本文選題：快速修補(bǔ)材料 + 磷酸鎂水泥��； 參考：《中國(guó)科學(xué)院研究生院(青海鹽湖研究所)》2014年碩士論文

【摘要】：磷酸鎂水泥(Magnesium Phosphate Cement,MPC)材料是一種氣硬性膠凝材料。由于其具備快硬、早強(qiáng)、黏結(jié)力強(qiáng)、體積穩(wěn)定性好、耐久性好和環(huán)境溫度適應(yīng)能力強(qiáng)等優(yōu)點(diǎn)而備受關(guān)注,但是傳統(tǒng)的MPC制備成本很高,所以限制了其在工程上大量的使用。本文首次利用鹽湖提鋰副產(chǎn)含硼氧化鎂作為重?zé)齅gO的替代原料用來(lái)制備MPC。首先對(duì)含硼氧化鎂在不同溫度下進(jìn)行了熱處理,測(cè)定了其在不同熱處理溫度下物理性質(zhì)和化學(xué)性質(zhì)的變化。然后通過(guò)系統(tǒng)實(shí)驗(yàn),探討了含硼氧化鎂熱處理溫度、M/P、不同種類(lèi)磷酸鹽對(duì)MPC性能的影響,通過(guò)性能對(duì)比找出了制備MPC的最優(yōu)配比,并分析了最優(yōu)配比下的MPC物相組成和微觀(guān)形貌。此外,在最優(yōu)配比條件下通過(guò)摻加礦物摻合料,通過(guò)在空氣中養(yǎng)護(hù)、淡水和模擬海水中浸泡后MPC的性能變化,分析了物相和微觀(guān)形貌的變化,找出了最優(yōu)的礦物摻合料摻量,制備出的MPC材料不僅使MPC制備成本顯著降低,還實(shí)現(xiàn)了鹽湖資源循環(huán)利用。取得的主要研究成果如下:(1)測(cè)定了含硼氧化鎂的熱處理及其物理與化學(xué)性質(zhì)變化。采用不同溫度熱處理含硼氧化鎂,并采用低真空掃描電鏡(SEM)和X射線(xiàn)衍射-全譜分析(XRD-Total Pattern Solution,XRD-Topas)定性定量法分析了含硼氧化鎂在不同熱處理溫度下的物相組成及微觀(guān)形貌;采用粒度分析儀(Laser particle size analyzer,LSPA)和靜態(tài)氮吸附儀(Static nitrogen adsorption analyzer,SNAA)分別測(cè)定了含硼氧化鎂在不同熱處理溫度下的粒度分布、比表面積和總孔體積,并用水合法測(cè)定了其在不同溫度下熱處理后其中活性MgO含量。結(jié)果表明:熱處理溫度對(duì)含硼氧化鎂的物相組成產(chǎn)生影響。在熱處理以前,大量的Mg(OH)2存在于原材料含硼氧化鎂中;在熱處理以后,Mg(OH)2全部轉(zhuǎn)化成MgO。此外,含硼氧化鎂的比表面積、形變系數(shù)、總孔體積和活性MgO含量隨含硼氧化鎂熱處理溫度的升高而降低。(2)確定了制備MPC的最優(yōu)配比。以凝結(jié)時(shí)間以及早期、后期抗壓強(qiáng)度為性能考察指標(biāo),并結(jié)合制備成本來(lái)系統(tǒng)地研究了含硼氧化鎂的熱處理溫度、含硼氧化鎂與磷酸鹽的摩爾比(M/P摩爾比)和磷酸鹽的種類(lèi)對(duì)MPC性能的影響。結(jié)果表明:制備低成本高性能的mpc材料的最優(yōu)配比為:含硼氧化鎂的熱處理溫度為1000℃~1200℃,m/p比為6,磷酸鹽為kh2po4。(3)利用礦物摻合料技術(shù)研究了高性能mpc(英文全稱(chēng),hpmpc)的制備技術(shù)、基本性能與耐久性。在最優(yōu)配比mpc的基礎(chǔ)上,分別研究了不同摻量的粉煤灰和礦渣對(duì)mpc的凝結(jié)時(shí)間、抗壓強(qiáng)度、抗水性和抗海水腐蝕性能的影響。結(jié)果表明:mpc的凝結(jié)時(shí)間隨礦物摻合料摻量的增加而逐漸延長(zhǎng)。隨著粉煤灰和礦渣的繼續(xù)增加,抗壓強(qiáng)度則隨礦物摻合料的增加先保持不變,而后持續(xù)下降;而mpc的抗水性和抗海水腐蝕性能則隨礦物摻合料的增加而逐漸增強(qiáng)。其中,當(dāng)粉煤灰摻量為40%,或礦渣摻量為20%時(shí),不僅可以滿(mǎn)足快速修補(bǔ)材料的性能要求,還可明顯改善mpc的抗水性和抗海水腐蝕性能。在水中和模擬海水中浸泡60d后,摻加粉煤灰和礦渣的hpmpc的軟化系數(shù)和抗海水腐蝕系數(shù)分別達(dá)到0.83~0.81和0.97~0.86。此外,礦物摻合料的摻加還可顯著降低mpc的制備成本。(4)分析了mpc的微觀(guān)物相和sem形貌。(a)基準(zhǔn)mpc微觀(guān)物相和形貌的分析。在制備mpc的最優(yōu)條件的基礎(chǔ)上,對(duì)基準(zhǔn)mpc的物相組成和微觀(guān)形貌進(jìn)行了分析。結(jié)果表明:mpc的主要水化產(chǎn)物為mgkpo4·6h2o(mkp),且隨著水化齡期的延長(zhǎng),水化反應(yīng)隨養(yǎng)護(hù)齡期延長(zhǎng)而不斷進(jìn)行。通過(guò)微觀(guān)結(jié)構(gòu)特征分析可發(fā)現(xiàn),mpc在水化早期(3h),水化產(chǎn)物為粗塊狀的凝膠。繼續(xù)養(yǎng)護(hù)至28d后,大量的細(xì)棒狀的成熟的mkp晶體生成。(b)摻礦物摻合料hpmpc的微觀(guān)物相和形貌的分析。礦物摻合料的摻入對(duì)hpmpc的水化產(chǎn)物和微觀(guān)結(jié)構(gòu)產(chǎn)生明顯的影響。摻加礦物摻合料之后隨著養(yǎng)護(hù)齡期的延長(zhǎng),mkp的含量逐漸增多,表明水化反應(yīng)不斷進(jìn)行。由微觀(guān)結(jié)構(gòu)分析可知,在水化早期(3h),大量的粗塊狀mkp凝膠生成。隨著齡期的延長(zhǎng),大量細(xì)棒狀mkp晶體形成,此外,礦物摻合料表面發(fā)生了火山灰反應(yīng)。(c)礦物摻合料hpmpc具有較高的抗水性與抗海水腐蝕性的微觀(guān)結(jié)構(gòu)機(jī)理。由物相分析可知,隨著在水中和模擬海水中養(yǎng)護(hù)齡期的延長(zhǎng),mkp含量逐漸增多,礦物摻合料hpmpc的水化反應(yīng)仍在緩慢進(jìn)行。通過(guò)微觀(guān)分析發(fā)現(xiàn),基準(zhǔn)MPC凈漿試件浸泡60 d后,基體孔隙較多。而摻礦物摻合料HPMPC在浸泡60 d后基體很密實(shí),這主要是由于礦物摻合料發(fā)揮了微集料效應(yīng)。(5)分析了水化產(chǎn)物的生長(zhǎng)機(jī)理。(a)基準(zhǔn)MPC水化產(chǎn)物的演變過(guò)程。在水化早期(3 h),形成了大量的粗塊狀的無(wú)定型的鎂-磷酸鉀鹽絡(luò)合物水化凝膠(MKP凝膠)。這種MKP凝膠的化學(xué)組成為缺鎂富磷的。隨著水化齡期的延長(zhǎng),在MPC硬化體內(nèi)部的飽和溶液中,水合Mg2+繼續(xù)進(jìn)入MKP凝膠的化學(xué)結(jié)構(gòu)中,從而導(dǎo)致MKP凝膠逐漸析晶、成核、生長(zhǎng)成“成熟”的細(xì)棒狀的水化產(chǎn)物MKP晶體。(b)礦物摻合料HPMPC的水化產(chǎn)物演變過(guò)程。在水化早期(3 h),形成大量的MKP凝膠。繼續(xù)水化至28 d后,成熟的MKP晶體大量形成。此外,礦物摻合料發(fā)揮了火山灰效應(yīng),其中的活性物質(zhì)與MKP晶體反應(yīng)生成含有鎂、鉀、磷、鋁、硅的凝膠水化產(chǎn)物(MKPAS凝膠),覆蓋在礦物摻合料表面。(c)基準(zhǔn)MPC和礦物摻合料HPMPC在水中和模擬海水中的水化產(chǎn)物演變過(guò)程�；鶞�(zhǔn)MPC在水中和模擬海水中浸泡60 d后,一部分MKP凝膠被溶蝕出來(lái),從而留下較多的孔隙,導(dǎo)致其抗水性和抗海水腐蝕性低。MPC摻入礦物摻合料之后,還發(fā)揮了微集料效應(yīng)和吸附效應(yīng),保留未成熟的MKP凝膠和MKPAS凝膠于基體中,使未成熟的MKP凝膠隨著浸泡時(shí)間的延長(zhǎng),逐漸成核、生長(zhǎng)成成熟的MKP晶體。因此,礦物摻合料HPMPC具有較高的抗水性與抗海水腐蝕性。其中,礦渣HPMPC的抗水性與抗海水腐蝕性要優(yōu)于粉煤灰HPMPC,其主要原因是由于礦渣自身水化形成了C-S-H凝膠,進(jìn)一步增強(qiáng)礦渣HPMPC的抗水性與抗海水腐蝕性。
[Abstract]:Magnesium phosphate cement (Magnesium Phosphate Cement, MPC) is a kind of pneumatic cementitious material. Because of its advantages of fast hardening, early strength, strong bonding force, good volume stability, good durability and strong adaptability to environmental temperature, the traditional MPC preparation is very high, so it restricts its large amount of use in Engineering. For the first time, the boron containing boron containing Magnesium Oxide Magnesium Oxide was used as a substitute for reburning MgO to prepare MPC. for the first time to heat the boron containing Magnesium Oxide at different temperatures. The physical and chemical properties of the boron containing boron were measured at different heat treatment temperatures. Then the heat treatment temperature of boron containing Magnesium Oxide was investigated by system test, and M/P was investigated. The effect of different kinds of phosphate on the performance of MPC was found through performance comparison, and the optimal ratio of MPC was found. The phase composition and Micromorphology of MPC under the optimal ratio were analyzed. In addition, the performance changes of MPC in fresh water and simulated seawater were analyzed by adding mineral admixtures in the optimum ratio. The best mineral admixture content was found out by the change of the phase and Micromorphology. The prepared MPC material not only reduced the cost of the preparation of MPC significantly, but also realized the recycling of Saline Lake resources. The main results obtained are as follows: (1) the heat treatment and the physical and chemical properties of boron containing Magnesium Oxide were measured. Boron containing Magnesium Oxide was treated with low vacuum scanning electron microscopy (SEM) and X ray diffraction full spectrum analysis (XRD-Total Pattern Solution, XRD-Topas). The phase composition and Micromorphology of boron containing Magnesium Oxide at different heat treatment temperatures were analyzed. The particle size analyzer (Laser particle size analyzer, LSPA) and static nitrogen adsorption apparatus were used. The particle size distribution, specific surface area and total pore volume of boron containing Magnesium Oxide at different heat treatment temperatures were measured by Static nitrogen adsorption analyzer, SNAA respectively. The content of active MgO was determined by water treatment at different temperatures. The results showed that the heat treatment temperature had an effect on the phase composition of boron containing boron. Before heat treatment, a large number of Mg (OH) 2 existed in the raw materials containing boron containing Magnesium Oxide; after heat treatment, Mg (OH) 2 was transformed into MgO.. The specific surface area of boron containing Magnesium Oxide, the deformation coefficient, the total pore volume and the content of active MgO decreased with the rise of the heat treatment temperature of the boron containing Magnesium Oxide. (2) the optimum ratio of the preparation of MPC was determined. Setting time was determined. And the early and late compressive strength is the performance evaluation index, and the preparation cost is combined to systematically study the heat treatment temperature of boron containing Magnesium Oxide, the effect of the types of Molby (M/P Molby) and phosphate on the properties of MPC with boron containing boron and phosphate. The results show that the optimum ratio of the preparation of low cost and high performance MPC is boron containing boron. The heat treatment temperature of Magnesium Oxide is 1000 ~1200 C, m/p ratio is 6, phosphate is kh2po4. (3) using mineral admixture technology to study the preparation technology of high performance MPC (English full name, HPMPC), basic properties and durability. On the basis of the optimal ratio MPC, the condensation time and compressive strength of the fly ash and slag on MPC are studied, and the compressive strength is strong. The results show that the setting time of MPC gradually extends with the increase of mineral admixture. With the increase of fly ash and slag, the compressive strength remains unchanged and then continues to decrease with the increase of mineral admixture, while the water resistance and corrosion resistance of MPC are followed by minerals. The addition of the admixture increases gradually. When the amount of fly ash is 40%, or the slag content is 20%, it can not only meet the performance requirements of the fast repair material, but also improve the water resistance and corrosion resistance of MPC. After soaking in water and simulated seawater for 60d, the softening coefficient of HPMPC mixed with fly ash and slag and the resistance to the sea can be obtained. The water corrosion coefficient is 0.83~0.81 and 0.97~0.86. respectively, and the addition of mineral admixture can also significantly reduce the preparation cost of MPC. (4) analysis of the microscopic phase and SEM morphology of MPC. (a) analysis of the phase and morphology of the reference MPC microphase. On the basis of the optimum conditions for preparing MPC, the phase composition and Micromorphology of the reference MPC are divided. The results show that the main hydration products of MPC are mgkpo4 6H2O (MKP), and with the prolongation of the age of hydration, the hydration reaction continues with the prolongation of the curing age. Through the analysis of microstructure characteristics, it is found that MPC is in the early hydration (3H) and the hydration products are thick lumpy gelation. After maintaining to 28d, a large number of fine rod like mature MKP crystals are maintained. Analysis of the microstructure and morphology of the mineral admixture (b) doped with mineral admixture HPMPC. The addition of mineral admixtures has a significant effect on the hydration products and microstructure of HPMPC. After adding mineral admixtures, the content of MKP increases with the prolongation of the curing age, indicating that the hydration reaction is continuously carried out. In the early period (3H), a large number of coarse MKP gels were formed. With the prolongation of the age, a large number of fine rod like MKP crystals were formed. In addition, the surface of mineral admixtures had a volcanic ash reaction. (c) mineral admixture HPMPC had a high water resistance and corrosion resistance of the microstructure mechanism. By phase analysis, it is known that with the water and simulated seawater The content of MKP increases gradually, and the hydration reaction of mineral admixture HPMPC is still slow. It is found that the matrix pore is more than that of the base MPC paste specimen after 60 d immersion. And the mineral admixture HPMPC is very dense after soaking 60 d, which is mainly due to the effect of the mineral admixture on the micro aggregate. (5) The growth mechanism of the hydration products was analyzed. (a) the evolution process of the datum MPC hydration products. At the early stage of hydration (3 h), a large number of thick, amorphous magnesium phosphate potassium salt complex hydrogel (MKP gel) was formed. The chemical composition of this MKP gel was magnesium deficiency and phosphorus rich. With the prolongation of the age of hydration, the saturated solution inside the MPC hardened body was extended. In addition, the hydration of Mg2+ continues to enter the chemical structure of the MKP gel, resulting in the gradual crystallization of MKP gels, nucleation and growth of a "mature" fine rod like hydration product MKP crystal. (b) mineral admixture HPMPC hydration product evolution process. In the early hydration (3 h), a large number of MKP gels are formed. After continued hydration to 28 d, a large number of mature MKP crystals In addition, mineral admixtures play a volcanic ash effect, which reacts with the MKP crystal to produce magnesium, potassium, phosphorus, aluminum, silicon gel hydration products (MKPAS gels), covering the mineral admixture surface. (c) reference MPC and mineral admixture HPMPC in water and simulated seawater, the evolution process of hydrated products in water and simulated seawater. The reference MPC is in water. After soaking in the simulated seawater for 60 d, a part of the MKP gel was dissolved and left more pores, resulting in its water resistance and low corrosion resistance to the mineral admixture, and after the addition of mineral admixture, the micro aggregate effect and adsorption effect were also played. The immature MKP gels and MKPAS gels were retained in the matrix, so that the immature MKP gel was soaked with the.MPC. The prolongation of bubble time, gradually nucleation, and mature MKP crystal. Therefore, mineral admixture HPMPC has high water resistance and seawater corrosion resistance. Among them, the water resistance and seawater corrosion resistance of the slag HPMPC are superior to the fly ash HPMPC. The main reason is that the slag itself hydrated to form the C-S-H gel and further enhanced the slag HPMPC. Water resistance and seawater corrosion resistance.

【學(xué)位授予單位】：中國(guó)科學(xué)院研究生院(青海鹽湖研究所)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：TQ172.7
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本文編號(hào)：1797960