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Grain growth kinetics of dolomite, magnesite and calcite: A comparative study

机译:白云石,菱镁矿和方解石的晶粒生长动力学:比较研究

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The rates of grain growth of stoichiometric dolomite [CaMg(CO3)2] and magnesite (MgCO3) have been measured at temperatures T of 700-800°C at a confining pressure Pc of 300 MPa, and compared with growth rates of calcite (CaCO3). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO3)2, MgCO3, and CaCO3, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO3)2, MgCO3, and CaCO3, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (?5 × 10-5 μm3/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.
机译:在700℃的围压Pc下,在700-800°C的温度T下测量了化学计量的白云石[CaMg(CO3)2]和菱镁矿(MgCO3)的晶粒生长速率,并将其与方解石(CaCO3 )。通过热等静压(HIP)从高纯度粉末中合成出三种碳酸盐的干燥,细颗粒的聚集体。对于CaMg(CO3)2,MgCO3和CaCO3,HIP合成碳酸盐的初始平均粒径分别为1.4、1.1和17μm,孔隙率为2、28和0.04%(体积)。在随后的等静压退火过程中,所有碳酸盐的晶粒尺寸均发生了粗化,CaMg(CO3)2,MgCO3和CaCO3的平均值在1周内分别达到3.9、5.1和27μm。白云石的晶粒生长比菱镁矿或方解石的生长速度慢得多。假设所有三种碳酸盐的晶粒长大正常且n = 3,则在T = 800°C时白云石的速率常数K(?5×10-5μm3/ s)比菱镁矿的速率常数K低约30倍。比方解石要高三个数量级。碳酸盐晶粒生长的变化可能会受到阳离子组成和晶界孔密度的降低(降低晶界迁移率)的影响。但是,粗化率与固溶程度最相关。对于方解石,K是最大的方解石,其中镁被Ca广泛取代,而对于固溶体可以忽略不计的白云石,K最小。次生相可能在前进的白云石晶界处成核,这对碳酸盐的变形过程,流变学和反应动力学具有影响。

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