技术领域Technical field
本发明属于连续玄武岩纤维表面改性领域，尤其涉及一种改性玄武岩纤维并提升环氧树脂界面性能的方法。The invention belongs to the field of surface modification of continuous basalt fibers, and in particular relates to a method of modifying basalt fibers and improving the interface properties of epoxy resin.
背景技术Background technique
玄武岩纤维，是在1450℃~1500℃条件下，由熔融后的天然玄武岩高速拉制而成，长径比很高，不易吸入肺部，制备过程无污染，成本低，具有优异的力学性能，其强度高，耐磨和抗拉增强性能优异，是E型玻璃纤维的1.4至1.5倍。连续玄武岩纤维化学稳定好，具有隔热、防潮、防水、耐酸碱、保温、吸声、耐腐蚀、长期使用不退变劣化等很多独特的优异性能，是碳纤维等高技术纤维的低价替代品。并且它取于自然矿石，无任何添加剂，抗紫外、使用温度范围广、绝缘性好、高温过滤性好等优点，是目前为止唯一的无环境污染的不致癌的绿色玻璃质纤维产品。可应用于隔热、防护、造船、汽车、高温过滤织物及纤维增强复合材料等领域。但玄武岩纤维表面光滑且惰性大，集束性差、浸润性差，与环氧树脂(EP)基体之间界面性能较差，导致力学性能较差，限制了纤维在复合材料方面的应用。为了改善界面相互作用，纤维表面改性旨在通过物理调节或通过对纤维表面进行化学改性来增强纤维与基体之间的粘附性，从而增加纤维与基体的接触面积。化学（酸或碱）蚀刻和等离子体处理等方法可以有效地增加表面粗糙度，但也会破坏玄武岩纤维的内部结构，对纤维本身造成一定程度的损伤。另一方面，涂层表面改性提供了较弱的物理粘附性，没有较强的机械性能。然而，偶联剂改性绕过了这一问题，充当了改善复合材料界面性能和提高其机械性能的“桥梁”。Basalt fiber is drawn at high speed from molten natural basalt at 1450°C to 1500°C. It has a high aspect ratio and is not easily inhaled into the lungs. The preparation process is pollution-free, low cost, and has excellent mechanical properties. It has high strength, excellent wear resistance and tensile reinforcement properties, which is 1.4 to 1.5 times that of E-type glass fiber. Continuous basalt fiber is chemically stable and has many unique and excellent properties such as heat insulation, moisture-proof, waterproof, acid and alkali resistance, heat preservation, sound absorption, corrosion resistance, and long-term use without deterioration. It is a low-cost alternative to high-tech fibers such as carbon fiber. Taste. And it is made from natural ores without any additives. It has the advantages of UV resistance, wide operating temperature range, good insulation, and good high-temperature filterability. It is the only green glass fiber product that has no environmental pollution, no carcinogen, etc. so far. It can be used in fields such as thermal insulation, protection, shipbuilding, automobiles, high-temperature filter fabrics and fiber-reinforced composite materials. However, the surface of basalt fiber is smooth and inert, with poor bundling and wettability, and poor interface properties with the epoxy resin (EP) matrix, resulting in poor mechanical properties and limiting the application of fibers in composite materials. In order to improve the interfacial interaction, fiber surface modification aims to enhance the adhesion between the fiber and the matrix through physical adjustment or through chemical modification of the fiber surface, thereby increasing the contact area between the fiber and the matrix. Methods such as chemical (acid or alkali) etching and plasma treatment can effectively increase surface roughness, but they will also destroy the internal structure of the basalt fiber and cause a certain degree of damage to the fiber itself. On the other hand, coating surface modification provides weak physical adhesion without strong mechanical properties. However, coupling agent modification bypasses this problem and serves as a "bridge" to improve the interfacial properties of the composite and improve its mechanical properties.
硅纳米线是最新发展起来的一种一维纳米材料，由于自身特有的荧光紫外等光学特性、热传导等特性引起了研究者们的广泛关注。一些研究人员能成功将一维硅纳米材料生长在载玻片、棉织物上。硅纳米线的表面包含丰富的活性基团，一端能够与玄武岩纤维表面上的化学基团反应，而另一端可以物理缠绕或化学与聚合物反应，从而增强了树脂基质和玄武岩纤维之间的粘附。目前，没有将硅纳米线改性到玄武岩纤维表面的研究报道。Silicon nanowires are the latest one-dimensional nanomaterials developed. They have attracted widespread attention from researchers due to their unique optical properties such as fluorescence, ultraviolet, and thermal conductivity. Some researchers have successfully grown one-dimensional silicon nanomaterials on glass slides and cotton fabrics. The surface of silicon nanowires contains rich active groups. One end can react with chemical groups on the surface of basalt fibers, while the other end can physically entangle or chemically react with polymers, thereby enhancing the adhesion between the resin matrix and the basalt fibers. Attached. Currently, there are no research reports on modifying silicon nanowires onto the surface of basalt fibers.
本文针对一维硅纳米线的优点，我们采用化学气相沉积法将硅纳米线生长在玄武岩纤维的表面，与涂层涂覆法协同作用于纤维表面，以此来增强与环氧树脂的力学性能。This article focuses on the advantages of one-dimensional silicon nanowires. We use chemical vapor deposition to grow silicon nanowires on the surface of basalt fibers, and use the coating method to synergize with the fiber surface to enhance the mechanical properties of epoxy resin. .
发明内容Contents of the invention
本发明的目的是针对现有技术中玄武岩纤维与环氧树脂基体等粘附力不强的问题，提供一种改性玄武岩纤维并提升环氧树脂界面性能的方法，提高了玄武岩纤维与环氧树脂的界面强度。The purpose of this invention is to provide a method for modifying basalt fiber and improving the interface performance of epoxy resin in order to solve the problem of weak adhesion between basalt fiber and epoxy resin matrix in the prior art. Interfacial strength of resin.
本发明提供的玄武岩增强环氧树脂的界面性能的方法，步骤如下:The method for enhancing the interfacial properties of epoxy resin with basalt provided by the invention has the following steps:
S1、采用有机混合溶剂回流清洗，再在超声清洗槽中清洗玄武岩纤维表面。S1. Use organic mixed solvent to reflux and clean, and then clean the basalt fiber surface in an ultrasonic cleaning tank.
S2、将玄武岩纤维固定于使用超声震荡清洗并干燥后的玻璃晶片上，浸入100℃的食人鱼溶液中，恒温浸泡20min，然后用去离子水清洗4次，置于烘箱中烘干，得到表面活化的玄武岩纤维。S2. Fix the basalt fiber on the glass wafer that has been cleaned and dried using ultrasonic vibration, immerse it in 100°C piranha solution, soak at a constant temperature for 20 minutes, then clean it 4 times with deionized water, and dry it in an oven to obtain the surface Activated basalt fiber.
S3、采用化学气相沉积法生长聚硅氧烷，向活化后的3g玄武岩纤维内部加入1.2ml乙基三氯硅烷，由氮气带动水分来控制湿度，在相对湿度62%条件下反应一段时间后取出玄武岩纤维，分别用丙酮、无水乙醇和去离子水洗涤干燥，得到表面生长硅纳米线和硅纳米管的玄武岩纤维。S3. Use the chemical vapor deposition method to grow polysiloxane. Add 1.2ml ethyltrichlorosilane to the inside of the activated 3g basalt fiber. Use nitrogen to drive water to control the humidity. After reacting for a period of time at a relative humidity of 62%, take it out. The basalt fiber was washed and dried with acetone, absolute ethanol and deionized water respectively to obtain a basalt fiber with silicon nanowires and silicon nanotubes grown on the surface.
S4、配置含质量分数为3%的水性聚氨酯浆液，将玄武岩纤维浸入溶液后，放入80℃烘箱下干燥10h，得到表面含有一层施胶膜的玄武岩纤维。S4. Prepare an aqueous polyurethane slurry containing 3% mass fraction, immerse the basalt fiber into the solution, and dry it in an oven at 80°C for 10 hours to obtain a basalt fiber with a sizing film on the surface.
可选地，在步骤S1中，所述有机混合溶剂为丙酮和石油醚，按照体积比3:1比例配置，将玄武岩纤维置于烧瓶中使用加热套加热至80℃加热回流清洗6h，并在超声震荡下反应10min，再将玄武岩纤维放入80℃烘箱中干燥24h，得到表面脱浆后的玄武岩纤维。Optionally, in step S1, the organic mixed solvent is acetone and petroleum ether, configured according to a volume ratio of 3:1. The basalt fiber is placed in a flask and heated to 80°C using a heating mantle, heated to reflux and cleaned for 6 hours, and then The reaction was carried out under ultrasonic vibration for 10 minutes, and then the basalt fiber was dried in an oven at 80°C for 24 hours to obtain the basalt fiber after surface desizing.
可选地，在步骤S2中，所述超声震荡清洗使用的清洗溶液为无水乙醇和去离子水，对作为衬底的玻璃晶片进行超声震荡清洗15min，并在氮气流下干燥，再将玄武岩纤维均匀缠绕固定于玻璃晶片，使晶片上下表面紧紧贴住一层纤维后，用导线将结点拴在晶片上，在100℃食人鱼溶液下恒温浸泡20min，放入60℃烘箱下干燥，所述食人鱼溶液为浓硫酸和质量分数30%的过氧化氢，按照体积比7：3比例配置，配制时注意将过氧化氢加入浓硫酸中。Optionally, in step S2, the cleaning solution used in the ultrasonic cleaning is absolute ethanol and deionized water. The glass wafer as the substrate is cleaned with ultrasonic cleaning for 15 minutes, and dried under a nitrogen flow, and then the basalt fiber is Evenly wind and fix it on the glass wafer, so that the upper and lower surfaces of the wafer are tightly attached to a layer of fiber, then tie the nodes to the wafer with wires, soak them in 100°C piranha solution for 20 minutes, and put them in a 60°C oven to dry. The piranha solution is concentrated sulfuric acid and hydrogen peroxide with a mass fraction of 30%, and is configured according to a volume ratio of 7:3. When preparing, pay attention to adding hydrogen peroxide to the concentrated sulfuric acid.
可选地，在步骤S3中，所述化学气相沉积法生长聚硅氧烷所采用的设备是由混合室、湿度调节器、反应室三部分组成，且湿度调节器一端连接带有干燥和加湿氮气的混合室，一端连接直型导管的反应室，其中加湿氮气是通过充水的气体洗涤瓶冲洗干燥的氮气产生的。Optionally, in step S3, the equipment used to grow polysiloxane by the chemical vapor deposition method is composed of three parts: a mixing chamber, a humidity regulator, and a reaction chamber, and one end of the humidity regulator is connected with a drying and humidifying device. The nitrogen mixing chamber is a reaction chamber connected to a straight pipe at one end, in which humidified nitrogen is generated by flushing dry nitrogen through a water-filled gas scrubber bottle.
可选地，在步骤S3中，湿度调节器是由三颈烧瓶、湿度计和密封胶组成，此装置处于密封状态。Optionally, in step S3, the humidity regulator is composed of a three-neck flask, a hygrometer and sealant, and this device is in a sealed state.
可选地，在步骤S3中，将3g玄武岩纤维固定于玻璃晶片上，置于直型导管中，在其左侧加入1.2ml乙基三氯硅烷，保持纤维与液体水平距离1-3cm。Optionally, in step S3, fix 3g of basalt fiber on a glass wafer, place it in a straight conduit, add 1.2ml of ethyltrichlorosilane to the left side, and keep the horizontal distance between the fiber and the liquid at 1-3cm.
可选地，在步骤S3中，控制相对湿度在62%，反应时间为4h，此反应需要保持动态平衡，反应后的玄武岩纤维依次用丙酮、无水乙醇和去离子水进行清洗3次。Optionally, in step S3, the relative humidity is controlled at 62% and the reaction time is 4 hours. This reaction needs to maintain dynamic equilibrium. The reacted basalt fiber is washed three times with acetone, absolute ethanol and deionized water in sequence.
可选地，在步骤S3中，得到的改性玄武岩纤维，其表面的硅纳米线和硅纳米管长度为4~8μm，直径为200～600nm。Optionally, in step S3, the silicon nanowires and silicon nanotubes on the surface of the modified basalt fiber obtained have a length of 4 to 8 μm and a diameter of 200 to 600 nm.
可选地，在步骤S4中，配置含质量分数为3%的水性聚氨酯浆液，将玄武岩纤维拉紧，保持绷直状态，浸入溶液15min后，用棍棒向一个方向挤压出多余液体，再放入80℃烘箱下干燥10h，得到表面生长硅纳米线和硅纳米管以及含有一层施胶膜的玄武岩纤维。Optionally, in step S4, prepare an aqueous polyurethane slurry containing 3% mass fraction, tighten the basalt fiber and keep it in a straight state. After immersing it in the solution for 15 minutes, use a stick to squeeze out the excess liquid in one direction, and then place it. Dry in an oven at 80°C for 10 hours to obtain surface-grown silicon nanowires and silicon nanotubes and basalt fibers containing a layer of sizing film.
与现有技术相比，本发明的有益之处在于：Compared with the prior art, the benefits of the present invention are:
其一、本发明以乙基三氯硅烷作为前驱体，玄武岩纤维为基体，食人鱼溶液为活化溶液；玄武岩纤维经活化液活化后表面含有大量活性基团，通过控制步骤S3的改性反应特定参数条件（氮气流速，相对湿度、硅烷含量，反应时间等参数），能够在玄武岩纤维的表面自组装生长出硅纳米线，水分含量的控制对乙基三氯硅烷的水解极其重要，过多水分会使纤维失去活性，太少则达不到催化水解的效果。通过控制反应时间，可以控制硅生长出的硅纳米线和硅纳米管的直径与长度，最佳反应时间控制在4h，生长出长度为4~8μm，直径为200～600nm的硅纳米线。First, the present invention uses ethyltrichlorosilane as the precursor, basalt fiber as the matrix, and piranha solution as the activation solution; the surface of the basalt fiber after being activated by the activation solution contains a large number of active groups, and the modification reaction in step S3 is controlled to specifically Parameter conditions (nitrogen flow rate, relative humidity, silane content, reaction time and other parameters) can self-assemble and grow silicon nanowires on the surface of basalt fibers. The control of moisture content is extremely important for the hydrolysis of ethyltrichlorosilane. Excessive moisture It will cause the fiber to lose activity, and too little will not achieve the effect of catalyzing hydrolysis. By controlling the reaction time, the diameter and length of silicon nanowires and silicon nanotubes grown from silicon can be controlled. The optimal reaction time is controlled at 4 hours to grow silicon nanowires with a length of 4 to 8 μm and a diameter of 200 to 600 nm.
其二、该制备方法试剂用量少，污染小，利用化学气相沉积法可以在玄武岩纤维表面原位生长出硅纳米线。硅纳米线是一种一维纳米材料，具有无机材料的优良性能，有着极高的热稳定性、化学稳定性等优点，将硅纳米线成功的改性到纤维表面可以改善纤维的化学稳定性和热稳定性。大量的硅纳米线产生并均匀地分布在玄武岩纤维的表面，这是由于乙基三氯硅烷完全水解出足够多的硅醇与食人鱼溶液活化后的羟基脱水缩合，硅醇之间同样进行脱水缩合，反复交联形成三维网状结构。并且乙基三氯硅烷的羟基与环氧树脂的羟基进行脱醇和脱水反应，增强了纤维和树脂之间的机械啮合与化学键合作用，从而增加了与树脂结合的力学性能。Secondly, this preparation method uses less reagents and causes less pollution. The chemical vapor deposition method can be used to grow silicon nanowires in situ on the surface of basalt fibers. Silicon nanowires are a one-dimensional nanomaterial with excellent properties of inorganic materials and extremely high thermal stability and chemical stability. Successfully modifying silicon nanowires onto the fiber surface can improve the chemical stability of the fiber. and thermal stability. A large number of silicon nanowires are produced and evenly distributed on the surface of the basalt fiber. This is due to the complete hydrolysis of ethyltrichlorosilane to produce enough silanol and dehydration condensation of hydroxyl groups after activation of the piranha solution. The silanol is also dehydrated. Condensation and repeated cross-linking form a three-dimensional network structure. Moreover, the hydroxyl group of ethyltrichlorosilane undergoes dealcoholization and dehydration reaction with the hydroxyl group of epoxy resin, which enhances the mechanical meshing and chemical bonding between the fiber and the resin, thereby increasing the mechanical properties of the combination with the resin.
其三、所用水性聚氨酯溶液是一种绿色环保，耐光性、耐腐蚀、施工方便的一种溶剂，所含羟基、环氧基、氨基能与树脂交联，不仅有效的改善了玄武岩纤维与环氧树脂之间的润湿性，还能通过化学反应形成共价键，提高树脂基与玄武岩纤维之间界面粘结性能。通过测试单纤维的拉伸强度、界面剪切强度和接触角，结果证明硅纳米线生长在玄武岩纤维上的单丝拉伸强度提高了41.4%，界面剪切强度提高64.3%，与环氧树脂的接触角减小。Third, the water-based polyurethane solution used is a solvent that is green, environmentally friendly, light-resistant, corrosion-resistant, and easy to construct. The hydroxyl, epoxy, and amino groups it contains can cross-link with the resin, which not only effectively improves the bond between the basalt fiber and the environment. The wettability between oxygen resins can also form covalent bonds through chemical reactions, improving the interfacial bonding performance between the resin base and basalt fiber. By testing the tensile strength, interfacial shear strength and contact angle of single fibers, the results show that the tensile strength of single fibers grown with silicon nanowires on basalt fibers increases by 41.4%, and the interfacial shear strength increases by 64.3%, which is comparable to that of epoxy resin. The contact angle decreases.
附图说明Description of the drawings
本发明的其它优点、目标和特征将部分通过下面的说明体现，部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。Other advantages, objects, and features of the present invention will be apparent in part from the description below, and in part will be understood by those skilled in the art through study and practice of the present invention.
图1为本发明的制备流程图；Figure 1 is a preparation flow chart of the present invention;
图2为本发明的反应机理图；Figure 2 is a reaction mechanism diagram of the present invention;
图3为未处理玄武岩纤维的扫描电子显微镜图；Figure 3 is a scanning electron microscope image of untreated basalt fiber;
图4为硅纳米线改性玄武岩纤维的扫描电子显微镜图；Figure 4 is a scanning electron microscope image of silicon nanowire modified basalt fiber;
图5为不同湿度改性工艺下的玄武岩纤维单丝拉伸强度；Figure 5 shows the tensile strength of basalt fiber monofilament under different humidity modification processes;
图6为不同时间改性工艺下的玄武岩纤维单丝拉伸强度；Figure 6 shows the tensile strength of basalt fiber monofilament under different modification processes at different times;
图7为改性前后玄武岩纤维单丝拉伸强度；Figure 7 shows the tensile strength of basalt fiber monofilament before and after modification;
图8为改性前后玄武岩纤维界面剪切强度。Figure 8 shows the interfacial shear strength of basalt fiber before and after modification.
具体实施方式Detailed ways
结合实施例和附图对本发明做更进一步的说明。The present invention will be further described with reference to the embodiments and drawings.
实施例1Example 1
如图1所示，本发明提供的一种改性玄武岩纤维并提升环氧树脂界面性能的方法，通过以下步骤制备而成：As shown in Figure 1, the invention provides a method for modifying basalt fiber and improving the interfacial properties of epoxy resin, which is prepared through the following steps:
S1、按照体积比3:1比例配置丙酮和石油醚，置于烧瓶中，再将玄武岩纤维放入烧瓶，使用加热套加热至80℃加热回流清洗6h，并在超声震荡下反应10min，然后将玄武岩纤维放入80℃烘箱中干燥24h，得到表面脱浆后的玄武岩纤维。S1. Prepare acetone and petroleum ether according to the volume ratio of 3:1, place it in a flask, then put the basalt fiber into the flask, use a heating mantle to heat to 80°C, reflux and clean for 6 hours, and react under ultrasonic vibration for 10 minutes, and then The basalt fiber was dried in an oven at 80°C for 24 hours to obtain the basalt fiber after surface desizing.
S2、食人鱼溶液为浓硫酸和质量分数30%的过氧化氢，按照体积比7：3比例配置，备用。超声震荡清洗使用的清洗溶液为无水乙醇和去离子水，对作为衬底的玻璃晶片进行超声震荡清洗15min，并在氮气流下干燥，再将玄武岩纤维均匀缠绕固定于玻璃晶片，使晶片上下表面紧紧贴住一层纤维后，用导线将结点拴在晶片上，在100℃食人鱼溶液下恒温浸泡20min，放入60℃烘箱下干燥，得到表面活化的玄武岩纤维。S2. The piranha solution is concentrated sulfuric acid and 30% hydrogen peroxide by mass, configured in a volume ratio of 7:3 and set aside. The cleaning solution used in ultrasonic cleaning is absolute ethanol and deionized water. The glass wafer as the substrate is cleaned with ultrasonic vibration for 15 minutes and dried under a nitrogen flow. The basalt fiber is evenly wound and fixed on the glass wafer to make the upper and lower surfaces of the wafer After a layer of fiber is tightly attached, the nodes are tied to the chip with wires, soaked in 100°C piranha solution for 20 minutes, and dried in a 60°C oven to obtain surface-activated basalt fibers.
S3、先搭制化学气相沉积法生长聚硅氧烷所采用的设备，由混合室、湿度调节器、反应室三部分组成，且湿度调节器一端连接带有干燥和加湿氮气的混合室，一端连接直型导管的反应室，其中加湿氮气是通过充水的气体洗涤瓶冲洗干燥的氮气产生的，湿度调节器是由三颈烧瓶、湿度计和密封胶组成，此装置处于密封状态。将3g玄武岩纤维固定于玻璃晶片上，置于直型导管中，在其左侧加入1.2ml乙基三氯硅烷，保持纤维与液体水平距离1-3cm。控制相对湿度在62%，反应时间为4h，此反应需要保持动态平衡，反应后的玄武岩纤维依次用丙酮、无水乙醇和去离子水进行清洗3次。S3. First build the equipment used to grow polysiloxane by the chemical vapor deposition method. It consists of three parts: a mixing chamber, a humidity regulator, and a reaction chamber. One end of the humidity regulator is connected to the mixing chamber with dry and humidified nitrogen. The reaction chamber is connected to a straight conduit, in which humidified nitrogen is generated by flushing dry nitrogen with a water-filled gas scrubber. The humidity regulator is composed of a three-neck flask, a hygrometer and sealant. This device is in a sealed state. Fix 3g of basalt fiber on the glass wafer, place it in a straight catheter, add 1.2ml of ethyltrichlorosilane to the left side, and keep the horizontal distance between the fiber and the liquid at 1-3cm. The relative humidity is controlled at 62% and the reaction time is 4 hours. This reaction needs to maintain dynamic balance. The reacted basalt fiber is washed three times with acetone, absolute ethanol and deionized water.
S4、配置含质量分数为3%的水性聚氨酯浆液，将玄武岩纤维拉紧，保持绷直状态，浸入溶液15min后，用棍棒向一个方向挤压出多余液体，再放入80℃烘箱下干燥10h，得到表面生长硅纳米线和硅纳米管以及含有一层施胶膜的玄武岩纤维。S4. Prepare a water-based polyurethane slurry with a mass fraction of 3%. Tighten the basalt fiber and keep it straight. After immersing in the solution for 15 minutes, use a stick to squeeze out the excess liquid in one direction, and then dry it in an 80°C oven for 10 hours. , obtaining surface-grown silicon nanowires and silicon nanotubes and basalt fibers containing a layer of sizing film.
玄武岩纤维表面自组装硅纳米线生长机理见图2。大量的硅纳米线产生并均匀地分布在玄武岩纤维的表面，这是由于乙基三氯硅烷完全水解出足够多的硅醇与食人鱼溶液活化后的羟基脱水缩合，硅醇之间同样进行脱水缩合，如此反复交联形成三维网状结构。将未处理的玄武岩纤维命名为BF，经过食人鱼溶液改性后的玄武岩纤维命名为BF-OH，在不同相对湿度，不同反应时间下改性的玄武岩纤维命名为(例如玄武岩纤维在相对湿度62%，沉积时间4小时下改性，将其命名为BF-H62-T4)，再将水性聚氨酯的玄武岩纤维命名为BF-H62-T4-WPU。The growth mechanism of self-assembled silicon nanowires on the surface of basalt fiber is shown in Figure 2. A large number of silicon nanowires are produced and evenly distributed on the surface of the basalt fiber. This is due to the complete hydrolysis of ethyltrichlorosilane to produce enough silanol and dehydration condensation of hydroxyl groups after activation of the piranha solution. The silanol is also dehydrated. Condensation, and repeated cross-linking to form a three-dimensional network structure. The untreated basalt fiber is named BF, the basalt fiber modified by piranha solution is named BF-OH, and the basalt fiber modified under different relative humidity and different reaction time is named (For example, the basalt fiber is modified under a relative humidity of 62% and a deposition time of 4 hours, and is named BF-H62-T4), and then the basalt fiber of water-based polyurethane is named BF-H62-T4-WPU.
对比例1Comparative example 1
不对玄武岩纤维进行任何改性处理，如图3。硅纳米线改性玄武岩纤维，如图4。The basalt fiber is not modified in any way, as shown in Figure 3. Silicon nanowire modified basalt fiber, as shown in Figure 4.
对比例2Comparative example 2
与实施例1相比，改变S3中，相对湿度分别为58%、64%，探究改性前后玄武岩纤维的力学性能，对单丝拉伸强度进行了测试。测试结果如图5所示。图5说明了未改性的玄武岩纤维单丝断裂强度较低，食人鱼溶液处理后的断裂强度有所下降，对纤维本身的损失较小。在不同相对湿度下改性后，看出湿度为62%的断裂强力和拉伸强度最高，硅纳米线中存在Si-O-Si化学键，具有较高的键能，能够稳定存在。但当湿度过高，没有多余的间隙生长硅纳米线，与原有的硅纳米线竞争，造成一些倒伏的现象，从而造成脱落。Compared with Example 1, the relative humidity in S3 was changed to 58% and 64% respectively. The mechanical properties of the basalt fiber before and after modification were explored, and the tensile strength of the single filament was tested. The test results are shown in Figure 5. Figure 5 illustrates that the breaking strength of unmodified basalt fiber monofilaments is low. The breaking strength after treatment with piranha solution has decreased, and the loss to the fiber itself is small. After modification under different relative humidity, it can be seen that the breaking strength and tensile strength are the highest when the humidity is 62%. There are Si-O-Si chemical bonds in the silicon nanowires, which have high bond energy and can exist stably. But when the humidity is too high, there is no extra gap for the growth of silicon nanowires, which competes with the original silicon nanowires, causing some lodging, resulting in shedding.
对比例3Comparative example 3
与实施例1相比，改变S3中，反应时间分别为1h、3h、5h，对单丝拉伸强度进行了测试，测试结果如图6所示。图6说明了沉积4小时后的拉伸强度最高，时间过短生长的硅纳米线不能均匀的覆盖纤维表面，甚至造成脱落，时间过长会产生界面应力，使纤维更容易变脆，适量接枝的硅纳米线可最大限度增强表面粗糙度和机械结合效应，从而增加了力学性能。Compared with Example 1, in S3, the reaction times were changed to 1h, 3h, and 5h respectively, and the tensile strength of the single filament was tested. The test results are shown in Figure 6. Figure 6 shows that the tensile strength is the highest after 4 hours of deposition. Silicon nanowires grown for too short a time cannot evenly cover the fiber surface and may even fall off. If the time is too long, interfacial stress will be generated, making the fiber more likely to become brittle. The branched silicon nanowires maximize surface roughness and mechanical bonding effects, thereby increasing mechanical properties.
对比例4Comparative example 4
与实施例1相比，加入S4中水性聚氨酯溶液后，对单丝拉伸强度进行了测试，测试结果如图7。图7说明水性聚氨酯不仅能提高纤维表面与树脂之间的润湿性，还能通过化学反应形成共价键，所含羟基、环氧基、氨基能与树脂交联，能极大地提升拉伸强度。Compared with Example 1, after adding the aqueous polyurethane solution in S4, the tensile strength of the single filament was tested. The test results are shown in Figure 7. Figure 7 shows that water-based polyurethane can not only improve the wettability between the fiber surface and the resin, but also form covalent bonds through chemical reactions. The hydroxyl groups, epoxy groups, and amino groups contained in it can cross-link with the resin, which can greatly improve the tensile strength. strength.
为验证玄武岩纤维与环氧树脂基体之间的界面粘附性，进行微滴脱粘测试，测试结果如图8。图8说明了未改性玄武岩纤维表面光滑，与环氧树脂基体之间的界面相互作用较差，接枝活性基团表面变得粗糙，表面残留部分环氧树脂。当接枝硅纳米线后，较多的树脂残留在表面，提高了表面粗糙度。涂覆水性聚氨酯后，外部一些凹槽被填满，形成了一种湿胶膜，大量树脂残留。主要原因是由楔形效应所引起的，该“楔形”使树脂与纤维表面更好地嵌合，因为硅纳米线与纤维的表面结合主要是通过化学接枝生成的共价键来执行的，所以当纤维从树脂基材中拔出时，界面破坏形式转变成了共价键的破坏，也就是说不仅仅是纤维与环氧树脂之间的分离，而且还包括硅纳米线与树脂新的组合层被破坏，因此玄武岩纤维与树脂基材的界面剪切强度得以大幅度提高，说明此方法改性纤维，能有效增强与树脂基体之间的界面相互作用。In order to verify the interfacial adhesion between basalt fiber and epoxy resin matrix, a droplet debonding test was performed. The test results are shown in Figure 8. Figure 8 illustrates that the surface of the unmodified basalt fiber is smooth, the interface interaction with the epoxy resin matrix is poor, the surface of the grafted active groups becomes rough, and some epoxy resin remains on the surface. When silicon nanowires are grafted, more resin remains on the surface, increasing the surface roughness. After applying water-based polyurethane, some of the outer grooves are filled, forming a wet glue film with a large amount of resin remaining. The main reason is caused by the wedge effect, which allows the resin to fit better with the fiber surface, because the surface binding of silicon nanowires to the fiber is mainly performed through covalent bonds generated by chemical grafting, so When the fibers are pulled out of the resin matrix, the form of interfacial damage changes to the destruction of covalent bonds, which means not only the separation between the fibers and the epoxy resin, but also the new combination of the silicon nanowires and the resin. The layer is destroyed, so the interface shear strength between the basalt fiber and the resin matrix is greatly improved, indicating that the fiber modified by this method can effectively enhance the interfacial interaction with the resin matrix.
以上所述，并非对本发明作任何形式上的限制，虽然本发明已通过上述实施例揭示，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些变动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。The above does not limit the present invention in any form. Although the present invention has been disclosed through the above embodiments, it is not used to limit the present invention. Any skilled person familiar with the art, without departing from the scope of the technical solution of the present invention, When the technical content disclosed above can be used to make some changes or modifications into equivalent embodiments with equivalent changes, any simple modifications or equivalents made to the above embodiments based on the technical essence of the present invention will not deviate from the content of the technical solution of the present invention. Changes and modifications still fall within the scope of the technical solution of the present invention.
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| CN202311556014.7ACN117263527B (en) | 2023-11-21 | 2023-11-21 | Method for modifying basalt fiber and improving interface performance of epoxy resin |
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