the formula amount of polyethylene terephthalate, polypropylene and rosin, heating and stirring until the materials are completely liquefied, standing and cooling to 80 ℃ to obtain the high-performance high-temperature-resistant high-temperature-pressure-resistant high-temperature-resistant high-pressure-resistant high-temperature-pressure-resistant high-pressure-temperature-resistant high-pressure-resistant high-temperature-resistant high-pressure-temperature-resistant material.

Test example I, mechanical property test of 3D printing material

First, experimental sample

3D printing materials prepared in examples 1-4 and comparative examples 1-3.

Second, Experimental methods

2.1 tensile test

The formed part is prepared according to the experimental design standard of GB/T1041-2006 plastic tensile strength, the total length of the formed part is 100mm, the width of two ends is 10mm, the length of a middle narrowing part is 30mm, the width of the middle narrowing part is 5mm, and the height of the formed part is 5mm, then the formed part is fixed to two ends of a universal testing machine, and stretching is carried out at the speed of 5mm/min until the formed part is broken. Automatically collecting experimental data, and loading the experimental temperature to room temperature. In order to reduce experimental errors, 3 molded parts were printed per group and averaged in conjunction with the above orthogonal test table.

2.2 compression test

The compression forming part is prepared according to GB/T1041-2008 plastic compression strength experiment standard, a three-dimensional model of a cylindrical compression forming part with the diameter of 10mm and the height of 30mm is drawn by using Pro/E software, two ends of the forming part are wrapped by polytetrafluoroethylene adhesive tapes before the forming part is compressed, the friction coefficient in the experiment process is reduced, the accuracy of experiment data is ensured, downward loading is started by a load of 3KN initially, the loading speed is 5mm/min until a test piece cracks, the experiment data are automatically collected, and the loading experiment temperature is room temperature. In order to reduce experimental errors, 3 molded parts were printed per group and averaged in conjunction with the above orthogonal test table.

Third, experimental results

The tensile test and the compression test results of each sample are shown in tables 1 and 2.

TABLE 1 average tensile Strength results for each sample

TABLE 2 average compressive Strength results for each sample

As can be seen from the data in tables 1 and 2, the 3D printing materials prepared in examples 1 to 4 of the present invention have good tensile strength and compressive strength, and as can be seen from the experimental results of examples 1 to 4 and comparative examples 1 to 3, the tensile strength and compressive strength of the 3D printing material finally prepared in comparative examples 1 to 3 are significantly inferior to those of the examples of the present invention due to the lack of the toughening agent and the rosin component or the lack of one of the components, so that it can be proved that the interaction between the toughening agent and the rosin component in the present invention can effectively enhance the mechanical properties of the final 3D printing material.

Test example two, printing Performance test

First, experimental sample

3D printing materials prepared in examples 1-4 and comparative examples 4-5.

Second, Experimental methods

This study evaluated the extrudability of the printed material by comparing the smoothness of the material extrusion process, the extrusion line uniformity, and the surface condition. Wherein, the single-layer printing lifting height and the printing speed are set as fixed values, which are respectively 10mm and 100 mm/s. Considering that the printing lines can deform after being extruded by the upper layer material, three extrusion lines are sequentially and vertically printed and overlapped to be used as a group of samples, and the shape of each sample extrusion line is observed to evaluate the extrusion performance of the material.

Third, experimental results

The extrusion performance results are shown in table 3.

TABLE 3 print Performance test results for each sample

As can be seen from the experimental results in table 3, the low-temperature material suitable for 3D printing prepared in embodiments 1 to 4 of the present invention has a smooth printing process, and the printed lines have smooth surfaces and high uniformity, so as to further improve the quality of the finally printed 3D product; in the comparative example 4, the final printed line width is not uniform due to the fact that the paraffin temperature is not controlled within the range of 200-250 ℃ in the preparation process, the line width is obvious in granular sensation, and the printing process is interrupted; from the experimental results of the embodiments 1 to 4 and the comparative example 5, it can be seen that the quality of the obtained 3D printing material can be effectively improved by adding the raw material components in a specific ratio according to a specific sequence in the preparation process of the low-temperature material suitable for 3D printing, and the smoothness of the printing process can be favorably improved.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.