水泥基材料用微膠囊自修復技術與原理的研究
發(fā)布時間：2019-05-30 11:29
【摘要】：混凝土開裂損傷部位的智能化感知和即實時自修復是水泥混凝土微裂紋修復的新技術和新方法,對于改善混凝土材料耐久性,提高混凝土構筑物服役壽命具有重要意義。 本文運用混凝土材料科學、有機高分子化學和物理化學等相關理論與知識,創(chuàng)立了適用于水泥基材料的微膠囊自修復體系,分析了相關技術原理,提出了自修復效果的評價方法。 采用原位聚合法合成了一種適用于水泥基材料裂縫修復的UF/E型微膠囊,它是以脲醛樹脂為囊壁包裹以環(huán)氧樹脂膠液組成的囊芯構成的直徑為微米級的球形顆粒。通過正交試驗,并基于微觀分析和合成反應動力學,分析了表征UF/E微膠囊的粒徑、囊壁厚度、表面形貌和包封率等技術參數(shù)的主要影響因素,得出了微膠囊最優(yōu)合成工藝路線與參數(shù),將尿素和甲醛摩爾比為1.5：1.0的溶液在70℃下反應1h合成脲醛樹脂預聚體,環(huán)氧樹脂膠液芯材/脲醛樹脂預聚體壁材的質(zhì)量比為(1.0～1.2)：1.0,酸化階段適宜溫度為50℃,囊壁形成的pH值為2-3,囊壁固化增強階段的適宜溫度為60℃。 研發(fā)了一種可在水泥基材料中發(fā)生固化反應并具有良好膠粘性的環(huán)氧樹脂基裂縫修復劑,它由E-51環(huán)氧樹脂、正丁基縮水甘油醚(BGE)稀釋劑、咪唑類固化劑(MC120D)等組分構成�；贙issinger和Arrhenius方程,分析了E-51/BGE/MC120D修復劑的固化反應動力學,當BGE為E-51質(zhì)量的17.5%、MC120D為E-51質(zhì)量的20%時,修復劑的固化反應活化能最低,有利于在水泥基材料中常溫固化；借助差熱和紅外技術探討了固化反應機理,MC120D摻量為10～30%時,修復體系固化分兩步進行,而其摻量超過30%時,固化反應一步完成；運用毛細動力和虹吸原理,分析了水泥基材料中微膠囊破裂、環(huán)氧樹脂膠液流出并滲入到裂縫處與固化劑發(fā)生固化反應修復裂縫的界面性能要求。由此得到了環(huán)氧樹脂基修復劑的最優(yōu)組成。 設計并制備了一種基于微膠囊技術的自修復水泥基材料,試件由合成纖維、硅酸鹽水泥、砂子、微膠囊和固化劑等組分構成。分析了含有微膠囊的水泥基材料的自修復機理,當水泥基材料開裂時,裂縫處的微膠囊破裂,環(huán)氧樹脂膠液滲入裂縫內(nèi)并與裂縫壁滲出的固化劑發(fā)生固化反應,形成具有強膠黏性的固化物,填塞縫隙,降低了孔隙率,阻斷了連續(xù)孔縫,從而,修復了水泥基材料的強度和抗?jié)B性,實現(xiàn)水泥基材料的自修復功能。 建立了水泥基材料自修復性能評價方法,利用電化學阻抗譜法(EIS)、壓汞法(MIP)和氮吸附法(BET),以滲流結(jié)構參數(shù)、孔結(jié)構參數(shù)和吸附-脫附曲線特征等指標,評價水泥基材料在不同荷載作用下?lián)p傷程度,并得出外加荷載達40～50%σmax時,水泥基材料開始出現(xiàn)明顯裂縫—損傷；以損傷水泥基材料的強度、氯離子滲透性作為水泥基材料自修復率的評價指標,探討了摻有微膠囊的水泥基材料自修復率的主要影響因素,其影響程度順序為：微膠囊摻量微膠囊直徑損傷程度修復齡期。得出獲得最大修復率的條件組合是6.0%微膠囊摻量、微膠囊直徑為230μm、預壓力為60%σmax時的損傷程度、修復齡期7d。 通過上述研究,創(chuàng)立了一種水泥基材料自修復的UF/E型微膠囊技術,并試驗驗證了該技術可使水泥基材料具有一定的自修復功能,分析了微膠囊修復率的主要影響因素及其規(guī)律。但仍有一些問題需進一步研究,以實現(xiàn)該技術的工程化應用。
[Abstract]:The intelligent sensing and real-time self-repairing of the concrete crack damage part is a new technology and a new method for repairing the micro-crack of the cement concrete, which is of great significance in improving the durability of the concrete material and improving the service life of the concrete structure. In this paper, the self-repairing system of micro-capsule, which is suitable for cement-based materials, is established by using the related theories and knowledge of material science, organic polymer chemistry and physical chemistry. A UF/ E-type microcapsule suitable for crack repair of cement-based material is synthesized by in-situ polymerization method, The main influencing factors of the parameters such as the size of the UF/ E microcapsule, the thickness of the capsule wall, the surface morphology and the encapsulation rate were analyzed based on the micro-analysis and the synthesis reaction kinetics. The optimum synthetic route of the microcapsule was obtained. The method comprises the following steps of: reacting a solution with a molar ratio of urea and formaldehyde at a molar ratio of 1.5: 1.0 at 70 DEG C for 1 hour to synthesize a fluorocarbon prepolymer, wherein the mass ratio of the core material of the epoxy resin glue solution to the prepolymerized body wall material is (1.0-1.2): 1.0, the appropriate temperature of the acidification stage is 50 DEG C, and the pH value formed by the capsule wall is 2-3. The appropriate temperature for the solidification and enhancement phase of the capsule wall is 60. degree. C., an epoxy-based crack repair agent that can be cured in a cement-based material and has a good adhesive tack, which is formed from an E-51 epoxy resin, a n-butyl glycidyl ether (BGE) diluent, a detomidine curing agent (MC120D), The curing reaction kinetics of E-51/ BGE/ MC120D repairing agent is analyzed based on Kissinger and Arrhenius equation. When BGE is 17.5% of E-51, MC120D is 20% of E-51 mass, the activation energy of curing reaction of the repairing agent is the lowest, which is beneficial to the cement-based material. The curing reaction mechanism is discussed by means of differential thermal and infrared technology. The cure system is cured in two steps by means of differential thermal and infrared technology, and the curing reaction is completed in two steps when the content of MC120D is more than 30%. The capillary force and the siphon principle are used to analyze the cement-based material. the boundary of the crack is repaired by the solidification reaction of the epoxy resin glue solution and the curing agent when the microcapsule is broken and the epoxy resin glue solution flows out and penetrates into the crack and the surface property requirement is obtained, thereby the epoxy resin-based repairing agent is obtained, The self-repairing cement based material based on the microcapsule technology is designed and prepared, and the test piece is made of synthetic fiber, silicate cement, sand, microcapsule and solid. the self-repairing mechanism of the cement-based material containing the microcapsule is analyzed, And the strength and the impermeability of the cement-based material are fixed, and the cement base material is realized. The self-repairing function of cement-based material was established. The self-repairing performance evaluation method of cement-based material was established, using electrochemical impedance spectroscopy (EIS), mercury-mercury method (MIP) and nitrogen adsorption (BET) method to measure the flow structure parameters, pore structure parameters and adsorption- The characteristics of the desorption curve and other indexes are used to evaluate the degree of damage of the cement-based material under different loads, and when the applied load is 40-50%/ max, the cement-based material will start to have obvious cracks and damage; in order to damage the strength of the cement-based material, the chloride ion permeability is used as the cement-based material. The main influencing factors of the self-repair rate of the cement-based material with micro-capsule are discussed in this paper. The condition combination of the maximum repair rate was 6.0%, the diameter of the microcapsule was 230. m u.m, and the pre-pressure was 60%. The technology of self-repairing of cement-based material was established by the above-mentioned research, and the self-repairing function of the cement-based material was tested. The repair rate of the microcapsules was analyzed. However, there are still some problems that need to be further studied.
【學位授予單位】：中南大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TU528
本文編號：2488796
[Abstract]:The intelligent sensing and real-time self-repairing of the concrete crack damage part is a new technology and a new method for repairing the micro-crack of the cement concrete, which is of great significance in improving the durability of the concrete material and improving the service life of the concrete structure. In this paper, the self-repairing system of micro-capsule, which is suitable for cement-based materials, is established by using the related theories and knowledge of material science, organic polymer chemistry and physical chemistry. A UF/ E-type microcapsule suitable for crack repair of cement-based material is synthesized by in-situ polymerization method, The main influencing factors of the parameters such as the size of the UF/ E microcapsule, the thickness of the capsule wall, the surface morphology and the encapsulation rate were analyzed based on the micro-analysis and the synthesis reaction kinetics. The optimum synthetic route of the microcapsule was obtained. The method comprises the following steps of: reacting a solution with a molar ratio of urea and formaldehyde at a molar ratio of 1.5: 1.0 at 70 DEG C for 1 hour to synthesize a fluorocarbon prepolymer, wherein the mass ratio of the core material of the epoxy resin glue solution to the prepolymerized body wall material is (1.0-1.2): 1.0, the appropriate temperature of the acidification stage is 50 DEG C, and the pH value formed by the capsule wall is 2-3. The appropriate temperature for the solidification and enhancement phase of the capsule wall is 60. degree. C., an epoxy-based crack repair agent that can be cured in a cement-based material and has a good adhesive tack, which is formed from an E-51 epoxy resin, a n-butyl glycidyl ether (BGE) diluent, a detomidine curing agent (MC120D), The curing reaction kinetics of E-51/ BGE/ MC120D repairing agent is analyzed based on Kissinger and Arrhenius equation. When BGE is 17.5% of E-51, MC120D is 20% of E-51 mass, the activation energy of curing reaction of the repairing agent is the lowest, which is beneficial to the cement-based material. The curing reaction mechanism is discussed by means of differential thermal and infrared technology. The cure system is cured in two steps by means of differential thermal and infrared technology, and the curing reaction is completed in two steps when the content of MC120D is more than 30%. The capillary force and the siphon principle are used to analyze the cement-based material. the boundary of the crack is repaired by the solidification reaction of the epoxy resin glue solution and the curing agent when the microcapsule is broken and the epoxy resin glue solution flows out and penetrates into the crack and the surface property requirement is obtained, thereby the epoxy resin-based repairing agent is obtained, The self-repairing cement based material based on the microcapsule technology is designed and prepared, and the test piece is made of synthetic fiber, silicate cement, sand, microcapsule and solid. the self-repairing mechanism of the cement-based material containing the microcapsule is analyzed, And the strength and the impermeability of the cement-based material are fixed, and the cement base material is realized. The self-repairing function of cement-based material was established. The self-repairing performance evaluation method of cement-based material was established, using electrochemical impedance spectroscopy (EIS), mercury-mercury method (MIP) and nitrogen adsorption (BET) method to measure the flow structure parameters, pore structure parameters and adsorption- The characteristics of the desorption curve and other indexes are used to evaluate the degree of damage of the cement-based material under different loads, and when the applied load is 40-50%/ max, the cement-based material will start to have obvious cracks and damage; in order to damage the strength of the cement-based material, the chloride ion permeability is used as the cement-based material. The main influencing factors of the self-repair rate of the cement-based material with micro-capsule are discussed in this paper. The condition combination of the maximum repair rate was 6.0%, the diameter of the microcapsule was 230. m u.m, and the pre-pressure was 60%. The technology of self-repairing of cement-based material was established by the above-mentioned research, and the self-repairing function of the cement-based material was tested. The repair rate of the microcapsules was analyzed. However, there are still some problems that need to be further studied.
【學位授予單位】：中南大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TU528
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