Terminally functionalized polyethylenes as compatibilizers for wood–polyethylene composites

Isocyanate‐terminated polyethylenes (PE), PE‐MDI and PE‐PMDI, were synthesized by reacting polyethylene monoalcohol (PEA) with 4,4′‐methylenediphenyl diisocyanate (MDI) and polymeric methylene diphenyl diisocyanate (PMDI), respectively. Effects of PEA, PE–MDI, and PE–PMDI on the mechanical properties and water resistance of wood–PE composites were investigated. All three compatibilizers increased the strength of the wood–PE composites. Composites containing PE–MDI or PE–PMDI exhibited a higher modulus of rupture (MOR) than those with PEA. The addition of PE–MDI and PE–PMDI decreased the water uptake rate of the composites while PEA increased this rate. The superior compatibilization effects of PE–MDI and PE–PMDI were attributed to the formation of covalent bonding between isocyanate and wood. This covalent bonding was demonstrated by the FTIR spectra of the wood residues after a p‐xylene extraction. Scanning electron microscope (SEM) images revealed that isocyanate‐terminated PE samples improved the interfacial adhesion between wood and PE. POLYM. ENG. SCI., 46:108–113, 2006. © 2005 Society of Plastics Engineers     

Studies of surface functional modification of nanosized α-alumina

Surface functional modification of nanosized α-alumina is an effective way to improve its dispersion in polymer and to enhance interfacial agglutinate force between particles and polymer. In this paper, diphenylmathane-4,4'-diisocyanate(MDI) was used as a surface grafting agent to react with the hydroxyl group on the surface of nanosized α-alumina. The surface properties of the grafted α-alumina were studied by FT-IR spectra X-ray photoelectron spectroscopy(XPS), surface tensiometer and transmission electron microscope (TEM). It was found that the reaction between the isocyanate group and the hydroxyl group on the surface of α-alumina nanoparticles was attribute to additional reaction of the double bond between C and N in the isocyanate group. The surface of MDI grafted α-alumina nanoparticles showed an extremely hydrophobic property and good dispersibility in ethanol. The most important influence was that there was a quantity of isocyanate groups with an active chemical property on the surface of the grafted particles, which could readily react with compounds containing -OH, -NH₂ or -COOH groups.     

316L不锈钢在硫酸盐还原菌与铁氧化菌溶液中的腐蚀及电化学行为

1 INTRODUCTION Type 316L stainless steel has good corrosion re- sistance and has been used increasingly for cooling water service in the chemical, petrochemical and power utility industries. However stainless steel is susceptible to localized corrosion by chloride ions and reduced sulfur compounds[1]. The presence of micro- organisms on a metal surface often leads to highly localized damages in the concentration of the electro- lyte constituents, pH and oxygen levels[2]. These mi- croorg…     

几种金属材料在乳酸中的腐蚀性能研究

采用失重法对316L不锈钢、Ti、Ni 3种材料在不同条件下的耐乳酸腐蚀行为进行了研究,详细考察了反应温度和反应时间对316L腐蚀的影响。结果表明,316L在L-乳酸中腐蚀速率随反应温度的升高而增大,在反应时间36 h,反应温度90℃和120℃下,腐蚀速率分别为0.382 mm/a和0.801 3 mm/a,属尚耐腐蚀;150℃和180℃下腐蚀速率分别为3.85 mm/a和6.01 mm/a,属不耐腐蚀。金相显微镜分析表明,316L不锈钢表面在较低温度的乳酸中以点蚀为主。现场挂片腐蚀实验结果表明,当温度低于120℃,316L可以作为乳酸生产设备的选材。     

不锈钢金属双极板TiW和TiTa膜的制备及性能

针对质子交换膜燃料电池金属双极板耐蚀性和导电性有待提高的问题,本文用磁控溅射双靶共溅的方法,在316L不锈钢基体表面沉积TiW和TiTa两种非贵金属膜层。通过X射线衍射、扫描电子显微镜-能谱仪、X射线光电子能谱仪、电化学和接触电阻测试等方法,表征了涂覆膜层后不锈钢的微观结构、表面形貌、化学组成、耐腐蚀性和导电性。实验结果表明,磁控溅射制备得到的TiTa膜表面较为均匀,且TiTa膜沉积的不锈钢具有较好的耐腐蚀性,其恒电位极化电流密度能够维持在0.3μA/cm²;从导电性来看,TiW膜与碳纸之间的接触电阻小于TiTa膜。综合考虑材料的各项性能,认为沉积TiTa膜的316L不锈钢有用作金属双极板材料的潜力。     

Crosslinked acrylic pressure sensitive adhesives. 3. Effect of adherend on film formation

The reaction of isocyanate in pressure sensitive adhesive (PSA) films adhered on to various adherends having different surface tensions was monitored by depth profiling using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.In the latter stages of crosslinking reaction, unreacted isocyanate and its derivatives exist more in the bulk of the PSA than in the interfaces between PSA and adherends which are Teflon sheet and PE film having relatively lower surface tensions. In the case of using stainless steel having relatively higher surface tension as adherend, opposite segregation was observed compared to Teflon and PE.From X-ray photoelectron spectroscopy (XPS), it was revealed that N atoms exist more in surface than in bulk when stainless steel is used as adherend. We conclude that polyisocyanates migrate in the PSA film in order to minimize the magnitude of interfacial free energy between the PSA and the adherend, which leads to the change of surface tension of PSA film.     

Effects of NCO:OH ratio on the mechanical properties and chemical structure of Kraft lignin–based polyurethane adhesive

ABSTRACT

This work aimed to evaluate the influence of the aliphatic and aromatic hydroxyl level on the polyurethane adhesive property and chemical structure. This adhesive was obtained through the reaction of technical Kraft lignin (TKL) as polyol with diphenylmethane diisocyanate (MDI). Thus, lignopolyurethane adhesives were obtained with NCO:OH ratios of 0.8:1.0, 0.9:1.0, 1.0:1.0, 1.1:1.0, and 1.2:1.0. Initially only the TKL aliphatic hydroxyl level was taken into consideration in the stoichiometry in order to define the mass ratio between MDI and polyol. Subsequently, lignopolyurethane adhesive was obtained using the same NCO:OH ratios considering TKL total hydroxyls’ level, and aromatic and aliphatic hydroxyls. The chemical structures of the synthesized adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹³C NMR). The mechanical property of the adhesively bonded joints, comprising wood substrates and synthesized adhesives, was measured using single lap shear tests. Results illustrated that by increasing the NCO:OH ratio, there is an increase in the free isocyanate content leading to higher shear strength values. Higher free isocyanate content leads to MDI dimer formation in the lignopolyurethane structure.     

水源热泵用换热设备常用金属的腐蚀性能

目前有关金属腐蚀的研究多集中在探讨影响腐蚀的因素以及防腐蚀相关技术,有关换热器金属腐蚀经济性的文献较少。本文采用挂片失重试验,结合电镜分析,分别研究了碳钢10^#、不锈钢316L、紫铜T2和铝合金LF21在海水和污水中的腐蚀速率、电偶腐蚀速率以及微观腐蚀形貌;并运用模糊综合评价法进行评价,为合理选择换热设备金属材料提供依据。结果表明,根据金属均匀腐蚀耐蚀性十级标准,不锈钢316L、紫铜T2与铝合金LF21都属于耐蚀金属,不锈钢316L在静止和流动水环境中,均具有最好的耐蚀性;在严格避免与电位较正金属偶合使用的前提下,铝合金LF21比碳钢10^#和紫铜T2耐蚀,其经济性也较为优秀;碳钢10^#虽耐蚀性差但胜在价格优势,是实际工程最常用的金属材料。     

生物质锅炉积灰特性与露点腐蚀

以ND钢为研究对象,选取316 L不锈钢为对比材料,主要研究了65 t·h^-1生物质循环流化床锅炉烟气深度冷却条件下的积灰与露点腐蚀耦合特性。对积灰和腐蚀层进行了XRF、XRD、SEM和EDS分析。实验结果表明：实验管件表面沉积物可分为腐蚀层、耦合层和灰沉积层（NH₄Cl、SiO₂和（NH₄）₂SO₄）。耦合层包含了灰沉积物和金属腐蚀产物,且与灰沉积层黏结紧密易剥落;腐蚀层多为金属的氯化物和氧化物,其厚度随实验进口水温降低而降低,当管壁温低于烟气水露点时,ND钢被腐蚀的程度急剧加重。在实验条件下,ND钢的抗露点腐蚀能力弱于316L不锈钢。     

Metallization of cross-linked polyurethane resins by reduction of polymer-incorporated metal ion

Polyurethane (PU) resins having different degree of cross-linking were prepared by the reaction of 4,4′-methylenebis(phenyl isocyanate) (MDI) with various molar ratio of two kind of pentaerythritol ethoxylates (PEE15, ratio of ethyleneoxy (EO) unit/hydroxyl (OH) unit=15/4; PEE3, EO/OH=3/4) in the presence of cobalt(II) chloride at 100 °C for 48 h. Metallization behavior of the CoCl₂-containing PU resins by reduction with aqueous sodium tetrahydroborate solution was investigated by means of infra-red (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). It was confirmed by the measurement of degree of swelling and glass transition temperature that the PU resin having a higher molar ratio of PEE15/PEE3 has a lower degree of cross-linking. When the PU films were reduced at 20 °C, the PU resins with PEE15/PEE3=10/0, 8/2, and 6/4 afforded the films with a metallic luster, whose surface resistance increased in this order. The formation of cobalt metal on both the sides of the PU film was revealed from the results of the XPS and EPMA measurements. The PU resin having a lower degree of cross-linking could be more easily metallized by this reduction treatment.     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

PTA装置不锈钢材料腐蚀磨损的探讨

采用自制的实验装置,模拟PTA生产装置中回转式干燥机蒸汽列管工作条件,对奥氏体不锈钢0Cr18Ni9(304)、00Cr17Nd4Mo2(316 L)、00Cr19Ni13M03(317 L)和双相不锈钢00Cr22Ni5Mo3N(2205)在含有溴离子和对苯二甲酸颗粒的醋酸介质中,进行腐蚀磨损性能研究。结果表明,4种不锈钢的腐蚀磨损速率随着腐蚀介质温度的升高而增加;在低温时,腐蚀磨损速率差别不大;当温度超过80℃以后,腐蚀磨损性能的差异变大,其中2205的耐腐蚀磨损性能最好,其次为317 L,316 L,而304则最差。相同条件下,腐蚀磨损速率大于均匀腐蚀速率。建议用2205代替316 L制作PTA同转蒸汽管干燥机的加热列管。     

Effect of stress on the passivation of Si-DLC coating as stent materials in simulated body environment

DLC coating can be used for vascular stents to prevent the stainless steel substrate from eluting Ni and Cr by plastic deformation and corrosion environment. The stress corrosion cracking (SCC) of Si-diamond-like carbon (Si-DLC) coated on 316L stainless steel was studied in a simulated body environment of a deaerated 0.89 wt.% NaCl electrolyte at 37 °C. This paper investigated the effect of Si-DLC coating on the SCC of 316L SS by slow-strain-rate test (SSRT), constant load test (CLT), and electrochemical impedance spectroscopy (EIS). The EIS data were monitored for the elastic and plastic regions under CLT to determine the electrochemical behavior of the passive film during SCC phenomena. The Si-DLC coated steel exhibited more ductility than uncoated steel and less susceptibility to SCC in this environment. According to X-ray photoelectron spectroscopy (XPS) analysis, the film repassivation occurs due to the presence of the silicon oxide layer on the Si-DLC film surface.     

316L钢在含H_2S、Cl~-水溶液中的慢应变速率腐蚀试验研究

通过慢应变速率法 (SSRT)应力腐蚀试验 ,得到了 31 6L钢的应力腐蚀敏感性指数 ,回归出计算应力腐蚀敏感性指数的方程 ,表明水溶液中Cl- 对 31 6L钢的应力腐蚀影响较大 ,而H2 S的影响小。     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

Catalytic mechanisms of triphenyl bismuth,dibutyltin dilaurate,and their combination in polyurethane-forming reaction

The catalytic mechanisms of triphenyl bismuth (TPB), dibutyltin dilaurate (DBTDL) and their combination have been studied in a model polyurethane reaction system consisting of copolyether (tetrahydrofuran–ethyleneoxide) and N-100; NMR spectroscopy was used to detect the associations between reactants and catalysts. A relatively stable complex was shown to be formed between hydroxyl and isocyanate; the catalysts showed different effects on the isocyanate–hydroxyl complex, therefore resulting in different curing characteristics. The formation of hydrogen bonding between the complexed hydroxyl and other hydroxyl or the resulting urethane provided an “auto-catalysis” to urethane formation. DBTDL destroyed the isocyanate–hydroxyl complex before catalyzing the reaction through the formation of a ternary complex, whereas TPB was able to activate the isocyanate–hydroxyl complex directly to form urethane. The reaction catalyzed by the combination of TPB and DBTDL gained advantages from the multiple catalytic entities, i.e., TPB, DBTDL, and a TPB–DBTDL complex. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1217–1225, 1997     

Wear of poly (methyl methacrylate) against a metallic surface in dry conditions

Wear of Poly (methyl methacrylate), PMMA, against a metallic surface, AISI 316L stainless steel (SS) has been investigated in dry conditions. These materials have been used to simulate the degradation of the contact, femoral stem‐bone cement in the field of hip prosthesis. First of all, no significant wear was observed on the 316L SS. PMMA wear has been quantified: the energy wear coefficient, slope of the line, and wear volume according to the cumulated dissipated energy, don't depend on the normal load, F_N. This energy analysis allows predicting the PMMA wear depth. According to the comparison between the measured dissipated energy and the energy breaking polymer chains, mechanical dissipated energy is used essentially to transform third body structure and to expel it from the contact between the two materials. Moreover, the experimental results have highlighted the stick‐slip phenomenon. Lastly, Attenuated Total Reflectance‐Fourier Transform InfraRed and Reflection Absorption‐Fourier Transform InfraRed have shown that PMMA debris configuration and conformation have changed after wear against 316L SS. The driving force of these changes seems to be the acid–base interactions between PMMA and hydroxyl groups of the SS surface. POLYM. ENG. SCI., 47:633–648, 2007. © 2007 Society of Plastics Engineers.     

A new precursor for fabricating TiN coating on 316L stainless steel at low temperature without corrosive byproducts

High quality TiN coated 316L stainless steel can hardly be fabricated by the traditional chemical vapor deposition (CVD) methods because of the formation of HCl (g) corrosive byproduct and phase transformation at high deposition temperature. To address the problem, herein, for the first time a novel TiCl₂ precursor is proposed to fabricate TiN coating on 316L substrate in N₂ atmosphere at low temperature. The idea is based on that metastable TiCl₂ can release fresh Ti atoms by its disproportionation reaction, and then the fresh Ti atoms react easily with N₂ to form TiN coating at low temperature without HCl byproduct. The reaction path, interface reaction, and performance of the TiN coating were investigated. The optimized nanograin TiN (45 nm) coating was successfully fabricated on 316L at 750 °C and it exhibited excellent corrosion resistance.     

Side reactions of phenylisocyanate in N,N-dimethylacetamide

Side reactions of isocyanate groups in N,N-dimethylacetamide (DMAC) were studied. Although 4,4′-diphenylmethane diisocyanate (MDI) in DMAC was stable and no changes occurred at 3°C, the isocyanate content decreased and a gel was finally formed at 40°C. Using phenyl isocyanate (PI) as a model compound of MDI, the identification of PI side-reaction products in DMAC were studied. From these experiments, the following five products were identified; (1) 1,3-diphenylurea (DPU), (2) 1,3-diphenyl-5-phenylcarbamyl-6-dimethylaminouracil (PUR), (3) 1,3,5-triphenylbiuret (TPB), (4) triphenyl-s-triazine-2,4,6-trione (TTT), and (5) 1,1-dimethyl-3-phenylurea (DMPU). Among these identified products, the novel side reaction product PUR, which was formed between PI and DMAC as solvent, was found along with TPB and TTT, which were already known to cause three-dimensional network formation.     

The passivity of AISI 316L stainless steel in 0.05 M H2SO4

The passivity of AISI 316L stainless steel (AISI 316L) in 0.05 M H₂SO₄, in the steady-state condition, has been explored using various electrochemical techniques, including potentiostatic polarization, electrochemical impedance spectroscopy (EIS), and Mott–Schottky analysis. Based on the Mott–Schottky analysis in conjunction with the point defect model (PDM), it was shown that the calculated donor density decreases exponentially with increasing passive film formation potential. The thickness of the barrier layer was increased linearly with the film formation potential. These observations were consistent with the predictions of the PDM, noting that the point defects within the barrier layer of the passive film are metal interstitials, oxygen vacancies, or both. Also no evidence for p-type behavior was obtained, indicating that cation vacancies do not have any significant population density in the passive film.