Plastic deformation and tearing in high density polyethylene blown films

Polymer films produced by tubular film blowing have a unique morphology that results from the large elongational flow in melt draw down and biaxial orientation due to bubble blow-up. Three high density polyethylene (HDPE) blown films were produced under similar processing conditions from resins which varied principally in molecular weight (MW) and molecular weight distribution (MWD). Scanning electron microscopy (SEM) showed that the lower MW and narrower MWD resin produced film which had a uniaxial orientation of stacked lamellar crystals. The higher MW (HMW) and broad MWD resins produced films consisting of a network of nearly orthotropically oriented lamellar stacks. Greater high molecular weight fraction (MW > 10⁶) in the resin resulted in more random orientation. The influence of these different structures on properties was studied by examining the plastic zone formation at crack tips and uniaxial tensile deformation with the SEM and comparing them to the macroscopic stress-strain behavior. A continuous deformation of the network structure was observed in the HMW films. Lamellar deformation occurred primarily in regions of stacks oriented parallel to the tensile axis. Macroscopic yield occurred at 6 to 10 percent strain via a shearing and opening the lamellar crystals. Irreversible deformation occurred from ?50 to 400 percent strain by transformation of the oriented lamellae to microfibrils. Eventually all the lamellar stacks in the network become aligned with the tensile axis. This process was found to improve the tear resistance in the crack propagation experiments. The lamellar stacks in the network orient perpendicular to the crack independent of crack propagation direction, insuring a more uniform transmission of stress and preventing local yielding. The tensile modulus, yield stress, and ultimate strength were highest in the film containing more high molecular weight polymer.     

Molecular characteristics of room‐temperature soluble fractions of low‐density polyethylene film resins

The molecular characteristics of the room‐temperature soluble fractions (RT solubles) of three low‐density polyethylene film resins were characterized by size‐exclusion chromatography (SEC), SEC combined with FTIR (SEC–FTIR), and nuclear magnetic resonance spectroscopy (NMR). The high‐molecular‐weight components of the RT solubles were found to be highly branched components with uniform short‐chain branching (SCB) profiles. For the low‐molecular‐weight components, however, SCB content was a function of molecular weight (MW), increasing with an increase in MW. When the chain ends were considered as SCB equivalents, the distribution of the sum of SCB and chain ends across the molecular weight distribution was practically flat, suggesting that the driving force for polymer chains remaining in solution at RT was the length of the undisrupted methylene sequence in the backbone, or methylene run length, which was too short to form crystal lamellae with a melting temperature above RT, regardless of the molecular weight of the polymer. Moreover, the NMR results revealed that the polymer components of the RT solubles had “superrandom” SCB distributions, that is, the fraction of comonomer clusters in the polymer chains of the RT solubles was lower than that predicted by Bernoullian statistical analysis, indicating that the probability of adding a comonomer to a comonomer‐ended propagating chain was lower than that of adding a comonomer to an ethylene‐ended one, presumably because of an unfavorable steric effect. Furthermore, contrary to the common belief that RT solubles are mainly low‐molecular‐weight polymers, high‐molecular‐weight components were found in high concentrations in the RT solubles, with a cutoff MW as high as 1,000,000 g/mol. The proportion of RT solubles in the film resins was found to depend on the type of resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4992–5006, 2006     

HDPE/LLDPE reactor blends with bimodal microstructures—Part II: rheological properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components.     

高分子量HDPE薄膜级树脂的开发

综述了国内外高分子量高密度聚乙烯薄膜级树脂的性能、生产工艺、代表牌号、市场、应用领域和发展趋势，重点介绍了几种代表性的生产工艺，并根据我国该薄膜级树脂生产和消费现状，提出了今后发展的建议。     

The aminolysis of styrene–maleic anhydride copolymers for a new modifier used in urea-formaldehyde resins

Styrene (St) and maleic anhydride (MA) alternating copolymers with different molecular weights (MW) were synthesized via radical copolymerization. The copolymers were subsequently transferred into water-soluble maleic amic acid derivatives (SMAA) via the aminolysis of anhydride groups using (NH₄)₂CO₃ as the ammonia sources. The synthesized polymers were applied as a new kind of macromolecular modifier and added into the reaction system during the synthesis of urea-formaldehyde (UF) resins via the traditional alkaline–acidic–alkaline three-step process. The UF resins modified with SMAA were characterized using Fourier Transform Infrared Spectroscopy (FT-IR), ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy, and thermal gravimetric analysis (TGA). All the results confirmed the successful incorporation of SMAA chains into the crosslinking network of the UF resins. The modified UF resins were further employed as wood adhesives and the effect of synthesis parameters on their performance was investigated. Meanwhile, the influence of SMAA molecular weight (MW) on the properties of the modified UF resins was also studied. When the UF resins were synthesized with a low molar ratio of formaldehyde/urea (F/U) and a predetermined amount of SMAA added into the reaction system at the second step, plywood bonded using these modified UF resins showed much improved bonding strength (BS) and depressed formaldehyde emission. Moreover, the as-modified UF resins showed good storage characteristics.     

Synthesis and the effects of water-soluble sulfonated acetone-formaldehyde resin on the properties of concrete

Water-soluble sulfonated acetone-formaldehyde (SAF) resins were synthesized by the reaction among acetone, formaldehyde, and sodium bisulfite. The surface activity of SAF resins and their performance in concrete were evaluated. The effect of molecular weight (MW) of synthesized SAF resins on the performance of the superplasticized concrete was determined. The results showed that the SAF resin has the potential to be developed as a superplasticizer used in concrete.     

HDPE/LLDPE reactor blends with bimodal microstructures—part I: mechanical properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and, vice versa, HMW homopolymer to LMW copolymer. The physical properties of the blends were found to be consistent with the nature of the individual components. For the tensile properties, the stiffness decreases with increasing the fraction of the copolymer, regardless of the molecular weight of the homopolymer fraction. For these blends with bimodal microstructures, it was confirmed that the degree of crystallinity governs the stiffness of the polymer. However, the energy dampening properties of the polymers benefit from the presence of the copolymer. A balance of stiffness and toughness can be obtained by altering the composition of the blends. For some blends, the presence of HMW homopolymer can dominate the tensile properties, showing little variation in the stiffness with increased addition of copolymer. It was also demonstrated that the testing conditions and thermal treatment of the polymer greatly influence the resulting elastic and energy dampening properties. Depending on the desired application, annealing these polymers (especially very low density copolymers) not only increases the crystallinity and stiffness, but also changes the frequency response of the dynamic mechanical properties.     

涂料用固体丙烯酸树脂的悬浮聚合研究

本文系统考察了悬浮聚合中影响涂料用固体丙烯酸树脂分子量及其分布的各种因素；对丙烯酸酯的悬浮二元共聚及加入第三组分共聚进行了研究，考察了不同单体对产物的影响；并且探讨了悬浮聚合的稳定性和粒径大小的影响因素，确定了合成涂料用固体丙烯酸酯较好的工艺条件。     

Water‐soluble sulfonated phenolic resins. III. Effects of degree of sulfonation and molecular weight on concrete workability

The effects of the degree of sulfonation (DS) and molecular weight (MW) of sulfonated phenolic resins (SPF) on the flow properties of cementitious materials were investigated. SPF resin was prepared from phenol, formaldehyde, and sodium bisulfite through a four‐step reaction. It was found that an increase in either DS or MW would enhance the dispersion effects in the system. The results indicate that the fluidity of cement pastes and the workability of concrete increased with higher DS until the resin was fully sulfonated. For resins with sufficient sulfonation, the performance of cementitious materials would increase with increasing MW. Apparently, resins with MW of about 3 × 10⁴ are most effective in promoting concrete properties in terms of workability and compressive strength. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1762–1766, 2000     

高效催化剂对聚丙烯树脂分子量、分子量分布及纺丝性能的影响

燕山石化公司化纤地毯厂在采用高效催化剂前、后生产的新、老3702聚丙烯树脂(熔体流动指数MFI均为12—15)纺丝时,纺丝温度和纤维性能发生了显著变化。研究结果表明,这种差别主要是由于它们的分子量分布不同所引起的。新3702由于分子量分布较窄,与老3702聚丙烯树脂相比,即使在相同的MFI条件下,粘均分子量和零切变粘度也是较低的,因而纺丝温度也低。在工业生产中表明,除测定MFI外还应测定聚丙烯熔体在230℃下的零切变速率粘度,这对指导生产,能提供可靠依据。采用高效催化剂生产MFI为7—11的新3602牌号聚丙烯在燕山石化公司化纤地毯厂试纺中,废丝率下降了7%以上,成丝质量得到了提高。     

Practical relationship between apparent viscosity and molecular weight of urea-formaldehyde resin adhesives

The proper viscosity of urea-formaldehyde (UF) resin adhesive for optimum adhesion depends on the type of a raw wood material for wood-based composite panels. This study investigated the practical relationship between apparent viscosity and molecular weight (MW) of UF resin adhesives during the control of their synthesis. The UF resins were synthesized at various formaldehyde/urea (F/U) mole ratios ranging from 0.8 to 1.5 with different apparent viscosities. In addition, low- and high-viscosity UF resins with 1.0 and 1.2 F/U mole ratios, respectively, were mixed at five different blending ratios of 100:0, 75:25, 50:50, 25:75, and 0:100 to obtain different viscosities. The MW of each resin was measured by gel permeation chromatography, and the relationship between apparent viscosity and MW was derived using the Mark-Houwink (M-H) equation. The results showed a good relationship between the two parameters, allowing the prediction of the MW of UF resins based on their apparent viscosity after synthesis. The weight average molecular weight (Mw) values fit well with the M-H equation, while the number average molecular weight (Mn) values did not. For the first time, this paper has reported that k and α, constants of the M-H equation based on Mw of the UF resin, ranged from 0.015 to 0.017 and 1.172 to 1.276, respectively. These suggest that the relationship between apparent viscosity and Mw should be considered for the synthesis of UF resin adhesives.     

MCS树脂的结构与性能

将甲基丙烯酸甲酯(MMA)苯乙烯(St)在氯化聚乙烯(CPE)存在下进行悬浮溶胀接枝共聚,获得MCS树脂。本文着重考察了MCS树脂的结构与性能。结果表明,连续相的透光性、橡胶相CPE的含量、两相折光指数的匹配都显著地影响MCS树脂的透明性;接枝可以改善MCS的抗冲强度,适当提高接枝率有利于MCS抗冲强度的进一步提高,但不利于其加工流动性;塑料相分子量的降低虽降低了MCS的抗冲强度,但可改善其加工流动性。     

用固体核磁技术分析PE 100管材料的抗熔垂性

用固体核磁技术分析了2种具有不同抗熔垂性能的聚乙烯管材料的凝聚态结构与流变性能。管材树脂的抗熔垂性能与其核磁迟豫特性紧密相关,好的抗熔垂性能对应更长的纵向迟豫时间。抗熔垂性能好的双峰管材料的重均分子量更高,高相对分子质量部分的含量更多。     

Fenton氧化法处理填埋渗滤液

Central composite design (CCD), the most popular design of response surface methodology (RSM), was employed to investigate the effect of total organic carbon (TOC) ratio of high molecular weight organic matter (HMW) to low molecular weight organic matter (LMW), the LMW strength and molar ratio of hydrogen peroxide to ferrous ion on landfill leachate treatment by Fention process. Based on the experimental data, a response surface quadratic model in terms of actual factors was obtained through analysis of variance (ANOVA). The model showed that TOC removal increased with the increase of HMW to LMW ratio and the decrease of LMW strength. There existed an optimal hydrogen peroxide to ferrous ion molar ratio for TOC removal.     

A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

The reversible addition-fragmentation chain transfer (RAFT) polymerization of N-acryloyl morpholine (NAM), a water-soluble bi-substituted acrylamide derivative, has been investigated in the presence of tert-butyl dithiobenzoate (tBDB), a chain transfer agent (CTA) which showed good fragmentation/reinitiation efficiency as reported in a previous comparative study. The influence of several experimental parameters, such as temperature, monomer concentration [M], dithioester to initiator molar ratio ([CTA]/[AIBN]) and monomer to dithioester molar ratio ([M]/[CTA]), has been studied with respect to polymerization duration, conversion limit, adequacy between experimental and calculated molecular weight (MW) values and polydispersity index (PDI). The kinetics has been followed over the whole conversion range by ¹H NMR spectroscopy and the MW determined by aqueous size exclusion chromatography with on-line light scattering detection. This study evidences the preponderant parameters leading to an excellent control of MW and PDI. Kinetics appear strongly influenced by both temperature and [CTA]/[AIBN] ratio, and to a lesser extent by monomer concentration. A high [CTA]/[AIBN] ratio resulted in a long induction time, which could be reduced by replacing the CTA by a macroCTA. Surprisingly, the control over MW and PDI was improved by an increase in temperature from 60 to 90 °C. Moreover, an increase of the [CTA]/[AIBN] molar ratio from 3.3 to 10, also improved the MW control; however, an additional increase of this ratio to 20 led to a marked loss of control, indicating the existence of an optimal [CTA]/[AIBN] ratio. In addition, MALDI–TOF MS and ¹H NMR analyses confirmed the end-functionalization of the chains with a dithiobenzoate group.     

Modeling of mass transfers in a porous green compact with two-component binder during thermal debinding

Mass transfers and phase changes of two-component binder in a porous green compact during thermal debinding process are modeled. The evaporation of low molecular weight (LMW) component and volatile fragments, the thermal degradation of high molecular weight (HMW) component, the capillary driven and pressure driven liquid phase transports, the binary diffusion in solutions, the convection and diffusion of gas phases, and the heat transfer in a porous medium are captured in the model. The model is validated with experimental data. The simulated results show that mass transfers during the early stage of thermal debinding are mainly due to capillary driven and pressure driven liquid transports. During the final stage of thermal debinding, both convective liquid and gas transports are important in binder removal. The developed model provides physical understanding of binder removal mechanisms that are essential for process optimization.     

Preparation of high‐molecular‐weight poly(N‐vinylcarbazole) by the photoinduced low‐temperature solution polymerization of N‐vinylcarbazole in 1,1,2,2‐tetrachloroethane

For the preparation of high‐molecular‐weight (HMW) poly(N‐vinylcarbazole) (PVCZ) with a narrow molecular weight distribution, N‐vinylcarbazole (VCZ) was solution‐polymerized in 1,1,2,2‐tetrachloroethane (TCE) at ?20, 0, and 20°C with photoinitiation. The effects of the polymerization temperature and the concentrations of the polymerization solvent and photoinitiator on the polymerization behavior and molecular parameters of PVCZ were investigated. A low polymerization temperature with photoirradiation was successful in obtaining HMW PVCZ with a smaller temperature rise during polymerization than that for thermal free‐radical polymerization by azobisisobutyronitrile (AIBN). The photo‐solution‐polymerization rate of VCZ in TCE was proportional to [AIBN]^0.45. The molecular weight was higher and the molecular weight distribution was narrower for PVCZ made at lower temperatures. For PVCZ prepared in TCE at ?20°C with a photoinitiator concentration of 0.00003 mol/mol of VCZ, a weight‐average molecular weight of 920,000 was obtained, with a polydispersity index of 1.46, and the degree of transparency converged to about 99%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2391–2396, 2003     

Nylon 6 nanocomposites prepared by a melt mixing masterbatch process

A melt mixing masterbatch process for preparing nylon 6 nanocomposites that provides good exfoliation and low melt viscosities has been investigated. It is known that high molecular weight (HMW) grades of nylon 6 lead to higher levels of exfoliation of organoclays than do low molecular weight (LMW) grades of nylon 6. However, LMW grades of nylon 6 have lower melt viscosities, which are favorable for certain commercial applications like injection molding. To resolve this, a two-step process to prepare nanocomposites based on nylon 6 is explored here. In the first step, a masterbatch of organoclay in HMW nylon 6 is prepared by melt processing to give exfoliation. In the second step, the masterbatch is diluted with LMW nylon 6 to the desired montmorillonite (MMT) content to reduce melt viscosity. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain analysis were used to evaluate the effect of the clay content in the masterbatch on the morphology and physical properties of the final nanocomposite. The melt viscosity was characterized by Brabender Torque Rheometry. The physical properties of the nanocomposites prepared by the masterbatch approach lie between those of the corresponding composites prepared directly from HMW nylon 6 and LMW nylon 6. A clear trade-off was observed between the modulus and melt processability. Masterbatches that have lower MMT content offer a significant decrease in melt viscosity and a small reduction in modulus compared to nanocomposites prepared directly from HMW nylon 6. Higher MMT concentrations in the masterbatch lead to a less favorable trade-off.     

Processing-structure-property investigation of blown HDPE films containing both machine and transverse direction oriented lamellar stacks

A series of blown films were prepared using two high density polyethylene resins of differing molecular weight and molecular weight distribution, using a high stalk process. Both the resins were processed at three frost line heights (FLHs) and three draw down ratios to determine the effect of processing parameters and resin characteristics on final film morphology and mechanical properties. By changing the FLH and the time to initiate transverse direction (TD) expansion, the relative number of lamellae stacked both perpendicular and parallel to the machine direction (MD) could be controlled for a constant blow up ratio (BUR) of 4:1. It was determined that the proportion of lamellae stacked parallel to the MD increased with increasing FLH. This effect was found to be related to the relaxation behavior of the melt and bubble shape. Increasing the stress in the stalk region was observed to lead to a reduction in stalk diameter just prior to bubble expansion, resulting in a greater effective BUR. Film morphology was observed to strongly influence end mechanical properties. Elmendorf tear resistance was found to increase in the MD and decreased in the TD with increasing FLH. The dart impact strength of these films was characterized with the surprising result that for one of the two resins studied, the dart impact increased with decreasing film gauge.     

一种高密度PE-RTⅡ型管材树脂分子链结构剖析

采用溶剂梯度分级结合凝胶渗透色谱(GPC)、核磁共振碳谱(13C-NMR)、差示扫描量热仪(DSC)等分析表征方法对利安德巴塞尔公司的高密度耐热聚乙烯管材树脂(PE-RT)4731B的分子链结构及聚集态结构进行了分析。结果表明,该PE-RT的结晶度为63 %,晶片厚度31 nm;相对分子质量呈双峰分布,相对分子质量分布达到18.0,低相对分子质量部分的重均相对分子质量(MW)为4.0×103~3.0×104,高相对分子质量部分的MW为3.0×105~6.0×105;短支链均匀分布于高分子链上,共聚单体含量高于1.25 %;高低相对分子质量组分配比为(50~55)∶(45~50)。