技术领域technical field
本发明涉及一种3D打印聚合物耗材，特别是涉及一种基于熔融沉积3D打印的形状记忆聚合物合金及其制备方法。The invention relates to a 3D printing polymer consumable, in particular to a shape memory polymer alloy based on fused deposition 3D printing and a preparation method thereof.
背景技术Background technique
3D打印技术是20世纪80年代开始发展起来的一种快速成型技术，按工作原理可分为选择性激光烧结技术、立体光固化技术、熔融沉积成型技术等。其中，熔融沉积成型因其原理简单、操作方便、成本较低等特点而成为了当前应用最为广泛的3D打印技术之一，可普遍应用在医疗、汽车、军事、航空航天、电子产品、教育文化、艺术设计等领域。3D printing technology is a rapid prototyping technology developed in the 1980s. According to its working principle, it can be divided into selective laser sintering technology, stereolithography technology, and fused deposition modeling technology. Among them, fused deposition modeling has become one of the most widely used 3D printing technologies due to its simple principle, convenient operation, and low cost. It can be widely used in medical, automotive, military, aerospace, electronic products, education and culture. , art design and other fields.
随着3D打印技术的发展日趋成熟，人们的需求已远远不止满足于“3D打印”，2013年提出的“4D打印”概念，引起了学者们广泛的兴趣。4D打印，顾名思义，指的是在三维制品的基础上引入第四维度——时间，制品在外部刺激下(如热、电、光、磁、水分等)可随着时间而发生结构、性质、形态、功能等方面的变化。其中，热致形状记忆是目前研究最多的4D打印技术之一，指的是3D制品的形状能在热刺激下随时间而发生变化，而形状记忆材料是该技术赖以发展的基础。由于形状记忆聚合物具有区别于形状记忆合金、形状记忆陶瓷的优点，如密度低、响应温度低、形变量大、易加工，成本低等，且更适用于熔融沉积3D打印，因此近些年来在4D打印技术中获得了快速发展，能有效满足很多先进领域的应用，如生物医用、军事防空、机械传感装置、制动器等。With the development of 3D printing technology becoming more and more mature, people's needs are far from being satisfied with "3D printing". The concept of "4D printing" proposed in 2013 has aroused widespread interest among scholars. 4D printing, as the name suggests, refers to the introduction of the fourth dimension—time—on the basis of three-dimensional products. Under external stimuli (such as heat, electricity, light, magnetism, moisture, etc.), the product can change its structure, properties, Changes in form and function. Among them, thermal shape memory is one of the most researched 4D printing technologies at present, which means that the shape of 3D products can change over time under thermal stimulation, and shape memory materials are the basis for the development of this technology. Since shape memory polymers have advantages different from shape memory alloys and shape memory ceramics, such as low density, low response temperature, large deformation, easy processing, and low cost, and are more suitable for fused deposition 3D printing, so in recent years It has achieved rapid development in 4D printing technology, which can effectively meet the applications in many advanced fields, such as biomedicine, military air defense, mechanical sensing devices, brakes, etc.
目前已经商用的熔融沉积3D打印聚合物耗材主要有丙烯腈-丁二烯-苯乙烯共聚物(ABS)和聚乳酸，但ABS在打印过程容易翘曲变形、有轻微“难闻”气味，聚乳酸则存在打印制品脆性大、热变形温度低、成本高的不足，且两者普遍缺乏导电导热、形状记忆等功能性，这些缺点限制了熔融沉积成型技术的广泛应用和发展。随着人们对打印耗材要求的日益提高，低成本、高性能以及多功能的新型耗材，尤其是具有较好3D打印性能以及形状记忆功能的聚合物耗材，具有广泛的应用前景。Currently commercially available polymer consumables for fused deposition 3D printing mainly include acrylonitrile-butadiene-styrene copolymer (ABS) and polylactic acid. Lactic acid has the shortcomings of high brittleness of printed products, low heat distortion temperature, and high cost, and both of them generally lack functions such as electrical conductivity, heat conduction, and shape memory. These shortcomings limit the wide application and development of fused deposition modeling technology. With the increasing requirements for printing consumables, low-cost, high-performance and multi-functional new consumables, especially polymer consumables with good 3D printing performance and shape memory function, have broad application prospects.
聚烯烃是常见的通用热塑性塑料，具有相对密度小、机械性能好、耐化学腐蚀、耐热、易加工、电绝缘性能好等众多优点，但由于制品收缩率大等问题目前很难应用于熔融沉积成型。中国发明专利申请CN103739954A公开了一种可用于熔融沉积3D打印的聚丙烯复合材料及其制备方法，其原料组成的重量百分比为聚丙烯70-98％、透明增韧剂1-20％、无机填料0-10％、成核剂0.1-0.5％、稳定剂0.2-2％、其它添加剂0-5％，该发明可以有效提高材料的韧性、降低材料的收缩率，并保持较好的透明度，具有良好的综合性能。Polyolefin is a common general-purpose thermoplastic, which has many advantages such as low relative density, good mechanical properties, chemical corrosion resistance, heat resistance, easy processing, and good electrical insulation performance. depositional molding. Chinese invention patent application CN103739954A discloses a polypropylene composite material that can be used for fused deposition 3D printing and its preparation method. The weight percentage of its raw material composition is polypropylene 70-98%, transparent toughening agent 1-20%, inorganic filler 0-10%, nucleating agent 0.1-0.5%, stabilizer 0.2-2%, other additives 0-5%, the invention can effectively improve the toughness of the material, reduce the shrinkage of the material, and maintain good transparency, with Good overall performance.
中国发明专利申请CN104086891A则提供了一种用于熔融沉积3D打印的聚丙烯和聚乙烯复合耗材，其组分及质量百分含量为聚丙烯40-80％、聚乙烯10-40％、无机填充料3-15％、成核剂0.2-3％、增粘剂0.2-1.5％，该打印耗材表面刚度和抗划痕特性很好，不存在环境应力开裂问题，安全性高，可用于打印成各种食品级要求的制品，其水中的吸水率仅为0.01％，故打印而成的制品不吸水、不受潮，同时表面光泽好，易于着色；该打印耗材还具有高耐热性、高耐冲击性、优异的抗弯曲性、抗腐蚀性、抗电压、耐电弧性。Chinese invention patent application CN104086891A provides a polypropylene and polyethylene composite consumable for fused deposition 3D printing, its components and mass percentages are polypropylene 40-80%, polyethylene 10-40%, inorganic filler Material 3-15%, nucleating agent 0.2-3%, tackifier 0.2-1.5%, the printing consumables have good surface rigidity and anti-scratch properties, there is no environmental stress cracking problem, high safety, and can be used for printing The water absorption rate of various food-grade products is only 0.01%, so the printed products do not absorb water and moisture, and at the same time have a good surface gloss and are easy to color; the printing consumables also have high heat resistance, high resistance Impact resistance, excellent bending resistance, corrosion resistance, voltage resistance, arc resistance.
尼龙是一种典型的工程塑料，具有优良的综合性能，如刚性大，蠕变小，机械强度高，耐热性好，电绝缘性好等，可在较苛刻的化学、物理环境中长期使用。理论上也能用作熔融沉积3D打印耗材，但实际上由于其收缩率大，打印过程层间剥离及翘曲严重甚至不能成型，打印制品也容易收缩变形，其应用受到了极大的限制。Nylon is a typical engineering plastic with excellent comprehensive properties, such as high rigidity, small creep, high mechanical strength, good heat resistance, good electrical insulation, etc., and can be used in harsh chemical and physical environments for a long time . Theoretically, it can also be used as fused deposition 3D printing consumables, but in fact, due to its large shrinkage rate, the layer peeling and warping during the printing process are serious or even impossible to form, and the printed products are also easy to shrink and deform, and its application is greatly restricted.
中国发明专利申请CN106433108A公开了一种可用于熔融沉积3D打印的耐高温尼龙丝材及其制备方法和应用其进行3D打印的方法，该耐高温尼龙丝材包括如下重量份的原料：尼龙树脂90-100份、增强剂有机改性蒙脱土1-10份、抗氧剂0.3-0.6份、润滑剂0.1-0.3份，该发明以高强度的尼龙树脂为基材，利用有机改性蒙脱土、抗氧剂和润滑剂对尼龙树脂进行物理改性，通过调节不同配比的各成分间的协同作用，改善了尼龙树脂的收缩性、提高热变性温度，得到可用于熔融沉积3D打印的耐高温尼龙丝材，其强度高、收缩率低、翘曲形变程度低、成型精度低、耐高温、支撑易去除。Chinese invention patent application CN106433108A discloses a high-temperature-resistant nylon filament that can be used for fused deposition 3D printing, its preparation method, and its application in 3D printing. The high-temperature-resistant nylon filament includes the following raw materials in parts by weight: nylon resin 90 -100 parts, 1-10 parts of organically modified montmorillonite as reinforcing agent, 0.3-0.6 parts of antioxidant, 0.1-0.3 parts of lubricant. Soil, antioxidants and lubricants are used to physically modify the nylon resin. By adjusting the synergistic effect of the various components in different proportions, the shrinkage of the nylon resin is improved and the thermal denaturation temperature is increased. High temperature resistant nylon wire, with high strength, low shrinkage, low degree of warping and deformation, low forming precision, high temperature resistance, and easy removal of supports.
然而，中国发明专利申请CN103739954A、CN104086891A和CN106433108A等聚烯烃类或尼龙类打印耗材综合性能较好，但由于其原材料的组分类型较为单一，只具有用于改善打印性能和加工性能的无机填料、增韧剂、添加剂等组分，而缺乏成为半结晶性聚合物形状记忆体系必须具备的可逆相和固定相，因而缺乏形状记忆等功能性，使得其应用受到了明显的功能性限制。However, the Chinese invention patent applications CN103739954A, CN104086891A and CN106433108A and other polyolefin or nylon printing consumables have better overall performance, but due to the relatively simple component types of their raw materials, they only have inorganic fillers for improving printing performance and processing performance. Tougheners, additives and other components, but lack the reversible phase and stationary phase that must be possessed in semi-crystalline polymer shape memory systems, and thus lack functionality such as shape memory, making its application subject to obvious functional limitations.
发明内容SUMMARY OF THE INVENTION
针对上述具备功能性的熔融沉积3D打印耗材存在的问题，本发明的目的在于提供一种同时具有制品翘曲度、表面质量、力学性能、热性能等优异的3D打印性能，并还具有形状记忆功能的形状记忆聚合物合金及其制备方法。In view of the above-mentioned problems existing in the functional fused deposition 3D printing consumables, the purpose of the present invention is to provide a 3D printing performance that has excellent product warpage, surface quality, mechanical properties, thermal properties, etc., and also has shape memory. Functional shape memory polymer alloys and methods for their preparation.
为达到以上目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
基于熔融沉积3D打印的形状记忆聚合物合金，其特征在于，按重量百分比计，形状记忆聚合物合金的原料组成为：聚烯烃塑料30-50％、尼龙树脂10-40％、热塑性弹性体接枝物20-40％、过氧化物交联剂0.1-1％、助交联剂0-5％、纳米填料1-5％；The shape-memory polymer alloy based on fused deposition 3D printing is characterized in that, by weight percentage, the raw material composition of the shape-memory polymer alloy is: polyolefin plastic 30-50%, nylon resin 10-40%, thermoplastic elastomer bonded Branches 20-40%, peroxide crosslinking agent 0.1-1%, co-crosslinking agent 0-5%, nano filler 1-5%;
所述的聚烯烃塑料为高密度聚乙烯、低密度聚乙烯或聚丙烯；The polyolefin plastic is high-density polyethylene, low-density polyethylene or polypropylene;
所述的尼龙树脂为尼龙6、尼龙66或尼龙1010；Described nylon resin is nylon 6, nylon 66 or nylon 1010;
所述热塑性弹性体接枝物为POE-g-MAH、SEBS-g-MAH、EPDM-g-MAH和The thermoplastic elastomer grafts are POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH and
EVA-g-MAH中的一种或多种；One or more of EVA-g-MAH;
所述的助交联剂为苯乙烯或松节油；Described co-crosslinking agent is styrene or turpentine;
所述的纳米填料为纳米二氧化硅或纳米碳酸钙。The nano filler is nano silicon dioxide or nano calcium carbonate.
为进一步实现本发明目的，优选地，所述的过氧化物交联剂过氧化二异丙苯DCP或过氧化苯甲酰BPO。To further realize the object of the present invention, preferably, the peroxide crosslinking agent is dicumyl peroxide DCP or benzoyl peroxide BPO.
优选地，所述的低密度聚乙烯为线性低密度聚乙烯。Preferably, the low-density polyethylene is linear low-density polyethylene.
所述的基于熔融沉积3D打印的形状记忆聚合物合金的制备方法，包括以下步骤：The preparation method of the described shape memory polymer alloy based on fused deposition 3D printing comprises the following steps:
1)按原料的重量百分比称取原料；1) take raw materials by weight percentage of raw materials;
2)将称取好的聚烯烃塑料、尼龙树脂、热塑性弹性体接枝物和纳米填料进行干燥处理；2) Drying the weighed polyolefin plastic, nylon resin, thermoplastic elastomer graft and nanofiller;
3)将称量好的原料放入高速混合机中进行混合；3) Put the weighed raw materials into a high-speed mixer for mixing;
4)将混合好的原料加入双螺杆挤出机中进行熔融挤出并造粒；4) adding the mixed raw materials into a twin-screw extruder for melt extrusion and granulation;
5)将得到的均匀混合的粒料进行干燥处理后，通过双螺杆挤出机进行熔融挤出成型，得到可用于熔融沉积3D打印的聚合物合金线材。5) After the obtained uniformly mixed pellets are dried, they are melt-extruded through a twin-screw extruder to obtain polymer alloy wires that can be used for fused deposition 3D printing.
优选地，步骤2)所述的干燥处理是在鼓风烘箱内以60-100℃的温度干燥4-10小时，使原料含水量降至0.2-0.5％。Preferably, the drying treatment in step 2) is drying in a blast oven at a temperature of 60-100° C. for 4-10 hours to reduce the moisture content of the raw material to 0.2-0.5%.
优选地，所述的原料放入高速混合机中进行混合的时间为10-30分钟，混合温度为40-70℃。Preferably, the time for the raw materials to be mixed in a high-speed mixer is 10-30 minutes, and the mixing temperature is 40-70°C.
优选地，所述的熔融挤出并造粒的挤出温度为205-260℃，螺杆转速为50-80r/min。Preferably, the extrusion temperature of the melt extrusion and granulation is 205-260° C., and the screw speed is 50-80 r/min.
优选地，所述的熔融挤出成型的温度为205-260℃，螺杆转速为40-60r/min，线材直径为1.75±0.1mm。Preferably, the temperature of the melt extrusion molding is 205-260° C., the screw speed is 40-60 r/min, and the wire diameter is 1.75±0.1 mm.
优选地，步骤5)所述的干燥处理为60-100℃下干燥4-10小时。Preferably, the drying treatment in step 5) is drying at 60-100° C. for 4-10 hours.
相对于现有技术，本发明具有如下特点和优异的效果：Compared with the prior art, the present invention has the following characteristics and excellent effects:
1)本发明所使用的聚烯烃和尼龙树脂都是典型的半结晶性聚合物，尼龙树脂维持制品原始形状的固定相，能有效提高聚烯烃塑料的力学性能，聚烯烃作为可用于改变制品原始形状而形成临时形状的可逆相，还能大大降低尼龙树脂的吸水率，从而可得到具备优异力学性能和形状记忆性能的聚合物合金材料。1) Polyolefin and nylon resin used in the present invention are all typical semi-crystalline polymers. Nylon resin maintains the stationary phase of the original shape of the product, which can effectively improve the mechanical properties of polyolefin plastics. Polyolefin can be used to change the original shape of the product. The reversible phase that forms a temporary shape by changing the shape can also greatly reduce the water absorption of nylon resin, so that a polymer alloy material with excellent mechanical properties and shape memory properties can be obtained.
2)可逆相聚烯烃塑料在交联剂(和助交联剂)的作用下可发生微交联作用，从而调控结晶相，通常对制品形状发生改变的关键触发条件为温度，因而当温度达到聚烯烃的熔点即可使其分子链运动，然后通过快速冷却结晶赋予制品临时形状，当温度回复后，分子链结晶熔融并发生熵弹回复，从而呈现出形状回复的现象。2) Reversible phase polyolefin plastics can undergo micro-crosslinking under the action of crosslinking agents (and co-crosslinking agents), thereby regulating the crystalline phase. Usually, the key trigger condition for changing the shape of the product is temperature, so when the temperature reaches Polyolefin The melting point of olefin can make its molecular chain move, and then give the product a temporary shape through rapid cooling and crystallization. When the temperature returns, the molecular chain crystallization melts and undergoes entropy elastic recovery, thus showing the phenomenon of shape recovery.
3)本发明所制备的聚合物合金能通过熔融沉积3D打印制备出具备热致形状记忆功能的制品，即制品可在一定的变形温度下通过外力作用获得临时形状，并通过快速降温而固定下来，即使撤去外力后仍能保持，然后当温度回复到变形温度时又可快速恢复至初始形状，具有较高的形状固定率和形状回复率。3) The polymer alloy prepared by the present invention can produce a product with thermal shape memory function by fused deposition 3D printing, that is, the product can obtain a temporary shape by external force at a certain deformation temperature, and fix it by rapid cooling , even if the external force is removed, it can still be maintained, and then it can quickly return to the original shape when the temperature returns to the deformation temperature, with a high shape fixation rate and shape recovery rate.
4)本发明所使用的热塑性弹性体接枝物不仅充当着聚烯烃和尼龙树脂的增容剂，还可作为聚合物与纳米填料的界面改性剂，从而使得合金的性能得到进一步的提高；通过削弱该聚合物合金的结晶能力来缓解合金用于熔融沉积3D打印时由于其层层堆积的成型方式所导致的不均匀体积收缩，从而改善所产生的打印翘曲问题。4) The thermoplastic elastomer graft used in the present invention not only acts as a compatibilizer for polyolefins and nylon resins, but also as an interfacial modifier for polymers and nanofillers, thereby further improving the performance of the alloy; By weakening the crystallization ability of the polymer alloy, the alloy is used for fused deposition 3D printing to alleviate the uneven volume shrinkage caused by its layer-by-layer accumulation, thereby improving the printing warpage problem.
5)本发明所制备的聚合物合金由于加有少量的纳米填料，不仅适用于熔融沉积3D打印，而且具备优异的打印效果和打印性能，打印制品具有翘曲度低，尺寸稳定性高，表面光洁无缺陷，力学性能和耐热性能均较好等特点。5) The polymer alloy prepared by the present invention is not only suitable for fused deposition 3D printing due to the addition of a small amount of nano-filler, but also has excellent printing effect and printing performance. The printed product has low warpage, high dimensional stability, and surface Smooth and free of defects, good mechanical properties and heat resistance.
具体实施方式Detailed ways
为了更好地理解本发明，下面结合附图和实施例对本发明作进一步阐述，但本发明的实施方式不限于此，具体实施例中对于未特别注明的工艺参数，可参照常规技术进行。In order to better understand the present invention, the present invention will be further described below in conjunction with the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto. For the process parameters not specifically noted in the specific examples, conventional techniques can be referred to.
聚烯烃塑料30-50％、尼龙树脂10-40％、热塑性弹性体接枝物20-40％、过氧化物交联剂0.1-1％、助交联剂0-5％、纳米填料1-5％；所述热塑性弹性体接枝物为POE-g-MAH、SEBS-g-MAH、EPDM-g-MAH和EVA-g-MAH中的一种或多种；Polyolefin plastic 30-50%, nylon resin 10-40%, thermoplastic elastomer graft 20-40%, peroxide crosslinking agent 0.1-1%, auxiliary crosslinking agent 0-5%, nanofiller 1- 5%; the thermoplastic elastomer graft is one or more of POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH and EVA-g-MAH;
实施例1Example 1
基于熔融沉积3D打印的形状记忆聚合物合金的制备方法，包括以下步骤：按原料重量百分比计，将44wt％的聚丙烯塑料、30wt％的尼龙66、22wt％的POE-g-MAH、1wt％纳米二氧化硅于60℃下干燥5小时，然后将上述物料与0.2wt％过氧化二异丙苯DCP、2.8wt％松节油，一起放入高速混合机中进行混合，混合温度50℃，混合时间20分钟；混合好的原料加入双螺杆挤出机中熔融挤出并造粒，其中挤出温度为250℃，螺杆转速为80r/min；将得到的粒料于60℃下干燥6小时后，通过双螺杆挤出机中熔融挤出，得到直径为1.75±0.1mm的可用于熔融沉积3D打印的聚合物合金线材，其中挤出温度为255℃，螺杆转速为40r/min。The preparation method of the shape memory polymer alloy based on fused deposition 3D printing comprises the following steps: according to the weight percentage of raw materials, 44wt% polypropylene plastic, 30wt% nylon 66, 22wt% POE-g-MAH, 1wt% Nano-silica was dried at 60°C for 5 hours, and then the above materials were mixed with 0.2wt% dicumyl peroxide DCP and 2.8wt% turpentine in a high-speed mixer at a mixing temperature of 50°C and a mixing time of 20 minutes; the mixed raw materials are put into a twin-screw extruder to melt and extrude and pelletize, wherein the extrusion temperature is 250°C, and the screw speed is 80r/min; after drying the obtained pellets at 60°C for 6 hours, Through melt extrusion in a twin-screw extruder, a polymer alloy wire rod with a diameter of 1.75±0.1 mm that can be used for fused deposition 3D printing is obtained, wherein the extrusion temperature is 255° C., and the screw speed is 40 r/min.
将制备的线材送入打印设备的喷嘴，将相应测试样条模型的代码导入打印设备中，通过熔融沉积3D打印制备测试样条，其中打印排列方式为±45°，打印填充率为100％，打印设备的喷嘴温度为260℃，热床温度为120℃。Send the prepared wire into the nozzle of the printing device, import the code of the corresponding test sample model into the printing device, and prepare the test sample by fused deposition 3D printing, wherein the printing arrangement is ±45°, and the printing filling rate is 100%. The nozzle temperature of the printing device is 260°C, and the temperature of the hot bed is 120°C.
通过打印尺寸为80×10×4mm的条状样品来表征打印制品的翘曲度及评价其打印效果，如图1所示，本实施例所得合金材料具有较好的打印效果，能观察到样品与所设计的3D模型形状基本一致，成型精度较好；样品具有较高的尺寸稳定性，翘曲程度低，测得翘曲度仅为5.3％。翘曲度的测试方法：通过FDM设备打印出80×10×4mm的条状制品作为翘曲度测试的模型，测定方法如图2所示：将制品放置在平台上，测量制品中间位置距离水平面的最高高度h1，以及制品中间位置的厚度h2，按公式计算得翘曲度ω，每组测量5个试样，取算术平均值。Characterize the warpage of the printed product and evaluate its printing effect by printing a strip sample with a size of 80×10×4mm. As shown in Figure 1, the alloy material obtained in this example has a good printing effect, and the sample can be observed The shape is basically consistent with the designed 3D model, and the molding accuracy is good; the sample has high dimensional stability and low warpage, and the measured warpage is only 5.3%. Warpage test method: print out 80×10×4mm strip products through FDM equipment as a model for warpage test, the measurement method is shown in Figure 2: place the product on the platform, measure the distance between the middle position of the product and the horizontal plane The highest height h1 of the product and the thickness h2 of the middle position of the product are calculated according to the formula to obtain the degree of warpage ω, and 5 samples are measured for each group, and the arithmetic mean value is taken.
观察样品表面，可以发现其表面光滑，填充密实，没有出现孔洞、发白等缺陷，打印质量佳。Observing the surface of the sample, it can be found that the surface is smooth, the filling is dense, there are no defects such as holes and whitening, and the printing quality is good.
本实施例所得合金材料力学性能和耐热性能良好，按标准ISO 527-2-2012 1BA打印拉伸测试样条和执行拉伸试验，测得拉伸强度为25.6MPa；按标准ISO 178-2010打印弯曲测试样条和执行弯曲试验，测得弯曲强度为24.9MPa；按标准ASTM D256-2006打印缺口冲击测试样条和执行冲击试验，表现出极高的韧性，其冲击样条无法冲断；按标准GB/T 1633-2000打印维卡软化点测试样条和执行试验，测得维卡软化点为60.8℃。The alloy material obtained in this embodiment has good mechanical properties and heat resistance. According to the standard ISO 527-2-2012 1BA, the tensile test sample is printed and the tensile test is performed, and the measured tensile strength is 25.6MPa; according to the standard ISO 178-2010 Print the bending test sample and perform the bending test, and the measured bending strength is 24.9MPa; print the notched impact test sample and perform the impact test according to the standard ASTM D256-2006, showing extremely high toughness, and the impact sample cannot be broken; According to the standard GB/T 1633-2000, the Vicat softening point test sample was printed and the test was performed, and the measured Vicat softening point was 60.8°C.
材料的形状记忆性能一般通过形状固定率和形状回复率两个指标来表征，该指标可采用DMA的拉伸薄膜夹具和控制应力模式测定，设置程序如下：1)样条的初始形变为ε0，将其保持在变形温度下5min，然后施加某一固定应力σ使其形变；2)立刻降温至室温，在该温度和应力下保持3min以固定形变，形变为ε1,load；3)撤去外力，继续在该温度下保持3min，形变为ε1；4)快速回复至变形温度，并在该温度下保持20min，最终形变为ε0,rec。则形状固定率和回复率的计算公式如下：The shape memory performance of materials is generally characterized by two indicators: shape fixation rate and shape recovery rate, which can be measured by DMA tensile film fixture and controlled stress mode. The setting procedure is as follows: 1) The initial deformation of the spline is ε0 , keep it at the deformation temperature for 5 minutes, and then apply a certain fixed stress σ to make it deform; 2) immediately cool down to room temperature, and keep it at this temperature and stress for 3 minutes to fix the deformation, and the deformation becomes ε1,load ; 3) Remove External force, continue to maintain at this temperature for 3 minutes, the deformation is ε1 ; 4) quickly return to the deformation temperature, and maintain at this temperature for 20 minutes, and finally deform to ε0,rec . The calculation formulas of shape fixation rate and recovery rate are as follows:
形状固定率shape fixity
形状回复率Shape recovery rate
通过打印尺寸为60×5×1mm的拉伸薄膜样条进行形状记忆DMA测试。本实施例所得合金材料形状记忆性能优异，DMA测试结果如图3所示，根据应变可算得形状固定率为90.0％，形状回复率为89.1％。由于形状固定率反映的是临时形状被固定的有效性，形状回复率反映的是最终所回复的形状与初始形状的接近程度，因此，在本实施例中，形状固定率和形状回复率都在较高水平便说明了该合金所制备的制品能被稳定地赋予临时形状，且能在温度到达变形温度时基本回复到初始形状，具备优异的形状记忆性能。该形状记忆聚合物合金具有较好的力学性能、较低的翘曲度以及较高的形状固定率和回复率，与熔融沉积3D打印技术相结合，便能简单方便地实现复杂形状的热致形状记忆智能制品的制备，可推广应用于生物医学、航天航空、军事防空、机械传感装置、制动器等先进领域。例如，可用作血栓治疗设备的微驱动器，装配到治疗系统后，利用光电控制系统加热，即可使其恢复到螺旋形从而拉出血栓；又如，可用作热敏报警器，当感应到周围环境到达一定温度，开关会自动恢复至“关上”状态，即可实现“报警”效果。现有类似的合金材料一般由于缺乏交联网络，或是缺乏性质相差较远的两相来作为固定相和可逆相，因此不具有本实施例的形状记忆功能；而现有的形状记忆材料又普遍不适用于3D打印技术，当采用传统方法制备复杂形状的产品时技术难度大，制造成本高，而该合金材料能适用于熔融沉积3D打印技术，可简单方便地制备出几乎任意形状的复杂制品，而且具有优异的形状记忆功能，因此能大大地降低制造成本，提高生产效率，节约材料和能源。Shape memory DMA tests were performed by printing stretched film specimens with dimensions of 60 × 5 × 1 mm. The alloy material obtained in this example has excellent shape memory performance. The DMA test results are shown in FIG. 3 . According to the strain, the shape fixation rate is 90.0%, and the shape recovery rate is 89.1%. Since the shape fixation rate reflects the effectiveness of the temporary shape being fixed, and the shape recovery rate reflects the closeness of the final restored shape to the initial shape, therefore, in this embodiment, both the shape fixation rate and the shape recovery rate are between A higher level shows that the products prepared by the alloy can be stably endowed with a temporary shape, and can basically return to the original shape when the temperature reaches the deformation temperature, which has excellent shape memory properties. The shape memory polymer alloy has good mechanical properties, low warpage, and high shape fixation rate and recovery rate. Combining with fused deposition 3D printing technology, it can easily and conveniently realize the thermal induction of complex shapes. The preparation of shape memory intelligent products can be widely used in advanced fields such as biomedicine, aerospace, military air defense, mechanical sensing devices, and brakes. For example, it can be used as a micro-driver for thrombus treatment equipment. After being assembled into the treatment system, it can be heated by a photoelectric control system to restore the spiral shape to pull out the thrombus; another example, it can be used as a thermal alarm. When the surrounding environment reaches a certain temperature, the switch will automatically return to the "closed" state, and the "alarm" effect can be realized. The existing similar alloy materials generally do not have the shape memory function of this embodiment due to the lack of crosslinking network, or the lack of two phases with far different properties as the stationary phase and the reversible phase; and the existing shape memory materials have It is generally not suitable for 3D printing technology. When traditional methods are used to prepare products with complex shapes, the technology is difficult and the manufacturing cost is high. However, this alloy material can be applied to fused deposition 3D printing technology, which can easily and conveniently prepare complex shapes of almost any shape. products, and has excellent shape memory function, so it can greatly reduce manufacturing costs, improve production efficiency, and save materials and energy.
实施例2Example 2
将35wt％的高密度聚乙烯、30wt％的尼龙6以及32wt％的EPDM-g-MAH、2.5wt％纳米碳酸钙于80℃下干燥4小时，然后将上述物料与0.5wt％过氧化二异丙苯DCP一起放入高速混合机中进行混合，混合温度60℃，混合时间15分钟；将混合好的原料加入双螺杆挤出机中熔融挤出并造粒，其中挤出温度为235℃，螺杆转速为70r/min；将得到的粒料于80℃下干燥5小时干燥后，通过双螺杆挤出机熔融挤出，得到直径为1.75±0.1mm的可用于熔融沉积3D打印的聚合物合金线材，其中挤出温度为235℃，螺杆转速为50r/min。35wt% high-density polyethylene, 30wt% nylon 6 and 32wt% EPDM-g-MAH, 2.5wt% nano calcium carbonate were dried at 80°C for 4 hours, and then the above materials were mixed with 0.5wt% diisoperoxide Propylbenzene and DCP are put together in a high-speed mixer for mixing, the mixing temperature is 60°C, and the mixing time is 15 minutes; the mixed raw materials are put into a twin-screw extruder to melt and extrude and pelletize, and the extrusion temperature is 235°C. The screw speed is 70r/min; the obtained pellets are dried at 80°C for 5 hours, and then melted and extruded through a twin-screw extruder to obtain a polymer alloy with a diameter of 1.75±0.1mm that can be used for fused deposition 3D printing Wire rod, wherein the extrusion temperature is 235° C., and the screw speed is 50 r/min.
通过熔融沉积3D打印制备测试样条，其中打印排列方式为±45°，打印填充率为100％，打印设备的喷嘴温度为250℃，热床温度为110℃。经测试可发现，样品同样具有较高的尺寸稳定性，翘曲度仅为4.1％，且表面光滑无缺陷；力学性能和耐热性能良好，拉伸强度为23.3MPa，弯曲强度为22.3MPa，韧性极高，使得冲击样条无法冲断，维卡软化点则为53.8℃；形状记忆性能较好，形状固定率高达91.5％，形状回复率则为80.9％。The test sample was prepared by fused deposition 3D printing, where the printing arrangement was ±45°, the printing filling rate was 100%, the nozzle temperature of the printing equipment was 250 °C, and the hot bed temperature was 110 °C. After testing, it can be found that the sample also has high dimensional stability, the warpage is only 4.1%, and the surface is smooth without defects; the mechanical properties and heat resistance are good, the tensile strength is 23.3MPa, the bending strength is 22.3MPa, The toughness is so high that the impact spline cannot be broken, and the Vicat softening point is 53.8°C; the shape memory performance is good, the shape fixation rate is as high as 91.5%, and the shape recovery rate is 80.9%.
实施例3Example 3
将38wt％的聚丙烯、30wt％的尼龙1010以及28wt％的SEBS-g-MAH、3wt％纳米二氧化硅于70℃下干燥5小时，然后将上述物料与0.3wt％过氧化二异丙苯DCP、0.7wt％苯乙烯一起放入高速混合机中进行混合，混合温度40℃，混合时间30分钟；将混合好的原料加入双螺杆挤出机中熔融挤出并造粒，其中挤出温度为230℃，螺杆转速为60r/min；将得到的粒料于80℃下干燥4小时后，通过双螺杆挤出机熔融挤出，得到直径为1.75±0.1mm的可用于熔融沉积3D打印的聚合物合金线材，其中挤出温度为210℃，螺杆转速为60r/min。通过熔融沉积3D打印制备测试样条，其中打印排列方式为±45°，打印填充率为80％，打印设备的喷嘴温度为230℃，热床温度为80℃。经测试发现其形状记忆性能较好，形状固定率为84.4％，形状回复率为88.1％，表明该合金基本能满足对热致形状记忆制品的使用需求，且即使降低打印填充率也不影响其形状记忆性能，因此通过改变打印填充率可简单地实现任意形状的轻质形状记忆制品的制备。38wt% polypropylene, 30wt% nylon 1010 and 28wt% SEBS-g-MAH, 3wt% nano silicon dioxide were dried at 70°C for 5 hours, and then the above materials were mixed with 0.3wt% dicumyl peroxide DCP and 0.7wt% styrene are put together in a high-speed mixer for mixing, the mixing temperature is 40°C, and the mixing time is 30 minutes; the mixed raw materials are put into a twin-screw extruder to melt and extrude and granulate, wherein the extrusion temperature The temperature is 230°C, and the screw speed is 60r/min; after drying the obtained pellets at 80°C for 4 hours, they are melted and extruded through a twin-screw extruder to obtain fused deposition 3D printing with a diameter of 1.75±0.1mm A polymer alloy wire rod, wherein the extrusion temperature is 210° C., and the screw speed is 60 r/min. The test sample was prepared by fused deposition 3D printing, where the printing arrangement was ±45°, the printing filling rate was 80%, the nozzle temperature of the printing equipment was 230°C, and the hot bed temperature was 80°C. After testing, it is found that its shape memory performance is good, the shape fixation rate is 84.4%, and the shape recovery rate is 88.1%, which shows that the alloy can basically meet the requirements for the use of thermally induced shape memory products, and even if the printing filling rate is reduced, it will not affect its Shape memory properties, so the preparation of lightweight shape memory products of arbitrary shapes can be simply realized by changing the printing filling rate.
实施例4Example 4
将50wt％的线性低密度聚乙烯、16wt％的尼龙6、28wt％的EVA-g-MAH、5wt％纳米碳酸钙于60℃下干燥6小时，然后将上述物料与1wt％过氧化苯甲酰BPO一起放入高速混合机中进行混合，混合温度50℃，混合时间10分钟；将混合好的原料加入双螺杆挤出机中熔融挤出并造粒，其中挤出温度为215℃，螺杆转速为60r/min；将得到的粒料于60℃下干燥6小时后，通过双螺杆挤出机熔融挤出，得到直径为1.75±0.1mm的可用于熔融沉积3D打印的聚合物合金线材，其中挤出温度为215℃，螺杆转速为40r/min。通过熔融沉积3D打印制备测试样条，其中打印排列方式为0°/90°，打印填充率为100％，打印设备的喷嘴温度为230℃，热床温度为75℃。经测试发现其形状记忆性能较好，形状固定率为82.1％，形状回复率为80.0％，表明该合金基本能满足对热致形状记忆制品的使用需求。50wt% linear low density polyethylene, 16wt% nylon 6, 28wt% EVA-g-MAH, 5wt% nano calcium carbonate were dried at 60°C for 6 hours, and then the above materials were mixed with 1wt% benzoyl peroxide Put BPO together in a high-speed mixer for mixing, the mixing temperature is 50°C, and the mixing time is 10 minutes; put the mixed raw materials into a twin-screw extruder to melt and extrude and pelletize, wherein the extrusion temperature is 215°C, the screw speed 60r/min; after drying the obtained pellets at 60°C for 6 hours, melt extruding through a twin-screw extruder to obtain a polymer alloy wire rod with a diameter of 1.75±0.1mm that can be used for fused deposition 3D printing, wherein The extrusion temperature is 215° C., and the screw speed is 40 r/min. The test sample was prepared by fused deposition 3D printing, where the printing arrangement was 0°/90°, the printing filling rate was 100%, the nozzle temperature of the printing equipment was 230°C, and the hot bed temperature was 75°C. It is found that the shape memory performance of the alloy is good, the shape fixation rate is 82.1%, and the shape recovery rate is 80.0%, which shows that the alloy can basically meet the use requirements of thermally induced shape memory products.
实施例5Example 5
将40wt％的低密度聚乙烯、32wt％的尼龙6以及26wt％的POE-g-MAH、1.5wt％纳米二氧化硅于60℃下干燥6小时，然后将上述物料与0.5wt％过氧化二异丙苯DCP一起放入高速混合机中进行混合，混合温度60℃，混合时间20分钟；将混合好的原料加入双螺杆挤出机中熔融挤出并造粒，其中挤出温度为210℃，螺杆转速为80r/min；将得到的粒料以同样条件干燥后，通过双螺杆挤出机中熔融挤出，得到直径为1.75±0.1mm的可用于熔融沉积3D打印的聚合物合金线材，其中挤出温度为240℃，螺杆转速为40r/min。40wt% low-density polyethylene, 32wt% nylon 6 and 26wt% POE-g-MAH, 1.5wt% nano silicon dioxide were dried at 60°C for 6 hours, and then the above materials were mixed with 0.5wt% diperoxide Put cumene and DCP together in a high-speed mixer for mixing, the mixing temperature is 60°C, and the mixing time is 20 minutes; put the mixed raw materials into a twin-screw extruder to melt and extrude and pelletize, and the extrusion temperature is 210°C , the screw speed is 80r/min; after drying the obtained pellets under the same conditions, they are melt-extruded through a twin-screw extruder to obtain a polymer alloy wire rod with a diameter of 1.75±0.1mm that can be used for fused deposition 3D printing, Wherein the extrusion temperature is 240° C., and the screw speed is 40 r/min.
通过熔融沉积3D打印制备实体制品，其中打印排列方式为±45°，打印填充率为100％，打印设备的喷嘴温度为250℃，热床温度为100℃。The solid product is prepared by fused deposition 3D printing, where the printing arrangement is ±45°, the printing filling rate is 100%, the nozzle temperature of the printing device is 250°C, and the hot bed temperature is 100°C.
打印如图4所示的花朵形状实体制品，以验证使用该合金材料进行熔融沉积3D打印制备得实体制品的成型效果和形状记忆特性。首先将花朵制品放置到175℃的鼓风干燥箱中并保持20min，然后施加外力使制品产生形变，立刻用冷水将制品快速降温至室温以固定临时形状，此时呈现出花苞“合上”的现象；将制品重新放置到175℃的鼓风干燥箱中，图片显示了制品分别在第30、60、180秒时的形状，即表现出了花苞逐渐“打开”的现象，最终制品在该温度下3分钟内即可从临时形状回复至初始形状，形状记忆性能优异。经验证后发现，该合金应用到熔融沉积3D打印中，不仅能制备出成型精度高、尺寸稳定性好、形状结构复杂的实体制品，而且制品还具备很好的热致形状记忆性能，即既能有效地保持所赋予的临时形状，又能在到达一定温度时自动回复到初始形状，满足了实际应用时对制品形状记忆功能的要求。Print the flower-shaped solid product as shown in Figure 4 to verify the molding effect and shape memory properties of the solid product prepared by fused deposition 3D printing using the alloy material. First place the flower product in a blast drying oven at 175°C and keep it for 20 minutes, then apply an external force to deform the product, and immediately cool the product to room temperature with cold water to fix the temporary shape. At this time, the flower bud "closes" Phenomenon: put the product back into the blast drying oven at 175°C, the picture shows the shape of the product at the 30th, 60th, and 180th second respectively, that is, it shows the phenomenon that the flower buds gradually "open", and the final product is at this temperature It can return from the temporary shape to the original shape within 3 minutes, and has excellent shape memory performance. After verification, it was found that the application of this alloy in fused deposition 3D printing can not only produce solid products with high molding precision, good dimensional stability, and complex shape and structure, but also have good thermally induced shape memory properties, that is, both It can effectively maintain the given temporary shape, and can automatically return to the original shape when reaching a certain temperature, which meets the requirements for the shape memory function of the product in practical application.
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的技术人员来说，在任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those skilled in the art, any changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention within.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910289243.4ACN110079010B (en) | 2019-04-11 | 2019-04-11 | Shape memory polymer alloy based on fused deposition 3D printing and its preparation method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910289243.4ACN110079010B (en) | 2019-04-11 | 2019-04-11 | Shape memory polymer alloy based on fused deposition 3D printing and its preparation method |
| Publication Number | Publication Date |
|---|---|
| CN110079010Atrue CN110079010A (en) | 2019-08-02 |
| CN110079010B CN110079010B (en) | 2020-04-28 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910289243.4AActiveCN110079010B (en) | 2019-04-11 | 2019-04-11 | Shape memory polymer alloy based on fused deposition 3D printing and its preparation method |
| Country | Link |
|---|---|
| CN (1) | CN110079010B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793175A (en)* | 2020-06-19 | 2020-10-20 | 湖南电气职业技术学院 | Enhanced multi-thorn laser curing 3D printing shape memory material and preparation method thereof |
| CN112004656A (en)* | 2018-03-26 | 2020-11-27 | 昕诺飞控股有限公司 | Cross-linked polymer-filled polymer particles for 3D printed articles |
| CN113637298A (en)* | 2021-08-17 | 2021-11-12 | 浙江师范大学 | A kind of fused deposition molding product and preparation method thereof |
| CN113789052A (en)* | 2021-11-15 | 2021-12-14 | 富海(东营)新材料科技有限公司 | Shape memory nylon material and preparation method thereof |
| CN116063799A (en)* | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
| CN117986790A (en)* | 2024-01-12 | 2024-05-07 | 苏州智新复合材料有限公司 | Preparation method of shape memory 4D printing line suitable for fused deposition printing |
| TWI848636B (en)* | 2023-03-25 | 2024-07-11 | 財團法人鞋類暨運動休閒科技研發中心 | A thermoplastic elastomer, manufacturing method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936747A (en)* | 2016-05-13 | 2016-09-14 | 哈尔滨工业大学 | Method for preparing triple shape memory polymer through blending shape memory polyurethane with ABS resin, and application of triple shape memory polymer in 3D printing |
| CN107652668A (en)* | 2016-07-26 | 2018-02-02 | 四川鑫达企业集团有限公司 | A kind of activeness and quietness nylon material available for 3D printing and preparation method thereof |
| EP3375819A1 (en)* | 2017-03-13 | 2018-09-19 | TIGER Coatings GmbH & Co. KG | Use of a thermosetting polymeric powder compostion |
| CN108587136A (en)* | 2018-05-16 | 2018-09-28 | 哈尔滨工业大学 | A kind of material and preparation method thereof of photoresponse 4D printings |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936747A (en)* | 2016-05-13 | 2016-09-14 | 哈尔滨工业大学 | Method for preparing triple shape memory polymer through blending shape memory polyurethane with ABS resin, and application of triple shape memory polymer in 3D printing |
| CN107652668A (en)* | 2016-07-26 | 2018-02-02 | 四川鑫达企业集团有限公司 | A kind of activeness and quietness nylon material available for 3D printing and preparation method thereof |
| EP3375819A1 (en)* | 2017-03-13 | 2018-09-19 | TIGER Coatings GmbH & Co. KG | Use of a thermosetting polymeric powder compostion |
| CN108587136A (en)* | 2018-05-16 | 2018-09-28 | 哈尔滨工业大学 | A kind of material and preparation method thereof of photoresponse 4D printings |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112004656A (en)* | 2018-03-26 | 2020-11-27 | 昕诺飞控股有限公司 | Cross-linked polymer-filled polymer particles for 3D printed articles |
| CN112004656B (en)* | 2018-03-26 | 2022-09-23 | 昕诺飞控股有限公司 | Cross-linked polymer-filled polymer particles for 3D printed articles |
| CN111793175A (en)* | 2020-06-19 | 2020-10-20 | 湖南电气职业技术学院 | Enhanced multi-thorn laser curing 3D printing shape memory material and preparation method thereof |
| CN113637298A (en)* | 2021-08-17 | 2021-11-12 | 浙江师范大学 | A kind of fused deposition molding product and preparation method thereof |
| CN113789052A (en)* | 2021-11-15 | 2021-12-14 | 富海(东营)新材料科技有限公司 | Shape memory nylon material and preparation method thereof |
| CN113789052B (en)* | 2021-11-15 | 2022-03-08 | 富海(东营)新材料科技有限公司 | Shape memory nylon material and preparation method thereof |
| CN116063799A (en)* | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
| TWI848636B (en)* | 2023-03-25 | 2024-07-11 | 財團法人鞋類暨運動休閒科技研發中心 | A thermoplastic elastomer, manufacturing method and application thereof |
| CN117986790A (en)* | 2024-01-12 | 2024-05-07 | 苏州智新复合材料有限公司 | Preparation method of shape memory 4D printing line suitable for fused deposition printing |
| Publication number | Publication date |
|---|---|
| CN110079010B (en) | 2020-04-28 |
| Publication | Publication Date | Title |
|---|---|---|
| CN110079010A (en) | Shape-memory polymer alloy and preparation method thereof based on fusion sediment 3D printing | |
| Peng et al. | Shape memory effect of three-dimensional printed products based on polypropylene/nylon 6 alloy | |
| CN105176020B (en) | A kind of PBS/ carbon material composite wires for 3D printing and preparation method thereof | |
| CN103210020B (en) | Nucleating agent for polyethylene | |
| CN110835417B (en) | Barrier degradable antibacterial food preservative film and preparation method and application thereof | |
| CN109456563B (en) | Special material for UHMWPE alloy compatibilization toughening modified polypropylene corrugated pipe and preparation method thereof | |
| CN113185810B (en) | Renewable high-barrier polyester packaging material and preparation method thereof | |
| CN103289342A (en) | High heat conduction reinforced PC/PBT alloy | |
| CN107151443A (en) | A kind of PEI base graphene 3D printing composite and preparation method thereof | |
| Ajinjeru et al. | The influence of rheology on melt processing conditions of carbon fiber reinforced polyetherimide for big area additive manufacturing | |
| CN103665528A (en) | Polyolefin resin composition applicable to rotational molding and preparation method thereof | |
| CN105255122A (en) | PBS (poly butylenes succinate) 3D printing wire and preparation method thereof | |
| CN104877162B (en) | The composite foamed particle of in-situ micro-fibril polypropylene-based resin and its application | |
| CN106317579A (en) | High-polymer functional material with 3D (three-dimensional) printing function | |
| CN113022067A (en) | Multilayer-structure modified PETG material and preparation method thereof | |
| Zhou et al. | Fabrication of hydroxyapatite/ethylene-vinyl acetate/polyamide 66 composite scaffolds by the injection-molding method | |
| CN102675777A (en) | Manufacture method for biaxially oriented PVDF thin film | |
| CN105694340A (en) | High-strength ABS-based polymer alloy for FDM (fused deposition modeling) and preparation method of alloy | |
| CN107286447A (en) | A kind of etfe film and preparation method thereof | |
| CN108164856A (en) | A kind of superelevation is heat-resisting, high fondant-strength is blow molded ABS material and preparation method thereof | |
| CN100478392C (en) | High-temperature-resisting thermosensitive resistance composite material and its production | |
| CN111187456B (en) | High-density polyethylene composition, preparation method thereof, 3D printing material and application thereof | |
| CN110628149B (en) | 3D printing polyvinyl chloride polymer modified wire and preparation method thereof | |
| CN114630867A (en) | Thermoformable polymer sheets based on pseudo-amorphous polyaryletherketone | |
| CN106893266A (en) | A kind of resin combination and preparation method thereof, metal-resin composite |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |