本文關(guān)鍵詞：貝利特—硫鋁酸鋇鈣水泥熟料形成機(jī)制及形成動力學(xué)　出處：《濟(jì)南大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

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【摘要】：貝利特-硫鋁酸鋇鈣水泥是一種新型膠凝材料。與傳統(tǒng)硅酸鹽水泥相比，水化產(chǎn)物中Ca(OH)2含成量低，耐久性好；體積穩(wěn)定性好；長期穩(wěn)定增長；水泥水化熱較低；同時該水泥燒成溫度低，能耗低，可使用熱值低的燃料；水泥熟料的石灰飽和系數(shù)低，可使用低品質(zhì)石灰石。為了有效控制該新型水泥熟料的生產(chǎn)工藝，調(diào)控熟料體系的礦相組成和性能，必須研究該新型水泥熟料體系中熟料礦相的形成機(jī)制及形成動力學(xué)。本文系統(tǒng)研究和分析了該水泥熟料礦相形成機(jī)制，建立該水泥熟料體系的形成動力學(xué)模型，為工程應(yīng)用提供理論和技術(shù)指導(dǎo)。主要結(jié)論如下： BaO、BaSO4和CaF2均能夠促進(jìn)貝利特礦物的形成，其晶型主要為β-C2S和γ-C2S，對穩(wěn)定β-C2S有重要作用；當(dāng)BaSO4和BaO摻量分別為3.0%和5.0%時，還能形成少量高水化活性α'-C2S；純貝利特礦物的形成活化能為206kJ·mol-1，摻雜0.6%CaF2后形成活化能降為164kJ·mol-1，因此，少量CaF2可降低貝利特礦物形成勢壘。 當(dāng)煅燒溫度為1450℃時，摻雜BaSO4后阿利特主要晶型為M3-C3S，且存在少量的T3-C3S、R3-C3S和T1-C3S；隨著BaSO4摻量的增加，試樣中阿利特礦物含量降低，表明BaSO4不利于阿利特礦物形成。CaF2能夠促進(jìn)阿利特礦物的形成，當(dāng)煅燒溫度為1380℃時，阿利特主要晶型為M3-C3S、T3-C3S和R3-C3S；隨著CaF2摻量的增加，M3-C3S含量增加，T3-C3S和R3-C3S含量變化不大。 C2.75B1.25A3S礦物開始形成的溫度為1100℃，大量形成溫度為1350℃，分解溫度為1370℃。其形成的化學(xué)反應(yīng)方程為： 11/4CA+BaSO4+1/4Al2O3+1/4BaO→C2.75B1.25A3S 11/48C12A7+BaSO4+67/48Al2O3+1/4BaO→C2.75B1.25A3S 1/4CaO+BaSO4+3Al2O3+1/4BaO→C2.75B1.25A3S 11/48C12A7+BaSO4+1/4BA+55/48Al2O3→C2.75B1.25A3SC2.75B1.25A3S礦物的形成受擴(kuò)散機(jī)制的控制，符合的動力學(xué)模型為：D4=1-2α/3-(1-α)2/3。在1100-1300℃溫度范圍內(nèi)，C2.75B1.25A3S礦物形成的反應(yīng)活化能為227.5kJ·mol-1；在1300-1380℃溫度范圍內(nèi)， C2.75B1.25A3S礦物形成的反應(yīng)活化能為175.9kJ·mol-1。C2.75B1.25A3S礦物的分解受界面化學(xué)反應(yīng)的控制，符合的動力學(xué)模型為：R2=1-(1-α)1/3，分解活化能為449.78kJ·mol-1；主要分解產(chǎn)物為C3A、BA和SO3。 在C2S-C2.75B1.25A3S系統(tǒng)中，鋇、硫元素的存在使貝利特礦物的形成得到促進(jìn)，其晶型主要為β-C2S；在1300-1350℃的溫度范圍內(nèi)，貝利特礦物的存在為C2.75B1.25A3S礦物的形成提供了表面，降低了C2.75B1.25A3S礦物的形核勢壘，促進(jìn)了該礦物的大量形成，而且使其在高溫階段分解受到抑制。在C3A/C4AF-C2.75B1.25A3S系統(tǒng)中，當(dāng)煅燒溫度為1350℃和1380℃時，高鐵含量的中間相能夠促進(jìn)C2.75B1.25A3S礦物的形成，，當(dāng)中間相含量為16%時，能夠促進(jìn)C2.75B1.25A3S礦物的形成；此外，中間相粘度和含量對C2.75B1.25A3S礦物的生長發(fā)育有重要影響。 在水泥熟料中，MgO能夠促進(jìn)f-CaO的吸收，促進(jìn)阿利特礦物和白色中間相的形成。當(dāng)煅燒溫度為1380℃，并且MgO摻量為1.0%時，貝利特礦物有分解的跡象，此時形成的阿利特礦物尺寸較小；當(dāng)MgO摻量為3.0%-5.0%時，阿利特礦物的尺寸不均勻，且存在大尺寸礦物；當(dāng)MgO摻量為7.0%時，貝利特-硫鋁酸鋇鈣水泥熟料的安定性不良，這主要是因為形成了MgO礦巢。CaF2能夠很好地促進(jìn)水泥熟料形成，水泥熟料的形成符合的動力學(xué)模型為D4=1-2α/3-(1-α)2/3，摻雜0.6%CaF2的水泥熟料的形成活化能為195kJ·mol-1，比未摻水泥熟料形成活化能（250kJ·mol-1）降低了55kJ·mol-1。
[Abstract]:Baillet Calcium Barium Sulphoaluminate Cement is a new cementing material. Compared with the traditional Portland cement, hydration products Ca (OH) 2 with low amount, good durability; good volume stability; long-term stable growth; low hydration heat cement; the cement with low sintering temperature and low energy consumption and can use the low calorific value fuel; cement lime saturation coefficient is low, can use low quality limestone. In order to effectively control the production process of cement clinker, the clinker control system of mineral phase composition and properties, must study the formation mechanism and the formation of clinker mineral phases of the new cement clinker system. This paper studies and analyzes the formation mechanism of the cement clinker minerals, establish the dynamics model of formation of cement clinker system, provide theoretical and technical guidance for the engineering application. The main conclusions are as follows:
BaO, BaSO4 and CaF2 could promote the formation of Baillet minerals, the crystal type is mainly -C2S beta and gamma -C2S, has an important effect on the stability of beta -C2S; when the BaSO4 and BaO content is 3% and 5% respectively, but also the formation of a small amount of high hydration activity of alpha'-C2S; the formation of pure mineral Baillet activation energy is 206kJ mol-1, after 0.6%CaF2 doping formation activation energy reduced to 164kJ and mol-1, therefore, a small amount of CaF2 can reduce the formation of mineral Baillet barrier.
When the calcination temperature is 1450 degrees centigrade, after doping BaSO4 Alite main crystal type is M3-C3S, and there is a small amount of T3-C3S, R3-C3S and T1-C3S; with the increase of BaSO4 content, reduce the content of mineral samples showed that BaSO4 Alite, Alite is not conducive to the formation of minerals.CaF2 can promote the formation of Alite minerals, when the calcination temperature is 1380 DEG C Alite, the main crystal type of M3-C3S, T3-C3S and R3-C3S; with the increase of CaF2 content, M3-C3S content increased, T3-C3S and R3-C3S content changes little.
The temperature of the C2.75B1.25A3S mineral is 1100 C, the temperature is 1350 C and the decomposition temperature is 1370. The chemical reaction equation of the formation is as follows:
11/4CA+BaSO4+1/4Al2O3+1/4BaO - C2.75B1.25A3S
11/48C12A7+BaSO4+67/48Al2O3+1/4BaO - C2.75B1.25A3S
1/4CaO+BaSO4+3Al2O3+1/4BaO - C2.75B1.25A3S
The formation of 11/48C12A7+BaSO4+1/4BA+55/48Al2O3 and C2.75B1.25A3SC2.75B1.25A3S minerals by diffusion mechanism control with dynamic model is: D4=1-2 /3- alpha (1- alpha) 2/3. at 1100-1300 DEG C temperature range, C2.75B1.25A3S mineral formation reaction activation energy is 227.5kJ mol-1; 1300-1380 degrees in the temperature range of C2.75B1.25A3S mineral formation reaction activation energy is controlled by interface decomposition the chemical reactions of 175.9kJ mol-1.C2.75B1.25A3S minerals, with dynamic model is: R2=1- (1-) 1/3, the decomposition activation energy of 449.78kJ - mol-1; the main decomposition products of C3A, BA and SO3.
In the C2S-C2.75B1.25A3S system, barium, sulfur elements to form Baillet minerals can promote the crystal type mainly for beta -C2S; in the temperature range of 1300-1350 DEG C, Baillet minerals provides a surface for the formation of C2.75B1.25A3S minerals, reduced C2.75B1.25A3S mineral nucleation barrier and promote a large number of the mineral formation but, in the high temperature stage decomposition was inhibited. In C3A/C4AF-C2.75B1.25A3S system, when the calcination temperature is 1350 DEG and 1380 DEG C, intermediate high iron content which can promote the formation of C2.75B1.25A3S minerals, when the mesophase content is 16%, C2.75B1.25A3S can promote the formation of minerals; in addition, the intermediate phase viscosity and content are important effect on the growth and development of C2.75B1.25A3S mineral growth.
In the cement clinker, MgO can promote the absorption of f-CaO, promote the alite and white mesophase formation. When the calcination temperature is 1380 DEG C, and the content of MgO is 1%, there are signs of Baillet mineral decomposition, alite small size formed at this time; when the dosage of MgO is 3.0%-5.0%, the size of Alite not even, and there are large size minerals; when the dosage of MgO is 7%, Baillet Calcium Barium Sulphoaluminate Cement Clinker poor stability, this is mainly because of the formation of MgO nest.CaF2 can promote the formation of cement clinker formation, clinker dynamics model with D4=1-2 /3- (alpha 1- a) 2/3, formation of cement clinker doped 0.6%CaF2 the activation energy is 195kJ - mol-1, the activation energy than those of cement clinker formation (250kJ mol-1) - mol-1. reduced 55kJ

【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2014
【分類號】：TQ172.1

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