本文選題：纖維素醚　切入點：流變特性　出處：《武漢理工大學》2013年博士論文　論文類型：學位論文

【摘要】：我國目前正處于城鎮(zhèn)化高速發(fā)展的關鍵時期,外墻外保溫系統(tǒng)作為建筑節(jié)能的主要技術途徑,其中,粘結砂漿和抗裂砂漿等薄層砂漿對于保證外墻外保溫系統(tǒng)的節(jié)能效果和耐久性的實現(xiàn)起著重要的作用,在此背景下,研究薄層砂漿的水化關鍵問題具有特別重要的意義。本研究工作來源于“十二五”國家科技支撐計劃項目(2011BAJ04802)和國家自然科學基金(50902107)。通過研究纖維素醚(cellulose ether,CE)改性水泥漿體的流變性能和熱-電特性,探明多因素環(huán)境下水泥漿體的水化動力學過程。根據(jù)薄層CE改性水泥漿體的使用環(huán)境的不同,研究了快速失水條件下水泥漿體的水化規(guī)律。基于薄層水泥漿體流變特性、水化動力學過程和快速失水條件下的水化規(guī)律建立了薄層CE改性水泥漿體水化過程和界面過渡區(qū)微觀結構模型,闡述了薄層CE改性水泥漿體的水化特征。 本文主要的工作及所取得的重要成果如下： 1.根據(jù)CE在水溶液(拌和階段環(huán)境)和水泥漿體(水化階段環(huán)境)2種液相環(huán)境中的流變特性,系統(tǒng)研究了CE成膜過程及溶液環(huán)境(溫度、pH值、離子的種類和價態(tài))對水溶液和水泥漿體流變特性的影響,揭示了CE在不同液相環(huán)境中成膜過程及溫度、pH值、離子對其在水溶液和水泥漿體中的作用機理。 以表觀粘度、剪切應力、屈服應力和塑性粘度為評價指標,研究了CE種類和摻量對水溶液和水泥漿體流變特性的影響。探討了不同溫度和pH值時CE在水溶液和水泥漿體中的流變特性,確立了CE的低臨界溶解溫度和等電點。分別研究了陽離子、陰離子及其價態(tài)對CE溶液表觀粘度的影響,基于“感膠離子序”的規(guī)律闡述了離子種類和價態(tài)對CE溶液表觀粘度的作用機理,揭示了CE在復雜液相環(huán)境中的成膜特征,為研究塑性階段CE改性水泥漿體的流變特性提供了理論依據(jù)。 2.提出了CE-聚水與緩釋組分(CWRC)改性水泥漿體水化動力學過程的設計與制備方法,基于對水化熱和電阻率微分曲線分析,掌握了水泥水化初期的宏觀熱學效應及電化學特征變化規(guī)律,研究了水化熱和電阻率與水泥水化進程的關系,建立了CE-CWRC-水泥三元體系水化熱-電模型。 分別研究了CE和CWRC對水泥水化熱和電阻率的影響,指出CWRC對水泥水化各階段的延遲作用小于CE。研究了電阻率和水化放熱量與Ca(OH)2和化學結合水含量的關系,發(fā)現(xiàn)具有線性相關性,為研究水泥水化早期結構形成及水化進程提供了一種新的結構參數(shù)。通過對水化熱和電阻率微分曲線分析,建立了CE-CWRC-水泥三元體系水化熱-電模型,將水泥水化過程分為：溶解-析出平衡期、結構形成期、結構發(fā)展期和結構穩(wěn)定期4個階段,且模型中水化熱和電阻率微分在表征水泥早期水化動力學過程具有較好的一致性,可以準確描述水泥水化歷程及結構形成的瞬時狀態(tài)。 3.首次提出了CE改性薄層水泥漿體在快速失水條件下的試驗設計與評價方法,通過改變水泥漿體厚度、養(yǎng)護溫度和基體材料的種類,系統(tǒng)研究了CE改性薄層水泥漿體的早期失水特征、界面性能和微觀分析,探明了薄層水泥漿體的水化規(guī)律和微觀結構發(fā)展機制。 以失水速度和失水率為評價指標,研究了薄層水泥漿體在快速失水條件下的早期失水特征,并闡述了其失水機制。分析了水泥漿體厚度、養(yǎng)護溫度和基體材料的種類對薄層水泥漿體界面性能的影響,指出了不同齡期時的界面破壞形式。通過XRD、FTIR和TG-DSC分析,研究了薄層水泥漿體在快速失水條件下的水化規(guī)律。通過對快速失水條件下水泥漿體表層、中間層和界面層3個區(qū)域的微觀分析,探明了水化產物沿水泥漿體厚度方向上的分布規(guī)律,揭示了薄層水泥漿體的界面破壞原理,為研究外墻外保溫系統(tǒng)中保溫層脫落和保護層的空鼓、開裂等問題奠定了理論基礎。 4.根據(jù)薄層水泥-CE漿體中水分和離子的遷移、CE成膜、水泥漿體的硬化過程,分析了水化產物沿薄層水泥漿體厚度方向上的分布規(guī)律,建立了實際服役環(huán)境下的薄層水泥-CE漿體水化過程和界面過渡區(qū)微觀結構模型。 根據(jù)CE成膜與溶解過程、薄層水泥漿體的失水機制與離子遷移過程、水化歷程與微觀結構發(fā)展機制、水化產物的分布規(guī)律,建立了實際服役環(huán)境下薄層水泥-CE漿體的水化過程模型。根據(jù)基體材料的孔結構與吸水特性,分析了薄層水泥漿體的失水特征、界面微結構的變化、水化產物的種類和數(shù)量分布,建立了薄層水泥漿體與基體材料間的界面過渡區(qū)微觀結構模型,對于研究薄層水泥-CE漿體水化規(guī)律具有重要的理論與實際意義。
[Abstract]:Our country is in the key period of urbanization development, exterior insulation system as the main way of building energy saving technology, the bonding mortar and mortar mortar for TLC to realize energy-saving effect and durability of external thermal insulation system plays an important role in this context is very important the key problem of thin water mortar. This work comes from the "12th Five-Year" National Science and technology support program (2011BAJ04802) and the National Natural Science Foundation (50902107). Through the study of cellulose ether (cellulose ether, CE) and thermo rheological properties of modified cement paste electrical properties proved under many factors of cement the hydration kinetics. According to the thin layer of CE modified cement slurry used in different environment, study the hydration law of cement paste under the condition of rapid dehydration based on thin water. The rheological characteristics of slurry, hydration kinetics process and hydration rule under rapid dehydration conditions were established. The hydration process and interfacial transition zone microstructure model of thin layer CE modified cement paste were established, and the hydration characteristics of thin layer CE modified cement paste were expounded.
The main work of this article and the important achievements are as follows:
According to the 1. CE in aqueous solution (mixing phase) and cement paste (water phase environment) rheological properties of 2 kinds of liquid phase in the environment, the system of CE film forming process and solution environment (temperature, pH value, ion type and valence) on the rheological properties of aqueous solution and cement paste the CE revealed in different liquid phase in the film-forming process and temperature, pH value, the ions in aqueous solution and cement paste in mechanism.
The apparent viscosity, shear stress, yield stress and plastic viscosity as the evaluation index, the effects of CE type and content on the rheological properties of aqueous solution and cement paste. The effects of different temperature and pH value of CE rheological properties in aqueous solution and in cement paste, established a low Pro field solution temperature CE and isoelectric point. The Cation Anion valence were studied, and its influence on the apparent viscosity of CE solution, based on the "lyotopic series" rule describes the composition and valence state of CE ion on the apparent viscosity of the solution mechanism, reveals that the CE film characteristics in complex liquid phase in the environment, and provides a theoretical basis for the study on rheological properties of plastic phase CE modified cement slurry.
2. proposed CE- water and release components (CWRC) design and preparation method of modified dynamic process of hydration of cement pastes, analysis and differential curve of water resistivity based on the grasp of the macro thermal effect and electrochemical characteristics of changes at the early hydration of cement, studied the relationship between the resistivity and the hydration heat of cement the hydration process of cement, established the CE-CWRC- three element system of heat electric model.
The effects of CE and CWRC on cement hydration heat and resistivity were studied, pointed out that the delay is less than CE. on the resistivity and the hydration heat of cement hydration and Ca CWRC stages (OH) 2 and chemical binding relationship between water content, with linear correlation, and provides a kind of new structure parameters study on cement hydration early structure formation and hydration process. Through the analysis of thermal and electrical resistivity differential curve for water, set up three yuan CE-CWRC- cement hydration heat electric model, the cement hydration process is divided into: dissolution precipitation equilibrium phase structure, structure formation period, development period and the stable period of 4 stage structure the model of hydration heat and resistivity, and the differential has good consistency in characterization of cement early hydration kinetics, can accurately describe the instantaneous state of the formation and structure of the cement hydration process.
3. first proposed the experimental design and evaluation of CE modified thin cement slurry in rapid dehydration conditions, by changing the cement paste thickness, different curing temperature and substrate material, studied early dehydration characteristics of CE modified thin cement slurry, interfacial properties and micro analysis, proved the development mechanism water law of thin cement slurry and microstructure.
The water loss rate and water loss rate as the evaluation index, to study the early dehydration feature thin cement slurry in the rapid dehydration conditions, and expounds the mechanism of water loss. Cement paste thickness analysis, different curing temperature and substrate materials on the interfacial properties of thin cement slurry's influence, pointed out that the failure form of different age the period of the interface. Through the XRD analysis of FTIR and TG-DSC, studied the hydration law of thin cement slurry in the rapid dehydration conditions. The cement slurry under the condition of rapid loss of body surface, the micro analysis of the 3 area in the middle layer and interface layer, proved the distribution of hydration products of the cement paste thickness the direction, reveals the thin layer of cement paste interface failure principle, on the exterior insulation insulation layer and protective layer hollowing off system, cracking and other problems to lay a theoretical foundation.
4. according to the migration of moisture and ion thin cement paste -CE, CE film, the hardening process of cement paste, analyze the distribution of hydration products along the thin cement paste thickness direction, the establishment of the actual working environment of the -CE thin cement slurry hydration process and microstructure of interfacial transition zone model.
According to the CE film and the dissolution process, the mechanism of water loss and ion migration process of thin cement slurry, hydration process and microstructure development mechanism, distribution of hydration products, the establishment of the actual service hydration process model of thin cement slurry -CE environment. According to the pore structure and water absorption properties of the substrate materials, analysis the water loss characteristics of thin cement slurry, change the microstructure of interface, type and quantity distribution of hydration products, the establishment of the ITZ microstructure model of thin cement slurry and matrix materials, has important theoretical and practical significance for the study of -CE thin cement slurry water law.

【學位授予單位】：武漢理工大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TU578.1

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