Measurement of interfacial tension in PS/LDPE melts saturated with supercritical CO2

The effect of supercritical carbon dioxide (scCO₂) on the interfacial tension between a polymer melt pair—polystyrene (PS) and low density polyethylene (LDPE)—was studied using the pendant drop method at temperatures varying from 200 to 240°C and CO₂ pressures up to 18 MPa. The LDPE melt was prepared in a high pressure optical cell and the PS pendant drop was injected into the LDPE melt with a special high pressure syringe. For measurements with scCO₂, the optical cell was first pressurized with scCO₂ and measurements were taken after the saturation of scCO₂ into both polymer melts. Excellent agreement was found with literature data for the same system without using scCO₂. For the polymer pair saturated with scCO₂, it was found that the interfacial tension decreases significantly with increasing CO₂ pressure and appears to level off at higher CO₂ pressures.     

Optimization of coating solution viscosity of hollow fiber‐supported polydimethylsiloxane membrane for CO2/H2 separation

To optimize the CO₂ permeation and CO₂/H₂ separation performance of hollow fiber‐supported polydimethylsiloxane (PDMS) membranes, the effect of the viscosity of the PDMS coating solution on surface morphologies, thickness of PDMS layer, and solution intrusion into surface pores of hollow fiber supports was investigated. Increases in both stirring time and standing time could increase the viscosity of the PDMS solution. The PDMS layer thickness increased when the coating solution viscosity increased, whereas the surface roughness of the PDMS layer markedly decreased and then slightly changed. Moreover, when the stirring time of the PDMS coating solution was 9 min and the standing time was increased from 2 min to 25 min, the CO₂ permeance first decreased, then increased to ～2250 GPU probably due to the decreased intrusion depth, and finally decreased because of the substantially increased thickness of the PDMS layer. However, the CO₂/H₂ selectivity increased to 3.4 with an increase in coating solution viscosity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45765.     

Density and viscosity of the binary polyethylene glycol/CO2 systems

Density of CO₂ saturated solutions of polyethylene glycols (PEGs) of different molecular weight was measured in pressure range from 8.0 MPa up to 47.7 MPa at a temperature of 343 K by a volumetric method. To validate the method density of pure CO₂ was measured at different pressures and a temperature of 293 K. The results were compared to the literature data and the accuracy was better than 2%. The density was between 1.17 g/mL for PEG 1000/CO₂ at 14.5 MPa and 1.78 g/mL for the system PEG 4000/CO₂ at 35 MPa. Further, the data were compared to results, obtained by a gravimetric method using magnetic suspension balance (MSB).Viscosity of CO₂ saturated solutions of polyethylene glycols (PEGs) of different molecular weight at different pressures and at a temperature of 343 K was measured using a high pressure view cell. Also a temperature impact on the viscosity of pure PEGs was observed at ambient pressure. After saturating PEG 1500 with 10 MPa of CO₂ pressure its viscosity decreases from 76.6 mPa s to 2.24 mPa s at 333 K. Further addition of CO₂ and increasing the pressure results in even lower viscosity and the highest viscosity reduction was reached at the highest pressure; at 35 MPa viscosity of the system PEG 1500/CO₂ is only 0.665 mPa s.     

Measurement and prediction of diffusion coefficients of supercritical CO2 in molten polymers

The solubility and diffusivity of supercritical carbon dioxide (sc‐CO₂) in low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), polypropylene (PP), ethylene‐ethylacrylate copolymer (EEA) and polystyrene (PS) were measured at temperatures from 150°C to 200°C and pressures up to 12 MPa by using the Magnetic Suspension Balance (MSB), a gravimetric technique for gas sorption measurements. The solubility of CO₂ in each polymer was expressed by Henry's constant. The interaction parameter between CO₂ and polymer could be obtained from the solubility data, and it was used to estimate the Pressure‐Volume‐Temperature relationship and the specific free volume of polymer/CO₂ mixtures. The diffusion coefficients were also measured by the MSB for each polymer. The resulting diffusion coefficients were correlated with the estimated free volume of polymer/CO₂ mixture. Combining Fujita's and Maeda and Paul's diffusion models, a model was newly developed in order to predict diffusion coefficients for the polymers studied. Polym. Eng. Sci. 44:1915–1924, 2004. © 2004 Society of Plastics Engineers.     

Measurements and modeling of PS/supercritical CO2 solution viscosities

This paper presents a technology to determine the melt viscosity of a PS/super-critical CO₂ solution using a linear capillary tube die mounted on a foaming extruder. CO₂ was injected into the extrusion barrel and the content of CO₂ was varied in the range of O to 4 wt% using a positive displacement pump. Single-phase PS/CO₂ solutions were formed using a microcellular extrusion system and phase separation was prevented by maintaining a high pressure in the capillary tube die. By measuring the pressure drop through the die, the viscosity of PS/CO₂ solutions was determined. The experimental results indicate that the PS/CO₂ solution viscosity is a senstive function of shear rate, temperature, pressure, and CO₂ content. A theoretical model based on the generalized Cross-Carreau model was proposed to describe the shear-thinning behavior of PS/CO₂ solutions at various shear rates. The zero-shear viscosity was modeled using a generalized Arrhenius equation to accommo-date the effects of temperature, pressure, and CO₂ content. Finally, the solubility of CO₂ has been estimated by monitoring the pressure drop and the absolute pressure in the capillary die.     

The effect of CO2 on the viscosity of polystyrene/limonene solutions

We demonstrate the use of a quartz crystal viscometer to determine the viscosity of solutions of polystyrene in limonene in the presence of high pressure carbon dioxide. These measurements were determined up to 50 bar in the range of temperature from 20 to 40 °C and at 0.025, 0.05, 0.1, 0.2, 0.3 and 0.4 g PS per ml of limonene. The selected variables of study (pressure, temperature and concentration) were statistically significant over the range of viscosity studied. The viscosities of the solutions at all loadings were found to decrease with increasing temperature and pressure while the plastising effect of CO₂ prevailing over the hydrostatic pressure applied by the gas. The flow activation energies of the system were obtained from an Arrhenius fitting of the experimental data reaching a maximum of 40 kJ/mol. An empirical model correlating the viscosity of the mixtures to pressure and temperature was developed in order to interpolate and extrapolate in the study region or in a range close to the working limits. Finally, the viscosity data were used to determine the solvent quality and to quantify the demixing points of the mixtures.     

微通道内醇胺水溶液吸收CO2的压力降研究

采用高速摄像仪对400μm×400μm T型微通道内N-甲基二乙醇胺(MDEA)与单乙醇胺(MEA)混合醇胺水溶液(含0.2%SDS)吸收CO_2过程的气液两相流压力降进行了实验研究。观测到了泡状流、泡状-弹状流、弹状流、弹状-环状流流型。考察了弹状流型下气液两相流流量、醇胺溶液浓度、气液雷诺数与增强因子对压力降的影响。结果表明:压力降随着气液两相流量、气液雷诺数及增强因子的增大而增大。当Q_G﹥80 mL/h时,压力降随醇胺浓度的增大而减小。以分相流模型为基础,提出了微通道内伴有化学吸收的气液两相流压力降预测模型,平均偏差为8.46%,模型计算值与实验值吻合良好。     

Foam extrusion of LDPE with solid phase CO2 as blowing agent

Physical foaming usually requires special metering equipment to inject the blowing agent at high pressures. In this study, low density polyethylene (LDPE) was foamed in the extrusion process using dry ice as physical blowing agent. The blowing agent was metered in form of pellets over the hopper. To determine relevant process parameters and improve the understanding of the process a melting model is applied. The influence of the formation of a melt film and melt pool on the dissolution of the blowing agent is discussed. The theoretical considerations are validated in a design of experiment study. As a result, the efficiency of the process is especially affected by the throughput rate, granules temperature, and blowing agent concentration. Further varied parameters are the barrel temperature in the melting zone and diameter of the dry ice pellets. Fast melting and pressure build‐up were shown to reduce blowing agent losses. POLYM. ENG. SCI., 55:2821–2828, 2015. © 2015 Society of Plastics Engineers     

聚碳硅烷/二甲苯原液粘度特性的研究

研究了聚碳硅烷(PCS)/二甲苯溶液的粘度与PCS的摩尔质量、溶液中PCS的质量分数以及温度的关系,结果表明:PCS/二甲苯溶液的粘度随PCS摩尔质量的增加先增后减,在-Mw为9 200 g/mol时出现极大值;当PCS的质量分数超过60%后,溶液的粘度受PCS质量分数的影响较大,在PCS质量分数为67%时存在粘度随PCS质量分数变化的突变临界点;粘度的对数值与PCS质量分数的对数值呈线性关系,粘度和温度的关系符合阿仑尼乌斯方程;当溶液的温度在20~45℃、PCS的质量分数在60%~69%范围内时,PCS/二甲苯溶液的粘度变化更加明显。     

Electrochemical behaviour of copper/LDPE composites in the simulated uterine solution

Two metal/insulator composites, copper/low-density polyethylene (LDPE) microcomposites and copper/LDPE nanocomposites, were prepared in a uniform metal mass fraction. The corrosion characteristics of the two composites in the simulated uterine solution have been studied by cyclic voltammetry, potentiodynamic polarization measurement and electrochemical impedance spectroscopy. Results obtained during this study show that there are obvious differences on the corrosive rates and mechanisms between the two materials. The nanocomposites have stable corrosive reaction, hardly passivation, low corrosion rate and high transformation ratio of copper to soluble cupric ions compared with microcomposites, which indicate that the nanocomposites are perfect to be the novel material for intrauterine device. The corrosion behaviour of the microcomposites was controlled by both the processes of the pervasion of Cu²⁺ and the transfer of the charge, while that of the nanocomposites was only controlled by the transfer of the charge. This paper also compared the corrosion behaviours of the composites and bulk copper in the simulated uterine solution, there were more insoluble subproducts in the corrosion process of bulk copper than the composites. Further, the electrochemical method in this study is proved to be useful to characterize the corrosion behaviour of high electrical resistivity materials.     

The absorption rate of CO2/SO2/NO2 into a blended aqueous AMP/ammonia solution

The Inter-governmental Panel on Climate Change (IPCC) reported that human activities result in the production of greenhouse gases (CO₂, CH₄, N₂O and CFCs), which significantly contribute to global warming, one of the most serious environmental problems. Under these circumstances, most nations have shown a willingness to suffer economic burdens by signing the Kyoto Protocol, which took effect from February 2005. Therefore, an innovative technology for the simultaneously removal carbon dioxide (CO₂) and nitrogen dioxide (NO₂), which are discharged in great quantities from fossil fuel-fired power plants and incineration facilities, must be developed to reduce these economical burdens. In this study, a blend of AMP and NH₃ was used to achieve high absorption rates for CO₂, as suggested in several publications. The absorption rates of CO₂, SO₂ and NO₂ into aqueous AMP and blended AMP+NH₃ solutions were measured using a stirred-cell reactor at 293, 303 and 313 K. The reaction rate constants were determined from the measured absorption rates. The effect of adding NH₃ to enhance the absorption characteristics of AMP was also studied. The performance of the reactions was evaluated under various operating conditions. From the results, the reactions with SO₂ and NO₂ into aqueous AMP and AMP+NH₃ solutions were classified as instantaneous reactions. The absorption rates increased with increasing reaction temperature and NH₃ concentration. The reaction rates of 1, 3 and 5 wt% NH₃ blended with 30 wt% AMP solution with respect to CO₂/SO₂/NO₂ at 313 K were 6.05～8.49×10^?6, 7.16–10.41×10^?6 and 8.02～12.0×10^?6 kmol m^?2s^?1, respectively. These values were approximately 32.3–38.7% higher than with aqueous AMP solution alone. The rate of the simultaneous absorption of CO₂/SO₂/NO₂ into aqueous AMP+NH₃ solution was 3.83–4.87×10^?6 kmol m^?2s^?1 at 15 kPa, which was an increase of 15.0–16.9% compared to 30 wt% AMP solution alone. This may have been caused by the NH₃ solution acting as an alternative for CO₂/SO₂/NO₂ controls from flue gas due to its high absorption capacity and fast absorption rate.     

甲壳胺/乙酸溶液表观粘度的影响因素

在低剪切速率下,研究了甲壳胺的浓度、溶液静置时间、溶液温度及溶剂乙酸浓度对甲壳胺/乙酸溶液表观粘度的影响。结果表明:甲壳胺/乙酸溶液的表观粘度随甲壳胺浓度的增加而上升,随溶液温度的上升而降低,随乙酸浓度的增加有所降低。配制甲壳胺/乙酸纺丝原液时,需现用现配,甲壳胺质量分数4.5%,乙酸质量分数2.0%,溶液温度20℃为宜。     

Nonisothermal crystallization behavior of Cu/LDPE nanocomposites prepared by solution blending method

The nonisothermal crystallization behavior of Copper/low‐density polyethylene (LDPE) nanocomposites was investigated by differential scanning calorimetry (DSC). The nanocomposites were prepared by solution blending method, and the traditional extrusion melt method was also employed for comparison. The DSC results show that under identical copper content condition, the crystallization of the LDPE is facilitated owing to the higher degree of molecular regularity and the lesser chain entanglement for the nanocomposites prepared by the solution blending method in comparison with the traditional extrusion melt method. The differences of nonisothermal crystallization behavior diminish with the increasement of copper content between the nanocomposites prepared by the two methods. SEM/EDX was applied to study the dispersion of copper nanoparticles in the nanocomposites, and the results illustrate that the dispersion condition can be better when the solution blending method was employed. The investigation of the effective activation energy on the relative extent crystallization implies that the agglomeration of copper nanoparticles can facilitate the crystallization of the LDPE, while the well‐dispersed copper nanoparticles act as obstacles since the motion of the LDPE molecular chains is limited. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

LLDPE/LDPE/纳米TiO2复合薄膜的性能

采用熔融共混方式在线型低密度聚乙烯(LLDPE)／低密度聚乙烯(LDPE)复合体系中添加纳米TiO2制成LLDPE／LDPE／纳米TiO2复合薄膜。通过偏光显微镜、扫描电子显微镜、差示扫描量热法、紫外一可见光吸收光谱,研究了纳米TiO2填充LLDPE／LDPE复合薄膜的力学和光学性能。结果表明,纳米TiO2在薄膜中呈现出理想的分散水平,平均粒径在100nm以下。纳米TiO2在LLDPE／LDPE复合体系的结晶过程中,可起到明显的诱导成核作用,使球晶尺寸细化且数量增多,但复合体系的结晶度无明显变化。该薄膜的透光性仅轻微下降,可满足透明薄膜的使用要求,同时,表现出良好的紫外线吸收功能。     

O2/CO2气氛下醋酸调质石灰石煅烧/硫化特性

研究了醋酸溶液调质对石灰石在O2/CO2气氛下煅烧/硫化特性的影响,并结合氮吸附法、压汞法和XRD技术进行了分析。结果表明,与原石灰石相比,调质石灰石在煅烧/硫化过程中表现出更高的钙转化率,XRD图谱及其相定量分析证明了这一点;随温度升高,调质石灰石具有最佳的硫化温度,此温度下其钙转化率最高;随SO2浓度增大,初始阶段煅烧/硫化反应速率升高,调质石灰石钙转化率增大;随醋酸浓度增大,调质石灰石的钙转化率提高,提高幅度因石灰石种类而异;氮吸附及压汞分析表明调质石灰石较未调质石灰石具有发达的孔结构,促进了硫化反应的进行。     

Transient elongational viscosity of LLDPE/LDPE blends and its relevance to bubble stability in the film blowing process

Transient elongational viscosity of linear low density polyethylene (LLDPE) and its blends with 10% and 20% of low density polyethylene (LDPE) was measured at two temperatures by a constant strain rate elongational rheometer. In addition, the performance of the blends in the film blowing process was assessed in terms of bubble stability at two processing temperatures. An operating window for stable bubble production was determined. The elongational viscosity measurements on blends revealed stronger strain hardening characteristics at a higher temperature of testing. These results correlate favorably with findings from a bubble stability investigation where it was found that the size of the operating window for stable bubble production increased with increasing extrusion temperature. This work seems to indicate that increasing processing temperature during the film blowing of LLDPE-rich blends could lead to a processability improvement of these blends as far as bubble stability is concerned.     

Investigations of environmental stress cracking resistance of LDPE/UHMWPE and LDPE/EVA blends

Abstract

Low density polyethylene (LDPE)/ultrahigh molecular weight polyethylene (UHMWPE) and LDPE/poly(ethylene-co-vinylacetate) (EVA) blends were tested and compared with respect to their environmental stress cracking resistance (ESCR) using the Bell telephone test. The time to failure in the ESCR test improved with increasing UHMWPE and EVA content, and considerable improvements were produced when an UHMWPE weight fraction of 0.4 and EVA weight fraction of 0.03 were used. Thermal and morphological studies were conducted, and a relationship between morphological features and composition was established. Furthermore, the failed specimens were further characterised by scanning electron microscopy and fractographic methodology to investigate the failure mechanism for ESCR samples.     

基于TDLAS技术的CO_2浓度测量

基于可调谐半导体激光吸收光谱(TDLAS)技术,结合HITRAN数据库对CO_2吸收谱线进行分析,选择对1 572.3nm附近的CO_2吸收谱线进行扫描,搭建TDLAS单光路测量实验系统。采用直接测量方法,对一定浓度的CO_2气体进行浓度测量。针对线型函数,提出了拟合吸收谱线加宽调谐范围积分和加入线型积分修正系数两种方法,并对两种方法做出了比较,得到较为准确的修正方法。     

Ni/bentonite catalysts prepared by solution combustion method for CO2 methanation

A 20 wt% Ni/bentonite catalyst was prepared by a solution combustion synthesis (SCS), which exhibited higher activity for the CO₂ methanation than that of an impregnation method (IPM), and the catalyst prepared by SCS showed a CO₂ conversion of 85% and a CH₄ selectivity of 100% at 300℃, atmospheric pressure, and 3600 ml·(g cat)^-1·h^-1, and the catalyst exhibited stable within a 110-h reaction. The results showed higher metallic Ni dispersion, smaller Ni particle size, larger specific surface area and lower reduction temperature in the Ni/bentonite prepared by SCS than that of IPM. And the Ni/bentonite prepared by the SCS moderated the interaction between NiO and bentonite.