Thermoplastic Elastomers Based on Ethylene-vinyl Acetate Copolymer and Waste Nitrile Butadiene Rubber Powder Blends Compatibilized by Chlorinated Polyethylene

Thermoplastic elastomers (TPEs) based on ethylene-vinyl acetate (EVA)/waste nitrile butadiene rubber powder (WNBRP) blends compatibilized by chlorinated polyethylene (CPE) were prepared by melt-compounding. The tensile strength and the elongation at break of the EVA/CPE/WNBRP blends were increased significantly compared with those of the EVA/WNBRP blends. The fracture surfaces of the EVA/CPE/WNBRP blends were smooth; moreover, the WNBRP in the etched EVA/CPE/WNBRP blends were inserted in the EVA matrix tightly. DMA results revealed that when the CPE dosage was 5 phr in the EVA/CPE/WNBRP blend, the Payne effect was weakened significantly.     

Thermoplastic Elastomers Based on High-Impact Polystyrene/Waste Styrene Butadiene Rubber Powder Blends Enhanced by Styrene–Butadiene–Styrene Block Copolymer and Aromatic Oil

Thermoplastic elastomers (TPEs) based on high-impact polystyrene (HIPS)/waste styrene–butadiene rubber powder (WSBRP) blends were prepared by melt-compounding; they were enhanced by incorporation of styrene–butadiene–styrene block copolymer (SBS) and aromatic oil (AO). The effects of SBS and AO dosage on the mechanical properties, Mullins effect and morphological properties of the blends were investigated. Experimental results showed that the incorporation of SBS and AO in the HIPS/WSBRP blends could improve the mechanical properties significantly. Compared with that of HIPS/WSBRP blends, the elongation at break had a maximum value with 9 phr SBS and 15 phr AO loading, being improved by about 220%. The Mullins effect results showed that a softening effect appeared obviously after the first loading–unloading cycle, while the residual deformation and internal friction loss of the HIPS/SBS/AO/WSBRP TPEs were much lower than those of the HIPS/WSBRP blends, indicating the improvement of elasticity.     

地沟油特异性指标研究

精炼地沟油相比于食用植物油,经历了更长时间的高于200 ℃的高温历程,第三类地沟油或称煎炸老油也经历了长时间高温历程。本文应用ATR红外光谱法,研究了六种常用植物油中共轭脂肪酸甘油酯含量、反式脂肪酸甘油酯含量、不饱和度等三个指标值随加热温度及加热时间的变化情况,以期找出地沟油的特异性指标。研究结果表明: 从160 ℃开始,各植物油的共轭脂肪酸甘油酯含量及反式脂肪酸甘油酯含量随着加热温度升高及加热时间增长而增加,不饱和度则降低,当加热温度为200 ℃或以上、加热时间达到4 h或更长时,六种植物油的三个指标值有大幅变化。共轭脂肪酸甘油酯含量的变化幅度还与植物油中亚油酸含量有关,亚油酸含量越大其变化幅度越大;反式脂肪酸甘油酯含量变化幅度则还与植物油中油酸含量有关,油酸含量高者变化幅度大。此外,上述三个指标值与存储时间有关,随着六种植物油存放时间增长,共轭脂肪酸含量变大,不饱和度变小,而反式脂肪酸含量变化规律与高温长时间加热不同,其含量不是变大而是变小,保质期内三个指标值的变化幅度都小于经过高温长时间加热的变化幅度。因此,从三个指标值及其变化规律可以了解植物油是否经历了长时间高温历程,它们可以作为地沟油及精炼地沟油的特异性指标。     

NMR 1D-imaging of water infiltration into mesoporous matrices

It is shown that coupling nuclear magnetic resonance (NMR) 1D-imaging with the measure of NMR relaxation times and self-diffusion coefficients can be a very powerful approach to investigate fluid infiltration into porous media. Such an experimental design was used to study the very slow seeping of pure water into hydrophobic materials. We consider here three model samples of nuclear waste conditioning matrices which consist in a dispersion of NaNO₃ (highly soluble) and/or BaSO₄ (poorly soluble) salt grains embedded in a bitumen matrix. Beyond studying the moisture progression according to the sample depth, we analyze the water NMR relaxation times and self-diffusion coefficients along its 1D-concentration profile to obtain spatially resolved information on the solution properties and on the porous structure at different scales. It is also shown that, when the relaxation or self-diffusion properties are multimodal, the 1D-profile of each water population is recovered. Three main levels of information were disclosed along the depth-profiles. They concern (i) the water uptake kinetics, (ii) the salinity and the molecular dynamics of the infiltrated solutions and (iii) the microstructure of the water-filled porosities: open networks coexisting with closed pores. All these findings were fully validated and enriched by NMR cryoporometry experiments and by performing environmental scanning electronic microscopy observations. Surprisingly, results clearly show that insoluble salts enhance the water progression and thereby increase the capability of the material to uptake water.     

Effects of Blend Ratio on Rheology,Morphology, Mechanical and Oil-Resistant Properties in Chlorinated Polyethylene Rubber and Copolyamide Blends

The elastomeric chlorinated polyethylene (CPE) blended with a low melting point copolyamide (PA6/PA66/PA1010, PA) was prepared by a melt mixing technique. The mixing characteristics of the blends were analyzed from the rheographs. The influence of copolyamide (PA) content on the morphology, mechanical properties, crystallization and oil-resistance, and the addition of compatibilizers on the mechanical properties were also systematically investigated. Morphological examinations clearly revealed a two-phase system in which CPE/PA blends exhibit a cocontinuous morphology for 50/50 composition, and the continuous phase of PA turns into a disperse phase for 70/30, 80/20, and 90/10. There is a distinct interface between the two phases. The mechanical properties, crystallization, and oil-resistance have a strong dependence on the amount of PA. The blends with higher proportions of PA have superior mechanical properties; they are explained on the basis of the morphology of the blend and the cystallinity of PA. In addition, compatibilizers, including chlorinated polyethylene-graft-copolyamide (CPE-G-PA), chlorinated polyethylene-graft-maleic anhydride (CPE-G-MAH), ethylene-n-butyl acrylate-monoxide (EnBACO), and ethylene-n-butyl acrylate-monoxide-graft-maleic anhydride (EnBACO-g-MAH) were added into the blends. Tensile strength and elongation at break go through a maximum value at a compatibilizer resin content (on the basis of the total mass of the blend) of 20 wt% while the PA content is 30 wt%.     

Evaluation of Heat Transfer Coefficient During Drying of Typical Municipal Solid Waste Matrices with Significant Shrinkage at Medium Temperature

High-moisture municipal solid waste leads to lower heat value, lower combustion efficiency, and frequent and serious erosion during incinerating. Municipal solid waste should be dried before being efficiently incinerated. The purpose of this work is to carry out experimental study and simulation on characteristics of moisture migration of municipal solid waste matrices at medium temperature (100°C–200°C) in a muffle furnace. Obvious shrinkage during moisture migration of biological waste matrices with high initial moisture content was observed. The results showed the initial moisture content and framework mobility of waste matrices and the rate of moisture migration influence on shrinkage; and linear relationships between shrinkage and moisture content ratio of waste matrices during the first falling-rate period at certain drying temperature were established. Certain experimental results of drying characteristics of moisture migration of biological waste matrices, such as potato slices and watermelon peels, under medium temperature were simulated using the shrinkage model with introducing a shrinkage term in the governing equations. The model was numerically solved by applying the finite-differences method. The results show good agreement with experiment data. The shrinkage of biological waste matrices can enhance surface heat transfer of matrices. Thus, shrinkage plays an important role in the drying behavior of high-moisture biological municipal solid waste matrices.     

A Change of Phase Morphology in Poly Lactic Acid/Poly Methyl Methacrylate Blends Induced by Graphene Nano Sheets

Blending of polymeric materials is an effective way to obtain materials with specific properties, since the properties of these multiphase polymeric materials are not only affected by the properties of the component polymers but also by the morphology formed. The research described here was focused on investigation of the morphology of polymer blends of poly lactic acid (PLA) and poly methyl methacrylate (PMMA) and the PLA/PMMA blends containing various amounts of graphene nano plates, (GNP). In this work, the blends were prepared by solution casting and the morphologies of these nano filled polymer blends were studied. By adding graphene nano plates into the PLA/PMMA blends, the morphology changed for all compositions. It was very interesting to note that the GNP were found to be preferentially located in one of the polymer phases, different for the different loadings, and its location determined the final morphology of the PLA/PMMA blends. The morphology of the blends was observed by SEM and the composition-morphology dependence responses were investigated using a Fourier transform infra-red (FTIR) spectroscopy technique.     

抗酸化微生物复合菌系对餐厨垃圾堆肥腐殖质组分光谱学性质的影响

抗酸化微生物复合菌系（AAMC）通过多种耐酸、嗜酸微生物的协同作用,在克服由于酸化抑制导致的餐厨垃圾堆肥发酵崩溃问题方面效果显著,接种AAMC可明显加速有机物质降解。然而生物堆肥存在有机物彻底降解和碳重新固定（形成稳定的腐殖质类物质）两种途径,有机质降解与腐殖质形成具有互动关系,为腐殖质形成提供原材料。为探究接种AAMC对餐厨垃圾堆肥腐殖质品质的影响,采用树脂柱法进行腐殖质分组,分别研究接种AAMC对富里酸、亲水性组分和胡敏酸3个组分分子结构复杂度和稳定性的影响。设接种组（AAMC）、加碱组（MgO和K₂HPO₄）和自然堆肥组3个处理,采用三维荧光技术（EEM）结合两种定量表征方法区域体积积分（FRI）和平行因子分析（PARAFAC）,实现对富里酸、亲水性组分和胡敏酸3个组分光谱学性质定量表征的准确性和完整性。FRI结果显示,堆肥结束后3个腐殖质组分中表征简单分子结构组分例如羧基或蛋白源结构区域的P_{i, n}值均降低,接种组降低幅度显著大于对照组,降低幅度大小排序为：接种组＞加碱组＞对照组。表征高芳香度和缩聚程度的胡敏酸类物质区域的P_{i, n}值均上升,且接种组上升幅度显著高于其他两处理,上升幅度排序也为：接种组＞加碱组＞对照组。PARAFAC结果显示,富里酸和胡敏酸组分又可分成短波长胡敏酸、长波长胡敏酸和色氨酸或类蛋白类物质3个组分,亲水性组分又可分为短波长胡敏酸、色氨酸和酪氨酸3个组分。堆肥结束后,表征短波胡敏酸和长波胡敏酸组分的F_max升高,而表征色氨酸等类蛋白类物质组分的F_max降低,升高或降低的幅度接种组最高,显著高于加碱组和对照组。综上结果说明接种AAMC可明显促进腐殖质组分子结构复杂化、稳定化,提高腐殖质组分高芳香度和缩聚程度,改善餐厨垃圾堆肥腐殖质品质,利于施用堆肥土壤保水保肥。这可能与AAMC具有高的小分子有机酸降解、转化能力,可规避酸累积对堆肥微生物活性的抑制导致的堆肥腐殖化效率低的问题密切相关。添加化学缓冲剂也能一定程度促进腐殖质组分稳定化、结构复杂化和提高堆肥腐殖化程度。这可能与堆料pH的改善,使得小分子有机酸可被持续降解和转化,有利于堆肥腐殖化进程有关。     

Mechanical Properties and Crystallization Behavior of Polycarbonate/Polypropylene Blends

The mechanical properties, morphology, and crystallization behavior of polycarbonate (PC)/polypropylene (PP) blends, with and without compatibilizer, were studied by tensile and impact tests, scanning electron microscopy (SEM), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The tensile and impact strengths of PC/PP blends decreased with increasing the PP content due to poor compatibility between the two phases. But the addition of compatibilizer improved the mechanical properties of the PC/PP blends, and the maximum value of the mechanical properties, such as tensile and impact strengths of PC/PP (80/20 wt%) blends, were obtained when the compatibilizer was used at the amount of 4 phr. The SEM indicated that the compatibility and interfacial adhesion between PC and PP phases were enhanced. DSC results that showed the crystallization and melting peak temperatures of PP increased with the increase of the PP content, which indicated that the amorphous PC affected the crystallization behavior. However, both the PC and compatibilizer had little effect on the crystallinity of PP in PC/PP blends based on both the DSC and XRD patterns.     

Mechanical Properties and Morphology of LDPE/PP Blends

Two types of polypropylene (PP) with different molecular structure, namely, homogeneous PP (PPH) and PP block‐copolymer (PPC), were blended with a long chain, branched, low density polyethylene (LDPE) in a twin screw extruder and then injection moulded into test specimens; the mechanical properties and morphology of the blends are reported. The tensile strength, elastic modulus, flexural strength, and flexural modulus of the blends increased monotonically with increasing PP content, although exhibiting a slightly negative deviation from the rules of mixtures due to the relatively poor compatibility of the components, which caused the blends to separate into individual phases. Comparatively, these mechanical properties of the LDPE/PPH blend were much higher than that of the LDPE/PPC blend, which was attributable mainly to the fact that the mechanical properties of neat PPH are stronger than that of neat PPC. With respect to the impact strength of the blends, a maximum value appeared in LDPE/PPH blends when PPH content was about 20% and also in LDPE/PPC blends when PPC content was about 40%.     

Toughening Effect of Poly(ethene-co-1-butene)-graft-methyl Methacrylate and Acrylonitrile on Styrene-acrylonitrile Copolymer (SAN)

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN), synthesized by suspension grafting copolymerization of methyl methacrylate and acrylonitrile onto PEB, was blended with styrene-acrylonitrile copolymer (SAN). The mechanical properties, phase structure, toughening mechanism, miscibility, and thermal stability of the SAN/PEB-g-MAN blends were studied using a pendulum impact tester, tension tester, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TG). The results showed that PEB-g-MAN has an excellent toughening effect on SAN resin. The notched impact strength of the blends (containing 25 wt% PEB) was 63.3 kJ/m², which was nearly 60 times that of SAN resin. The brittle-ductile transition of SAN/PEB-g-MAN blends occurred when the weight percentage of PEB was between 17.5 and ～20 wt%. SAN and PEB-g-MAN were partially miscible. The toughening mechanism of the blends changed with the PEB content. When the PEB content was low, the toughening mechanism of the blends was branching and termination of cracks with slight cavitation. As the content of PEB increased, the toughing mechanism gradually changed from branching and termination of crack with slight cavitation to both branching and termination of crack and cavitation, to extensive cavitation, and finally to shear yielding accompanied by cavitation. The phase structure of the blends changed from a “sea-island’’ structure to a cocontinuous structure as the PEB content increased. ATG analysis showed that the thermal properties of the SAN resin in the blends were enhanced by adding the PEB-g-MAN.     

Polymer–Clay Nanocomposites Based on Blends of Various Types of Polyethylenes and PE-g-MA: Morphology,Thermal Properties,Microhardness, and Transparency

Polymer–clay nanocomposites have been prepared by melt blending of commercial organoclay Cloisite 15A with blends of polyethylenes (PE) and maleic-anhydride-grafted PE (PE/PE-g-MA) with wide range of composition. Three types of PE/PE-g-MA blends with different molecular structure, namely blends of high-density PE (HD) with HD-g-MA (HDMA), blends of low-density PE (LD) with LD-g-MA (LDMA), and blends of linear low-density PE (LL) with LL-g-MA (LLMA) were used. The influence of the molecular structure of the PE matrixes and the compatibility between the blend components on the morphology of the nanocomposites was studied. The thermal properties, microhardness, and transparency of the nanocomposites were investigated. The influence of the degree of exfoliation/intercalation on the materials characteristics is discussed.     

Evaluation of boron industrial solid waste in composite materials

Boron industrial solid waste is used as reinforcement for preparing composite materials. This waste has boron trioxide which holds unique properties may affect the surface or interface of the composite. The prepared composites are characterized in order to determine the dispersion and the structure by means of inverse gas chromatography (IGC), Fourier transform infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy (SEM) and X-ray diffraction (XRD). There is a strong relation between the dispersion of reinforcement and the properties of newly formed composite. The dispersive component of the surface energies of the composites and components are determined by IGC. This parameter is difficult to measure by other methods and it is related to the wettability and adhesive characters of solid materials. The effect of compounding ratios of reinforcement is also examined. Furthermore, XRD diffractograms and SEM images of composites showed well dispersion. Thermal analysis revealed that the addition of the boron industrial solid waste to the polymer increased the thermal stability of pure polymer. Infrared spectra of the composites indicated that the composites were formed from the waste reinforcement and the polymer matrix.     

Toughened Poly(Trimethylene Terephthalate) by Blending with a Functionalized Metallocenic Poly(Ethylene-Octene) Copolymer

New toughened poly(trimethylene terephthalate) (PTT) materials were obtained by melt blending with maleic anhydride grafted poly(ethylene-octene) (POEg). Rheological properties, mechanical properties, and morphological characteristics of PTT/POEg blends at four different compositions—95/5, 90/10, 80/20, and 70/30—were studied. The melt viscosity of the blends shows a linear decrease on increasing the POEg content. The addition of rubbery POEg to the PTT matrix increases the impact strength, while tensile properties decrease. Scanning electron microscopy (SEM) displayed a very good dispersion of POEg particles in the PTT matrix. Differential scanning colorimetry (DSC) experiments showed that for all samples the melting point was almost constant and the crystallinity did not show obvious differences. SEM results showed shear yielding of the PTT matrix was the major toughening mechanism.     

Damping Properties of Blends Based on EVM

The mechanical and damping properties of blends of ethylene-vinyl acetate rubber (VA content >40% wt) (EVM)/ethylene-propylene-diene copolymer (EPDM) and EVM/nitrile butadiene rubber (NBR), both with 1.4 phr BIPB (bis (tert-butyl peroxy isopropyl) benzene) as curing agent, were investigated by dynamic mechanical analysis (DMA). The effect of added polyvinyl chloride (PVC), amido donor N-cyclohexyl-2-benzothiazole sulfonamide (CZ), and dicumyl peroxide (DCP) as a substitute curing agent, on the damping and mechanical properties of both rubber blends were studied. The results showed that in EVM/EPDM/PVC blends, EPDM was immiscible with EVM and could not expand the damping range of EVM at low temperature. PVC was miscible with EVM and dramatically improved the damping property of EVM at high temperature while keeping good mechanical performance. In EVM/NBR/PVC blends, PVC was partially miscible with EVM/NBR blends and remarkably widened the effective damping temperature range (EDTR) from 41.1°C for EVM/NBR to 62.4°C. Curing agents BIPB and DCP had a similar influence on EVM/EPDM blends. DCP, however, dramatically raised the height of tan δ peak of EVM/NBR = 80/20 and expanded its EDTR to 64.9°C. CZ had no obvious influence on the EVM/EPDM blends cured with BIPB. However, a small content of CZ enlarged the tan δ peak of EVM/NBR = 80/20 in both height and width, but at the cost of a deterioration of mechanical performance.     

Foaming and Damping Properties of Ethylene Vinyl-Acetate Copolymer/Polylactic Acid Blends

With ethylene vinyl-acetate copolymer (EVM) and polylactic acid (PLA) blends as the matrix, dicumyl peroxide (DCP) as the curing agent and azodicarbonamide (AC) as the foaming agent, EVM/PLA foamed blends were prepared by compression molding. The effects of different amounts of AC, DCP, and silica, as well as varying foaming time, on the cell structure and damping properties of the EVM/PLA-foamed blends were examined by scanning election microscopy (SEM) and dynamic mechanical analysis (DMA). The results showed that the cell size and damping properties varied little with increasing AC content in the compounds; however, the cell size declined slightly as DCP increased and the damping properties rose slightly, exhibiting an optimum set of properties at 5 phr of DCP. The cell size declined dramatically and damping increased significantly as the foaming time was increased. Moreover, both suddenly increased after 5 min foaming. It was found that the damping properties of the foamed materials increased with decreasing cell size and increasing number of cells. The cell size also decreased and damping properties increased as the silica content was increased. The silica interacted more strongly with EVM than with PLA.     

基于投影寻踪的有机废弃物堆肥水溶性有机物荧光特性评价

水溶性有机物荧光特性是评价有机废弃物堆肥腐殖化程度的重要手段之一。针对现有方法大都局限于腐殖化程度的定性表征等问题,基于投影寻踪方法,该研究开展了堆肥腐熟程度分级评价的定量表征。通过对不同来源有机废弃物堆肥过程中样品水溶性有机物(DOM)荧光特性参数获取,采用统计分析表明,荧光参数I₄₃₆/I₃₈₃,FLR,P_HA/Pro,A₄/A₁,r_(A,C)两两之间显著相关(p<0.01),可作为综合评价指标。在此基础上,确定完全腐熟(Ⅰ级)、较腐熟(Ⅱ级)、基本腐熟(Ⅲ级)、未腐熟堆肥(Ⅳ级)4个腐熟等级荧光参数取值区间。模型运算得到各等投影值分别为2.01～2.22(Ⅰ级)、1.21～2.0(Ⅱ级)、0.57～1.2(Ⅲ级)、0.10～0.56(Ⅳ级)。模型验证证实,各样品的实际腐熟度等级与模型所得到腐熟与未腐熟样品的评价结果准确率为100%,因此,该评价方法对有机废弃物的实际堆肥具有重要的指导意义。     

Relationship between Microstructure and Mechanical Properties of Ethylene-Octene Copolymer Reinforced and Toughened PP

Polypropylene (PP)/ethylene-octene copolymer (POE) blends with 10–50wt% POE composition were prepared using a twin-screw extruder in the melt state. Mechanical properties of PP and PP/POE blends were tested and the effect of POE content on the crystalline morphology and structure, melting and crystallization behavior, compatiblilty, phase morphology, and the interface cohesiveness of the blends were investigated by polarizing optical microscope (POM), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and scanning electron microscopy (SEM). The relationship between mechanical properties and microstructure of the PP/POE blends is discussed. The results showed that POE had a dual function of both reinforcing and toughening PP in the range from 10–40wt%, which was attributed to the integrated functions of the degree of crystallinity of the PP phase, phase morphology, and interface cohesiveness of the blend.     

Effect of viscosity ratio of the components of thermoplastic and liquid-crystalline polymer blends on the properties

The effects of viscosity ratio on the rheological and mechanical properties of the blends of four thermoplastics of low viscosity and a liquid crystalline polymer (LCP) were studied. A polyamide of reduced crystallinity (amorphous PA), a polycarbonate (PC), a polyethylene-terephthalate (PET), and a cyclic polyolefin (COC) were investigated with the copolymer of 2-hydroxy-6-naphthoic acid (HNA) and 4-hydroxybenzoic acid (HBA) (Vectra A type LCP). The LCP content changed in the range of 0–50 w/w%. The mechanical properties were determined by tensile tests on injection molded test bars in parallel and perpendicular directions to the flow. Except for the PC/LCP blends, the viscosity decreased with increasing LCP content, the tensile strength increased significantly in the parallel and decreased in the perpendicular direction indicating formation of fibrillar phase morphology. In the case of PC/LCP blends, a reinforcing effect was observed at low LCP contents, but above 20 w/w% the viscosity increased and the parallel tensile strength dropped to the value measured in the perpendicular direction. The loss of the reinforcing effect might originate from chemical reactions of the two polymers.     

应用ICP-MS分析猪污物中铅砷镉的形态分布

为有效控制资源化过程中畜禽污物所含重金属对环境和人类健康的危害,需要监测污物中重金属的赋存形态和浓度。采集北京昌平种猪场的猪污物样品(鲜样和干清样),用BCR提取法、硝酸-高氯酸消化法和ICP-MS仪器检测铅砷镉(Pb,As,Cd)总量及各形态含量。结果表明,猪污物中Pb,As,Cd的总量分别为29.0,28.2和0.288 mg·kg-1 DW(鲜样)以及19.7,28.2 和0.134 mg·kg-1 DW(干清样),均没有超过我国的城镇垃圾农用控制标准(As接近标准值)。两类样品中重金属的形态分布规律明显不同：鲜样中三种金属可交换态及碳酸盐结合态均超过50%,有机物及硫化物结合态则低于20%;而干清样中高生态毒性的可交换态及碳酸盐结合态和Fe/Mn氧化物结合态的比例较鲜样中都明显降低(降幅可达20%以上),表明干清样用于堆肥对农田更安全。该研究结果将为北京地区养猪场污物的资源开发和生态安全评价提供重要基础数据。