盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白,用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDSPAGE)确定为Ⅰ型胶原;红外及紫外光谱表明胶原分子中存在三螺旋结构.分别采用小幅振荡剪切法、恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响.研究表明,随盐酸胍浓度的增大及作用时间的延长,盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体.在所研究的盐酸胍浓度范围(0~6.0 mol/L)内,盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变;随盐酸胍作用时间的延长(6~48 h),盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变.本文的研究结果有助于加深对触变性产生机理的认识.     

盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白, 用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)确定为Ⅰ型胶原; 红外及紫外光谱表明胶原分子中存在三螺旋结构. 分别采用小幅振荡剪切法、 恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响. 研究表明, 随盐酸胍浓度的增大及作用时间的延长, 盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体. 在所研究的盐酸胍浓度范围(0~6.0 mol/L)内, 盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变; 随盐酸胍作用时间的延长(6~48 h), 盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变. 本文的研究结果有助于加深对触变性产生机理的认识.     

纳米埃洛石管对HPAM性能的影响

采用油酸改性纳米埃洛石管(HNTs)将部分水解聚丙烯酰胺(HPAM)与改性HNTs(O-HNTs)共混制备一种稳定的分散体系HPAM/O-HNTs。采用红外和接触角对O-HNTs的化学结构进行表征,并系统考察HPAM/O-HNTs的增黏性、耐温耐盐性、抗剪切性和驱油效果。结果表明：O-HNTs分子链中含有长烷基链、双键等疏水基团,具有疏水作用。加入O-HNTs后,HPAM/O-HNTs黏度明显提高,表现为优异的增黏性。HPAM/O-HNTs在30～90℃的NaCl(0～12000 mg·L^-1)和CaCl₂(0～12000 mg·L^-1)溶液中的黏度均比HPAM高,表现出优异的耐温抗盐性能。90℃条件下,随着剪切速率增大,HPAM/O-HNTs黏度逐渐减小。500 r·s^-1条件下溶液黏度大于17.2 mPa䦆Wingdings 2VB@s,表现出优异的抗剪切性能。在相同条件下,HPAM/O-HNTs的驱油采收率比HPAM高12.3%,驱油效果显著。     

明胶微球粒径控制的研究

采用乳化-凝聚法,在油包水(w/o)的体系中对明胶微球(GMs)粒径、微球的形态和分散性等进行了研究.扫描电子显微镜(SEM)和粒径分布曲线的结果表明在乳化体系中,提高明胶溶液的浓度或水油比例,明胶微球的粒径增大;增加乳化剂的用量,微球的粒径减小;选择合适的乳化时间和搅拌速率,可以改善微球的分散性和表面光滑程度.同时,通过调控实验条件,在明胶溶液浓度0.100 g/mL,水油比1/5,乳化剂浓度0.05g/mL时研制出了平均粒径为3.58μm的表面光滑、分散性好的明胶微球.     

AM/AA/NAPA/NMQS两性离子共聚物的合成及表征

以丙烯酰胺(AM)、丙烯酸(AA)、N-烯丙基苯乙酰胺(NAPA)及N-甲基-N-烯丙基吗啉溴盐(NMQS)为原料,氧化还原体系下合成了一种水溶性两性离子共聚物AM/AA/NAPA/NMQS。最佳反应条件为:m(AM):m(AA)=4.0:6.0,NAPA 0.3 wt%,NMQS 0.15 wt%,引发剂0.1 wt%,pH=6,反应温度35℃,单体总浓度25wt%。对AM/AA/NAPA/NMQS四元共聚物进行了IR、1H NMR、SEM、特性粘数表征。当NaCl浓度为12000mg·L-1,CaCl2或MgCl2浓度为1200 mg·L-1时,溶液黏度保留率分别为13.7%、11.8%和12.7%;温度120℃时,溶液黏度保留率达到30.9%;当剪切速率在170 s-1时,溶液黏度保留率为24.6%。     

Fenton试剂增强电晕放电技术降解甲苯

通过气溶胶分散技术将芬顿(Fenton)试剂引入气相反应体系来增强电晕放电对污染物甲苯的降解.含Fe2 、Co2 和Mn2 等过渡金属离子的催化剂溶液以微液滴形式添加入反应器电晕区,考察了催化剂对甲苯蒸气降解速率的影响,发现甲苯平均降解速率均有显著提高.在这三种金属离子溶液浓度均为0.05mol/L,电极气流量为0.6m3/h和极间电压为23kV时,甲苯(初始浓度为900mg/m3)降解速率增强因子β分别为1.29,1.28和1.51.气相和液相中降解产物的分析表明,微液滴内发生的电Fenton反应将电晕放电产生的H2O2转化为具有更强氧化性的羟基自由基(HO.),而甲苯的中间产物溶解在微液滴中,增强了甲苯的降解速率.     

胶体模板法制备有序大孔TiO2材料

以单分散的聚甲基丙烯酸甲酯(PMMA)微球为胶体模板, 采用钛酸丁酯、水、乙醇、盐酸等配成的混合溶胶填充在微球间间隙, 经水解形成凝胶, 然后通过程序升温焙烧去掉单分散的PMMA微球, 可得有序TiO₂大孔材料. 实验结果表明, 溶胶的配比为V(钛酸丁酯)∶V(水)∶V(乙醇)∶V(盐酸)＝5∶2∶3∶1, 在空气中凝胶20 h. 去掉单分散的PMMA微球的程序升温控制的条件为1 ℃/min的升温速率升到250 ℃恒定3 h, 再以2 ℃/min的升温速率升到450 ℃恒定8 h, 最后以10 ℃/min的降温速率降到室温.     

磺化St/DVB窄分散微球的合成及其标记微量钇(Y~(3+))的生物相容性研究

采用复配分散体系和超速搅拌悬浮聚合工艺,合成粒径20~40μm的窄分散St/DVB微球,经磺化、纯化、化学修饰和Y~(3+)标记,检测其粒径分布及其在生理环境下Y~(3+)的稳定性与生物相容性。结果显示,微球呈淡黄色,经湿态水流筛分后粒径在20~40μm范围的占比95%,湿态交换容量为2.0mmol/m L,Y~(3+)标记量为5.0μg/m L,静态标记率为99.6%,在不同浓度浸提液中培养48h,细胞(L929)相对存活率101%~107%;在生理盐水中240h微球内Y~(3+)的渗出率0.01%,满足常规介入放疗载体所标记放射性元素渗出流失率不高于0.1%的要求。     

双硫腙改性的聚(二甲基丙烯酸乙二醇酯-甲基丙烯酸羟乙酯)微球的制备及其对铜离子的吸附研究

用悬浮聚合法由二甲基丙烯酸乙二醇酯(EGDMA)和甲基丙烯酸羟乙酯(HEMA)共聚制备得到聚(二甲基丙烯酸乙二醇酯-甲基丙烯酸羟乙酯)(PHEMA)微球,考察了NaOH浓度、反应时间等对用双硫腙进行PHEMA改性反应的影响以及铜离子水溶液浓度(5～500mg/L)、pH(2.0～6.5)、吸附时间等对改性后的微球对铜离子吸附性能影响的因素.改性的PHEMA微球对铜离子的最大吸附量为65.6mg铜离子/g双硫腙;而且,吸附有铜离子的改性PHEMA微球用0.1mol/L的硝酸的解吸率可达到90%以上,经过3次吸附-解吸循环后,解吸率仍基本不变,这表明双硫腙改性的PHEMA微球可以多次反复使用,具有良好的应用前景.     

一种新型交联羧甲基葡甘聚糖微球对Cr(Ⅵ)的吸附性能研究

通过Fe3+交联羧甲基葡甘聚糖制得了一种新型羧甲基葡甘聚糖凝胶球,研究了羧甲基葡甘聚糖铁凝胶球对Cr(Ⅵ)的吸附性能。分别考察了吸附时间、羧甲基葡甘聚糖浓度、FeCl3浓度、pH值、温度、Cr(Ⅵ)浓度和微球粒径对吸附的影响,同时用红外光谱初步表征了羧甲基葡甘聚糖铁凝胶球-Cr(Ⅵ)复合物的结构。结果表明,293K时,微球对Cr(Ⅵ)的吸附反应在12h时达平衡,当羧甲基葡甘聚糖质量分数为1.0%,FeCl3质量分数为1.0%,Cr(Ⅵ)浓度为400mg/L时,吸附量达到0.4385mmol/g。根据不同温度下微球吸附Cr(Ⅵ)的等温线,计算了吸附过程的热力学参数,同时用Freundlich方程对实验数据进行了拟合,发现该方程适用于所研究的吸附体系。该体系为自发放热过程,体系熵减少,降温有利于吸附。     

Investigation on the Stability of the Dispersion System of Cross-Linked Polyacrylamide Microspheres

The salt resistance, temperature resistance, and shear stability of a cross-linked polyacrylamide microsphere system are studied by microfiltration, light diffraction analysis, and optical microscopy. The results show that other conditions being equal, the particle diameter of cross-linked polyacrylamide microspheres decreases with increased NaCl concentration. When NaCl concentration is lower than 10,000 mg/L, its effect on the plugging performance of a cross-linked polyacrylamide microsphere system in regard to the nuclear pore membrane is weak in comparison with a linked polymer solution, but the former system has better salt tolerance. Particle diameter decreases with increased swelling temperature. When the swelling temperature is below 90°C, its effect on the plugging performance of the cross-linked polyacrylamide microsphere system in regard to nuclear pore membrane is weak in comparison with the linked polymer solution, but has better temperature tolerance. Particle size shows little change, with shearing rate being increased, while the shape remains about the same and the effect of shearing on the plugging performance of the cross-linked polyacrylamide microsphere dispersion system in regard to the nuclear pore membrane is weak in comparison with the linked polymer solution, but has better shear stability. The salt tolerance, temperature tolerance, and shear stability of microspheres are associated with a particular cross-linked structure.     

Effect of Composition of HPAM/Chromium(III) Acetate Gels on Delayed Gelation Time

A delayed crosslinking system employed with hydrolyzed polyacrylamide (HPAM) and chromium acetate was developed for high profile control in low-temperature reservoirs. The crosslinking system formed strong gel at polymer concentration range of 3000–5000 mg/L, and the gelation time was delayed to 8–30 days, which offered the crosslinking system enough time to flow into deep water-producing zones and plug large pore paths, forcing follow-up fluids to enter low-permeability layer and reduce disproportionate permeability. The effect of polymer hydrolysis degree, polymer concentration, pH, and crosslinker concentration on delaying gelation time was evaluated using bottle testing. Meanwhile, sand-packed tube displacement experiments revealed the plugging performance of delayed crosslinking system. According to Fourier transform infrared spectroscopy (FTIR) analysis, as well as crosslinking mechanism between polymer and chromium acetate, the delayed mechanism of crosslinked system demonstrated that due to stronger affinity of acetate complexes as a ligand, its substitution in situ by carboxylate group of polyacrylamide slowed down the initial rate-determining step of crosslinking reaction.     

低浓度部分水解聚丙烯酰胺/柠檬酸铝交联体系剪切稳定性研究

采用粘度法、核孔膜过滤和动态光散射(DLS)法,研究了高分子量低浓度的部分水解聚丙烯酰胺(HPAM)与柠檬酸铝(AlCit)反应所形成的交联体系的剪切稳定性和HPAM剪切降解后与AlCit反应所形成的体系的封堵性能及降解机理.研究结果表明,低浓度的HPAM与AlCit反应所形成的交联聚合物体系随剪切速率增加,其对1.2μm的核孔膜的封堵能力降低.HPAM稀溶液剪切降解后再与AlCit反应,低剪切速率对其封堵性能影响较小,而高剪切速率会使得其封堵性能大大降低.HPAM/AlCit交联体系和HPAM剪切降解后形成的交联体系的封堵性能下降的原因是HPAM/AlCit交联体系中交联聚合物线团(LPC)尺寸和HPAM中高分子线团的尺寸变小.     

The profile control and displacement mechanism of continuous and discontinuous phase flooding agent

In order to further explore the profile control and displacement mechanism of continuous and discontinuous phase flooding agent, the concentration distribution mathematical model of microsphere dispersion system in different branch channels is established, and its particle phase separation is simulated by using microfluidic technology. On this basis, in order to research the migration and plugging characteristics of microspheres, the visualization experiments on micro oil displacement mechanism of polymer solution and microspheres are carried out. And the experiment on the injection, migration, and plugging performance of microspheres in the multi-point core is performed. Results indicate that microspheres are in the axis of the channel due to the effect of fluid shear stress, and preferentially enter the large channel with low resistance and high flow velocity, which results in no particle or few particles in the small aperture and low flow velocity channel. The microspheres have better migration and retention capacity in the core and their migration shows the characteristic of “fluctuating pressure change”. Compared with polymer solution, the alleviation of “entry profile inversion” and the better migration and plugging performance of microsphere dispersion system can realize deep fluid diversion and expand sweep volume.     

Study of a shear thickening fluid: the suspensions of monodisperse polystyrene microspheres in polyethylene glycol

The monodisperse polystyrene (PS) microspheres were prepared by dispersion polymerization. The rheological properties of shear thickening fluid (STF) based on PS microspheres dispersing in polyethylene glycol with different concentrations were studied through the steady and oscillatory shear at different temperatures, respectively. All suspensions successively present the first shear thinning, the shear thickening, and the second shear thinning. The experimental results indicate that the shear thickening behavior of STF is controlled by the concentration of PS microspheres and temperature, as changed from continuous shear thickening (CST) to discontinuous shear thickening (DST) with increasing solid content or decreasing temperature. The STF is affected by shear rate, temperature, and the viscosity of the dispersed medium, and it is reversible absolutely and presents transient response ability. Both CST and DST behave as dilatancy. The PS microsphere aggregations formed under shear stress may result in the shear thickening in STFs.     

Effect of Physical Properties and Emulsification Conditions on the Microsphere Size Prepared Using a Solvent Extraction Process

Microspheres were prepared using a hydrocarbon-perfluorocarbon solvent extraction process. The effect of the physical properties and the emulsification conditions on the mean microsphere size was investigated. The viscosity of the dispersed and the continuous phase greatly affected the microsphere size. Smaller microspheres were produced at the same mixing intensity when the viscosity of the dispersed phase decreased. Increased continuous phase viscosity reduced the coalescenceof the droplets and hence smaller microspheres were produced. The mean microsphere size first decreased as the volume ratio of the dispersed phase to the continuous phase increased but upon further increase the mean microsphere size increased. The effect of the volume ratio on the microsphere size was linked to the surfactant concentration. The stability of the studied hydrocarbon-in-fluorocarbon emulsion is poor. One reason for the poor stability is the high density difference between the phases. The emulsion droplets were solidified by siphoning part of the emulsion in the fresh continuous phase, which extracted the solvent from the dispersed phase. The effect of emulsion transfer time between the emulsification and solidification steps on the particle size was studied but no significant effect was observedduring the controlled time interval.     

微流控法制备的多孔微球对Cr(Ⅵ)的吸附性能

利用玻璃毛细管搭建单级微流控装置制备单分散水包油（O/W）乳液,以乳液为模板,紫外光照射乳液引发自由基聚合,成功制备了单分散甲基丙烯酸甲酯/甲基丙烯酸二甲基氨基乙酯（MMA/DMAEMA）多孔微球。微球粒径偏差系数（CV）值小于5%,单分散性良好。研究了MMA/DMAEMA多孔微球对Cr(Ⅵ)的吸附性能、再生吸附性能、吸附机理。结果表明：pH对微球吸附Cr(Ⅵ)的量有较大影响,当pH=3时,微球对Cr(Ⅵ)吸附率达到52.9%;循环4次后微球吸附率基本不降低,循环性能好;微球吸附符合准二级动力学模型,属于化学吸附;微球等温吸附符合Langmuir模型,属于单分子层吸附。     

Rheology Properties and Plugging Performance of Fluorescent Polyacrylamide Microspheres in Fractures

Polyacrylamide microspheres have recently drawn great attention in conformance control due to their advantages over traditional gel treatments. One important question that has been raised is whether the tiny particles can be produced from production wells. However, current products are difficult to use for detecting fluids generated by production wells. In this paper, the fluorescent polyacrylamide microspheres were successfully synthesized; they can emit blue fluorescence under ultraviolet irradiation. Their swelling property, fluorescence characteristics, rheology property, creep-recovery property, and plugging performance were evaluated in the laboratory. The results indicated that the microspheres could emit blue fluorescence under ultraviolet irradiation after passing through a fracture model. Their creep-recovery ability after deformation was very high, and their elastic recovery rate extended to 94.1%, which suggests that the microspheres almost recover to their original shape and size after deformation. The transparent fracture model plugging test shows that the microspheres can migrate and plug a fracture with a width of 0.3 mm, which is much smaller than the diameter of the microspheres.     

Synthesis and plugging effect of inverse emulsion polymerization microspheres (OPME) for oil-based drilling fluids

It is difficult to seal oil-based drilling fluids in the large pore and micro-fracture formation, and there are few suitable materials for the oil phase with good sealing ability at present. In order to solve the problem of the lack of sealing ability of oil-based drilling fluids, acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, and acryloyl morpholine were used as monomers, N'N-methylenebisacrylamide was used as a cross-linking agent, Span-80 and Tween-60 were used as emulsifiers, and 2,2′-azobis(2-methylpropionamidine) dihydrochloride was used as an initiator. Polymer microsphere emulsion OPME was synthesized by inverse emulsion polymerization. The structure of polymer microspheres was characterized by infrared spectroscopy, scanning electron microscopy, electron microscopy, H NMR, laser particle size analysis and thermogravimetric analysis. The optimal synthesis conditions were determined by the control variable method: the monomer ratio of acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, and acryloyl morpholine was 45:20:15, the amount of emulsifier was 8%, and the reaction temperature was 55℃. The synthetic polymer microspheres were added to the oil-based drilling fluids to perform filtration and loss plugging at atmospheric pressure and high-temperature and high-pressure, as well as pore and artificial fracture core plugging evaluation. The evaluation results show that the permeability reduction rate of pore core can reach 82%, and that of fracture core can reach 100% by adding polymer microspheres with 3% dosage. Finally, the pressure transmission experiment proves that the addition of polymer microspheres can slow the pressure transmission and filtrate intrusion, and enhance the stability of wellbore. Therefore, polymer microspheres are a micron-level plugging agent with good compatibility and high performance with oil-based drilling fluids, and the 3% dosage can better seal the formation of large pores and micro-fractures, which has a good potential for field application.     

Biodegradable heparin-loaded microspheres: carrier molecular composition and microsphere structure

Microspheres of amphiphilic triblock polymers PLLA-PEG-PLLA were investigated as carriers for heparin delivery. Two series of PLLA-PEG-PLLA triblock were synthesized and prepared into microspheres with heparin loaded. The microspheres were hollow and the surface morphology varied from smooth to porous. The pore size increased with increasing PEG content. The microsphere size distribution showed that higher PEG content increased the average microsphere size. The release rate of heparin was closely related to the surface morphology of the microspheres. DSC spectra showed that both cold crystalline temperature (Tc) and crystalline melting temperature (Tm) of heparin-loaded microspheres were related to the copolymer composition and the Tc was lower than those of corresponding pure microspheres. [IMAGES: SEE TEXT]