刚性聚合物稀溶液流变性质的计算 Ⅰ.定常流动

本文采用多棒刚杆分子模型,用Galerkin法计算了聚合物稀溶液在定常剪切流、平面拉伸流、单轴拉伸流、单轴拉伸与剪切流相组合的复杂流动的流变学性质。计算结果表明,多棒刚杆分子模型有希望成为描述聚合物稀溶液流变性质的较为完善的分子模型。本文的研究不仅可使人们用分子模型来代替连续介质本构方程进行粘弹性流体复杂流动的数值模拟,而且也为探讨描述聚合物浓溶液的分子模型提供了一种新的途径。     

不同类型聚合物溶液对采油残余油的作用机理研究

通过实验测定了HPAM溶液和黄原胶溶液的流变性、在多孔介质中的流变性和残余阻力系数 ,计算了衰竭层效应 .用不同的浓度和注入速度进行了驱油实验 .提出聚合物分子缠结作用的增强不仅引起表观粘度增加或衰竭层厚度降低 ,而且使平行于油水界面的拉动残余油的力增加 ,从而使残余油饱和度降低 ,采收率提高 .随浓度增加 ,HPAM溶液的表观粘度和残余阻力系数增加 ,衰竭层厚度减小 ;黄原胶溶液的浓度高于缠结浓度时 ,衰竭层厚度和表观粘度变化不大 .注入速度增加时 ,两种聚合物溶液的衰竭层厚度均降低 ,HPAM溶液的残余阻力系数不变 ,粘弹性增加 ;而黄原胶溶液的残余阻力系数下降 .不同浓度和注入速度情况下两种聚合物溶液的驱油结果证实了文中提出的聚合物分子缠结作用和衰竭层效应对残余油的作用机理 .分子结构的不同是造成两种聚合物溶液在多孔介质中渗流规律和对残余油作用机理的差别的根本原因 .     

疏水基含量和微嵌段长度对缔合聚合物溶液弹性的影响

研究了疏水基含量和微嵌段长度对缔合聚合物,聚(丙烯酰胺-丙烯酸钠-十六烷基二甲基烯丙基氯化铵)[P(AM-NaAA-C16DMAAC)],弹性行为的影响规律。研究结果表明,对于结构类似且具有相近零剪切粘度的缔合聚合物,疏水基含量越高,聚合物分子链间形成稠密网络结构的疏水缔合能力越强,其第一法向应力差N1越大,N1出现拐点处对应剪切速率越小,缔合聚合物溶液弹性越好;并且缔合聚合物溶液的弹性随着疏水微嵌段长度的增加先增加后降低,存在最佳微嵌段长度。因此,可以通过调整分子结构有效改变缔合聚合物溶液的弹性行为。     

耐温抗盐驱油聚合物溶液黏弹性

对3种不同结构类型的耐温抗盐驱油聚合物〔高分子量聚丙烯酰胺(HPAM)、磺化聚丙烯酰胺(S-HPAM)和疏水缔合聚丙烯酰胺(A-HPAM)〕的溶液黏弹性能进行了研究。在温度85℃下,通过稳态剪切和动态剪切试验,考察了质量浓度和矿化度对聚合物溶液黏弹性的影响。结果表明,随剪切速率增加,溶液表观黏度逐渐降低。质量浓度越高,溶液的储能模量(G')和损耗模量(G″)越大。由动态剪切实验数据,计算得到第一法向应力差(N1)。随质量浓度增加,聚合物溶液的N1逐渐增大;随矿化度增加,聚合物溶液的N1出现不同盐敏感区域,说明不同结构类型的驱油聚合物溶液对矿化度的弹性响应不同。研究结果为高温高盐油藏聚合物驱剂的选择及开发提供了理论参考。     

小分子表面活性剂作为牺牲剂降低聚合物吸附损失的研究

研究了利用小分子表面活性剂作为牺牲剂来降低聚合物在近井地带吸附量的方法,考察了小分子阳离子CA-1、小分子醇PEG10000和小分子阴离子木质素磺酸钠作为牺牲剂在石英砂上的吸附规律及其对聚合物静态吸附量的影响;利用岩心驱替实验研究了牺牲剂注入方式对聚合物动态吸附滞留量、注入压力及阻力系数的影响。实验结果表明,CA-1、PEG10000及木质素磺酸钠分别可以在50mg·L~(-1)、1 500 mg·L~(-1)、5 000mg·L~(-1)的浓度下使聚合物的静态吸附量分别降低40.5%,36.2%及30.5%。CA-1作为前置段塞注入后能够使聚合物动态吸附量降低30.1%,阻力系数降低了69.7%,能够满足降低聚合物在近井地带吸附滞留量及降低近井地带注入压力的要求,为确保配注量、使聚合物能够进入地层深部发挥驱油效果提供了一种便捷低成本方的方法。     

冷态模型系统模拟介质糖浆溶液粘弹性的分析

利用旋转流变仪和毛细管流变仪研究了不同葡萄糖浆溶液的粘弹性,结果表明:不同除水量的糖浆溶液的零剪切粘度(η0)呈现指数增长规律;不同PAM添加量对糖浆溶液的储能模量(G′)和损耗模量(G″)影响较大,且对G′的影响较为显著;随着PAM(聚丙烯酰胺)含量的增加,松弛时间和挤出胀大比(B)逐渐增大,糖浆溶液弹性越来越明显;其它条件相同,零剪切粘度越大,糖浆溶液的弹性效应越明显;糖浆溶液在20~80℃温度范围内粘度可逆,温度对糖浆溶液粘度的影响非常显著,且粘度变化相差可达1000倍。     

黏弹性聚合物溶液在突扩孔道内的流动特性

采用上随体Maxwell本构方程,描述油藏条件下以第一法向应力差为主要特征的聚合物溶液的流变性.利用有限体积法对黏弹性聚合物溶液在突扩孔道内的流动特征进行数值模拟.绘制了流函数和速度的等值线图.研究了黏弹性的变化对微观波及效率的影响.数值模拟结果表明,聚合物溶液的黏弹性是影响波及效率的主要因素.凹角处的流动区域随着弹性的增加在不断增大,因此滞留区域不断减小,微观波及效率不断增大.具有黏弹特性的聚合物溶液相比于纯黏性的牛顿流体更利于提高驱油效率.这一结论有助于驱油工业上聚合物溶液的设计和优选.     

水解聚丙烯酰胺溶液粘弹特性的研究

通过锥板测量系统对水解聚丙烯酰胺(HPAM)溶液的粘弹性进行了研究.结果表明, 这种锥板测量系统能较灵敏地检测出溶液粘弹性结构的存在,并得到了聚合物溶液的弹性成份和粘性成份的关系.发现随着HPAM溶液浓度的增大,聚合物溶液的弹性成份起初迅速增大,随后增大的趋势变慢而趋于平缓,在经历一最大值后又略有下降.在剪切速率ṝ =0.36 s－1下,超高分子量的HPAM(M=1.65×107)溶液(c = 1.5 g·L－1)具有明显的粘弹特性;随着盐的加入,溶液的粘弹性下降,当盐浓度达到一定值的时候,溶液内部的网络结构遭到破坏,其弹性行为完全消失.对于聚丙烯酰胺(PAAM, M=2.0×105)溶液(c = 2.0 g·L－1)在剪切速率(ṝ=0.36～1.36 s－1)范围内没有观察到粘弹行为,只在ṝ≥1.65 s－1时,才能观察到微弱的粘弹现象.     

聚合物微球调驱剂的制备及其在多孔介质中的微观渗流规律

采用反相微乳液法/乳液法制备了聚合物微球调驱剂，并在微流控芯片中进行了物模实验评价及模拟，分析了聚合物微球调驱剂在岩石孔隙中的输运机理。结果表明：多孔介质的孔隙大于聚合物微球调驱剂直径时，大量微球在微通道中的运移会增加流动阻力及近壁面区域的剪切力；多孔介质的孔隙略大于聚合物微球调驱剂直径时，多个聚合物微球一同进入；在随机生成的多孔介质结构中，微球大颗粒的通过能够导致更大的压力波动，但微球数量越多，滞留情况越严重。     

剪切作用对功能聚合物微观结构性能的影响研究

梳型聚合物和活性聚合物是目前常用驱油聚合物,其增黏性和黏弹性是评价其驱油能力的重要指标.为考察剪切作用对两种聚合物溶液性能的影响,分别研究了梳型聚合物和活性聚合物溶液经过模拟炮眼剪切前后的宏观和微观性能变化.结果表明,在高速剪切、拉伸应力作用下,梳型聚合物黏度损失率为40.73%,活性聚合物黏度损失率为70.10%;当剪切频率为0.02 Hz时,梳型聚合物界面扩张弹性降低了19.03%,而活性聚合物界面扩张弹性降低了68.03%;相比活性聚合物,梳型聚合物紧密的空间网状结构虽被部分破坏,但仍有疏松的网络结构,且以聚集体的形式紧密地分散在溶液中,通过DLS及AFM测定表明其粒径尺寸稍有变小;可见梳型聚合物抗剪切能力较活性聚合物强.     

黏弹性对介观液珠聚并的影响——液珠-细丝-液珠聚并现象及其分析

在四辊流变仪中,黏弹性高分子介观液滴经反复拉伸和松弛形成了有细丝相连的两个黏弹液珠,研究了黏弹液珠的聚并过程,依形状叫做BSB(bead-string-bead,液珠-细丝-液珠)聚并.BSB现象与常见的通过滴间液膜破裂实现的液滴聚并过程大不相同.根据界面上的Laplace力、液珠移动时的黏性阻力和细丝中黏弹应力之间的平衡,推导出一个力学模型来描述BSB现象,理论分析与实验结果相符较好.细丝直径的变化和稳定性由过程参数和物料参数共同决定,尤其是液滴的黏弹性有较大影响.这一效应对多相高分子与复杂流体加工过程的基础理解富有启发.     

Flow pattern maps for particle-fluid mixture transport in a horizontal pipe - application of a three-layer model

A modified three-layer model was applied to model particle-fluid mixture flow in a horizontal pipe, the viscoelastic properties of carrier polymer solution were taken into consideration, and the Deborah number was used to calculate solid-fluid friction factor. An energy equation was applied to determine temperature distribution of carrier fluid along a horizontal pipe to accurately represent the rheological properties of carrier fluid. During the transport process, particles quickly settle out of carrier fluid and accumulate on pipe bottom forming a particle bed, so a particle bed load flow is observed. The transport mechanisms of particles in moving particle bed are govern by fluidization, which causes the height of this layer to be small and equal to 2～5 times of particle diameter. In addition, the pressure drop is composed of solid-fluid and solid-solid friction loss, which dominate the hydrodynamic performance at different stages.     

A numerical study on viscoelastic droplet migration on a solid substrate due to wettability gradient

This study investigates the viscoelastic effects on droplet migration induced by a wettability gradient on a rigid substrate by a numerical simulation based on OpenFOAM with the volume‐of‐fluid method. The droplets are set with different rheological properties to investigate the effect of the elastic parameters. The Oldroyd‐B model was employed. Quantitative differences in the migration and deformation between Newtonian and viscoelastic droplets were investigated by changing the degree of elasticity. The droplet migration shows conspicuously higher mobility for high elasticity, especially during the accelerating period. Moreover, the displacement and velocity increased with the decrease of a viscoelasticity parameter, and the velocity enhancement was regulated by the elastic instability shown at a high Weissenberg number. In addition, the velocity of the droplet changes more significantly over the range of contact angles of 130° to 60° compared to other wettability‐gradient surfaces.     

Shear-thickening flow of nanoparticle suspensions flocculated by polymer bridging

The steady-shear viscosity, dynamic viscoelasticity, and stress relaxation behavior were measured for suspensions of silica nanoparticles dispersed in aqueous solutions of poly(ethylene oxide) (PEO). The suspensions of silica with diameters of 8-25 nm show striking shear-thickening profiles in steady shear and highly elastic responses under large strains in oscillatory shear. Since the silica particles are much smaller than the polymer coils, one molecule can extend through several particles by intrachain bridging. Each polymer coil may remain isolated as a floc unit and the silica particles hardly connect two flocs. Therefore, the flow of suspensions is Newtonian with low viscosity at low shear rates. When the polymer coils containing several nanoparticles are subjected to high shear fields, three-dimensional network is developed over the system. The shear-thickening flow may arise from the elastic forces of extended bridges. But, the polymer chain is easily detached from particle surface by thermal energy because of large curvature of particles. As a result, the network structures are reversibly broken down in a quiescent state and the suspensions behaves as viscoelastic fluids with the zero-shear viscosity.     

A new instrument for measuring the viscoelastic properties of dilute polymer solutions

A new oscillating capillary viscometer has been developed and used for measuring viscoelastic flow properties of dilute polymer solutions. These flow properties are determined from measurements of the pressure to volume flow relationships for sinusoidal flow in cylindrical glass capillaries. The theory for this measurement procedure is based upon the known theory for oscillatory flow of a viscoelastic fluid in circular tubes and which is presented with a few supplementations in this paper.The oscillatory flow is generated by a piezoelectric driver which is dipped directly into the aqueous solution. The advantage of this driver is that the excitation voltage for the piston is a direct measure of the motion of the piston. Changes in pressure are measured with a sensitive low-pressure quartz tranducer.The viscometer was tested with aqueous glycerol solutions and a gelatin gel. The viscoelastic flow properties of dilute polymer solutions (gelatin, gelatin/color-coupler, polyacrylamide) were then investigated in the frequency range 5 Hz to 150 Hz at very small volume flow amplitudes. The results presented illustrate the suitability of the method. The results are also evaluated with regard to the stabilizing action of slightly viscoelastic gelatinous coating liquids in the high-speed coating process in the manufacture of photographic materials.     

Gel kinetic characteristics and creep behavior of polymer microspheres based on bulk gel

Abstract

Deep profile control technology of polymer microspheres has become a widely used new method in improving oil recovery in heterogeneous reservoirs. The viscoelastic property of polymer microspheres plays an important role in the deformable migration behavior. In this study, a new method of measuring the viscoelastic properties of polymer microspheres based on bulk gel was proposed. Using mechanical rheometer and microrheometer, the effects on the storage modulus and gel performance were systematically researched. The creep-recovery test was applied to characterize the creep behavior of different polymer microsphere bulk gel. The results show that the storage modulus of polymer microspheres could be controlled by adjusting the agent concentration in the synthetic reaction. Moreover, the kinetic equation of gel time of polymer microspheres bulk gel and reaction temperature was established: ln(GT)?=?3289.18(1/T)-9.33. Elastic strain index was put forward as a new parameter to characterize the viscoelasticity of polymer microsphere in creep-recovery test. Finally, relationship between elastic strain index and storage modulus was constructed and a classification criterion of polymer microspheres with different viscoelasticity was proposed based on a large number of creep-recovery results. The research could provide a good theoretical guidance and technical support for the understanding of viscoelasticity of polymer microspheres.     

小形变时杨氏模量等于三倍的剪切模量

尽管高聚物是黏弹性材料,具有时间依赖性和温度依赖性,但在小形变时,弹性理论中的一些假定和定理仍能用来讨论黏弹性高聚物的形变。应力与应变之比是模量,在小形变时,单向拉伸的杨氏模量约等于三倍的剪切模量,E≈3G。     

Flow behaviors of a viscoelastic polymer solution at 3D micro pore-throat structure

Polymers are abundantly used in oil production industry, especially in enhanced oil recovery process. The underground oil reservoir is a kind of porous media where complex microscopic geometries lead to strong shearing and extensional components. This research focuses on a novel method used to investigate the flow behaviors of hydrolyzed polyacrylamide solution at a micro pore-throat structure with a comparison with Newtonian flow of water. For polymer solution, the flow velocimetry revealed the viscoelastic flow has two main characters compared with Newtonian fluid. First, the instability or non-linearity of polymer flows led to bending and distorted streamlines. The instability of the flow is mainly caused by the growth of high stress generated in the viscoelastic polymer fluid as it accelerates and decelerates into and out from the narrow throat, respectively speaking. The second character is the back-streams at the outlet of the throat.     

Effect of temperature on dynamic rheological behavior of discontinuous cubic liquid crystal

The dynamic rheological properties of discontinuous cubic liquid crystal, formed by nonionic surfactant C(12-14)E(12), were investigated in the discrete and continuous patterns of raising temperature. In the discrete pattern, the discontinuous cubic phase appears in two types of viscoelastic behaviors under the melting points of cubic phase: elastic gel and viscoelastic liquid. When the discontinuous cubic phase begins to melt, it has the weak polymer-like viscoelasticity. Temperature and shear frequency have completely different effects on the ratio of viscous and elastic components of samples in these three states. At low temperature, the samples dominate in elasticity and temperature and shear frequency has hardly any effect on viscoelasticity. At moderate temperature, its ratio of viscous and elastic components increases with increasing temperature and decreasing shear frequency. At the vicinity of the melting point of cubic liquid crystal, the cubic liquid crystal appears to have almost equaled viscous and elastic component; shear has obvious effect on the ratio of viscoelasticity at low frequency. The results from the continuous pattern of raising temperature are consistent with those from the discrete pattern.