Key factors controlling shale oil enrichment in saline lacustrine rift basin:implications from two shale oil wells in Dongpu Depression,Bohai Bay Basin

Comparative analyses of petroleum generation potential,reservoir volume,frackability,and oil mobility were conducted on 102 shale cores from the Dongpu Depression.Results show the shale has high organic matter contents composed of oil-prone type I and type II kerogens within the oil window.Various types of pores and fractures exist in the shale,with a porosity of up to 14.9%.The shale has high brittle mineral contents,extensive fractures,and high potential for oil mobility due to high seepage capacity and overpressure.Although the petroleum generation potential of the shale at Well PS18-8 is relatively greater than that at Well PS18-1,oil content of the latter is greater due to the greater TOC.The porosity and fracture density observed in Well PS18-1 are greater and more conducive to shale oil enrichment.Although the shales in Wells PS18-1 and PS18-8 have similar brittle mineral contents,the former is more favorable for anthropogenic fracturing due to a higher preexisting fracture density.Besides,the shale at Well PS18-1 has a higher seepage capacity and overpressure and therefore a higher oil mobility.The fracture density and overpressure play key roles in shale oil enrichment.

Effect of Nb and V on the continuous cooling transformation of undercooled austenite in Cr–Mo–V steel for brake discs

The increasing speed of trains necessitates the development of brake-disc materials that meet more stringent requirements.Therefore,Nb and V have been added to Cr–Mo–V steel to improve its thermal fatigue performance when used in brake discs.In this paper,the influences of Nb and V on the static continuous cooling transformation(CCT)behaviors of undercooled austenite were studied.The microstructures,hardness,and dislocation densities at different cooling rates and with the addition of different alloying elements were also investigated.The results show that the transformation products of ferrite,granular bainite,lower bainite,and martensite form under different cooling conditions.With increasing Nb and V contents,the CCT curves are shifted to the left,ferrite and bainite transformations are promoted,and the critical cooling rate of total martensite formation is increased.The added V mainly forms V-rich M_8C_7 precipitates and reduces the dissolved C content;therefore,the A_(c1),A_(c3),and M_s-point temperatures increase.Moreover,the stability of retained austenite is also reduced;its content therefore decreases.Compared with V,the effect of added Nb is weaker because of its smaller content.However,the addition of Nb improves the hardness at lower cooling rates because of the precipitation of fine Nb C particles and refining of the microstructure.

Effects of cooling rate and Al on MnS formation in medium-carbon non-quenched and tempered steels

The effect of Al on the morphology of MnS in medium-carbon non-quenched and tempered steel was investigated at three different cooling rates of 0.24, 0.43, and 200°C·s^-1. The formation mechanisms of three types of MnS were elucidated based on phase diagram information combined with crystal growth models. The morphology of MnS is governed by the precipitation mode and the growth conditions. A monotectic reaction and subsequent fast solidification lead to globular Type I MnS. Type II MnS inclusions with different morphological characteristics form as a result of a eutectic reaction followed by the growth in the Fe matrix. Type III MnS presents a divorced eutectic morphology. At the cooling rate of 0.24°C·s^-1, the precipitation of dispersed Type III MnS is significantly enhanced by the addition of 0.044wt% acid-soluble Al（Als）, while Type II MnS clusters prefer to form in steels with either 0.034wt% or 0.052wt% Als. At the relatively higher cooling rates of 200°C·s^-1 and 0.43°C·s^-1, the formation of Type I and Type II MnS inclusions is promoted, and the influence of Al is negligible. The results of this work are expected to be employed in practice to improve the mechanical properties of non-quenched and tempered steels.

As-cast microstructures and solidification paths of the Nb–Si–Ti ternary alloys in Nb_5Si_3–Ti_5Si_3region

Abstract The as-cast microstructures and solidification paths of the Nb-Si-Ti ternary alloys in the NbsSi3-TisSi3 region were investigated. Since there exist some isomor- phous compounds in the NbsSi3-TisSi3 region, such as aNbsSi3 with B3Cr5 prototype, 13NbsSi3 with Si3W5 pro- totype, 7NbsSi3 with MnsSi3 prototype, and TisSi3 with MnsSi3 prototype, the primary solidification areas of these compounds were not typically indentified in previous experiments. In the present paper, the microstructure observation, the phase identification, and the composition measurement were performed using scanning electron microscopy （SEM）, X-ray diffraction （XRD）, and electron probe microanalysis （EPMA）, respectively. No ternary compound is found. There exist three primary solidification areas, 13Nbs_x（Ti）xSi3, ~Nbs_x（Ti）xSi3, and Tis-x（Nb）xSi3 in the NbsSi3-TisSi3 region. Together with the literaturereported experimental data and optimization results, the liquidus projection of the whole Nb-Si-Ti ternary system is constructed, and totally ten primary solidification areas-- diamond-Si, Nb1-x（Ti）xSi2, Ti1-x（Nb）xSi2, Ti1-x（Nb）xSi, Ti5-x（Nb）xSi4, βNb5-x（Ti）xSi3,αNb5-x（Ti）xSi3, Ti5-x （Nb）xSi3, （Nb,Ti）3Si, and BCC--and nine transitional invariant reactions-L ＋ Nb1-x（Ti）xSi2 → Ti1-x（Nb）x Si2 ＋ Si, L ＋ Nb1-x（Ti）xSi2 → Ti1-x（Nb）xSi2 ＋ Ti5- （Nb）xSi4, L ＋ Ti5-x（Nb）xSi4 → Ti1-x（Nb）xSi2 ＋ Ti1-x （Nb）xSi, L ＋ 13Nb5-x（Ti）5Si3→ Nb1-x（Ti）xSi2 ＋ Ti5-x （Nb）xSi4, L ＋ βNb5-x（Ti）xSi3→b5-x（Ti）xSi3 ＋Ti5-x （Nb）xSi4, L ＋ αNb5-x（Ti）αSi3 → Ti5-x（Nb）xSi3 ＋ Ti5-x（Nb）x Si4, L ＋ αNb5-x（Ti）xSi3 →βNb5-x（Ti）xSi3 ＋ Ti5-x（Nb）xSi3, L ＋ βNb5-xTb-xSi3 → Ti5-x（Nb）xSi3 ＋ （Nb,Ti）3Si, and L ＋ （Nb,Ti）3Si → Ti5-x（Nb）xSi3 ＋ BCC are confirmed.

Investigation of the stable and the metastable liquidus miscibility gaps in Fe–Sn and Fe–Cu binary systems

Two kinds of experimental methods were tried in the present work:(i)the powder metallurgy method combined with differential thermal analysis(DTA)to determine the metastable liquidus miscibility gap for a Fe–Cu binary system and(ii)the high-temperature melting method combined with isothermal treatment to determine the stable liquidus miscibility gap for a Fe–Sn binary system.The experimental method was adopted according to the characteristics of the liquidus miscibility gap of the specific system.Using the powder metallurgy method,a uniform microstructure morphology and chemical composition was obtained in the DTA specimen,and the phase-separation temperature of the supercooled metastable liquid was measured.The isothermal treatment was applied for the samples inside the stable liquidus miscibility gap;here,equilibrated compositions were reached,and a layered morphology was formed after rapid cooling.The liquid miscibility gaps of the Fe–Cu and Fe–Sn binary systems were measured,and the peak temperatures of the corresponding miscibility gaps were determined to be about 1417°C at x(Cu)=0.465 at%and 1350°C at x(Sn)=0.487 at%,respectively.On the basis of the experimental results,both the Fe–Cu and the Fe–Sn binary systems were thermodynamically assessed.

Thermodynamic modeling of the Ge-La binary system

The Ge-La binary system was critically assessed by means of the calculation of phase diagram （CALPHAD） technique. The asso- ciate model was used for the liquid phase containing the constituent species Ge, La, Ge3La5, and Ge1.7La. The terminal solid solution diamond-（Ge） with a small solubility of La was described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, μ（Gel.7La）, β（Ge1.7La）, and （GeLa）, were modeled using two sublatrices asα（Ge,La）l.7La, β（Ge,La）l.7La, and （Ge,La）（Ge,La）, respectively. The intermediate phases with no solubility ranges, Ge4Las, GeaLa4, Ge3Las, and GeLa3, were treated as stoichiometric compounds. The three allotropic modifications of La, dhcp-La, fcc-La, and bcc-La, were kept as pure element phases since no solubility of Ge in La was reported. A set of self-consistent thermodynamic parameters of the Ge-La binary system was obtained. The calculation results agree well with the available experimental data from literatures.

Impact of volcanism on the formation and hydrocarbon generation of organic-rich shale in the Jiyang Depression, Bohai Bay Basin, China

Globally,most organic-rich shales are deposited with volcanic ash layers.Volcanic ash,a source for many sedimentary basins,can affect the sedimentary water environment,alter the primary productivity,and preserve the organic matter(OM)through physical,chemical,and biological reactions.With an increasing number of breakthroughs in shale oil exploration in the Bohai Bay Basin in recent years,less attention has been paid to the crucial role of volcanic impact especially its influence on the OM enrichment and hydrocarbon formation.Here,we studied the petrology,mineralogy,and geochemical characteristics of the organic-rich shale in the upper submember of the fourth member(Es_(4)^(1))and the lower submember of the third member(Es_(3)^(3))of the Shahejie Formation,aiming to better understand the volcanic impact on organic-rich shale formation.Our results show that total organic carbon is higher in the upper shale intervals rich in volcanic ash with enriched light rare earth elements and moderate Eu anomalies.This indicates that volcanism promoted OM formation before or after the eruption.The positive correlation between Eu/Eu*and Post-Archean Australian Shale indicates hydrothermal activity before the volcanic eruption.The plane graph of the hydrocarbon-generating intensity(S1+S2)suggests that the heat released by volcanism promoted hydrocarbon generation.Meanwhile,the nutrients carried by volcanic ash promoted biological blooms during Es_(4)^(1 )and Es_(3)^(3) deposition,yielding a high primary productivity.Biological blooms consume large amounts of oxygen and form anoxic environments conducive to the burial and preservation of OM.Therefore,this study helps to further understand the organic-inorganic interactions caused by typical geological events and provides a guide for the next step of shale oil exploration and development in other lacustrine basins in China.

Hydrocarbon expulsion model and resource potential evaluation of high-maturity marine source rocks in deep basins:Example from the Ediacaran microbial dolomite in the Sichuan Basin,China

Hydrocarbon expulsion features and resource potential evaluation of source rocks are crucial for the petroleum exploration.High-maturity marine source rocks have not exhibited a hydrocarbon expulsion mode owing to the lack of low-maturity source rocks in deep petroliferous basins.We considered the Ediacaran microbial dolomite in the Sichuan Basin,the largest high-maturity marine gas layer in China,to exhibit a method that quantitatively characterizes the hydrocarbon expulsion of high-maturity marine source rocks.The experiment of fluid inclusion,rock pyrolysis,and vitrinite reflectance(Ro)of 119 microbial dolomite core samples obtained from the Dengying Formation were performed.A hydrocarbon expulsion model of high-maturity source rock was established,and its resource potential was evaluated.The results showed that the Ediacaran microbial dolomite in the Sichuan Basin is a good source rock showing vast resource potential.The hydrocarbon expulsion threshold is determined to be vitrinite reflectance at 0.92%.The hydrocarbon expulsion intensities in the geologic history is high with maximum of 1.6×10^(7)t/km^(2).The Ediacaran microbial dolomite expelled approximately 1.008×10^(12)t of hydrocarbons,and the recoverable resource was 1.5×10^(12)m^(3).The region can be categorized into areasⅠ,Ⅱ,Ⅲ,andⅣ,in decreasing order of hydrocarbon expulsion intensity.Areas with a higher hydrocarbon expulsion intensity have a lower drilling risk and should be prioritized for exploration in the orderⅠ>Ⅱ>Ⅲ>Ⅳ.Two areas,northern and central parts of Ediacaran in the Sichuan Basin,were selected as prospects which had the drilling priority in the future gas exploration.The production data of 55 drilled wells verified the high reliability of this method.This model in this study does not require low-maturity samples and can be used for evaluating high-maturity marine source rocks,which has broad applicability in deep basins worldwide.

Research progress and challenges of natural gas hydrate resource evaluation in the South China Sea

As an efficient clean energy,natural gas hydrate(NGH)has become a hot topic in recent researches.Since1990 s,China has made great achievements and progress in NGH exploration in the South China Sea(SCS),including determination of the favorable distribution areas and favorable strata thickness,identification of the dual source for accumulation,evaluation of the prospective gas contents,verification of the widespread existence,and confirmation of the technical recoverability of NGH resources.However,there are three major challenges in the NGH studies.First,all the 24 national key and major projects in the SCS focused on trial production engineering and geological engineering in the past 20 years,while 8 of the 10 international NGH research projects focused on resource potential.Second,resource evaluation methods are outdated and some parameter selection are subjective.Third,the existing resource evaluation results are low-level with a great uncertainty,and cannot be used to guide NGH exploration and production or strategic research.To improve the evaluation of NGH resources in the SCS,future researches should focus on four aspects:(1)improve the research on the criterion of the objective existence of NGH and the method of prediction and evaluation;(2)apply new theories and methods from the global NGH research;(3)boost the research on the difference and correlation of the conditions of hydrocarbon migration and accumulation in different basins;(4)innovate the theory and method of NGH resource potential evaluation.

Thermodynamic analysis of the compositional control of inclusions in cutting-wire steel

Data from a thermodynamic database and the calculation software FactSage were used to investigate the phase diagrams of the MnO？CaO？SiO2？Al2O3 system in cutting-wire steel and the effects of oxide components on the low-melting-point （LMP） zone in the cor-responding phase diagrams. Furthermore, the activities of oxide components in the quaternary system at an Al2O3 content of 25wt%were calculated. The contents of dissolved [Al] and [O] in liquid steel in equilibrium with LMP inclusions in the MnO-CaO-SiO2-Al2O3 system were optimized. The results show that the MnO-CaO-SiO2-Al2O3 system possesses the largest LMP zone （below 1400℃） at an Al2O3 content of 25wt%and that the CaO content should be simultaneously controlled in the range of 40wt%to 45wt%. The activities of the oxide components CaO, MnO, and SiO2 should be restricted in the ranges of 0 to 0.05, 0.01 to 0.6, and 0.001 to 0.8, respectively. To obtain LMP inclusions, the [Al] and [O] contents in cutting-wire steel must be controlled within the ranges of 0.5 ×10^-6 to 1.0 ×10^-5 and 3.0 ×10^-6 to 5.0 × 10^-5, respectively.

Kinetics and formation mechanisms of intragranular ferrite in V?N microalloyed 600 MPa high strength rebar steel

To systematically investigate the kinetics and formation mechanisms of intragranular ferrite（IGF）, isothermal heat treatment in the temperature range of 450℃to 600℃ with holding for 30 s to 300 s, analysis of the corresponding microstructures, and observation of the precipitated particles were conducted in V-N microalloyed 600 MPa high strength rebar steel. The potency of V（C,N） for IGF nucleation was also analyzed statistically. The results show that the dominant microstructure transforms from bainite（B） and acicular ferrite（AF） to grain boundary ferrite（GBF）, intragranular polygonal ferrite（IPF）, and pearlite（P） as the isothermal temperature increases from 450℃ to 600℃. When the holding time at 600℃ is extended from 30 s to 60 s, 120 s, and 300 s, the GBF content ranges from 6.0vol% to 6.5vol% and the IPF content increases from 0.5vol% to 2.8vol%, 13.1vol%, and 13.5vol%, respectively, because the ferrite transformation preferentially occurs at the grain boundaries and then occurs at the austenite grains. Notably, V（C,N） particles are the most effective nucleation site for the formation of IPF, accounting for 51% of the said formation.

Carbide Evolution in High Molybdenum Nb-microalloyed H13 Steel during Annealing Process

Based on the Thermo-Calc thermodynamic software, the type of equilibrium precipitated carbides and their contents in high Mo Nb-microalloyed H13 steel （NMH13 steel） were calculated. The composition, morphology, and distribution of carbides after spheroidal annealing of two forged experimental steels were comparatively examined by means of optical microscopy （OM）, scanning electron microscopy （SEM）, electron dispersive spectroscopy （EDS） and transmission electron microscopy （TEM）. VC, M23 C6 and M6C are identified in H13 steel after spheroidizing annealing, while （V,Nb）C, M23C6 , M2C and M6C are observed in NMH13 steel. Moreover, it is found that the ad- dition of Nb significantly enhances the stability of MC phase and the high Mo content accelerates the precipitation of small rod-shape M2C phase in NMH13 steel. The amount of the fine carbides in NMH13 steel obviously increased with M2 C and M6 C precipitated from the ferrite phase, which is in accordance with the results of thermodynamic cal- culations.

Phase stability of Fe_(23)Zr_(6)and thermodynamic reassessment of Fe-Zr system

The stability of the Fe_(23)Zr_(6)phase in Fe–Zr system was studied,and the partial Fe–Zr phase diagram was revised by means of X-ray diffraction,electron probe microanalysis and differential thermal analysis methods.On the basis of the experimental results in the present work and literature,the Fe–Zr system was reassessed using CALculation of PHAse Diagram(CALPHAD)method.Solution phases,liquid,fcc,bcc and hcp,are modeled as the substitutional solution.The intermetallic compounds,hex.-Fe_(2)Zr,Fe_(2)Zr,FeZr_(2)and FeZr3 phases,are treated as Fe_(2)(Fe,Zr)1,(Fe,Zr)2(Fe,Zr)1,(Fe,Zr)1Zr_(2)and(Fe,Zr)1(Fe,Zr)3 by a two-sublattice model,respectively.The Fe_(23)Zr_(6)phase is treated as stoichiometric compound.A set of self-consistent thermodynamic parameters of the Fe–Zr system was obtained.The results confirm the stability of Fe_(23)Zr_(6)phase,improve the phase diagram of the Fe–Zr system and provide a theoretical reference for the development of Zr alloys.

Formation and capturing of nanoparticles in Cu-1wt.%Fe alloy melt during directional solidification process

A single crystal Cu-1wt.%Fe alloy with finely dispersed iron-rich nanoparticles which keep coherent interface with the copper matrix was prepared under directional solidification.Formation of nanoparticles in the alloy melt was investigated by performing differential scanning calorimeter tests and designed water quenching experiment at a certain temperature.Results show that iron-rich nanoparticles are formed in the Cu-1wt.%Fe alloy melt before primaryα-Cu forms,which is not consistent with equilibrium phase diagram.Mechanism that iron-rich nanoparticles are uniformly captured in the matrix was described,which is that numerous nanoparticles follow Brownian motions and are engulfed in the solidified matrix which makes it possible to form uniformly distributed nanoparticles reinforced single crystal Cu-1wt.%Fe alloy.

Effect of yttrium treatment on alumina inclusions in high carbon steel

Aluminum oxide inclusions in SWRS82B steel seriously affect the drawing performance of steel strands.The effects of different addition amounts of yttrium(within the range of 0%–0.026%)on the composition,morphology,size and spacing of aluminum oxide inclusions were studied by scanning electron microscopy and energy spectrum analysis.Based on classical thermodynamics and FactSage software,the predominance diagram of inclusions in Fe–O–S–Y system and the effect of the addition of rare earth yttrium on the stability of alumina inclusions were calculated.The results showed that molten steel was modified by adding the rare earth element yttrium.It can be inferred that the approximate route of target inclusion modification was:Al_(2)O_(3)→Y_(2)S_(3)+YAlO_(3)+Al_(2)O_(3)→Y_(2)S_(3)+YAlO_(3)+Y_(2)O_(2)S+YAlO_(3)+Al_(2)O_(3)→Y_(2)S_(3)+Y_(2)O_(2)S.The experimental samples with 0.026%added yttrium had the best inclusion characteristics,in which the inclusion surface density distribution was uniform,and the interfacial distance between inclusions was mainly in the range of 100–500μm.After modification,the average inclusion size in molten steel was reduced by 6.9–8.6μm.The mechanism of yttrium modification was discussed based on actual calculation results and experimental results.