Phase inversion during compounding with a low melting major component: Polycaprolactone/polyethylene blends

Most of the morphology development in compounding of immiscible blends is known to occur at short mixing times. In this investigation, the effect of rheology of the minor component on its tendency to form a continuous phase at short mixing times is studied. it was shown that phase inversion during compounding can occur even with a low-melting major component. Four different blends with polyethylene as the high-melting-point minor component and polycaprolactone as the low-melting-point major component were chosen. Rheological measurements on the individual components were made both in the solid and melt states. Softening temperatures from these measurements were more representative of the observed processing behavior than the peak values as calculated from differential scanning calorimetry data. Compounding runs in a batch intensive mixer indicated that the minor component formed the continuous phase at short mixing times, in the blends with the low viscosity polyethylene. This was shown to correlate with its low modulus in the solid state and its low viscosity in the melt. A ramped temperature protocol during compounding delayed the melting of polyethylene thus preventing phase inversion from occurring. The blends with the higher viscosity polyethylene did not show phase inversion during compounding.     

Efficient mixing of polymer blends of extreme viscosity ratio: Elimination of phase inversion via solid‐state shear pulverization

A novel, continuous process, solid‐state shear pulverization (S³P), efficiently mixes blends with different component viscosities. Melt mixing immiscible polymers or like polymers of different molecular weight often requires long processing times. With a batch, intensive melt mixer, a polyethylene (PE)/polystyrene (PS) blend with a viscosity ratio (low to high) of 0.019 required up to 35 min to undergo phase inversion. Phase inversion is associated with a morphological change in which the majority component, the high‐viscosity material in these blends, transforms from the dispersed to the matrix phase, and may be quantified by a change from low to high mixing torque. In contrast, such blends subjected to short‐residence‐time (～3 min) S³P yielded a morphology with a PS matrix and a PE dispersed phase with phase diameters ≤ 1 μm. Thus, S³P directly produces matrix and dispersed phases like those obtained after phase inversion during a melt‐mixing process. This assertion is supported by the similarity in the near‐plateaus in torque obtained in the melt mixer at short times with the pulverized blend and at long times with the non‐pulverized blend. The utility of S³P to overcome problems associated with melt mixing like polymers of extreme viscosity ratio is also shown.     

Effect of viscosity variation with temperature on the compounding behavior of immiscible blends

Morphology development in the compounding of immiscible blends depends on a number of material properties and process conditions. In this work, different model blend systems are considered to outline the effects of the relative transition temperatures and viscosities of the blend components. We focus on the evolution of blend morphology, specifically phase continuity. A framework based on these factors is presented for analyzing the compounding behavior of immiscible blend systems. With the minor component at 10 wt%, it was found that phase inversion during compounding occurred in blends with a viscosity ratio of less than 0.2, independent of the relative transition temperatures. It was shown that in these constant mixer temperature runs, the torque trace was not a completely reliable indicator of phase inversion. When a temperature ramping program was used, the lower melting point component formed the continuous phase initially, independent of the viscosity ratio. Quantitative measures of the amount of minor component which was continuous at different mixing times were made using selective extraction in a Soxhlet apparatus. Results from compounding runs of polycarbonate/ polyethylene, an amorphous copolyester/polyethylene and polybutylene/polycaprolactone blends are presented.     

Supercritical carbon dioxide assisted blending of polystyrene and poly(methyl methyacrylate)

A method for blending polystyrene and poly(methyl methacrylate), (PMMA), with the addition of supercritical carbon dioxide has been investigated. The first series of blends was a PMMA and polystyrene with similar melt viscosities. The second series of blends was a PMMA and polystyrene with a viscosity ratio (ηPMMA/ηpolystyrene) of about 20. The results show that a reduction in the size of the minor or dispersed phase is achieved when supercritical carbon dioxide is added to the blend system. A high-pressure mixing vessel was used to prepare the blends under pressure with carbon dioxide for batch blending. The solubilities of CO₂ in PMMA and polystyrene, measured in the high-pressure mixing vessel at 200°C and 13.78 MPa (2000 psi) was 5.8 and 3.6 wt%, respectively. A single screw extruder was used to study the effects of carbon dioxide on the viscosity of polymer melts. The melt viscosity of PMMA was reduced by up to 70% with approximately 0.4 wt% CO₂. The melt viscosity of polystyrene was reduced by up to 56% with a CO₂ content of 0.3 wt%. A twin screw extruder was used to study the effects of injecting carbon dioxide in a continuous compounding operation.     

Effect of supercritical carbon dioxide on morphology development during polymer blending

Supercritical carbon dioxide (scCO₂) was added during compounding of polystyrene and poly(methyl methacrylate) (PMMA) and the resulting morphology development was observed. The compounding took place in a twin screw extruder and a high‐pressure batch mixer. Viscosity reduction of PMMA and polystyrene were measured using a slit die rheometer attached to the twin screw extruder. Carbon dioxide was added at 0.5, 1.0, 2.0 and 3.0 wt% based on polymer melt flow rates. A viscosity reduction of up to 80% was seen with PMMA and up to 70% with polystyrene. A sharp decrease in the size of the minor (dispersed) phase was observed near the injection point of CO₂ in the twin screw extruder for blends with a viscosity ratio, ηPMMA/ηpolystyrene, of 7.3, at a shear rate of 100 s^?1. However, further compounding led to coalescence of the dispersed phase. Adding scCO₂ did not change the path of morphology development; however, the final domain size was smaller. In both batch and continuous blending, de‐mixing occurred upon CO₂ venting. The reduction in size of the PMMA phase was lost after CO₂ venting. The resulting morphology was similar to that without the addition of CO₂. Adding small amounts of fillers (e.g. carbon black, calcium carbonate, or nano‐clay particles) tended to prevent the de‐mixing of the polymer blend system when the CO₂ was released. For blends with a viscosity ratio of 1.3, at a shear rate of 100 s^?1, the addition of scCO₂ only slightly reduced the domain size of the minor phase.     

The effect of scaleup on the processing behavior of a blend exhibiting phase inversion during compounding

The scaleup behavior of blends exhibiting phase inversion during compounding in batch mixers was studied. Similar morphological changes were observed during compounding of polystyrene/polyethylene blends of different batch sizes ranging from 12g to 240g. The time to achieve a continuous phase of the major component, polystyrene, was shown to depend on the scale of the mixing device. Based on visual observation of the morphological changes, a constant nominal‐maximum‐shear‐rate scaleup condition was used. Upon a five‐fold increase in batch size the time to phase inversion increased by a factor of 3. This change is explained using a combination of the reduced specific area and reduced mechanical energy input under the experimental conditions. A novel blade design using modular triangular elements was constructed and results from radial and axial scaleup using the new blades are presented. Similarities between the triangular and roller blades are used to highlight the importance of the high‐shear region in determining the softening rate of the polystyrene pellets. The flexibility of the blade design was exploited to study the effect of blade configuration on the time to phase inversion. A relative stagger parameter is introduced to explain the observed dependence. Increasing the relative stagger decreased the stress transfer to the batch and increased the time to phase inversion. Implications of these results for mixing in the kneading sections of twin‐screw extruders is discussed.     

Effect of addition protocol on mixing in miscible and immiscible polymer blends

The effects of the addition protocol are investigated for very‐low‐viscosity‐ratio model miscible and immiscible blends consisting of two polyethylenes (PE) and polystyrene (PS)/polyethylene (PE), respectively, are investigated. Miscible and immiscible blends with a matched viscosity ratio of 0.003 are compounded using three different addition protocols: simultaneous solids addition; sequential solids addition; and sequential liquids addition. These protocols correspond to addition of a solid additive to the feed hopper of an extruder; addition of a solid additive into the melting zone in an extruder; and addition of a liquid additive into the melting zone of an extruder. Both of these blends are shown to exhibit phase‐inversion‐like behaviors using a simultaneous solids addition protocol, regardless of concentration. Using either of the sequential addition protocols results in macroscopic segregation of the minor‐phase material to high‐shear‐rate regions of the mixer, delaying mixing. At long mixing times, however, all three protocols achieve a similar dispersed droplet morphology. Furthermore, the simultaneous solids addition protocol is shown to be the least energetically intensive, and the simultaneous solids requires the least amount of time of the three protocols to achieve maximum mixing torque for blends consisting of 20 wt% minor phase.     

Effect of aspect ratio of clay on melt extensional process of maleated polyethylene/clay nanocomposites

Summary Maleated polyethylene composites with different aspect ratios of clays and SiO₂ were prepared by melt compounding. Aspect ratio of clay affects significantly the physical and mechanical properties of a nanocomposite. The composite with the highest aspect ratio of clay (Closite 20A) shows the higher storage modulus, complex viscosity, the higher melt tension of polymer and the longer drawability and lower neck-in during the melt processing than those with the low aspect ratio clay (SCPX2231) and SiO₂. It also shows an easy orientation in the polymer in melt drawing direction. Received: 12 April 2001/Revised version: 16 May 2001/Accepted: 31 May 2001     

(Re)processing effects on linear low-density polyethylene/silica nanocomposites

A linear low density polyethylene matrix was melt compounded with a given amount (2 vol.%) of both untreated (hydrophilic) and surface treated (hydrophobic) fumed silica nanoparticles with the aim to investigate the influence of the time under processing conditions on the microstructure and thermo-mechanical properties of the resulting materials. Crosslinking reactions induced by thermal processing caused a remarkable increase of the melt viscosity, as revealed by the melt flow index values of both neat matrix and nanocomposites. Thermal oxidation of the matrix was slightly reduced by the introduction of fumed silica nanoparticles, especially for long compounding times. Differential scanning calorimetry evidenced how silica nanoparticles had a nucleating effect on the matrix, while both the melting temperature and the relative crystallinity were decreased by the compounding process. Nanosilica addition promoted a general improvement of the tensile properties, that progressively decreased with the processing time.     

UHMWPE/PEG共混方式及配比对UHMWPE缠结行为及性能的影响

超高分子量聚乙烯（UHMWPE）是常用的高性能聚合物。由于高黏度的影响,极大地限制了其加工成型与应用。聚乙二醇（PEG）具有高流动性,被广泛用来改善UHMWPE的流变行为,但复合材料中添加相的分散效果对材料的性能有重要影响。采用干粉混合、溶液混合、熔融挤出共混等方式制备了不同配比UHMWPE/PEG复合材料。基于熔融拉伸实验研究了共混方式及配比对UHMWPE缠结行为及性能的影响。结果表明,PEG的加入降低了复合材料的链缠结密度。三种混合方式中,加入5%PEG时干粉混合与挤出混合解缠作用较明显,链缠结密度均降低26%左右。     

Rheological and mechanical properties of composites made from wood flour and recycled LDPE/HDPE blend

The effect of compounding method is studied with respect to the rheological behavior and mechanical properties of composites made of wood flour and a blend of two main components of plastics waste in municipal solid waste, low-density polyethylene (LDPE) and high-density polyethylene (HDPE). The effects of recycling process on the rheological behavior of LDPE and HDPE blends were investigated. Initially, samples of virgin LDPE and HDPE were thermo-mechanically degraded twice under controlled conditions in an extruder. The recycled materials and wood flour were then compounded by two different mixing methods: simultaneous mixing of all components and pre-mixing, including the blending of polymers in molten state, grinding and subsequent compounding with wood flour. The rheological and mechanical properties of the LDPE/HDPE blend and resultant composites were determined. The results showed that recycling increased the complex viscosity of the LDPE/HDPE blend and it exhibited miscible behavior in a molten state. Rheological testing indicated that the complex viscosity and storage modulus of the composites made by pre-mixing method were higher than that made by the simultaneous method. The results also showed that melt pre-mixing of the polymeric matrix (recycled LDPE and HDPE) improved the mechanical properties of the wood–plastic composites.     

Influence of intercalated montmorillonite/polyethylene glycol binary processing aids on the rheological and mechanical properties of metallocene linear low-density polyethylene

Summary Organomodified Na⁺-montmorillonite/polyethylene glycol (PEG) processing aids were prepared. Melt compounding was used to prepare nanocomposites of exfoliated montmorillonite platelets dispersing in a metallocene linear low-density polyethylene (mLLDPE) matrix. The extent of intercalation of PEG into montmorillonite layers and clay platelet exfoliation in the mLLDPE matrix was studied by X-ray diffraction. The influence of montmorillonite/PEG binary processing aids on the rheological properties and sharkskin melt fracture of mLLDPE was studied using a capillary rheometer and scanning electron microscope (SEM). The crystallization and melting characters were also studied by differential scanning calorimetry (DSC) and X-ray diffraction. The montmorillonite/PEG binary processing aids could reduce the viscosity of mLLDPE. Meanwhile, the critical apparent shear rate of the onset of sharkskin melt fracture of mLLDPE was increased by adding the aids. Also the nanocomposite prepared with the montmorillonite/PEG processing aids had better mechanical properties than pure mLLDPE. And the crystallinity, crystallization temperature, crystallization rate and melting temperature of mLLDPE/BPA nanocomposites were increased by adding the binary processing aids, and crystallization of mLLDPE became more complete.     

BMDPE／LDPE／LLDPE共混熔体的流变行为与力学性能

研究了双峰中密度聚乙烯（BMDPE），低密度聚乙烯（LDPE）与线型低密度聚乙烯（LLDPE）共混熔体的流变行为和力学性能，讨论了共混物的组成，剪切应力和剪切速率以及温度对熔体流变行为，熔体粘度和膨胀比的影响，测定了不同配比熔体的非牛顿指数，熔体流动速率，粘流活性能及屈服应力，断裂应力和断裂伸长率，为BMDPE的加工和使用以及开发高性能价格比的PE材料提供了依据。     

熔纺氨纶的流变性能

研究了聚氨酯(TPU)切片、氨纶无油丝和不同混合比例的TPU与交联剂的混合物的流变性能,发现4种样品在熔融状态下均为切力变稀流体,熔体的剪切黏度随剪切速率的增大而减小;交联剂加入越多,熔体剪切黏度越大,在同样剪切速率下其熔融温度越高;随着熔融温度提高,熔体的剪切黏度减小。目前纺丝生产的经验值是TPU切片的熔融温度约为210℃,熔体管路及纺丝箱的温度约在200℃左右。     

Melt spinning flow behaviour of high-density polyethylene blended with low-density polyethylene

ABSTRACT

The melt spinning flow behaviour of a high-density polyethylene (HDPE) blended with a low-density polyethylene (LDPE) was studied using a melt spinning technique in temperature ranging from 160 to 200°C and die extrusion velocity varying from 9 to 36?mm?s^?1. The results showed that the melt apparent extension viscosity of the blends was higher than those of the LDPE and HDPE; the melt apparent extension viscosity decreased with increasing temperature; while the melt apparent extension viscosity increased with increasing extension strain rate when the extension strain rate was lower than 0.2?s^?1, and then decreased; the melt apparent extension viscosity reached up to a maximum value when extension strain rate was about 0.2?s^?1; the relationship between the melt apparent extension viscosity and the LDPE weight fraction did not follow the mixing rule.     

Influence of the method of mixing on homogeneity and crystallization kinetics of blends of linear and branched polyethylene

The influence of mixing method—solution and melt mixing—on the homogeneity and crystallization kinetics of a series of blends of single‐site materials of linear polyethylene and ethyl‐branched polyethylene was studied by differential scanning calorimetry. Data obtained for heats of melting and crystallization, melting and crystallization peak temperatures, and melting and crystallization temperature profiles were essentially the same for the samples obtained by the two mixing methods. The results obtained can be interpreted as indicating that melt mixing is capable of producing homogeneous melts of these relatively low molar mass polymers, given that solution mixing is considered to give perfectly homogeneous blends. The heat associated with the high temperature melting peak after crystallization at 125°C of the blend samples, obtained by the two preparation methods, was higher than that of the linear polyethylene included in the blends, suggesting that a part of the branched polyethylene crystallized at 125°C. The unblended branched polyethylene showed no crystallization at 125°C. Samples obtained by powder mixing showed independent crystallization and melting of the linear and branched polyethylene components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1730–1736, 2004     

TGIC副产物在热熔胶黏剂中的应用

添加了抗氧化剂的TGIC副产物经蒸馏,得到较纯净的副产物,并将其与热熔胶黏剂按一定比例混合,得到一种复合胶黏剂.分析了副产物与热熔胶黏剂的配比对持黏性、T—剥离强度、180°剥离强度、软化点、熔融黏度的影响.当TGIC副产物与热熔胶黏剂的配比为2∶8时,所制备胶黏剂的主要力学、理化指标仍能满足家具封边、胶订等领域的行业...     

The production of glass fiber-reinforced poly(butylene terephthalate) on a continuous kneader

In poly(butylene terephthalate) based compositions, thermal degradation of the polymer matrix during processing has to be minimized to achieve quality products. Experience has shown a temperature-residence time relationship, indicating that for mixing systems with high product temperatures, the residence time of the product has to be reduced to avoid excessive thermal degradation. The power density of the mixing system is related to the specific energy input and the residence time of the product. From rheology, the power density is also known for a simple shear deformation which can thus be used to characterize the shear intensity of a particular mixing process. Comparing two different mixing systems by their power density provides us with a qualitative better understanding why higher shear is permitted with lower residence time. From theoretical considerations it was found that for a temperature-sensitive product, like PBT, the power density in the mixing operation can be further raised, taking into account that with shorter residence time a higher product temperature is permitted. Production-scale test work was carried out on a 200 mm screw-diameter continuous kneader to investigate the effect of running conditions and screw design on the thermal degradation of two different types of PBT. Results have shown that for the high-viscosity PBT a linear relationship exists between product temperature and the viscosity retained upon compounding. In a two-stage kneader only minor thermal degradation is encountered in the melting section, but conditions become critical in the mixing stage due to the viscosity increase after introducing the glass fibers to the melt. A new feature in compounding thermodegradable products is the addition of unmolten polymer into the mixing stage of the kneader since this leads to a reduction in the product end temperature and, consequently, thermal degradation of the matrix material. The limited results obtained so far indicate that an optimum exists as to the amount of pellets added. At a 15 percent level the product temperature was reduced by 20°C as compared to 10°C at 20 percent. An energy balance carried out on the continuous kneader indicates that because of the low melt viscosity approximately 30 percent of the energy put into the product in the melting section of the kneader originates from external heating. A rough comparison shows that the power density of a continuous kneader is twice that of a single-screw extruder designed for compounding PBT, but, can be tolerated because of the considerably lower residence time in the former mixing system.     

Electrical and mechanical properties of expanded graphite‐reinforced high‐density polyethylene

High‐density polyethylene (HDPE) was reinforced with expanded and untreated graphite in a melt‐compounding process. Viscosity increased upon addition of graphite phase, with the expanded graphite (EG) showing more dramatic rise than the untreated graphite (UG) in viscosity. The increase in viscosity was attributed to the increased surface‐to‐volume ratio for the EG filler after acid treatment. Electrical conductivity also increased from that pertaining to an insulator to one characteristic of a semiconductor. The EG system showed a lower percolation threshold for transition in conductivity compared to that in the UG system. DSC results indicated that the fillers acted as a nucleating agent in inducing the crystallization of HDPE in the composites. However, the overall degree of crystallinity and melting temperature of HDPE decreased with the addition of EG and UG. Mechanical properties improved as a function of filler content but the overall enhancement was not impressive. It was conjectured that the filler–matrix interface was not optimized in the melt‐mixing process. However, the role of EG as a reinforcement phase for both electrical and mechanical properties was unambiguously established. The EG composites demonstrated potentially useful attributes for antistatic, barrier, mechanical, electrical, and cost‐effective applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:2781–2788, 2004     

Polystyrene/polybutadiene blends: An analysis of the phase‐inversion region and cophase continuity and a comparison with theoretical predictions

Blends of polystyrene and polybutadiene were prepared by melt mixing. The melt rheology behavior of the blends was studied with a capillary rheometer. The morphology of the blends was examined with scanning electron microscopy. The levels of continuity and cocontinuity were studied by both morphology and dissolution techniques. The region of phase inversion was observed at 50 wt % polystyrene. Various theoretical models were applied to determine the region of cophase continuity and to locate the point of phase inversion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1007–1016, 2003