Structure and properties of polyimide‐bonded magnets processed from prepolymers based on diacetyl derivatives of aromatic diamines and dianhydrides

We report a novel method of polyimide (PI) synthesis from prepolymers based on dianhydrides and diacetyl derivatives of aromatic diamines that facilitate the preparation of a melt processable mixture at 300 ± 10°C of the prepolymer and magnetic Nd‐Fe‐B alloy to provide PI‐bonded magnets with enhanced properties. It is shown that chemical structure of the prepolymers strongly influences viscosity behavior via crystallization of the oligoimide in the melt, leading to formation of PI with rigid‐rod like structure. This structural ordering of the prepolymers based on diacetyl derivative of diamine used in this study, if not controlled, leads to exponential increase of melt viscosity with time, making it practically impossible to prepare melt processable mixture of the magnetic particles and the PI prepolymers at elevated temperatures. The results obtained demonstrate that appropriate dianhydrides and diacetyl derivatives of diamines that do not lead to crystallization of oligoimides in prepolymer mixture can be used under controlled processing conditions to prepare melt‐processable PI‐bonded magnets containing rigid‐rod like PI structure that significantly increases thermal stability of the magnets. The temperature dependencies of the magnetic properties of the PI‐bonded magnets under conditions that they are likely to encounter during their service life were found to be remarkably similar to that of commercial thermoplastic magnets such as injection‐molded nylon magnets. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 478–485, 2006     

Three‐dimensional thermorheological behavior of isotactic polypropylene across glass transition temperature

The aim of this work was to determine the three‐dimensional thermorheological behavior of isotactic polypropylene (i‐PP) in the region of its glass transition temperature (T_g) by a master curve. The i‐PP is a widespread polymer with a T_g ～ 0°C. Dynamic mechanical analysis (DMA) at varying frequencies and temperatures and bulk tests at varying temperatures and times are carried out to obtain the relaxation spectra. Traditionally, the combination of time and temperature is done for thermorheological simple material by the creation of a master curve based on the Arrhenius or William–Landel–Ferry (WLF) equation. This investigation shows that these equations do not fit the behavior across the glass transition of i‐PP. Instead, a new arc tangent function is derived. Additionally, it can be shown that the shifting factors differ from shear to bulk load. Therefore, the mode of mechanical stress seems to have an influence on the thermorheological behavior. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 877–880, 2004     

Polymer/surfactant interaction—Its relevance to detergent systems

The field of polymer/surfactant interaction is reviewed in this work. Results from two investigative methods,viz., dialysis and surface tension, are discussed, illustrating the main behavioral patterns and outlining the principles of the interactions. Next, aspects of the interaction phenomena that appear to have relevance to detergent formulation are presented. These include solution rheology, solubility control and surface conditioning. Lastly, the importance of surface activity of the polymer itself is stressed, culminating in a discussion of the properties of hydrophobically modified water-soluble polymers (“polymeric surfactants”), both alone and in the presence of conventional surfactants. Based on the Samuel Rosen Memorial Award lecture, given at the AOCS Annual Meeting, Anaheim, CA, April 1993.     

辐照改性聚丙烯拉伸流变行为及其挤出发泡的研究

通过在线形聚丙烯中加入双官能团丙烯酸酯类单体,经小剂量γ射线高能辐照,制备了高熔体强度聚丙烯,研究了其拉伸流变行为及其在挤出发泡方面的应用。Rheotens拉伸流变测试表明,辐照改性后由于形成了长支化分子结构,聚丙烯的熔体强度、拉伸黏度显著提高,具有明显的应变硬化特征。实验表明,ZnO可明显降低AC发泡剂分解温度,缓和分解放热;在辐照改性制备的高熔体强度聚丙烯中加入AC／ZnO复合发泡剂,可挤出发泡得到泡孔尺寸较为均一、分布均匀、具有闭孔结构的发泡材料。     

Effect of degree of polymerization on gelation and flow processability of poly(vinyl chloride)

The effect of degree of polymerization (DP) on the gelation and flow processability of poly(vinyl chloride) (PVC) was studied. Sheets with adjusted degree of gelation were prepared by rolling rigid pipe formulation suspension PVC compounds with DPs of 800, 1050 and 1300 by changing the milling temperature. Their degrees of gelation were measured with DSC and their capillary flow properties were measured with a capillary rheometer at 150, 170 and 190°C and the effect of DP on the relation between gelation and flow processabilities was studied. Because of the higher shearing heat during milling, the sample with the higher DP had a higher history temperature and thus tended to show a higher degree of gelation. The viscosity increased as the gelation increased. The dependency of viscosity on DP was higher at higher milling and extrusion temperatures and thus at a higher degree of gelation and a lower shear rate. This was assumed to be attributed to the more prominent uniform molecular flow as against the particle flow. The die swell increased with increasing the milling and extrusion temperatures and hence with increasing the gelation. A sample with a lower DP tended to show a larger die swell and this tendency was even more pronounced at the higher extrusion temperature. The melt fracture easily occurred when a sample with advanced gelation was extruded at low temperature. Whereas at low milling temperatures a sample with the lower DP showed a lower critical shear rate at onset of melt fracture, and thus easily generating melt fracture, at high milling temperatures it showed a higher critical shear rate and hence scarcely generated melt fracture. These experimental results were explained by the fact and concept that a sample with a lower DP shows a higher increase in the gelation during extrusion and/or the slighter feature of particle flow as against the uniform molecular flow at the same gelation level. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1915–1938, 2004     

Effect of poly(ethylene glycol) on the hydrophobic interactions and rheology of proanthocyanidin biopolymers from Pinus radiata

The rheology of solutions of extracts from the bark of Pinus radiata was investigated in the presence of poly(ethylene glycol)s (PEGs) of different molecular weights. PEG with a molecular weight of 4600 (1% w/w) was sufficient to reduce the viscosity of a concentrated (40% w/w) pine tannin extract by one order of magnitude. The reduction of the viscosity was due to the inhibition of molecular association via hydrogen bonding and hydrophobic interactions between tannin and PEG and depended on the molecular weight of PEG. PEG effectively reduced the viscosity of polyphenolic tannins but retained high reactivity toward paraformaldehyde for adhesive formulations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1254–1260, 2005     

Ultrasonic oscillations effect on rheological and processing properties of metallocene‐catalyzed linear low density polyethylene

The effects of ultrasonic oscillations and die materials on die pressure, productivity of extrusion, melt viscosity of metallocene‐catalyzed linear low density polyethylene (mLLDPE), as well as their mechanism were studied in a special ultrasonic oscillations extrusion system developed in our lab. Die materials used in our experiment included steel, brass, and polytetrafluoroethylene (PTFE)_. The experimental results showed that ultrasonic oscillations as well as die materials have great influence on the rheological and processing behavior of mLLDPE. Ultrasonic oscillations can greatly increase the productivity of mLLDPE melt extruded through different dies, and can decrease the die pressure and the melt viscosity of mLLDPE. Compared with steel or brass die, mLLDPE melt extruded through PTFE die is more sensitive to ultrasonic oscillations. A possible mechanism for the improved processability of mLLDPE is proposed in this article. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1873–1878, 2003     

Effect of fatty acids on the strain‐induced crystallization of natural rubber detected by tear energy measurements

The strain‐induced crystallization of natural rubber (NR) was investigated by the measurement of the tear energy of a crosslinked blend consisting of NR and noncrystalline styrene–butadiene rubber (SBR). When NR was dispersed into the SBR matrix, the tear energy of SBR increased at various temperatures and tear rates. After the application of the principle of time–temperature superposition to the tear energy according to the Williams–Landel–Ferry equation, two distinct curves were found for the NR/SBR blend with respect to the reduced tear rate, despite the fact that the tear energy of SBR or the SBR/SBR blend gave its own single composite curve. When the fatty acid in the NR/SBR blend was removed by acetone extraction, the tear energy of the blend drew a single composite curve. The conversion of the two curves into the single composite curve for the NR/SBR blend suggested that the tear energy depended on the strain‐induced crystallization of NR dispersed in the SBR matrix, which was suppressed by the removal of the fatty acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 613–619, 2005     

油水乳化液流变性研究进展

综述了油水乳化液流变性研究进展，介绍了目前国内外乳化液流变性的研究情况、乳化液的流变模式及乳化液流变性的评价方法。乳化液的剪切应力-剪切速率关系明显受油滴尺寸的影响，在含油量一定时，表观黏度随油滴尺寸的减小而增加。绝大多数乳化液在低剪切速度下(低于50s^-1)，呈现剪切变稀行为；在剪切速率超过1000s^-1时呈现牛顿行为。高含水原油的视黏度是温度、含水率以及剪切速率的函数。介绍了乳化液的3种流变模式，并给出了流变性评价方法实例。提出了油水乳化液流变性研究的发展方向。