CN113105163A - 一种高强度改性合成纤维增强的高延性混凝土 - Google Patents

一种高强度改性合成纤维增强的高延性混凝土 Download PDF

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CN113105163A
CN113105163A CN202010189332.4A CN202010189332A CN113105163A CN 113105163 A CN113105163 A CN 113105163A CN 202010189332 A CN202010189332 A CN 202010189332A CN 113105163 A CN113105163 A CN 113105163A
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殷石
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Abstract

本发明公开了一种高强度改性合成纤维增强的高延性混凝土，高延性混凝土中掺入了高强度改性合成纤维，高强度改性合成纤维在高延性混凝土中的含量为1.5kg/m3‑110kg/m3，高强度改性合成纤维由改性剂对合成树脂或合成纤维进行改性后得到，高延性混凝土由水泥、胶凝材料、集料、外加剂和纤维为原材料组成，按比例加水搅拌、成型的高韧性特种混凝土。由于改性剂将Si、Si‑O、‑OH、‑COOH等极性基团等极性基团接枝到合成纤维的表面，这些基团与高延性混凝土中的胶凝材料发生作用和反应，因此极大提高了纤维的强度、分散和与混凝土的粘结力。

Description

一种高强度改性合成纤维增强的高延性混凝土
技术领域
本发明属于材料领域，涉及混凝土材料，具体涉及一种高强度改性合成纤维增强的高延性混凝土。
背景技术
传统混凝土是由水泥、砂子、石头、水，按比例混合后浇筑而成。然而，传统混凝土脆性高，易开裂，极限拉应变仅有0.01％左右。高延性混凝土主要是由水泥、胶凝材料、集料、外加剂和纤维等原材料组成，按一定比例加水搅拌、成型以后，具有高韧性、高抗裂性能和高耐损伤能力的特种混凝土。这种混凝土的极限拉应变可以高达1-3％，非常适合应用于旧房、桥梁的加固，极大提高了建筑的抗震性能和耐久性。高延性混凝土中的纤维为赋予混凝土高延展的性能起到了主要的作用。混凝土开裂后，纤维桥架在裂纹上，将混凝土紧紧连在一起，因此混凝土不再是脆性断裂，而是由纤维连接的韧性断裂。因此，纤维含量越高，纤维与混凝土的粘结力越强，纤维自身强度越高，纤维的桥架作用就越好，为混凝土提高的韧性就越多。然而，传统高延性混凝土用的合成纤维，如聚丙烯纤维、聚乙烯醇纤维、超高分子量纤维、聚甲醛纤维等，都是有机纤维，由于未经过改性，他们与无机的混凝土粘结力较差。此外，有机的纤维在无机的胶凝材料中，分散性也很差，因此高含量的纤维就很难分散均匀。
普通混凝土与高延性混凝土在成分和增强机理上，都有很大的差别。普通混凝土的成分简单，主要由水泥、砂子、石子、水组成。高延性混凝土，成分复杂，除了水泥、砂子、水外，还有外加剂和胶凝材料。普通混凝土主要追求的是混凝土的抗压强度，而高延性混凝土追求的是混凝土的延展性。由于高延性混凝土的用水量与混凝土相似，但是由于高延性混凝土使用了大量减水剂，就还需要增稠剂对混凝土进行调整，以避免混凝土的离析现象发生。高延性混凝土除了使用粉煤灰、硅灰来调整混凝土级配外，还需要使用胶粉、聚合物乳液以及纤维来追求混凝土的延性，这些都是不普通混凝土所不需要的。具体如下：
Figure BDA0002415285050000011
Figure BDA0002415285050000021
发明内容
有鉴于此，本发明的目的在于提供一种高强度改性合成纤维增强的高延性混凝土。为达到上述目的，本发明提供如下技术方案：
一种高强度改性合成纤维增强的高延性混凝土，高延性混凝土中掺入了高强度改性合成纤维，所述高强度改性合成纤维在高延性混凝土中的含量为1kg/m3-100kg/m3，所述高强度改性合成纤维由改性剂对合成树脂或合成纤维进行改性后得到，所述高延性混凝土由水泥、胶凝材料、集料、外加剂和纤维为原材料组成，按比例加水搅拌、成型的高韧性特种混凝土。
进一步，所述高强度改性合成纤维在高延性混凝土中的含量为15kg/m3～50kg/m3。
进一步，所述高延性混凝土中，按质量份数计，水泥用量为1-1.5、胶凝材料用量为0.1-0.3、集料用量为0.4-1、水灰比为0.2-0.5。
进一步，所述合成纤维的原料包括聚丙烯、聚乙烯、聚丙烯腈纤维、聚酯、超高分子量聚乙烯、聚酰胺、聚甲醛、聚乙烯醇、聚乙烯醇缩甲醛、聚对苯二甲酸乙二酯、聚苯咪唑、聚四氟乙烯、聚对苯二甲酰对苯二胺、聚酰亚胺中的一种或一种以上混合物。
进一步，所述改性合成纤维包括极性改性合成纤维、官能团接枝改性合成纤维、填料改性合成纤维和/或母粒改性合成纤维。
进一步，所述改性剂为硅烷偶联剂Si-69、KH570、KH560、KH550、KH151、硅胶抗粘连剂、钛酸酯偶联剂、铝酸酯偶联剂、正硅酸乙酯、成核剂母粒、色母粒、增塑母粒、耐高温母粒、防腐母粒、消泡母粒、氯化聚丙烯、马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸二烯丙烯酯、四甲基丙烯酸季戊四醇、聚乙二醇、聚己二酸丁二醇酯、聚己内酯、二丙二醇丁醚、二乙烯基苯、过氧化二异丙苯、硅油、表面活性剂、乙醇、二甲苯、无机物超细颗粒、炭黑、碳酸钙、TiO2、滑石粉、高岭土、二氧化硅、硅土、硅灰石、云母、硫酸钡、玻璃微珠、玻璃纤维、硅藻土、蒙脱土、水滑石、木粉、淀粉中的任一种或一种以上的混合物。
进一步，所述高强度改性合成纤维长度5-80mm，直径0.01-1.5mm，拉伸强度300-2000MPa，弹性模量4-100GPa。
进一步，所述高强度改性合成纤维长度10-30mm，直径0.1-0.5mm，拉伸强度500-1500MPa，弹性模量5-40GPa。
进一步，所述高强度改性合成纤维的制备方法有以下三种：
4)将改性剂与合成树脂按比例混合后，进行熔融拉丝或熔融纺丝后，制成改性合成纤维；
5)先将合成树脂通过熔融拉丝或熔融纺丝的方法制成纤维，然后使用改性剂对纤维进行改性后，制成改性合成纤维；
6)先将改性剂与合成树脂按比例混合后，进行熔融拉丝或熔融纺丝，然后再次使用改性剂对纤维进行改性后，制成改性合成纤维。
本发明对合成纤维进行改性，以提高纤维三个方面的性能：(1)纤维强度；(2)纤维与混凝土的粘结力；(3)纤维的分散性。本发明的改性合成纤维，通常包括但不限于以下四类：
(1)极性改性合成纤维，该纤维是通过改性剂对纤维进行极性与非极性的调节，使纤维与增强基体的极性进行匹配，从而提高纤维的分散性。所用改性剂为马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸二烯丙烯酯、四甲基丙烯酸季戊四醇、聚乙二醇、聚己二酸丁二醇酯、聚己内酯、二丙二醇丁醚、二乙烯基苯、过氧化二异丙苯、硅油、表面活性剂、乙醇、二甲苯中的一种或一种以上的混合物。
(2)官能团接枝改性合成纤维，该纤维是通过改性剂为纤维引入适当的官能团，如Si、Si-O、-OH、-COOH等，使纤维与基体产生较强的粘结力，以及其他特殊功能。所用改性剂为硅烷偶联剂Si-69、KH570、KH560、KH550、KH151、硅胶抗粘连剂、钛酸酯偶联剂、铝酸酯偶联剂、正硅酸乙酯、氯化聚丙烯中的一种或一种以上的混合物。
(3)填料改性合成纤维，该纤维是通过填料对纤维进行增强，从而提高纤维刚性、弹性模量、拉伸强度等，部分无机填料还可以提高纤维的耐高温性。所用改性剂为无机物超细颗粒、炭黑、碳酸钙、TiO2、滑石粉、高岭土、二氧化硅、硅土、硅灰石、云母、硫酸钡、玻璃微珠、玻璃纤维、硅藻土、蒙脱土、水滑石、木粉、淀粉中的一种或一种以上的混合物。
(4)母粒改性合成纤维，母粒的加入可以使纤维在熔融拉丝或熔融纺丝时，具有相应的性能和功能，也可以使制备纤维时所用的两种或两种以上合成树脂产生更好的相容性。所用改性剂为成核剂母粒、色母粒、增塑母粒、耐高温母粒、防腐母粒、消泡母粒中的一种或一种以上的混合物。
本发明的有益效果在于：(1)通过填料改性改性剂，提高合成纤维的拉伸强度和弹性模量，使其具有和高延性混凝土相匹配的拉伸强度和弹性模量，大大提高纤维的增强效果。
(2)通过官能团接枝改性剂，使纤维表面产生Si、Si-O、-OH、-COOH等基团，这些基团不但可以参与到水泥的水合反应中，还会与混凝土中的胶凝材料(硅灰、粉煤灰、矿粉等)有很强的粘合力，大大提高纤维的增强效率。
(3)通过极性改性剂和母粒改性剂将不同的树脂合金，使纤维同时具有两种或两种以上树脂的性能和优势，树脂表面不同的基团可以与高延性混凝土中的外加剂和水，具有一定程度的粘结性，借此提高纤维在混凝土中的分散性。
(4)通过提高合成纤维的强度，来提高纤维的增强效果。
(5)提高纤维与高延性混凝土的粘结性，进一步提高混凝土的韧性。
(6)提高纤维的分散性，以降低施工难度，提高纤维用量，提高混凝土韧性、抗裂性和耐损伤的能力。
具体实施方式
下面对本发明的优选实施例进行详细的描述。
一种高强度改性合成纤维增强的高延性混凝土，是先将改性剂与合成树脂按表1所列混合后，进行熔融拉丝或熔融纺丝后，部分组进行二次表面改性，从而制备成高强度改性合成纤维；然后将高强度改性合成纤维加入到高延性混凝土中充分搅拌，直至均匀；最后进行混凝土的浇筑，养护28天。
表1为高强度改性合成纤维增强高延性混凝土的试件信息，其中对照组1为不加纤维的混凝土，对照组2为加低强度未改性合成纤维的混凝土，对照组3为高强度未改性合成纤维的混凝土。对照组4和对照组5分别是纤维用量低于和高于保护范围组。试件1-6为加入用不同改性剂改性的不同合成树脂在不同用量下得到的试件。表2表征了这些纤维混凝土实施例试件的主要力学性能。
表1高强度改性合成纤维增强高延性混凝土的试件信息
Figure BDA0002415285050000041
Figure BDA0002415285050000051
表2高强度改性合成纤维增强高延性混凝土的力学性能
Figure BDA0002415285050000052
表2测试遵照标准《DBJ61/T112-2016高延性混凝土应用技术规程》，可以得出结论：
对照组1为未加纤维的素混凝土，延性几乎为零，混凝土显示出明显的脆性。脆性的混凝土在使用中会出现崩塌式的断裂，因此通常会使用钢筋网或纤维来提高混凝土韧性，以避免崩塌式的断裂。
对照组2为未改性的普通聚丙烯纤维，可以看出因没有改性，纤维拉伸强度和弹性模量都较低。此外，由于未改性，纤维分散性也不好，所以在高延性混凝土中通常最高用量仅可达到18kg/m3，过高的用量会导致纤维分散不均匀。
对照组3为未改性聚乙烯醇纤维，由于聚乙烯醇具有较高的拉伸强度和弹性模量，其增强效果远远高于对照组2，但聚乙烯醇表面大量的极性基团，使其非常容易团聚，故分散非常困难，最高用量通常仅能达到24kg/m3。
对照组4是纤维用量低于保护范围，由于纤维用量过少，在混凝土中不能起到任何增强的效果，因此其力学性能基本和未加纤维的素混凝土一样。
对照组5中纤维用量高于保护范围，由于纤维用量过高，导致了纤维分散困难，很多纤维不能均匀分散而是成团聚在一起，导致纤维混凝土的力学性能不能持续提高反而下降，可以看出纤维的用量要在最佳配合比的范围内。
试件1是使用在聚乙烯醇纤维表面添加改性剂硅油，以此来降低聚乙烯醇纤维的极性，减少纤维的团聚力。此外，硅油会与高延性混凝土中的外加剂，产生相互作用，随着外加剂的分散，会将纤维进一步分散均匀，因此纤维的分散性有了极大的提高，故在高用量48kg/m3，纤维依然分散均匀，增强效果明显。
试件2使用二氧化硅与聚丙烯熔融拉丝后制备成纤维。由于二氧化硅改性增强后，纤维的拉伸强度和弹性模量有了极大的提高，此外二氧化硅的基团与混凝土中胶凝材料的基团会发生反应，提高了纤维与混凝土的粘结力，故增强效果显著提高。
试件3使用成核剂母粒在熔融拉丝的过程中，进一步提高聚丙烯纤维的结晶度，以此提高纤维的强度。熔融改性后，对纤维进行硅烷偶联剂的改性，使纤维表面具有SiO2基团，从而提高纤维与混凝土的粘结力。因此，纤维的增强效果有显著提高。
试件4将使钛酸酯偶联剂与聚乙烯醇树脂混合后，通过熔融拉丝，制成高强度改性合成纤维。聚乙烯醇纤维本身拉伸强度和弹性模量较高，但是由于纤维有-OH基团的存在，易结团，通过钛酸酯偶联剂对纤维进行改性后，不但降低了纤维之间的缠结力，还提高了纤维在混凝土中的分散性以及纤维与混凝土的粘结力，故该纤维增强的高延性混凝土具有很好的性能。
试件5使用KH570与聚甲醛混合，通过熔融纺织制备成纤维。聚甲醛纤维本身强度较高，使用KH570改性后，其分散性和与混凝土的粘结力都得到了显著的提高，故大大提高了纤维的增强效果。
试件6是先用马来酸二烯丙烯酯改性聚丙烯和聚乙烯醇的混和树脂，之后用Si69对纤维进行表面处理。聚丙烯和聚乙烯醇混合树脂具有较高的强度，但两种树脂之间的粘结力较差，需要马来酸二烯丙烯酯作为相容剂，对树脂进行改性，改性后两种树脂的粘合性有了极大的改善，由于极性基团的引入，纤维的分散性有了显著提高。改性后的纤维，再次经过Si69的改性，使表面接枝含硅基团，大大提高纤维与混凝土的粘结力。因此该改性纤维增强的高延性混凝土，具有非常高的力学性能。
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。

Claims (9)

1.一种高强度改性合成纤维增强的高延性混凝土，其特征在于：高延性混凝土中掺入了高强度改性合成纤维，所述高强度改性合成纤维在高延性混凝土中的含量为1.5kg/m3-110kg/m3，所述高强度改性合成纤维由改性剂对合成树脂或合成纤维进行改性后得到，所述高延性混凝土由水泥、胶凝材料、集料、外加剂和纤维为原材料组成，按比例加水搅拌、成型的高韧性特种混凝土。
2.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于：所述高强度改性合成纤维在高延性混凝土中的含量为15kg/m3～50kg/m3。
3.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于：所述高延性混凝土中，按质量份数计，水泥用量为1-1.5、胶凝材料用量为0.1-0.3、集料用量为0.4-1、水灰比为0.2-0.5。
4.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于，所述合成纤维的原料包括聚丙烯、聚乙烯、聚丙烯腈纤维、聚酯、超高分子量聚乙烯、聚酰胺、聚甲醛、聚乙烯醇、聚乙烯醇缩甲醛、聚对苯二甲酸乙二酯、聚苯咪唑、聚四氟乙烯、聚对苯二甲酰对苯二胺、聚酰亚胺中的一种或一种以上混合物。
5.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于，所述改性合成纤维包括极性改性合成纤维、官能团接枝改性合成纤维、填料改性合成纤维和/或母粒改性合成纤维。
6.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于，所述改性剂为硅烷偶联剂Si-69、KH570、KH560、KH550、KH151、硅胶抗粘连剂、钛酸酯偶联剂、铝酸酯偶联剂、正硅酸乙酯、成核剂母粒、色母粒、增塑母粒、耐高温母粒、防腐母粒、消泡母粒、氯化聚丙烯、马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸二烯丙烯酯、四甲基丙烯酸季戊四醇、聚乙二醇、聚己二酸丁二醇酯、聚己内酯、二丙二醇丁醚、二乙烯基苯、过氧化二异丙苯、硅油、表面活性剂、乙醇、二甲苯、无机物超细颗粒、炭黑、碳酸钙、TiO2、滑石粉、高岭土、二氧化硅、硅土、硅灰石、云母、硫酸钡、玻璃微珠、玻璃纤维、硅藻土、蒙脱土、水滑石、木粉、淀粉中的任一种或一种以上的混合物。
7.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于：所述高强度改性合成纤维长度5-80mm，直径0.01-1.5mm，拉伸强度300-2000MPa，弹性模量4-100GPa。
8.根据权利要求1所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于：所述高强度改性合成纤维长度10-30mm，直径0.1-0.5mm，拉伸强度500-1500MPa，弹性模量5-40GPa。
9.根据权利要求1-8所述一种高强度改性合成纤维增强的高延性混凝土，其特征在于，所述高强度改性合成纤维的制备方法有以下三种：
1)将改性剂与合成树脂按比例混合后，进行熔融拉丝或熔融纺丝后，制成改性合成纤维；
2)先将合成树脂通过熔融拉丝或熔融纺丝的方法制成纤维，然后使用改性剂对纤维进行改性后，制成改性合成纤维；
3)先将改性剂与合成树脂按比例混合后，进行熔融拉丝或熔融纺丝，然后再次使用改性剂对纤维进行改性后，制成改性合成纤维。
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CN114751699A (zh) * 2022-05-06 2022-07-15 重庆大学溧阳智慧城市研究院 基于3d打印的固废资源化轻质高延性混凝土
CN115108778A (zh) * 2022-06-14 2022-09-27 上海二十冶建设有限公司 一种高延性混凝土复合材料及其制备方法
CN115340343A (zh) * 2022-09-06 2022-11-15 中国海洋大学 纤维加筋的抗裂性赤泥基泡沫轻质土及其制备方法
CN117534422A (zh) * 2024-01-10 2024-02-09 河北省多基复合材料产业技术研究院有限公司 一种废弃玻璃钢纤维改性混凝土及其制备工艺

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