WO2016127521A1 - 一种短纤维增强热固性树脂复合产品的3d打印制造方法 - Google Patents

一种短纤维增强热固性树脂复合产品的3d打印制造方法 Download PDF

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WO2016127521A1
WO2016127521A1 PCT/CN2015/079374 CN2015079374W WO2016127521A1 WO 2016127521 A1 WO2016127521 A1 WO 2016127521A1 CN 2015079374 W CN2015079374 W CN 2015079374W WO 2016127521 A1 WO2016127521 A1 WO 2016127521A1
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thermosetting resin
composite product
preform
printing
blank
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PCT/CN2015/079374
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English (en)
French (fr)
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闫春泽
朱伟
史玉升
刘洁
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华中科技大学
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Priority to EP15881682.7A priority Critical patent/EP3257658B1/en
Priority to PCT/CN2015/079374 priority patent/WO2016127521A1/zh
Priority to JP2017530287A priority patent/JP6386185B2/ja
Publication of WO2016127521A1 publication Critical patent/WO2016127521A1/zh
Priority to US15/615,795 priority patent/US20170266882A1/en
Priority to US16/740,511 priority patent/US20200147900A1/en

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    • B29C67/04—Sintering
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B11/00—Making preforms
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    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions

  • the invention belongs to the field of rapid prototyping, and more particularly to a 3D printing manufacturing method.
  • thermosetting resin composites As an important lightweight material, fiber-reinforced thermosetting resin composites have been widely used in aerospace, automotive and other fields for their excellent physical, chemical and mechanical properties. If high-strength, lightweight thermosetting epoxy/carbon fiber composite products are used to replace the metal materials currently used in large quantities, it is an important way to realize the lightweight of transportation vehicles such as airplanes and automobiles. Boeing's latest 787 aircraft adopts thermosetting epoxy over a large area. The resin/carbon fiber composite product greatly reduces the weight of the aircraft, thereby saving a lot of fuel and expanding the flight range. In order to improve product performance, the functional parts of aerospace, automotive and other fields are increasingly complex, resulting in an increasingly improved manufacturing cycle and cost of conventional forming methods, and some optimized design structures cannot even be formed.
  • 3D printing also known as additive manufacturing or rapid prototyping
  • 3D printing technology utilizes layer-by-layer manufacturing and superposition principles to create 3D solid parts directly from CAD models.
  • 3D printing technology has evolved from prototyping to direct or near-product manufacturing, and rapid prototyping complex structure is the biggest advantage of 3D printing technology.
  • the resin used in the fiber-reinforced resin composite product manufactured by 3D printing is mainly a thermoplastic resin and an ultraviolet-curable resin, and the processes adopted are as follows: 1) mixing of a thermoplastic resin powder (such as nylon, polyetheretherketone, etc.) and reinforcing fiber powder, 3D printing manufacturing by selective laser sintering (selective laser sintering); 2) composite fiber or prepreg tow of reinforcing fiber and thermoplastic resin, 3D printing manufacturing by fused deposition (FDM) technology; 3) The reinforcing fiber is uniformly mixed with the ultraviolet curing resin, and is manufactured by 3D printing using a photo-curing (SLA) technique.
  • SLA photo-curing
  • Thermosetting resin is a reactive resin that requires a curing agent at a specific curing temperature and pressure.
  • the curing reaction (chemical crosslinking) is carried out for several hours to form a stable network cross-linking, and the cross-linked product has the advantages of high rigidity, high hardness, and good heat resistance.
  • the initial viscosity of the thermosetting resin is low, and the viscosity gradually increases with the curing reaction. According to the 3D printing principle, the shape is not easily maintained when the viscosity is too low, but if the viscosity is too large, the material is not easily extruded from the nozzle or heated by the laser.
  • thermosetting resin composite products have been developed by means of three-dimensional extrusion (Compton, BG & Lewis, JA, Adv Mater, 2014, 26, 34). ).
  • this method is difficult to directly form a complicated structure having a cantilever structure or the like due to limitations of its own principle. Therefore, the current use of 3D printing technology to form thermosetting resins and their composite products still faces many problems.
  • the present invention provides a 3D printing manufacturing method of a short fiber reinforced thermosetting resin composite product, which can rapidly manufacture a fiber reinforced thermosetting structure with complicated shape and structure, light weight, high strength and high heat resistance. Resin composite products.
  • a 3D printing manufacturing method of a short fiber reinforced thermosetting resin composite product comprising the steps of:
  • the composite powder comprises the following raw materials by volume: 10% to 50% of polymer binder, and 90% to 50% of short fiber;
  • the formed shaped blank has a porosity of 10% to 60%, and a bending strength of 0.3 MPa or more;
  • thermosetting resin precursor for post-impregnation treatment
  • thermosetting resin precursor having a viscosity of less than 100 mPa ⁇ s
  • the composite powder described in the step 1) has a particle size distribution of from 10 to 150 ⁇ m.
  • the short fibers described in the step 1) have a diameter of 6 to 10 ⁇ m and a length of 10 to 150 ⁇ m.
  • the process parameters formed by the selective laser sintering technique in step 2) are as follows: laser power 5-15 W, scanning rate 1500-3000 mm/s, scanning pitch 0.08-0.15 mm, powder layer thickness 0.1-0.2 mm, preheating The temperature is 50 to 200 °C.
  • step 3.2 the preform and the liquid thermosetting resin precursor are placed in a vacuum oven and evacuated to accelerate the impregnation of the liquid thermosetting resin into the pores of the preform.
  • the temperature of the curing treatment in the step 4) is 50 to 200 ° C, and the curing time is 3 to 48 hours.
  • the polymer binder described in the step 1) is nylon 12, nylon 6, nylon 11, polypropylene, epoxy resin and/or phenolic resin.
  • the staple fibers described in step 1) are carbon fibers, glass fibers, boron fibers, silicon carbide whiskers and/or aramid fibers.
  • thermosetting resin used in the liquid thermosetting resin precursor in the step 3.1) is an epoxy resin, a phenol resin, a polyurethane, a urea resin or an unsaturated polyester resin.
  • step 4 the green body is removed from the liquid thermosetting resin precursor, and then the resin is cleaned and then cured.
  • the selective laser sintering technique of the present invention is a kind of 3D printing technology, which can directly form a part by selectively sintering the powder of the required area layer by layer according to the CAD model, and can directly manufacture the shape and structure.
  • Parts such as a complex structure with a cantilever structure.
  • the process has a short design cycle, no mold, and can be integrated. The advantages of manufacturing complex structural parts.
  • thermosetting resin composite material produced by the present invention has better mechanical properties and better heat resistance
  • the method of the present invention is applicable to a wide range of applications, and can be applied to different reinforcing fibers and different thermosetting resin systems.
  • Figure 1 is a flow chart of the operation of the present invention.
  • a 3D printing manufacturing method of a short fiber reinforced thermosetting resin composite product comprises the following steps:
  • the composite powder comprising the following raw materials by volume: 10% to 50% of a polymer binder, and 90% to 50% of a short fiber;
  • the polymer binder/short fiber composite powder has a particle size distribution of 10 to 150 ⁇ m, preferably 10 to 100 ⁇ m.
  • the longer the fiber length the better the reinforcing effect, but when the fiber length exceeds 150 ⁇ m In the future, it will affect the quality of the powder, and ultimately affect the accuracy of the parts; if the fiber is too short, the surface area will increase and the roll will be easily adhered;
  • the volume content of the polymer binder is further preferably 10 to 30%, because the basic shape of the blank is guaranteed. Under the premise of strength, the smaller the content of the polymer binder, the larger the porosity of the blank, and the more resin that penetrates later, the higher the final strength.
  • the polymer binder used is one or a combination of a polymer material having a certain heat resistance such as nylon 12, nylon 6, nylon 11, polypropylene, epoxy resin, and/or phenol resin. .
  • the short fibers used may be carbon fiber, glass fiber, boron fiber, silicon carbide crystal.
  • High-strength fibers such as whiskers and/or aramid fibers having a fiber diameter of 6 to 10 ⁇ m and a length distribution ranging from 10 to 150 ⁇ m, preferably from 50 to 100 ⁇ m.
  • whiskers and/or aramid fibers having a fiber diameter of 6 to 10 ⁇ m and a length distribution ranging from 10 to 150 ⁇ m, preferably from 50 to 100 ⁇ m.
  • the longer the fiber length the better the reinforcing effect, but when the fiber length exceeds 150 microns, the quality of the powder is affected.
  • the bending strength of the blank is above 0.3 MPa, and if the strength is too low, some thin-walled portions will be easily destroyed; at the same time, there is a need for interconnected pores in the blank to enable the resin to be immersed. Infiltrated into the blank, and the higher the porosity, the more resin is infiltrated, and the final performance will be better.
  • the porosity is required to be 10 to 60%. The porosity is too low, the resin is infiltrated less, and the final part strength is low; the porosity is too high, and the initial blank strength is low, which cannot meet the post-treatment requirements.
  • the process parameters of selective laser sintering technology are as follows: laser power 5 ⁇ 15W, scanning rate 1500 ⁇ 3000mm / s, scanning spacing 0.08 ⁇ 0.15mm, powder layer thickness 0.1 ⁇ 0.2mm, preheating temperature 50 ⁇ 200 ° C
  • the specific process parameters are determined according to the type of polymer binder and short fiber selected for actual processing.
  • thermosetting resin precursor for post-impregnation treatment
  • thermosetting resin precursor having a viscosity of 100 mPa ⁇ s or less, because if the viscosity is too large, the resistance of the liquid flow increases, and the resin penetration is hindered;
  • the liquid thermosetting resin precursor It is prepared in a resin box; wherein the thermosetting resin used in the liquid thermosetting resin precursor may be a thermosetting resin which can be formulated into a low-viscosity liquid precursor such as an epoxy resin, a phenol resin, a polyurethane, a urea resin or an unsaturated polyester resin.
  • the impregnation viscosity is further preferably controlled to 50 mPa ⁇ s or less, and at this time, the liquid resin has good fluidity and can smoothly penetrate into the pores of the initial green body.
  • the impregnation process can be carried out in the air; preferably, it can be carried out under vacuum: the slab It is placed in a vacuum oven together with a resin box of a liquid thermosetting resin precursor, and a vacuum is applied to accelerate the impregnation of the liquid thermosetting resin into the pores of the preform.
  • the excess resin may be brushed off with a brush or the excess resin may be scraped off with a plate, and then cured; preferably, curing treatment
  • the temperature is 50 to 200 ° C, and the curing time is 3 to 48 hours.
  • the general idea of the present invention mainly includes two aspects, one is to form a reinforcing phase skeleton blank with high porosity bonded by a polymer by selective laser sintering technology;
  • the thermosetting resin-based composite product reinforced by the chopped fiber can be obtained by infiltrating the thermosetting resin and then curing at high temperature and crosslinking.
  • a composite powder of nylon 12 and chopped carbon fibers was prepared by a solvent precipitation method.
  • the volume percentage of the nylon 12 is 20%, and the composite powder having a powder particle size of 10 to 100 ⁇ m is selected for selective laser sintering.
  • the selective laser sintering technique is used to form the blank with pores.
  • the process parameters of selective laser sintering are as follows: laser power 5W, scanning rate 2000mm/s, scanning pitch 0.1mm, powder layer thickness 0.1mm, preheating temperature
  • the preform of the nylon 12/carbon fiber composite product was formed at 168 ° C, and the flexural strength was 1.5 MPa and the open porosity was 58%.
  • a composite powder of nylon 12 and chopped glass fibers was prepared by a solvent precipitation method.
  • the volume percentage of nylon 12 is 25%, and a composite powder having a powder particle size of 20 to 150 ⁇ m is obtained for selective laser sintering.
  • the selective laser sintering technique is used to form the blank with pores.
  • the process parameters of selective laser sintering are as follows: laser power 8W, scanning rate 2500mm/s, scanning pitch 0.1mm, powder layer thickness 0.15mm, preheating temperature At 168 ° C, a blank of nylon 12/glass fiber composite product was obtained, which was tested to have a flexural strength of 2.0 MPa and an open porosity of 53%.
  • epoxy resin CYD ⁇ 128 and curing agent methyltetrahydrophthalic anhydride according to 100:85, and adding curing accelerator 2, 4, 6 to 3 (2) by weight of epoxy resin 0.1% Methylaminomethyl)phenol (abbreviated as DMP-30) was heated to 110 ° C and stirred vigorously until homogeneously mixed to adjust the viscosity of the infiltration system to less than 30 mPa ⁇ s.
  • epoxy resin CYD ⁇ 128 is Yueyang Baling Petrochemical
  • methyltetrahydrophthalic anhydride and DMP ⁇ 30 are products of Shanghai Chengyi High-tech Development Co., Ltd.
  • the impregnated parts are placed in an oven for curing; the curing conditions are 130 ° C for 3 hours, 150 ° C for 5 hours, and then 200 ° C for 10 hours; after the parts are cooled with the furnace,
  • the glass fiber reinforced epoxy resin composite product parts can be obtained by surface grinding.
  • the selective laser sintering technique is used to form the blank with pores.
  • the process parameters of selective laser sintering are as follows: laser power 11W, scanning rate 2500mm/s, scanning pitch 0.1mm, powder layer thickness 0.1mm, preheating temperature At 105 ° C, a blank of a polypropylene/aramid fiber composite product was obtained. It has been tested to have a flexural strength of 1.3 MPa and an open porosity of 43%.
  • the phenolic resin and the alcohol are formulated into a phenolic resin solution according to a mass ratio of 1:1, and the solution is heated in a constant temperature water bath to 40 to 60 ° C to adjust the viscosity of the infiltration system to 50 mPa ⁇ s or less.
  • the phenolic resin used is a boron-modified phenolic resin product of Xi'an Taihang Flame Retardant Co., Ltd., and its model is THC-400, and alcohol is commercially available.
  • the slab is directly immersed in the phenolic resin solution, but the upper surface thereof is exposed to the liquid surface so that the gas in the green body can be discharged from the upper surface during the impregnation; repeated infiltration several times until the porous structure is completely It is filled, the resin tank is placed in a vacuum oven, and a vacuum is applied, which is more advantageous for the resin to be impregnated into the blank. The impregnated blank is taken out and the excess resin on the surface is cleaned.
  • the infiltrated parts are placed in an oven for curing.
  • the curing condition is cured at 180 ° C for 24 hours, and the parts are taken out after cooling with the furnace, and the surface of the boron fiber reinforced phenolic resin-based composite material is obtained by surface grinding.
  • the selective laser sintering technique is used to form the blank with pores.
  • the process parameters of selective laser sintering are as follows: laser power 15W, scanning rate 1500mm/s, scanning pitch 0.08mm, powder layer thickness 0.2mm, preheating temperature
  • the preform of the nylon 6/silicon carbide whisker composite product was formed at 200 ° C, and the flexural strength was 1.6 MPa and the open porosity was 60%.
  • Isocyanates and polyols are the two main components of polyurethane thermosetting resins.
  • Polyether polyol, polymethylene polyphenyl polyisocyanate (PAPI), stannous octoate, triethanolamine and water are uniformly mixed at a mass ratio of 100:100:0.4:0.6:0.1, and heated to 40 ° C to adjust the viscosity.
  • a polyurethane resin precursor solution is obtained up to 100 mPa ⁇ s or less.
  • a composite powder of epoxy resin and chopped glass fiber is prepared by a mechanical mixing method.
  • the percentage of the epoxy resin is 10%, and a composite powder having a powder particle size of 10 to 100 ⁇ m is obtained for selective laser sintering.
  • the selective laser sintering technique is used to form the blank with pores.
  • the process parameters of selective laser sintering are as follows: laser power 8W, scanning rate 3000mm/s, scanning pitch 0.15mm, powder layer thickness 0.1mm, preheating temperature At 50 ° C, a blank of epoxy resin / chopped glass fiber composite product was obtained, which was tested to have a flexural strength of 0.8 MPa and an open porosity of 57%.
  • a low-viscosity urea-formaldehyde resin precursor is synthesized by an alkali-acid-base method. Firstly prepare 500ml of 36% formaldehyde solution, and add 8g of hexamethyltetramine, heat the oil bath to 55 ° C, add 50g of the first batch of urea, react for 60min; continue to heat up to 90 ° C reaction, add the second batch of urea 70g, the reaction During the process, the pH was adjusted to 5-6 with 20% sodium hydroxide for 40 min; the pH was adjusted to 7-8 and then the third batch of urea was added for 20 min, the reaction was carried out for 20 min, and the pH was adjusted to 7-8 before stopping the reaction. Low viscosity urea formaldehyde resin precursor.

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Abstract

本发明公开了一种短纤维增强热固性树脂复合产品的3D打印制造方法，包括以下步骤：1)制备适用于选择性激光烧结3D打印技术的复合粉末；2)采用选择性激光烧结技术成形具有孔隙的形坯；3)将形坯放入液态热固性树脂前驱体中进行浸渗后处理：3.1)配制粘度在100mPa·s以下的液态热固性树脂前驱体；3.2)将形坯浸入液态热固性树脂前驱体中，让形坯的上端露出液面，以使形坯孔隙中的气体排出；4)从液态热固性树脂前驱体中取出形坯，清除多余树脂后进行固化处理；5)对固化处理后的形坯进行打磨处理，即得到成品。本发明可以快速制造形状结构复杂的、轻质高强度、高耐热的纤维增强热固性树脂复合产品。

Description

一种短纤维增强热固性树脂复合产品的3D打印制造方法 【技术领域】
本发明属于快速成形领域，更具体地，涉及一种3D打印制造方法。
【背景技术】
纤维增强热固性树脂复合材料作为一种重要的轻质材料，以其优良的物理、化学和机械性能，在航空航天、汽车等领域获得广泛应用。如采用高强度、轻质热固性环氧树脂/碳纤维复合产品来替代目前大量使用的金属材料是实现飞机、汽车等交通运输工具轻量化的重要途径，波音最新的787型飞机大面积采用热固性环氧树脂/碳纤维复合产品，大大降低飞机重量，从而节省大量燃料、扩大飞行范围。为了提高产品性能，航空航天、汽车等领域的功能零件结构日益复杂，造成传统成形方法的制造周期、成本日益提高，某些优化设计结构甚至无法成形。3D打印(也称为增材制造或快速成形制造)技术利用逐层制造并叠加原理，可直接从CAD模型制造三维实体零件。随着技术的发展和工业需求的推动，3D打印技术已由原型制造发展到直接产品或近产品制造，而快速成形复杂结构正是3D打印技术的最大优势。
目前3D打印制造的纤维增强树脂复合产品中所用树脂主要是热塑性树脂和紫外光固化树脂，采用的工艺方法有：1)热塑性树脂粉末(如尼龙、聚醚醚酮等)和增强纤维粉末混合，利用选择性激光烧结(选择性激光烧结)进行3D打印制造；2)将增强纤维与热塑性树脂制成复合丝材或预浸丝束，利用熔融沉积(FDM)技术进行3D打印制造；3)将增强纤维与紫外光固化树脂均匀混合，利用光固化(SLA)技术进行3D打印制造。但是,方法1)制造的产品的强度较低，方法2)、3)均难以成形具有悬臂结构的复杂产品。
热固性树脂为反应性树脂，需要在特定的固化温度和压力下与固化剂 进行数小时的固化反应(化学交联)，形成稳定的网状交联，交联后的产物具有刚性大、硬度高、耐热性好等优点。热固性树脂初始粘度较低，随着固化反应进行粘度逐渐增大，根据3D打印原理可知，粘度过低则形状不易保持，但若粘度过大，则材料不易从喷嘴挤出或激光加热熔融。近日，哈佛大学研制出了一种适用于3D打印的环氧树脂并通过三维挤出的方式首次实现了热固性树脂复合产品的3D打印(Compton,B.G.&Lewis,J.A.,Adv Mater,2014,26,34)。但是该方法由于其自身原理的限制，难以直接成形具有悬臂结构等的复杂结构。因此，目前利用3D打印技术成形热固性树脂及其复合产品仍面临着诸多问题。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明提供了一种短纤维增强热固性树脂复合产品的3D打印制造方法，可以快速制造形状结构复杂的、轻质高强度、高耐热的纤维增强热固性树脂复合产品。
为实现上述目的，按照本发明的一个方面，提供了一种短纤维增强热固性树脂复合产品的3D打印制造方法，包括以下步骤：
1)制备适用于选择性激光烧结3D打印技术的复合粉末，所述复合粉末按体积比包括以下原料：高分子粘结剂10％～50％，短纤维90％～50％；
2)采用选择性激光烧结技术成形具有孔隙的形坯，成形的形坯的孔隙率为10％～60％，弯曲强度在0.3MPa以上；
3)将形坯放入液态热固性树脂前驱体中进行浸渗后处理，后处理过程如下：
3.1)配制粘度在100mPa·s以下的液态热固性树脂前驱体；
3.2)将形坯浸入液态热固性树脂前驱体中以使液态热固性树脂浸渗到形坯的孔隙中，并将形坯的上端露出液面以使形坯孔隙中的气体排出；
4)从液态热固性树脂前驱体中取出形坯后进行固化处理；
5)对固化处理后的形坯进行打磨处理，即得到成品。
优选地，步骤1)中所述的复合粉末的粒径分布在10～150微米。
优选地，步骤1)中所述的短纤维的直径为6～10微米，长度为10～150微米。
优选地，步骤2)中选择性激光烧结技术成形的工艺参数如下：激光功率5～15W，扫描速率1500～3000mm/s，扫描间距0.08～0.15mm，铺粉层厚0.1～0.2mm，预热温度50～200℃。
优选地，步骤3.2)中将形坯和液态热固性树脂前驱体放入真空烘箱中，抽真空，以加速液态热固性树脂浸渗到形坯的孔隙中。
优选地，步骤4)中固化处理的温度为50～200℃，固化时间为3～48小时。
优选地，步骤1)中所述的高分子粘接剂为尼龙12、尼龙6、尼龙11、聚丙烯、环氧树脂和/或酚醛树脂。
优选地，步骤1)中所述的短纤维为碳纤维、玻璃纤维、硼纤维、碳化硅晶须和/或芳纶纤维。
优选地，步骤3.1)中所述液态热固性树脂前驱体中采用的热固性树脂为环氧树脂、酚醛树脂、聚氨酯、脲醛树脂或不饱和聚酯树脂。
优选地，步骤4)中将形坯从液态热固性树脂前驱体中取出后先清理树脂，然后再进行固化处理。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：
1)本发明采用选择性激光烧结技术是3D打印技术的一种，该工艺能够直接根据CAD模型，通过逐层有选择地烧结所需要区域的粉末并叠加来成形零件，可以直接制造形状结构复杂的零件，譬如具有悬臂结构等的复杂结构。相对于传统的热固性树脂复合产品的加工成型方法，如手糊成型、模压成型、树脂传递模塑成型、喷射成型和连续缠绕成型等而言，该工艺具有设计制造周期短，无需模具，可整体制造复杂结构零件等优点。
2)相对于目前通过3D打印方法制造的热塑性树脂复合材料而言，由本发明制造的热固性树脂复合材料的力学性能更优，耐热性能更好；
3)本发明的方法应用范围广泛，可以适用于不同的增强纤维以及不同的热固性树脂体系。
【附图说明】
图1是本发明的工作流程图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
如图1所示，一种短纤维增强热固性树脂复合产品的3D打印制造方法，包括以下步骤：
1)制备适用于选择性激光烧结3D打印技术的复合粉末，所述复合粉末按体积比包括以下原料：高分子粘结剂10％～50％，短纤维90％～50％；其中，所述高分子粘接剂/短纤维复合粉末的粒径分布在10～150微米之间，优选范围为10～100微米，一般地，纤维长度越长，增强效果越好，但是当纤维长度超过150微米以后，将影响铺粉的质量，最终影响零件的精度；纤维过短将导致表面积增大，容易粘辊；高分子粘接剂的体积含量进一步优选为10～30％，因为在保证形坯基本强度的前提下，高分子粘接剂的含量越少，形坯的孔隙率越大，后期渗入的树脂越多，最终强度越高。
另外，所采用的高分子粘接剂为尼龙12、尼龙6、尼龙11、聚丙烯、环氧树脂和/或酚醛树脂等具有一定耐热性能的高分子材料中的一种或几种的组合。
此外，所采用的短纤维可以是碳纤维、玻璃纤维、硼纤维、碳化硅晶 须和/或芳纶纤维等高强纤维，其中纤维直径为6～10微米，长度分布范围为10～150微米，优选为50～100微米。一般地，纤维长度越长，增强效果越好，但是当纤维长度超过150微米以后，将影响铺粉的质量。
2)采用选择性激光烧结技术成形具有孔隙的形坯，选用优化的选择性激光烧结技术的工艺参数成形零件的形坯，该形坯为既能满足后续处理强度要求，又存在大量连通孔隙的多孔结构；
其中，为了满足后续处理的强度要求，形坯的弯曲强度在0.3MPa以上，如果强度太低，一些薄壁部分将容易被破坏；同时，形坯中需要存在连通的孔隙，以使树脂能够浸渗入形坯中，且孔隙率越高，渗入的树脂越多，最终的性能也会越好，一般要求孔隙率为10～60％。孔隙率太低，渗入树脂少，最终零件强度低；孔隙率太高，初始形坯强度低，无法满足后处理要求。
另外，选择性激光烧结技术成形的工艺参数如下：激光功率5～15W，扫描速率1500～3000mm/s，扫描间距0.08～0.15mm，铺粉层厚0.1～0.2mm，预热温度50～200℃，具体的工艺参数根据实际加工时所选用的高分子粘接剂和短纤维的种类而定。
3)将形坯放入液态热固性树脂前驱体中进行浸渗后处理，后处理过程如下：
3.1)通过提高温度或者添加稀释剂的方法调节粘度，配制粘度在100mPa·s以下的液态热固性树脂前驱体，因为如果粘度太大，液体流动的阻力增大，树脂渗入受阻；液态热固性树脂前驱体在树脂箱内配制；其中，液态热固性树脂前驱体中所采用的热固性树脂可以为环氧树脂、酚醛树脂、聚氨酯、脲醛树脂或不饱和聚酯树脂等可配制成低粘度液态前驱体的热固性树脂,浸渗粘度进一步优选控制为50mPa·s以下，此时液态树脂的流动性较好，能够顺利地渗入初始形坯的孔隙当中。
3.2)将形坯浸入液态热固性树脂前驱体中以使液态热固性树脂浸渗到 形坯的孔隙中，并将形坯的上端露出液面以使形坯孔隙中的气体排出；浸渗过程可以在空气中进行；作为优选，可以选择在真空环境下进行：将其内有形坯和液态热固性树脂前驱体的树脂箱一起放入到真空烘箱中，抽真空，以加速液态热固性树脂浸渗到形坯的孔隙中。
4)待完全浸透后，从液态热固性树脂前驱体中取出形坯后，先进行清洁，可以用毛刷刷掉多余树脂或者用板刮掉多余树脂，然后再进行固化处理；优选地，固化处理的温度为50～200℃，固化时间为3～48小时。
5)对固化处理后的形坯进行打磨处理，即得到成品。
综上所述，本发明的总体思路主要包括两个方面，一是利用选择性激光烧结技术成形由高分子粘接的，具有较高孔隙率的增强相骨架形坯；二是在对形坯浸渗热固性树脂，再经高温固化交联后就可以得到由短切纤维增强的热固性树脂基复合产品。
实施例1
(1)采用溶剂沉淀法制备尼龙12和短切碳纤维的复合粉末。其中尼龙12的体积百分比为20％，筛选得到粉末粒径为10～100微米的复合粉末以备选择性激光烧结成形。
(2)采用选择性激光烧结技术成形具有孔隙的形坯，选择性激光烧结的工艺参数如下：激光功率5W，扫描速率2000mm/s，扫描间距0.1mm，铺粉层厚0.1mm，预热温度168℃，成形得到尼龙12/碳纤维复合产品的形坯，经测试其弯曲强度为1.5MPa,开口孔隙率为58％。
(3)将酚醛环氧树脂F～51和固化剂甲基纳迪克酸酐按照100:91混合，并加入重量为环氧树脂0.1％的固化促进剂2,4,6～三(二甲氨基甲基)苯酚(简称DMP～30)加热到130℃并剧烈搅拌至混合均匀，调节浸渗体系的粘度至20mPa·s。其中F～51酚醛环氧为岳阳巴陵石化产品，甲基纳迪克酸酐和DMP～30为上海成谊高新科技发展有限公司产品。
(4)将树脂箱放入真空烘箱中，再将形坯直接浸入前驱液中，但将形 坯的上端露出液面，以便在浸渗过程中形坯中的气体可以从其上端排出；抽真空，这样更有利于树脂浸渗到毛坯里面；将浸渗好的形坯取出，清理表面多余的树脂。
(5)将浸渗后的零件放入烘箱中进行固化；固化条件为先150℃固化5小时，再200℃固化5小时；待零件随炉冷却后取出，经表面打磨处理即可得到碳纤维增强的酚醛环氧树脂基复合产品零件。
实施例2
(1)采用溶剂沉淀法制备尼龙12和短切玻璃纤维的复合粉末。其中尼龙12的体积百分比为25％，筛选得到粉末粒径为20～150微米的复合粉末以备选择性激光烧结成形。
(2)采用选择性激光烧结技术成形具有孔隙的形坯，选择性激光烧结的工艺参数如下：激光功率8W，扫描速率2500mm/s，扫描间距0.1mm，铺粉层厚0.15mm，预热温度168℃，成形得到尼龙12/玻璃纤维复合产品的形坯，经测试，其弯曲强度为2.0MPa,开口孔隙率为53％。
(3)将环氧树脂CYD～128和固化剂甲基四氢邻苯二甲酸酐按照100:85混合，并加入重量为环氧树脂0.1％的固化促进剂2,4,6～三(二甲氨基甲基)苯酚(简称DMP～30)加热到110℃并剧烈搅拌至混合均匀，调节浸渗体系的粘度至30mPa·s以下。其中环氧树脂CYD～128为岳阳巴陵石化产品，甲基四氢邻苯二甲酸酐和DMP～30为上海成谊高新科技发展有限公司产品。
(4)将树脂箱放入真空烘箱中，再将形坯直接浸入前驱液中，但将形坯的上端露出液面，以便在浸渗过程中形坯中的气体可以从其上端排出；抽真空，这样更有利于树脂浸渗到毛坯里面；将浸渗好的形坯取出，清理表面多余的树脂。
(5)将浸渗后的零件放入烘箱中进行固化；固化条件为130℃固化3小时，再150℃固化5小时，然后200℃固化10小时；待零件随炉冷却后取出， 经表面打磨处理即可得到玻璃纤维增强的环氧树脂基复合产品零件。
实施例3
(1)采用机械混合法制备聚丙烯与短切芳纶纤维均匀混合的复合粉末，其中聚丙烯的体积百分比为30％，筛选得到粉末粒径为10～80微米的复合粉末以备选择性激光烧结成形。
(2)采用选择性激光烧结技术成形具有孔隙的形坯，选择性激光烧结的工艺参数如下：激光功率11W，扫描速率2500mm/s，扫描间距0.1mm，铺粉层厚0.1mm，预热温度105℃，成形得到聚丙烯/芳纶纤维复合产品的形坯。经测试其弯曲强度为1.3MPa，开口孔隙率为43％.
(3)将不饱和聚酯树脂和固化剂过氧化甲乙酮按照100:1混合，并加入重量比0.1％的固化促进剂环烷酸钴，加热到45℃并剧烈搅拌至混合均匀，调节浸渗体系粘度为30～40mPa·s。其中不饱和聚酯树脂为金陵帝斯曼产品Synolite 4082～G～33N，过氧化甲乙酮为江阴市前进化工有限公司产品，环烷酸钴为市售。
(4)将树脂箱放入真空烘箱中，再将形坯直接浸入前驱液中，但将形坯的上端露出液面，以便在浸渗过程中形坯中的气体可以从其上端排出；抽真空，这样更有利于树脂浸渗到毛坯里面；将浸渗好的形坯取出，清理表面多余的树脂。
(5)将浸渗后的零件放入烘箱中进行固化；固化条件为100℃固化24小时；待零件随炉冷却后取出，经表面打磨处理即可得到芳纶纤维增强的不饱和聚酯树脂基复合产品零件。
实施例4
(1)采用机械混合法制备尼龙11与短切硼纤维均匀混合的复合材料粉末，其中尼龙11的体积百分比为25％，筛选得到粉末粒径为10微米～100微米的复合粉末以备SLS成形。
(2)采用选择性激光烧结技术成形具有孔隙的形坯，选择性激光烧结 的工艺参数如下：激光功率11W，扫描速率2000mm/s，扫描间距0.1mm，铺粉层厚0.15mm，预热温度190℃，成形得到尼龙11/硼纤维复合材料的初始形坯，经测试其弯曲强度为0.8MPa,开口孔隙率为48％。
(3)将酚醛树脂与酒精按照1:1的质量比配成酚醛树脂溶液，将溶液置于恒温水浴锅中加热至40～60℃调节浸渗体系的粘度至50mpa·s以下。所用酚醛树脂为西安太航阻燃有限公司的硼改性酚醛树脂产品，其型号为THC～400，酒精为市售。
(4)再将形坯直接浸入酚醛树脂溶液中，但将其上表面露出液面，以便在浸渗过程中形坯中的气体可以从其上表面排出；反复浸渗几次至多孔结构完全被填充，将树脂槽放入真空烘箱中，抽真空，这样更有利于树脂浸渗到毛坯里面。将浸渗好的形坯取出，清理表面多余的树脂。
(5)将浸渗后的零件放入烘箱中进行固化。固化条件为180℃固化24小时，待零件随炉冷却后取出，经表面打磨处理即可得到硼纤维增强的酚醛树脂基复合材料零件。
实施例5
(1)采用机械混合法法制备尼龙6与碳化硅晶须均匀混合的复合粉末，其中尼龙6的体积百分比为50％，筛选得到粉末粒径为10～100微米的复合粉末以备选择性激光烧结成形。
(2)采用选择性激光烧结技术成形具有孔隙的形坯，选择性激光烧结的工艺参数如下：激光功率15W，扫描速率1500mm/s，扫描间距0.08mm，铺粉层厚0.2mm，预热温度200℃，成形得到尼龙6/碳化硅晶须复合产品的形坯，经测试其弯曲强度为1.6MPa,开口孔隙率为60％。
(3)异氰酸酯和多元醇是聚氨酯热固性树脂的两个主要组成部分。将聚醚多元醇、多亚甲基多苯基多异氰酸酯(PAPI)、辛酸亚锡、三乙醇胺和水按照质量比100：100：0.4：0.6：0.1均匀混合，并加热到40℃，调节粘度至100mPa·s以下，得聚氨酯树脂前驱体溶液。
(4)将树脂箱放入真空烘箱中，再将形坯直接浸入前驱液中，但将形坯的上端露出液面，以便在浸渗过程中形坯中的气体可以从其上端排出；抽真空，这样更有利于树脂浸渗到毛坯里面；将浸渗好的形坯取出，清理表面多余的树脂。
(5)将浸渗后的零件放入烘箱中进行固化；固化条件为100℃固化24小时，待零件随炉冷却后取出，经表面打磨处理即可得到碳化硅晶须增强的聚氨酯基复合产品零件。
实施例6
(1)采用机械混合法法制备环氧树脂和短切玻璃纤维的复合粉末。其中环氧树脂的百分比为10％，筛选得到粉末粒径为10～100微米的复合粉末以备选择性激光烧结成形。
(2)采用选择性激光烧结技术成形具有孔隙的形坯，选择性激光烧结的工艺参数如下：激光功率8W，扫描速率3000mm/s，扫描间距0.15mm，铺粉层厚0.1mm，预热温度50℃，成形得到环氧树脂/短切玻璃纤维复合产品的形坯，经测试其弯曲强度为0.8MPa,开口孔隙率为57％。
(3)通过碱-酸-碱的方式合成低粘度的脲醛树脂前驱体。首先配制36％的甲醛溶液500ml,并加入8g六甲基四胺，油浴升温至55℃，加入第一批尿素50g，反应60min；继续升温至90℃反应，加入第二批尿素70g，反应过程中用20％氢氧化钠调节PH值为5-6,反应40min；调节PH值至7-8再加入第三批尿素20g，反应20min，在停止反应之前调节PH值为7-8，得到低粘度的脲醛树脂前驱体。
(4)将树脂箱放入真空烘箱中，再将形坯直接浸入前驱液中，但将形坯的上端露出液面，以便在浸渗过程中形坯中的气体可以从其上端排出；抽真空，这样更有利于树脂浸渗到毛坯里面；将浸渗好的形坯取出，清理表面多余的树脂。
(5)将浸渗后的零件放入烘箱中进行固化；固化条件为50℃固化48小 时；待零件随炉冷却后取出，经表面打磨处理即可得到玻璃纤维增强的脲醛树脂基复合产品零件。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：包括以下步骤：
    1)制备适用于选择性激光烧结3D打印技术的复合粉末，所述复合粉末按体积比包括以下原料：高分子粘结剂10％～50％，短纤维90％～50％；
    2)采用选择性激光烧结技术成形具有孔隙的形坯，成形的形坯的孔隙率为10％～60％，弯曲强度在0.3MPa以上；
    3)将形坯放入液态热固性树脂前驱体中进行浸渗后处理，后处理过程如下：
    3.1)配制粘度在100mPa·s以下的液态热固性树脂前驱体；
    3.2)将形坯浸入液态热固性树脂前驱体中以使液态热固性树脂浸渗到形坯的孔隙中，并将形坯的上端露出液面以使形坯孔隙中的气体排出；
    4)从液态热固性树脂前驱体中取出形坯后进行固化处理；
    5)对固化处理后的形坯进行打磨处理，即得到成品。
  2. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤1)中所述的复合粉末的粒径分布在10～150微米。
  3. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤1)中所述的短纤维的直径为6～10微米，长度为10～150微米。
  4. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤2)中选择性激光烧结技术成形的工艺参数如下：激光功率5～15W，扫描速率1500～3000mm/s，扫描间距0.08～0.15mm，铺粉层厚0.1～0.2mm，预热温度50～200℃。
  5. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印 制造方法，其特征在于：步骤3.2)中将形坯和液态热固性树脂前驱体放入真空烘箱中，抽真空，以加速液态热固性树脂浸渗到形坯的孔隙中。
  6. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤4)中固化处理的温度为50～200℃，固化时间为3～48小时。
  7. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤1)中所述的高分子粘接剂为尼龙12、尼龙6、尼龙11、聚丙烯、环氧树脂和/或酚醛树脂。
  8. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤1)中所述的短纤维为碳纤维、玻璃纤维、硼纤维、碳化硅晶须和/或芳纶纤维。
  9. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤3.1)中所述液态热固性树脂前驱体中采用的热固性树脂为环氧树脂、酚醛树脂、聚氨酯、脲醛树脂或不饱和聚酯树脂。
  10. 根据权利要求1所述的一种短纤维增强热固性树脂复合产品的3D打印制造方法，其特征在于：步骤4)中将形坯从液态热固性树脂前驱体中取出后先清理树脂，然后再进行固化处理。
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