先驱体转化法制备SiOC多孔木质陶瓷

用杉木木粉浸渍高分子先驱体有机硅树脂,改变烧结温度和保温时间制备 SiOC 多孔木质陶瓷。用 X 射线衍射、扫描电子显微镜、红外光谱及热分析对样品的物相及微观结构进行了表征,并用四探针法测试样品的电学性能。结果表明：样品由 SiOC 玻璃相、α-石英和自由碳组成,化学结构主要含有 Si—O,Si—O—R,Si—C,C=C 和 C—H2。α-石英颗粒呈球状分布在样品的孔洞表面。样品在 Ar 中具有较好的热稳定性。但由于 SiOC 玻璃相和自由碳的氧化反应,样品在 O2中的质量损失较大。当烧结温度达 1200 ℃,保温 1h 时,样品具有较低的体积电阻率（0.03 ·cm）。     

Cathodic Delamination of an Epoxy/Polyamide Coating from Steel

X-ray photoelectron spectroscopy (XPS) has been used to determine the mechanism responsible for debonding of an epoxy/polyamide coating from steel during cathodic delamination in 3.5% aqueous NaCl solutions. Coating failure always occurred near the interface between the coating and the oxide. The nitrogen content of the free surface of the prepared coatings was about 10%. However, the nitrogen content of the free surface dropped to only 5% after exposure to 1 N NaOH for four weeks and that of the coating failure surface after cathodic delamination was only about 2%, implying that the failure involved degradation of the polyamide curing agent by hydroxide ions formed at the steel surface by reduction of oxygen. That conclusion was supported by results obtained from curve fitting of C(1s) and O(1s) spectra. The intensity of components in the C(1s) spectra due to C—N and C≡O bonds in amide functional groups decreased significantly after coatings were exposed to NaOH or subjected to cathodic delamination. Small amounts of organic materials characteristic of the coating were observed on the substrate failure surface, perhaps indicating that the failure was cohesive within the coating but very close to the interface or that some products from degradation of the curing agent precipitated on the substrate. Use of silane coupling agents to retard cathodic delamination was also investigated. Coupling agents were added directly to the coating or applied to the substrate as a primer before application of the coating. Significant reduction in the rate of cathodic delamination was seen only when the silane coupling agent was applied to the substrate and cured at elevated temperatures before the epoxy/polyamide coating was applied.     

聚醚型水性聚氨酯热分解动力学的研究

以聚醚N-210为原料,利用丙酮法合成了水性聚氨酯,使用热重分析技术考察了聚醚型水性聚氨酯分别在氮气条件和氧气条件下的热稳定性,并采用"无模式法"研究了在不同气氛氛围下的热分解动力学,同时计算了不同热分解阶段反应的活化能Ea、指前因子A等动力学参数。结果表明:合成的聚醚型水性聚氨酯的热分解过程在氮气条件和氧气条件下均为二阶段过程,第一阶段为硬段链的分解,第二阶段为软段链的分解,同时氧气的存在促进了水性聚氨酯主链上C—C和C—O键的断裂。     

Surface modification of poly(aryl ether ether ketone) film by remote oxygen plasma

Surface modification of poly(aryl ether ether ketone) (PEEK) film surfaces by oxygen plasma treatment was investigated. Two procedures, the direct plasma treatment and the remote oxygen plasma treatment, were used as oxygen plasma treatments, and the efficiency of the hydrophilic modification was discussed. The direct and remote oxygen plasma treatments lead to degradation of the PEEK film as well as hydrophilic surface modification. The degradation disturbs the surface modification. The remote oxygen plasma treatment rather than the direct oxygen plasma is suitable for the hydrophilic surface modification of the PEEK film. The remote oxygen plasma treatment at 10 W for 60 s forms predominantly C—O groups rather than C=O groups as an oxygen-containing group on the PEEK surface and gives a highly hydrophilic surface with a contact angle of 44 degrees. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68:271–279, 1998     

Ag表面乙醇选择性催化氧化的密度泛函理论研究

采用密度泛函理论计算对Ag(111)和Ag(211)表面乙醇催化氧化过程进行了系统性研究。研究发现原子氧物种是常温下乙醇氧化的关键中间体。在表面原子氧物种辅助下,乙醇O—H键和α-C—H键依次断裂,生成乙氧基中间体和乙醛产物（活化能（E _a）<38.0 kJ/mol）。乙醛随后与表面原子氧和羟基氧物种作用,导致CCOO（在Ag(111)表面发生CCOO \stackrel{}{\to } C+ CO₂）和CH₂COO（在Ag(211)表面发生CH₂COO \stackrel{}{\to } CH₂+ CO₂）中间体C—C键断裂生成CO₂,该过程是速率控制步骤（E _a>95.5 kJ/mol）。计算结果表明乙醇在Ag表面催化氧化过程为结构敏感反应,降低表面缺陷位数量可提高产物中乙醛选择性。     

Enzyme-catalyzed polymerization of 8-hydroxyquinoline-5-sulfonate by in situ nuclear magnetic resonance spectroscopy

In this report, we describe the use of in situ NMR spectroscopy to elucidate the mechanism of horseradish peroxidase-catalyzed oxidative free-radical coupling of phenols. We demonstrate the potential of the technique for the polymerization of 8-hydroxyquinoline-5-sulfonate (HQS). Based on the structural changes, we establish the involvement of ortho- and para-position protons (to the hydroxyl group) in the oxidative free-radical coupling polymerization with their relative preferences. For example, in HQS, we establish that the positions 2, 4, and 7 are involved in the chemical bonding with the order of preference being 7 ≥ 2 > 4. Analyses of ¹³C-NMR data suggest the formation of C—C- and C—O—C-type coupling bonds during enzymatic polymerization. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1257–1264, 1998     

Thermal stability of metal-doped diamond-like carbon fabricated by dual plasma deposition

Metal incorporation into amorphous diamond-like carbon films can provide superior properties as metal nano-clusters or nanocrystalline metallic carbides can be embedded in the carbon network. In this work, a filtered metal plasma cathodic arc technique is used to generate a metal plasma and acetylene is introduced to the metal plasma plume to deposit metal-containing DLC (Me-DLC) films and form nanocrystalline carbide phases in the amorphous carbon matrix. The films exhibit high thermal stability up to annealing temperatures of 500 °C as revealed by X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. At treatment temperature over 500 °C, a large amount of hydrogen is lost from the Me-DLC films as shown by elastic recoil detection. Breakdown and structural collapse of the film at high temperature can be attributed to the breaking of C–H bonds. Consequently, the C–C networks become more graphite-like to facilitate the formation of volatile C–O and metal oxides phases.     

Structure and properties of styrenic thermoplastic elastomer functionalised through ozone treatment

Abstract

Styrenic thermoplastic elastomers are hydrophobic polymer. Through ozone treatment, some oxygen containing groups such as carboxyl groups [C=O(O)] are introduced onto the molecular chains of styrenic thermoplastic elastomers [poly(styrene-b-butadiene-b-styrene) (SBS) and hydrogenated poly(styrene-b-isoprene/butadiene-b-styrene) (SEEPS)], their hydrophilicity are thus improved. Compared with SEEPS4044, SBS791 contains much more C=C double bonds and is more susceptible to ozone oxidation. The polarity of ozonised SBS791 is higher than that of ozonised SEEPS4044. Ozone treatment causes also the degradation of styrenic thermoplastic elastomers, their molecular weights are decreased. After ozone treatment, the tensile strength at 100 and 300% elongation of styrenic thermoplastic elastomers decreases.     

Cathodic Delamination of an Epoxy/Polyamide Coating from Steel

X-ray photoelectron spectroscopy (XPS) has been used to determine the mechanism responsible for debonding of an epoxy/polyamide coating from steel during cathodic delamination in 3.5% aqueous NaCl solutions. Coating failure always occurred near the interface between the coating and the oxide. The nitrogen content of the free surface of the prepared coatings was about 10%. However, the nitrogen content of the free surface dropped to only 5% after exposure to 1 N NaOH for four weeks and that of the coating failure surface after cathodic delamination was only about 2%, implying that the failure involved degradation of the polyamide curing agent by hydroxide ions formed at the steel surface by reduction of oxygen. That conclusion was supported by results obtained from curve fitting of C(1s) and O(1s) spectra. The intensity of components in the C(1s) spectra due to C—N and C≡O bonds in amide functional groups decreased significantly after coatings were exposed to NaOH or subjected to cathodic delamination. Small amounts of organic materials characteristic of the coating were observed on the substrate failure surface, perhaps indicating that the failure was cohesive within the coating but very close to the interface or that some products from degradation of the curing agent precipitated on the substrate. Use of silane coupling agents to retard cathodic delamination was also investigated. Coupling agents were added directly to the coating or applied to the substrate as a primer before application of the coating. Significant reduction in the rate of cathodic delamination was seen only when the silane coupling agent was applied to the substrate and cured at elevated temperatures before the epoxy/polyamide coating was applied.     

Properties of hybrid materials derived from hydroxy‐containing linear polyester and silica through sol–gel process. I. Effect of thermal treatment

The transparent hybrid material, HLP/SiO₂, was prepared by an in situ sol–gel process of tetraethoxysilane (TEOS) at 30°C in the presence of hydroxy‐containing linear polyester (HLP) obtained by ring‐opening reaction of diglycidyl ether of bisphenol A (DGEBA) with adipic acid under the catalyzation of triphenylphosphine (TPP). The hetero‐associated hydrogen bonds between the HLP and the residual silanol of silica in the hybrids were investigated by FTIR spectroscopy. Upon heating the hybrid, the interfacial force between the HLP matrix and the silica network changed from hydrogen bonds into covalent Si—O—C bonds through dehydration of hydroxy groups in HLP with residual silanol groups in the silica network. The existence of covalent Si—O—C bonds was proved by solid‐state ²⁹Si‐NMR spectra. Other properties such as tensile strength, glass transition temperature (T_g ), solubility, and thermal stability of the hybrids before and after heat treatment were studied in detail. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1179–1190, 2000     

Preparation,characterization, and mechanical-optical properties of telluro-borate glasses containing tungsten

The current work is interested in the preparation, characterization, and mechanical-optical properties of the glasses in the (75-x)B₂O₃–10SrO–8TeO₂–7ZnO−xWO₃ system, with (x = 0 (BSTZW0), 1 (BSTZW1), 5 (BSTZW2), 10 (BSTZW3), 22 (BSTZW4), 27 (BSTZW5), 34 (BSTZW6), and 40 mol% (BSTZW7). The preparation of the glasses has involved the melt-quenching route. The new glasses are characterized by different characterization techniques using densimeter, microhardness, Raman spectroscopy, UV–visible absorption and emission, and X-ray diffraction. Photoluminescence can determine the impact of substituting B₂O₃ with WO₃ on the mechanical-optical parameters and the structure of the present glasses. The prepared samples’ X-ray patterns showed amorphous states. The density value rises from 2.88 to 4.50 g/cm3, with the amount of WO₃ rising from 0 to 40 mol% as a result of the difference in molecular weight between WO₃ and B₂O₃. The Vickers microhardness (Hv) rises as the amount of WO₃ increases as a result of a decrease in free volume and the formation of covalent bonds. The elastic moduli were found to increase when the WO₃ concentrations increased from 0 to 40 mol%. This increase depends on the formation of bridging oxygen atoms. The Raman bands are designed to correspond to the bonds that form the structure of the current glass and detect the insertion of WO₃ content by the attribution of the new W–O–W and W–O bonds. The UV–Visible spectroscopy analysis showed no band characteristic for the reduced species of W⁵⁺ ions identified by dark blue. However, the photoluminescence spectra showed emission bands (under excitation at 300 nm) that are associated with the active centers of W⁴⁺, W⁵⁺, and W⁶⁺ ions.     

Molecular structure of interfaces between plasma-polymerized acetylene films and steel substrates

Plasma-polymerized films of acetylene were deposited onto steel substrates in an inductively coupled reactor by exciting the plasma in an argon carrier gas and then injecting the monomer into the afterglow region. The molecular structure of the film/substrate interface was determined using reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS) to characterize the films as a function of thickness. RAIR showed that thick (∼ 900 Å) as-deposited plasma-polymerized acetylene films had a complicated molecular structure and contained methyl and methylene, mono- and disubstituted acetylene, vinyl, and cis- and trans-disubstituted olefin groups. Evidence of oxidation resulting from the reaction of trapped radicals with atmospheric oxygen and moisture to form O—H and C=O groups was also obtained. The molecular structure of thin films (∼ 60 Å) was similar although evidence was obtained to indicate that acetylide groups (H—C≡C⁻) were present at the film/substrate interface. Results obtained using angle-resolved XPS analysis showed that carbonaceous contamination was removed from the substrate and that oxides and hydroxides on the substrate surface, especially FeOOH, were chemically reduced during deposition of the films. XPS also confirmed that plasma-polymerized acetylene films deposited on steel substrates contained groups. Preliminary results also showed that films deposited in an inductively coupled reactor were good primers for rubber-to-metal bonding, whereas films deposited in a capacitively coupled reactor were not. The differences may be due to the wide variety of functional groups found in the former type of films but not in the latter. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1283–1298, 1998     

铈在介孔氧化锆中的液相移植

利用Ce(NO3) 3·6H2 O溶液与介孔氧化锆原粉在一定pH值的液相中反应 ,将Ce/CeO2 催化剂移植到多孔氧化锆材料中 .用XRD ,TEM ,N2 吸附 -脱附及UV -VIS吸收光谱等手段对产物进行表征 ,结果表明 :铈经Zr—O—Ce键成功地负载于多孔ZrO2 骨架中 ,并且分散于孔表面及孔道中 ,同时保持孔道的有序性及多孔氧化锆较高的比表面积 .     

煤表面含P侧链基团对氧分子的物理吸附机理

应用量子化学密度泛函理论研究了煤表面带有含磷基团侧链与多氧分子物理吸附机理.煤表面中的含P基团与氧分子进行吸附组成的吸附态中,含P侧链中的P37原子和C14的电子向氧分子中的氧原子转移,P原子和C原子失去的电子主要被吸附在煤表面的氧得到,其中O23和O24得到较多电子,其他的氧原子得到的电子较少.由于吸附在煤表面上的氧分子都得到了电子,导致氧分子的O-O键被削弱,键长出现了不同程度的拉长.与自由氧分子相比,吸附在煤表面的氧分子O-O键的伸缩振动频率向低波数位移.计算得到氧分子与煤表面组成的吸附态的吸附能为606.09 kJ/mol,由此可知,煤表面含P侧链易与多个氧分子发生物理吸附.     

液态聚硼硅氮烷的陶瓷化过程

采用Fourier红外光谱、热重–差热以及X射线衍射分析对新型液态SiBNC先驱体进行了结构表征,重点研究了先驱体的陶瓷化过程。结果表明：先驱体以—CH3和—CH=CH2为侧链基团,含有C—H、C=C、Si—H、B—N、N—H、Si—N等化学键;N2气氛保护下的陶瓷产率约为85%,质量损失主要发生在300～800℃;随着温度的升高,聚合物中有机基团逐渐减少,900℃完成无机化转变,得到含有自由碳的非晶态SiBNC陶瓷,1200℃以上非晶态SiBNC陶瓷开始晶化,1500℃得到由C、SiC、Si3N4和BN组成的复相陶瓷。     

Structural aspects of sub-bituminous coal deduced from solvation studies. 1. Anthracene-oil solvents

In order to study coal structure indirectly and the role of hydrogen donors, an investigation of the major parameters involved in the solvation of a Wyoming sub-bituminous coal has been made. This study utilized the catalytic and non-catalytic hydrogenation of anthracene oil and coal-solvent slurries. Indirect evidence concerning major structural units in the coal was obtained and the net contribution of coal to liquefaction products was estimated. The significance of each parameter to the degradation of coal molecules was also estimated. Data support the concept that coal liquefaction follows a solid → asphaltene → resin → oil route. This stepwise dissociation of the solid is directly related to the breaking of CO, CN, and to a lesser degree CC bonds, resulting in the formation of free radicals of relatively low molecular weight. These free radicals are stabilized by hydrogen transfer from hydroaromatic solvent molecules. A lack of significant quantities of high-molecular-weight hydrocarbons derived from coal solvation implies the prevalence of small molecular units in the coal structure.     

Crosslinking of poly(vinyl chloride)—I. Grafting of vinyltri(alkoxy)silanes using UV irradiation

In a nitrogen atmosphere the UV irradiation of thin PVC films (ca. 0.1 mm thick) containing vinyltri(isopropoxy)silane results in a grafting reaction. By appropriate choice of conditions, dehydrochlorination can be kept to a minimum while up to 60% gel content is realized. Reaction of the pendent alkoxy groups, either with HCl byproduct or subsequent hydrolysis by exposure to water, results in the formation of Si—O—Si bonds that serve as chemical crosslinks. Although the addition of photosensitizers favors the grafting reactions at short exposure times, the ultimate level of crosslinking is greatly diminished by their presence. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1901–1906, 1998     

Thermosetting mechanism study of silicon-containing polyarylacetylene via in situ FTIR and solid-state NMR spectroscopy

Silicon-containing polyarylacetylene (abbreviated as PSA) resins, which contain Si-(R₁, R₂) (R₁ and R₂ represent methyl or phenyl groups) and —CC—, exhibits high thermal stability upon curing up to 250 °C. The structure and thermosetting mechanism of PSA were characterized using FTIR, in situ FTIR, ¹³C and ²⁹Si CP-MAS spectroscopy, and thermogravimetric analysis. From the experimental results we can conclude that: (1) biphenyl and naphthalene rings are formed via a Diels–Alder reaction between the Ph—CC and CC groups at 210 °C, (2) the terminal alkyne mainly transforms into ethylenic bonds at 170 and 210 °C, and (3) an oxidation reaction occurs to give the oxide structure (Si—O—Si) and carbon dioxide at 250 °C. A new curing procedure has been proposed to maximize the T_d5 up to 635.2 °C on that basis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47301.     

Removal efficiency of heavy oil by free and immobilised microorganisms on laboratory‐scale

This study explored free and immobilised microorganisms to degrade heavy oil. Two oil‐degrading bacterial strains (W‐1 and W‐2) were isolated from heavy oil wastewater samples collected from Shengli Oil Field in China. W‐1 and W‐2, identified as Rhosococcus sp. and Bacillus cereus sp., respectively, were tested for their growth behaviour and optimal growth conditions in the laboratory. The obtained results showed that the optimal growth conditions for W‐1 and W‐2 were identified as pH of 8, temperature of 40°C, and salinity of 2% and 4%, respectively. The environmental conditions affecting oil‐degrading efficiency by W‐1 and W‐2 were optimised in the media containing 0.3% heavy oil. The results showed that the optimal degradation and optimal growth conditions were similar, and the oil degradation rates of W‐1 and W‐2 were about 34.6% and 45.3%, respectively after 5 days. W‐1 and W‐2 capable of degrading oil was immobilised in calcium alginate gel beads containing active carbon and used for degradation of heavy oil. The heavy oil biodegradability of immobilised bacteria improved dramatically, compared with that of the free ones. The heavy oil biodegradation rates of immobilised W‐2 were found to be maximal at the same optimal growth conditions of pH, temperature, and salinity as the free ones. The best biodegradation rate of immobilised W‐2 reached above 78%, which is 33% than that of the free W‐2. © 2011 Canadian Society for Chemical Engineering     

Ion beam ablation of polytetrafluoroethylene

Polytetrafluoroethylene (PTFE) was irradiated with 300 keV Ar⁺ ions to the fluences of 1 × 10¹⁴ to 1 × 10¹⁶ cm⁻²; the PTFE structural changes induced by the ion irradiation were studied by X-ray diffraction and UV–vis and IR spectroscopies. The electrical conductivity of the ion beam modified PTFE was also investigated using the standard technique, and the alterations of the surface polarity were determined by contact angle measurements. The ion irradiation leads to intensive PTFE ablation due to the breaking of the C—C bonds in the polymer molecular chains and due to the production and liberation of the molecular fragments C_xF_y. In contrast to other polymeric materials, the irradiated PTFE carbonizes to a lesser extent and the observed irradiation induced increase of the electrical conductivity is also not significant. In-coming ions cause a reduction of the crystalline phase content in the PTFE samples. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 1257–1261, 1998