氯氧镁水泥复合材料

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漳州师范学院毕业论文氯氧镁水泥复合材料MagnesiumOxychlorideCementCompositematerials姓名：陈浩系别：化学与环境科学系专业：应用化学年级：08级指导教师：郑子山（教授）2011年11月28日I 摘要本课题旨在通过研究植物纤维对水泥复合材料性能的影响，探讨纤维对水泥复合材料增强的机理，以求获得植物纤维掺量与水泥复合材料性能之间的关系，使纤维在水泥工程中能得到更广泛的应用。关键词：MgO；MgCl2；水泥复合材料；植物纤维；性能AbstractThisstudyaimstomakeexplorationsforthemechanismoftheintensivecementcompositematerialswhichfilledwithplantfibers,throughtheresearchofplantfibersimpactingoncementcompositematerialproperties,inordertoobtaintherelationshipbetweencementcompositematerialperformancesandplantfibercontent,sothatplantfiberincementengineeringpracticecanbeappliedmorewidely．Keywords:MgO；MgCl2；cementcomposite；plantfiber；performanceI 目录中英文摘要………………………………………………………………I1氯氧镁水泥复合材料的发展现状…………………………………………11.1引言…………………………………………………………………11.2氯氧镁水泥的形成机理………………………………………………11.3氯氧镁水泥复合材料的制备方法………………………………………22实验部分………………………………………………………………32.1原料和仪器…………………………………………………………32.2样品制备……………………………………………………………42.3样品测试……………………………………………………………43结果与讨论……………………………………………………………53.1不同的液固比对样品强度的影响……………………………………53.2不同的氯化镁溶液对样品强度的影响………………………………63.3不同的植物纤维掺量对样品强度的影响………………………………83.4掺加石膏粉对样品强度的影响………………………………………94总结…………………………………………………………10参考文献………………………………………………………………11致谢……………………………………………………………………1314 1　氯氧镁水泥复合材料的发展现状1.1引言氯氧镁水泥又称索瑞尔(Sorel)水泥或菱镁水泥，是Sorel于1867年发明的。与其他水泥不同，此水泥是一种MgCl2-NaOH-H2O体系组成的镁质胶凝材料，其主要成分为碱式氯化镁，可以用通式Mgx(OH)·Cl·nH2O表示[1]。氯氧镁水泥具有一系列显著的优点：(1)凝结硬化快且具有很好的机械强度。50～80MPa的抗压强度是很常见的，通过加入改性剂最高抗压强度可达200MPa以上；(2)弱碱性和低腐蚀性。氯氧镁水泥浆体滤液的pH值在8.15～9.15之间,比硅酸盐水泥的碱度低很多，一般只对金属有腐蚀作用；(3)粘结性好。与一些有机或无机骨料如锯木屑、木粉、矿石粉末和砂石等有很强的粘结力；(4)耐磨性好。优于硫铝酸盐水泥、矾土水泥和硅酸盐水泥,有文献表明它是普通硅酸盐水泥耐磨性的3倍；(5)阻燃性优良。MgO、MgCl2都是不可燃的,且制品水化物中大量结晶水都能阻止点燃；(6)抗盐卤能力强。通过添加改性剂可以使氯氧镁水泥抵抗各种浓度的卤水,因此,它可用作轻质墙体材料和装饰板材,防水堵漏材料,防火涂层材料,或直接制成防火材料,房屋建筑或工业厂房的地面材料以及木屑板和胶合板的胶粘剂等。[2-4]氯氧镁水泥虽然具有一系列显著的优点，但是其耐水性差、返卤、翘曲较严重,无法广泛使用。利用不同种类的外加剂可以在很大程度上改善镁水泥石的强度、变形性、抗水性、耐久性等重要工程力学性能,拓宽其应用领域。天然植物纤维对水泥有阻凝或缓凝作用而且镁水泥由于其碱性较低对植物纤维腐蚀较小，所以将植物纤维与水泥胶凝材料相结合制备水泥基植物纤维复合材料是一种解决氯氧镁水泥耐水性差、易返卤等缺陷的有效途径。本试验主要研究了植物纤维对镁水泥水化以及力学强度的影响，为更好的开发镁水泥基植物纤维复合材料提供理论基础。1.2氯氧镁水泥的形成机理各国学者对氯氧镁水泥水化机理方面的研究作了大量的工作，研究表明：活性氧化镁、氯化镁和水在常温下的水化反应的产物中，其相组成为3Mg(OH)2·MgCl2·8H2O和5Mg(OH)2·MgCl2·8H2O的强度较高。[5]从事镁水泥研究的学者公认的镁水泥硬化反应过程有以下3个:(1)5MgO+MgCl2+13H2O==5Mg(OH)2·MgCl2·8H2O(5·1·8相)14 (2)MgO+H2O==Mg(OH)2(3)3MgO+MgCl2+11H2O==3Mg(OH)2·MgCl2·8H2O(3·1·8相)[6]我国的夏树屏等人在前人的氯氧化镁络离子聚合而成的结论基础上,通过平衡相图、结晶动力学、热效应、固化过程中物相的组成和电子显徽镜图像的综合研究,对镁水泥形成初期,中期和后期的形成机制进行了系统的研究,认为在形成初期MgO与MgCl2水溶液接触,MgO先水化成Mg(OH)2，Mg(OH)2溶于水中，在Mg2+，Cl-，H2O分子存在下，加速Mg(OH)2解离为Mg2+和OH-，同时溶液形成浓度梯度的非平衡状态，分别生成5·1·8相和3·1·8相结晶,通过溶解络合方式,经扩散、蒸发和结晶的综合物理化学作用后,形成针状交错网络结构。[7]现在一般可以认为，氯氧镁水泥水化初期存在着一个凝胶阶段，随后水化相在凝胶表面析晶。氯氧镁水泥晶相的形成过程分为以下三个阶段:(1)中和过程(neutralizing)。MgO溶解于溶液中,被MgCl2溶液中的H+中和,这个过程增加了Mg2+和OH-离子的浓度；(2)水化过程(hydrolyzing)。Mg2+和OH-溶度的增加促进了Mg2+离子的水化桥连反应,形成了多核[Mgx(OH)y(H2O)z]2x-2y；(3)晶化过程(crystalliz2ing)。这些多核聚合物和Cl-离子、H2O分子相互吸附,形成交联的无定型凝胶,这些凝胶最终转化成晶型的晶相,网架状结构中的孔隙不断被晶型产物填充密实,强度不断增加。1.3氯氧镁水泥复合材料的制备方法（1）纤维先掺法：是将纤维与基体材料先干混合均匀，然后再加水混和均匀。图1为水泥基复合材料的纤维先掺法（2）纤维后掺法，将基体材料加水混合均匀后再加入纤维混合均匀，是通常较多采用的工艺，本实验采取后掺法。14 图2为水泥基复合材料的纤维后掺法2实验部分2.1原料和仪器2.1.1原料：MgOAR（汕头市西陇化工厂有限公司）MgCl2·6H2OAR（汕头市西陇化工厂有限公司）橡胶纤维天然橡胶纤维石膏粉工业用石膏粉水自来水2.1.2主要仪器：1、托盘天平（上海精科天平）2、DF-101集热式恒温加热磁力搅拌器（郑州长城工贸有限公司）3、弹簧测力计（广州市威衡电子有限公司）4、水泥抗折性能测试装置（实验室自造）2.2样品制备2.2.1氯氧镁水泥浆液的配制室温下，用托盘天平称取一定量的MgO和MgCl2·6H2O，量取适量的水。14 首先将MgCl2·6H2O溶于水中使之形成有一定浓度的MgCl2水溶液，再加入已称量过的镁粉，然后搅拌均匀得氯氧镁水泥浆液。2.2.2掺加填料与纤维用托盘天平称取适量的石膏粉，橡胶纤维掺入氯氧镁水泥浆液，在500ml的烧杯中慢速搅拌约1min，形成混合物浆液。2.2.3制备样品模型将混合物浆液倒入成型空心槽的试模中制造成型试样，制取形状为12mm×12mm×80mm的条形试样。2.2.4自然固化成样品将制备好的，尺寸为12mm×12mm×80mm条形试样，成型后以报纸覆盖表面，以防止水分蒸发，静置一昼夜自然固化成样品。2.3性能测试2.3.1样品抗折强度的测定方法：样品在静置一昼夜自然固化后，用水泥抗折性能测试装置测量样品的抗折强度。抗折强度按下式计算：σ=P/F式中，σ—抗折强度，Mpa；P—破坏强度，N；F—试样受力面积，mm2。2.3.2具体测定步骤：测试样品的条形试样的抗折强度试验采用的是三点加载简支梁。先将试样插入抗折试验装置的支梁上，使加荷辊与两个支承辊保持等距，普通试样的成型面应与受力方向垂直（接触面积为60mm2），如图所示：图3为水泥抗折性能测试装置14 逐渐地加大试样成型面的受力直至样品从受力位置断裂，利用弹簧测力计测试受力的大小，记录样品所承受力。3　结果与讨论3.1不同的液固比对样品强度的影响液固比是指拌制水泥浆、砂浆和混凝土混合料时，原材料中水与固体原料的质量比（W/C），氯氧镁水泥的液固比一般在0.4—0.6之间。计算液固比应考虑氯化镁溶液中带入的水分，实际加水量为总需水量减去氯化镁溶液带入的水(以后试验部分实际需水量均按此计算)。本试验固定植物纤维的掺加量为1.5g/L，氧化镁用量为25g，氯化镁用量为12.4g（ρ=1.24g.cm-3），石膏粉用量为10g,为保持料浆稠度一致,每个编号其它材料配方均相同，采用不同的液固比进行试验取样，成型尺寸为12mm×12mm×80mm的条形试样，自然固化24h后测样品的强度，如表1所示。表1不同的液固比样品的抗折强度编号液固比水(mL）氯氧镁水泥（氧化镁+氯化镁+石膏粉+纤维/g）抗折强度(Mpa）10.3818.6492.0420.3919.1492.1130.4019.6492.2440.4120.1492.3450.4220.6492.4860.4321.1492.3670.4421.6492.1780.4522.1492.0990.4622.5491.9214 图4不同液固比样品的抗折强度折线图综合表1、图4可以看出：随着液固比的增大，氯氧镁水泥复合材料的流动度不断增大，水泥复合材料容易成型。当水泥复合材料的液固比超过一定程度时，由于高液固比带来的过多水分，将提高水泥复合材料内部的孔隙率，降低水泥复合材料的强度；如果氯氧镁水泥复合材料的液固比过小，导致水泥复合材料的粘度大，不易将其搅拌均匀，结果水泥复合材料成型困难，试件不致密，最终降低了氯氧镁水泥复合材料的强度。[8]在本试验条件下，确定氯氧镁水泥复合材料的液固比为0．42，在此液固比下，样品试样的抗折强度达到最高值，并且在此液固比下，氯氧镁水泥复合材料试样的流动度适中，可以满足需要。因此，氯氧镁水泥复合材料的液固比确定为0．42。3.1不同的氯化镁溶液对样品强度的影响为保证样品成型时氯氧镁水泥浆具有一定的流动性与可塑性，必须保证一定的液固比，即保证一定的液相用量。由于氧化镁与水的反应速度慢，制品强度低，因此，常采用氯化镁溶液作为氧化镁的调和剂。[9]氯化镁溶液的溶度对样品成型状况有着重要作用,氯化镁溶液的比重一般应选在1.20～1.26g.cm-3。[10]14 本试验固定活性氧化镁的用量为25g，氯化镁溶液的比重选在1.18～1.28g.cm-3。为保持料浆稠度一致，每个编号氯化镁溶液重水的用量(体积)都取10mL，其它材料配方均相同，成型尺寸为12mm×12mm×80mm条形试样，自然固化24h后测样品的强度，结果如表2所示。表2不同的氯化镁溶液样品的抗折强度编号ρ(MgCl2)/g.cm-3MgO/MgCl2抗折强度/Mpa11.182.121.7921.22.082.1131.222.052.3541.242.022.4851.261.982.2261.281.952.03图5不同氯化镁溶液样品的抗折强度折线图综合表2，图5可很清楚看出，在配比及原材料不变的情况下，卤水比重变化实质上是MgO/MgCl2摩尔比变化的反映：在一定的范围内，随着摩尔比减小，强度逐渐增高。MgO/MgCl2的摩尔比也不是越小越好，有一个最佳值，超过这个最佳值以后，对样品的强度反而有不利的影响。14 在本试验条件下，确定氯化镁溶液的比重为1.24g.cm-3。在此比重下，样品试样的抗折强度达到最佳，并且在此比重下，氯氧镁水泥浆具有具有较好的可塑性与耐水性。若MgCl2溶液的浓度过低，将导致体系中原料反应不完全，制品强度下降；若MgCl2溶液的浓度过高，制品表面上的水化相5Mg(OH)2·MgCl2·8H2O就会分解出MgCl2而产生游离氯化镁，使返卤现象变得更严重,最终导致制品结构的破坏。[11]因此，确定氯化镁溶度液的比重为1.24g.cm-3。3.1不同的植物纤维掺量对样品强度的影响天然植物纤维复合材料是以天然植物纤维作增强材料，以树脂或水泥作基体的一种复合材料。传统的纤维增强复合材料是由聚丙烯纤维、玻璃纤维、芳香族聚酰胺纤维或碳纤维等化学纤维组成的，它们一般都存在着耗能大、造价高、易污染环境等问题。与化学纤维相比，各种天然植物纤维具有价廉、可回收、可降解、可再生等优点，并具有一般纤维的强度和刚度，且比重较小，比强度、比刚度均较高，以天然植物纤维为增强基的复合材料同样具有优良的性能。[12]普通的硅酸盐水泥由于碱性较高，对植物纤维有很强的腐蚀作用，其溶出物对水泥有阻凝和缓凝的负面影响，而氯氧镁水泥（后简称镁水泥）碱性相对于硅酸盐水泥较低，保持在10左右，对植物纤维腐蚀较小，因此将植物纤维与镁水泥结合起来制备镁水泥基植物纤维复合材料，具有很大的开发空间。本试验主要研究了不同的植物纤维掺量对镁水泥力学强度的影响。[13]本试验固定氧化镁用量为25g，氯化镁用量为12.4g（ρ=1.24g.cm-3），石膏粉用量为10g，采用不同的植物纤维掺加量进行试验取样，每个编号其它材料配方均相同，成型尺寸为12mm×12mm×80mm的条形试样，自然固化24h后测样品的强度，结果如表3所示。表3不同植物纤维掺量样品的抗折强度植物纤维掺量/g.L-1抗折强度/Mpa02.100.52.251.02.261.52.4814 2.02.32图6不同植物纤维掺量样品的抗折强度折线图综合表3、图6可很清楚看出：在本试验中，若不掺加植物纤维，样品的抗折强度比较弱；掺加0.5g.L-1的植物纤维时，强度略有上升；当纤维的含量由0.5g.L-1增长到lg.L-1时，样品的抗折强度有所增加，但增加趋势较小；当纤维的含量由lg.L-1继续增长到1.5g.L-1时，样品的抗折强度增加趋势明显，当纤维的含量由1.5g.L-1继续增长到2.0g.L-1时抗折强度却有少许下降。因此本试验选择植物纤维的掺加量为1.5g.L-1。3.4添掺加石膏粉对样品强度的影响在镁水泥材料配制过程中，为了改善其某些性能，有时要加入一定量的活性混合材，或者用活性混合材作为外加剂载体，与外加剂同时掺到镁水泥中。目前在镁水泥中使用的活性混合材主要有硅灰、粉石膏粉等[15]。不同的外加剂对水泥土强度有着不同的影响。掺合石膏粉可以提高氯氧镁水泥基材料的体积稳定性。硅酸盐水泥潮湿膨胀主要是由于水蒸气凝结使毛细孔中弯月面减小，表面张力降低，引起湿胀、水化产物的结晶压力和吸水湿胀变形等。氯氧镁水泥潮湿膨胀的主要原因在于水化物中过剩的MgO吸水生成水镁石。掺合石膏粉可以提高氯氧镁水泥基材料的体积稳定性[16]。本次试验采用石膏作为掺加剂(掺入量为10g)，试验固定植物14 纤维的掺加量为1.5g/L，氧化镁用量为25g，氯化镁用量为12.4g（ρ=1.24g.cm-3），为保持料浆稠度一致，每个编号其它材料配方均相同，采用不同的液固比进行试验取样，成型尺寸为12mm×12mm×80mm的条形试样，自然固化后观察样品的的体积变形情况，记录样品的稳定性，并与空白试验作比较，试验结果见表4。表4不同石膏粉掺量样品的稳定性样品稳定性液固比不加石膏粉掺加石膏粉0.40不稳定较稳定0.42不稳定很稳定0.44不稳定较稳定由表4可以很清楚的看出，在本试验条件下，掺加石膏粉可以提高氯氧镁水泥基复合材料的稳定性。石膏粉的主要成分是无定形的，颗粒极细，掺入镁水泥后，对溶液中OH-、Cl-等离子有很强的吸附能力，降低了MgO周围离子浓度，减少了镁水泥硬化结构中的内应力，减少了结晶接触点数量，从而提高了硬化结构的稳定性[15]。 少了镁水泥硬化结构中的内应力,减少了结晶接触点数量,从而提高了硬化结构的稳定性。4总结1、在本试验条件下，其它配方都相同的情况下，氯氧镁水泥复合材料的液固比为0．42，样品的抗折性能效果好；2、在本试验条件下，其它配方都相同的情况下，氯化镁溶液的比重为1.24g.cm-3样品的抗折性能效果好；3、在本试验条件下，其它配方都相同的情况下，植物纤维的掺加量为1.5g.L-1，样品的抗折性能效果好；4、在本试验条件下，其它配方都相同的情况下，掺加石膏粉可以提高氯氧镁水泥基复合材料的稳定性。14 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[17]李宇杰,岳祖润,赵勇.水泥土掺石膏的室内试验研究[J].国防交通工程与技术,2008,(6):42-44.[18]郭斌.天然植物纤维增强水泥复合物综述[J].江苏建材,2005(3),49-52.[19]陈旭东,翁睿.纤维增强氯氧镁复合材料增强体系改性研究[J].桂林工学院学报，2001-07,21(3):271-275.[20]DengDehua,ZhangChuanmei.Theformationmechanismofthehydratephasesinmagnesiumoxychloridecement[J].CementandConcreteResearch,1999,29:1365-1371.[21]DengDehua,ZhangChuanmei.Theeffectofaluminatemineralsonthephasesinmagnesiumoxychloridecement[J].CementandConcreteResearch,1996,26(8):1203-1211.[22]曲广善,谢凤琴.氯氧镁水泥耐久性研究[J].混凝土与水泥制品,1999-04,(2):42-44.[23]郑玉顺,李剑波,丁建形,等.氯氧镁水泥的预处理改性及其工艺参数的研究[J].泥凝土与水泥制品,1999,(6):43-46.[24]CouttsRSP.Woodfiberreinforcedcementcomposites[C].NaturalFiberReinforcedCementandConcrete,London:Blackie,1998.12-62.14 致谢本研究及学位论文是在郑子山教授的亲切关怀和悉心指导下完成的。他严肃的科学态度，严谨的治学精神，精益求精的工作作风，深深地感染和激励着我。他踏实勤奋的作风，开拓新的思维，丰富而精湛的知识储备也是我终生学习的榜样和努力的方向。从课题的选择到项目的最终完成，郑老师都始终给予我细心的指导和不懈的支持。他对实验要求严格，给我们自己思考实验问题的机会多，又能适时给我们一些建议，是个很好的指导老师。郑老师不仅在学业上给我以精心指导，同时还在思想、生活上给我以无微不至的关怀，郑子山老师的年轻心态感染着我，在此谨向郑老师致以诚挚的谢意和崇高的敬意。最后，衷心感谢在百忙之中抽出时间审阅本论文的专家教授！内部资料仅供参考14 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