含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为

采用联苯二酐与3种含酰胺结构二胺制备了具有不同取代基团的聚酰胺-酰亚胺薄膜, 考察了酰胺结构对薄膜力学、 耐热及尺寸稳定性的影响, 研究了聚集态结构与薄膜热膨胀行为的关系和规律. 该系列薄膜具有超高强度和优异的耐热性能, 拉伸强度高达280.5 MPa, 玻璃化转变温度在389~409 ℃, 并在30~300 ℃温度范围内表现出超低负膨胀, 热膨胀系数(CTE, ppm/℃, 即10 ⁶ cm·cm ^-1·℃ ^-1)在-3.05~-1.74 ppm/℃之间. 聚集态分析结果表明, 酰胺结构使分子链间形成了强氢键相互作用, 分子链在薄膜面内方向高度有序取向, 并在膜厚方向堆积更为紧密, 使薄膜表现出热收缩现象. 通过不同体积大小的取代基团进一步调控分子链间相互作用及排列堆积, 可实现薄膜在高温下近乎零尺寸形变, 为设计制备超低膨胀聚合物基板材料提供了新思路.     

The unusual tribological behavior of diamond-like carbon films under high vacuum

We fabricate F-doped and F-S-codoped diamond-like carbon (DLC) films using plasma-enhanced chemical vapor deposition system. The hardness, Raman spectra, and high-vacuum tribological behaviors indicate that the films are DLC films. The hardness is close related to the tribological properties of DLC films under high vacuum. The high hardness of DLC films would be helpful for obtaining the long lifetime under high vacuum. The lifetimes of F-S-codoped DLC films are about 120 and 140 seconds, which is attributed to the fast graphitization under high vacuum. The lifetime of F-doped DLC films is prolonged to the value of around 300 and 440 seconds, X-ray photoelectron spectroscopy analysis exhibits the existence of the “adsorption” F, and transmission electron microscopy analysis shows that the “adsorption” F could react with Fe to form layered FeF₂ nanocrystal at the initial sliding, which could be helpful for prolonging the lifetime of F-doped DLC films under high vacuum. This investigation opens a new window to overcome the disadvantage of F, S-doped DLC films under high vacuum.     

Curing behavior and properties of high biosourced epoxy resin blends based on a triepoxy monomer and a tricarboxylic acid hardener from 10-undecenoic acid

Renewable propane-1,2,3-triyl tris(9-(oxiran-2-yl) nonanoate) (EGU, 100 wt% biogenic) and a tricarboxylic acid triglyceride (CGTU) hardener (85.7 wt% biogenic) were synthesized from 10-undecenoic acid (10-UDA) and used to produce epoxy resins with 52–92 wt% biobased carbon. CGTU was prepared by thermally activated thiol-ene coupling of thioglycolic acid onto propane-1,2,3-triyl tris(undec-10-enoate), (GUD) in the absence of solvent. The characterized CGTU was used as a green hardener of blends based on EGU and a conventional bisphenol A-based epoxy pre-polymer (DGEBA) at various mass percentages (0–100 wt%) with an stoichiometric epoxy/acid equivalent ratio. Calorimetric studies revealed higher peak temperature, lower reaction heats, and longer gelation times in resins with high EGU proportion, evidencing the lower reactivity of aliphatic EGU compared with aromatic DGEBA. Cured resins were yellowish transparent rubber-like materials with glass transition temperatures (Tg) varying from −14 °C to −42 °C and tensile strength in the range of 1750 kPa–790 kPa, for 0 and 100 wt % EGU, respectively. The soluble fraction of all resins was less than 4.3%, reflecting a high level of crosslinking. Thermosets with high biobased content showed both UV-light protection and visible light transparency.     

Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 363–371     

Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU.     

Comprehensive performance of a ball-milled La0.5Pr0.5Fe11.4Si1.6B0.2Hy/Al magnetocaloric composite

Due to the hydrogen embrittlement effect, La(Fe,Si)₁₃-based hydrides can only exist in powder form, which limits their practical application. In this work, ductile and thermally conductive Al metal was homogeneously mixed with La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2 using the ball milling method. Then hydrogenation and compactness shaping of the magnetocaloric composites were performed in one step via a sintering process under high hydrogen pressure. As the Al content reached 9 wt.%, the La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2H_y/Al composite showed the mechanical behavior of a ductile material with a yield strength of ~44 MPa and an ultimate strength of 269 MPa accompanied by a pronounced improvement in thermal conductivity. Due to the ease of formation of Fe-Al-Si phases and the several micron and submicron sizes of the composite particles caused by ball milling process, the magnetic entropy change of the composites was substantially reduced to ~1.2 J/kg· K-1.5 J/kg· K at 0 T-1.5 T.     

一系列由柔性N,N''-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)4](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}_n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)2·9H₂O}_n (5),其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构,配合物5为二维层状结构,其中金属离子由质子化的bpma配体桥连。值得注意的是,采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构,配合物3和4为螺旋链结构,配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

邻位取代基对芳基杂环磷酸盐成核有效性的影响

以2,4-二叔丁基苯酚为原料分别合成2,2'-亚甲基双(4,6-二叔丁基苯基)磷酸钠(NA-1)和2,2'-亚甲基双(4-叔丁基苯基)磷酸钠(NA-2),并将其应用于等规聚丙烯(i PP),研究该类芳基杂环磷酸盐成核剂邻位取代基对其成核有效性的影响.通过红外吸收光谱(FTIR)、核磁共振谱(NMR)、X-Ray多晶粉末衍射(XRD)、扫描电镜分析(SEM)和热分析对其化学结构、凝聚态结构、颗粒形貌和物性特征进行了表征,确定了NA-1和NA-2的分子结构和凝聚态颗粒的结构、形貌和物性特征.利用偏光显微观察(POM)、扫描电镜(SEM)断口分析、示差式扫描量热分析(DSC)和雾度测试分析对其与i PP的复合材料的晶粒结构、结晶行为及宏观光学性能进行测试表征.结果表明,添加量0.2%时,邻位叔丁基(NA-1)的存在可使复合材料球晶尺度更加细密,结晶温度比无邻位叔丁基(NA-2)增加5.1 K,等温结晶速率提高至0.56 w/g是NA-2的7倍,半结晶时间由NA-2的11.55 min下降至2.36 min,邻位叔丁基存在对材料透光率和雾度值的影响分别达到4.3%,7.4%.SEM断口分析表明二者在i PP基体中分散均匀,平均粒径相近分别为0.79μm和0.82μm,粒径分布曲线相近,二者分散分布的差异性不显著.     

界面扩张流变法研究C12mimBr对Gemini12-2-12在空气/水界面聚集行为的影响

采用界面扩张流变技术研究了季铵盐偶联表面活性剂C₁₂-(CH₂)₂-C₁₂·2Br (Gemini12-2-12)及其与离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C₁₂mimBr)复配体系的动态界面张力、扩张流变性质和界面弛豫过程等, 探讨了C₁₂mimBr 对C₁₂mimBr/Gemini12-2-12 混合体系界面性质的影响及C₁₂mimBr 对Gemini12-2-12界面聚集行为影响的机制. 结果表明, 随着离子液体表面活性剂的不断引入, 体系界面吸附达到平衡所需的时间逐渐缩短, 扩张模量和相角明显降低, 界面吸附膜由粘弹性膜转变为近似纯弹性膜; 同时, 界面及其附近的弛豫过程也发生显著变化, 慢弛豫过程消失, 快弛豫过程占主导地位, 且离子液体浓度越高, 快弛豫的贡献越大. 这些界面性质的变化主要归因于离子液体表面活性剂C₁₂mimBr参与界面形成及两表面活性剂在界面竞争吸附的结果. 少量离子液体表面活性剂C₁₂mimBr 的加入可以填补疏松的Gemini12-2-12 界面上的空位, 形成混合界面吸附膜. 随着C₁₂mimBr 含量的增加, 嵌入界面的C₁₂mimBr 分子数不断增多, 导致界面上相互缠绕的Gemini12-2-12烷基链“解缠”, 在体相和界面分子扩散交换的过程中“解缠”的Gemini12-2-12分子从界面上解吸回到体相, 与此同时, C₁₂mimBr 分子相对较小的空间位阻及较强的疏水作用促使其优先扩散至界面进而取代Gemini12-2-12分子, 最终界面几乎完全被C₁₂mimBr分子所占据.     

Li3V2（PO4）3/C正极材料在不同电压区间的电化学行为及容量衰减原因

采用溶胶-凝胶法制备锂离子电池正极材料Li3V2(PO4)3/C.通过恒电流充放电测试、循环伏安(CV)、电化学阻抗谱(EIS)等方法,研究了Li3V2(PO4)3/C在不同电压区间的电化学行为(3.0-4.5 V和3.0-4.8 V).结果表明,3.0-4.8 V电压区间的循环性能和倍率性能均不及3.0-4.5 V电压区间的.3.0-4.5 V区间0.1C (1C=150 mA?g-1)倍率首次放电比容量为127.0 mAh?g-1,循环50次后容量保持率为99.5%,而3.0-4.8 V区间的分别为168.2 mAh?g-1和78.5%.经过高倍率测试后再回到0.1C倍率充放电,3.0-4.5 V和3.0-4.8 V的放电比容量分别为初始0.1C倍率的99.0%和80.7%.经过3.0-4.8 V电压区间测试后,少部分第三个锂离子能够在低于4.5 V的电压脱出,使3.0-4.5 V电压区间的放电比容量提升了7.4%. CV结果表明3.0-4.8 V区间的容量损失主要表现为第一个锂离子的不可逆损失.极片的X射线衍射(XRD)和X射线光电子能谱(XPS)分析测试结果表明经过3.0-4.8 V测试后, Li3V2(PO4)3的结构发生了轻微的改变.电感耦合等离子体(ICP)测试结果表明循环后的电解液中含有少量的V.结构变形和V溶解可能是Li3V2(PO4)3在3.0-4.8 V区间容量衰减的主要原因.