石墨烯/聚乳酸3D打印复合线材制备及性能研究

采用熔融挤出成型工艺制备了石墨烯/聚乳酸复合线材,研究了模口温度、螺杆转速等工艺参数对复合线材导电性能的影响;研究了不同石墨烯含量对复合线材综合性能的影响;最后进行了石墨烯/聚乳酸复合线材3D打印实验。研究结果表明:只有当模口温度高于195℃时,才能获得表面光滑无气孔缺陷的线材;复合线材电导率随着模口温度和螺杆转速的增加,先增大后减小,合适的模口温度为200～210℃,螺杆转速为13～17 r/min。石墨烯/聚乳酸复合线材拉伸强度和断裂伸长率随着石墨烯含量增加而增大,当石墨烯质量分数为9%时,电导率最高,达到2.7×10~(-2) S/cm。在FDM打印实验中发现:添加石墨烯5%时,其抗弯强度提高了57.1%。与石墨烯/PLA复合线材相比,打印试样的电导率有所提高。     

工艺条件对PBAT/PLA原位成纤共混体系结构与性能的影响

将质量比为80/20的PBAT/PLA共混物在单螺杆挤出流延成型机中通过调控工艺条件（口模温度、拉伸速度）直接熔融共混制备PBAT/PLA原位成纤共混薄膜。结果表明,在较低口模温度时,随着拉伸速度的提高,PLA微纤细化程度加大,结晶度先提高后降低,纵向拉伸强度先增加后减小,力学性能各向异性明显。在口模温度为150℃、拉伸速度为5.0 m/min时,共混体系中PLA成纤效果最明显;PBAT和PLA的结晶度最高分别为4.8%和23.7%;纵向拉伸强度达到29.8 MPa,比纯PBAT提高了41%。     

高导电强韧性聚乳酸/多壁碳纳米管复合材料的制备及其结构调控

为了探究聚乙二醇丙烯酸酯(PEGDA)的引入对多壁碳纳米管/聚乳酸(MWCNT/PLA)复合材料结晶性能、热力学稳定性、导电性能和力学性能的影响,首先采用了化学改性的方法将小分子量PEGDA单体原位接枝到线型PLA分子链上,实现了具有一定柔性结构聚乳酸(GPLA)的改性制备;其次利用熔融加工的方法实现了多壁碳纳米管在PLA/GPLA/MWCNT复合材料内部的均匀富集分布,促进了复合材料内部导电网络的构筑。结果表明,通过化学原位接枝法可以成功将PEGDA接枝到PLA分子链上,形成长链结构,并且长链结构的形成能够提高复合材料的复数黏度、结晶性能和热力学稳定性。导电数据表明,随着MWCNT含量的增加,PLA/MWCNT复合材料的导电性能逐步改善,导电逾渗阈值约为0.8%;并且复合材料内部GPLA的引入,可以充分利用GPLA的异相成核能力和“晶体排斥”效应,促使PLA/MWCNT/GPLA复合材料的导电性能表现出了先升高后降低的现象,这主要是因为高含量的GPLA的引入,导致了复合材料内部的复数黏度提高,使复合材料内部MWCNT的团聚体表现出了不同的分布状态。当GPLA的含量增加到15%时,复合...     

高导电、低逾渗PLA/CNTs导电复合材料的结构设计及性能研究

通过溶液吸附?熔融法制备了具有低逾渗高导电性能的左旋聚乳酸/右旋聚乳酸/碳纳米管(PLA/PDLA/CNTs)复合材料。在PLA/CNTs复合材料内部通过添加PDLA以提高复合材料的结晶性能,起到良好的体积排斥作用,促进了CNTs的分散,对PLA/PDLA/CNTs复合材料的导电网络结构进行有效调控;随着PDLA含量的增加,PLA/PDLA/CNTs复合材料的导电性能表现出了先增加后降低的趋势,当PDLA的含量仅为0.2%时,PLA/0.2%PDLA/0.6%CNTs的电导率从10^-6 S/m提升到了10^-4 S/m,提高了2个数量级,并且复合材料的导电逾渗值从0.58%(PLA/CNTs)降低到0.45%(PLA/PDLA/0.6%CNTs)。此外,CNTs和PDLA的引入可以有效的提高复合材料的结晶性能和复数黏度,相比于纯PLA,PLA/0.5%PDLA/0.6%CNTs的开始结晶温度(T_o)和最大峰结晶温度(T_p)分别提高了30.6℃和20.8℃。通过力学性能数据分析发现,在CNTs和PDLA...     

PBS/PLA/滑石粉3D打印线材制备及熔融沉积成型工艺研究

以聚丁二酸丁二醇酯(PBS)为基体,滑石粉和聚乳酸(PLA)为改性剂,采用熔融挤出法制备了PBS/PLA/滑石粉三维 （3D）打印线材,并对其进行了熔融成型研究。通过分析结晶性能、流变性能、力学性能、断面形貌和打印效果对PBS/PLA/滑石粉体系进行了探究。结果表明,PLA的加入使PBS的结晶温度下降了5 ℃;随着PLA含量的增加,材料的复数黏度、储能模量和损耗模量均得到提高;而拉伸强度则随PLA含量的增加下降了1.71 MPa,缺口冲击强度下降了2.63 kJ/m2;PLA含量的增加使断面逐渐粗糙;在打印效果上复合材料的打印模型随PLA含量的增加而变得美观规整,当底板温度高于110 ℃时,打印制件的翘曲度较低,同时拉伸强度随着打印温度的升高而增加。     

3D打印制备PLA/MWCNT复合材料及其性能研究

聚乳酸作为基体材料,通过研磨共混法制备了多壁碳纳米管(MWCNT)/聚乳酸(PLA)复合粒料,应用3D打印技术打印了PLA/MWCNT复合材料样条。通过对复合材料导电性能测试,结果表明随着MWCNT掺杂量的增加,复合材料的电导率数值呈指数型增长,当MWCNT含量达6%时,电导率为10~(-2) S/cm。力学性能测试得到在MWCNT含量为6%时,样条的拉伸强度达63.7 MPa,比纯的PLA材料提升37.6%;弯曲强度为126.7 MPa,提高了16.9%。扫描电子显微镜(SEM)观察发现MWCNT在PLA基体中较为分散,PLA/MWCNT复合样条断面呈现多孔蜂窝状。样品热分解温度高达390.2℃,耐热效果明显提升。     

转速对PP-g-MA改性石墨烯/TPU/PP复合材料力学和电学性能的影响

以热塑性聚氨酯(TPU)和聚丙烯(PP)为基体,石墨烯为导电填料,聚丙烯接枝马来酸酐(PP-g-MA)为界面增容剂,制备了石墨烯/TPU/PP/PP-g-MA导电复合材料。研究了螺杆转速对复合材料力学性能和电学性能的影响以及石墨烯在复合材料中的选择性分布状态。结果表明,随着螺杆转速从10 r/min提高到50 r/min,复合材料的拉伸强度提高了103.62%,断裂伸长率提高了161.47%,电导率提高了155.49%,体系中石墨烯选择性分布在TPU中,石墨烯/TPU在基体中则形成了共连续的导电网络。     

聚乳酸/剑麻复合材料流变性能表征

利用转矩流变仪测量流变特性的方法,表征了不同剑麻纤维含量下,聚乳酸(PLA)/剑麻复合材料的流变性能,并测量实验后纤维的长度和宽度、PLA分子量,分析剑麻纤维含量和转速对复合材料体系中纤维长度的影响,以及PLA降解情况。结果表明,复合材料的非牛顿指数在纤维含量为10%左右出现峰值,并进一步随含量的增加而减小。复合体系中,刚性剑麻纤维受到来自于转子、聚合物和纤维之间的作用力,纤维被剪短,长径比减小;聚乳酸会受到转速和纤维含量的影响发生降解,这些因素都会影响PLA/剑麻复合材料的流变性能。     

用于脑电图监测的石墨烯/聚丙烯酸共聚酯/织物复合电极的制备与性能

为制备脑电检测用聚合物基柔性复合电极片,以石墨烯、丙烯酸(AA)、丙烯酸甲酯(MA)和丙烯酸乙酯(EA)为原料,通过原位聚合的方法制得了系列聚丙烯酸共聚酯/石墨烯复合乳液,并通过与织物浸渍的方法制备了复合电极片。研究了石墨烯含量变化对复合电极片电阻的影响、各单体含量对电极片柔性的影响,以及复合电极片用于脑电监测的性能。结果表明,当石墨烯的质量分数约为46.5%、反应温度80 ℃,反应时间3 h,AA、MA与EA的体积投料比为0.2∶1∶1.8,织物采用聚丙烯无纺布并与聚丙烯酸共聚酯复合乳液浸渍后,制备的复合电极片在室温下具有良好的柔性、导电及力学强度,适合用于脑电图监测,脑电信号强度及其稳定性与商用电极（Ag/AgCl）相比性能相近,且不需要涂抹导电膏,使用方便,不会污染皮肤及对皮肤造成损伤。     

静电纺丝法制备聚酰亚胺/碳化硅复合纳米纤维

利用聚酰胺酸(PAA)溶液和纳米碳化硅(SiC)混合物作为纺丝液,通过静电纺丝法制备聚酰胺酸/碳化硅(PAA/SiC)复合纳米纤维,PAA/SiC复合纳米纤维亚胺化后得到聚酰亚胺/碳化硅(PI/SiC)复合纳米纤维。研究了PAA溶液中PAA含量、纺丝电压、纺丝距离及SiC含量对PAA/SiC复合纳米纤维形貌的影响,利用热重法分析了PI/SiC复合纳米纤维的热稳定性。结果表明,使用固含量为15%的PAA溶液作为基体材料,再将纳米SiC以6%的含量均匀分散于基体材料中制备出纺丝液,在纺丝电压为10～18kV左右、纺丝距离为15cm时,可制备出直径250nm左右、光滑、连续、SiC分布均匀的PAA/SiC复合纳米纤维。PI/SiC复合纳米纤维热稳定性优异,氮气气氛中热分解温度为550℃。     

Polymorphism of LiGa5O8 and of LiGa5O8-MgGa2O4Solid Solutions

High-temperature X-ray diffraction and differential thermal analyses showed that LiGa₅O₈ exists in two polymorphs related by the first-order transition at 1138°±3°C of the low-temperature simple-cubic form, space group (probably) O⁷, to the high-temperature spinel (fcc) form, space group O _h ⁷. The transition is rapid, and the high-temperature form in pure LiGa₅O₈ could not be quenched to room temperature under the conditions used. However, the high-temperature polymorph can be quenched under equilibrium conditions when 40 mol% or more MgGa₂O₄ is present. The subsolidus equilibrium relations in the system MgGa₂O₄-LiGa₅O₈ are discussed.     

Magnetoresistance of CuxCo1-xFe2O4 Ferrites

Magnetoresistance measurements (Δ/R) were carried out on Cu _x Co_{1- x} Fe₂O₄ samples with x =1, 0.75, 0.50, 0.25 and cobalt ferrite in the range of magnetic intensity (H) from 1.0 to 4.5 kG. Linear plots were obtained between log (Δ/R) and log H for all compositions except that of cobalt ferrite. The values of n at x =0.5 do not agree with the results of some authors. The discrepancy may be attributed to the value of magnetic field intensity at which such measurements were carried out. The similarity of features of n and μ_D with composition leads us to believe that the magnetoresistance may arise from the scattering of conduction electrons by localized electrons involving the s-d exchange interaction.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Expansive properties of the mixture C4ASH12 − 2CS III. Effects of temperature and restraint

The effects of temperature and restraint upon the hydration and the expansion of $\text{C}{}_4\text{A}\text{S}\text{H}{}_{12}\text{? 2}\text{C}\text{S}$ mixture compacts in different contact solutions have been investigated. Temperatures above 20°C do apparently hinder the formation of an impervious felt-like layer of ettringite around the $\text{C}{}_4\text{A}\text{S}\text{H}{}_{12}$ particles, thus greatly reducing the retarding effect of the lime. An uniaxial restraint of 1 Kg/cm² is enough to reduce sensibly the expansions which remain however high (about 100%). The results can be satisfactorily interpreted by the reaction and expansion mechanism hypothesized in our previous papers.     

Preparation and properties of poly(Nε,Nε-dicarboxymethyl-l-lysine)

A new ampholytic homopolypeptide, $\text{poly}\text{(N}{}^{\mathrm{\epsilon }}\text{,N}{}^{\mathrm{\epsilon }}\text{-}\text{dicarboxy-methyl-}\text{l}\text{-lysine}\text{)}$, which has one tertiary amino and two carboxyl groups in the side chain has been derived from a hydrochloride salt of poly(L-lysine). The polymer in aqueous solution seems to be in the coil form with locally extended structure (LES) at neutral pH. In both the acidic and alkaline regions, the molar ellipticity of the polymer changes as a result of change in net charge on the side chain. The conformational changes may be from the coil with LES to other coiled forms. 5–7 M NaClO₄ and 80% aqueous methanol induce the α-helix in the polymer at neutral pH. Divalent cations, Cu²⁺ and Ca²⁺, do not induce any remarkably ordered structures such as α-helix or β-structure in the polymer in aqueous solution at any pH. Ultraviolet absorption studies show an absorption peak of the polymer-Cu²⁺ complex near 240 nm. Dependence of the peak intensity on pH at various q values ($\text{q =}\text{[}\text{Cu}{}^{\mathrm{2+}}\text{]}\text{[}\text{residue}\text{]}$) indicates the two steps of the complex formation. At q less than 0.64, the formation is described only with the first step. An average coordination number for Cu²⁺ at the first step was calculated to be about 2 by the method of Mandel and Leyte. The association constant of Cu²⁺ with the residue at the step was determined from the absorption data to be far smaller than that for the Cu²⁺-EDTA complex. The second step of the formation occurs in the case of large q but the absorption data for the second step cannot be obtained exactly due to precipitation.     

Raman Study of Glasses of Ba2TiSi2O8 and Ba2TiGe2O8

Raman spectra are reported for fresnoite (Ba₂Ti(Si,Ge)₂O₈ glasses, and comparison is made between the Raman spectra of the corresponding crystalline powders and glasses of Ba₂TiSi₂O₈ and Ba₂TiGe₂O₈. The Ba₂TiGe₂O₈ glass spectra show correspondence with the Ba₂TiGe₂O₈ crystalline Raman spectra; the v _s(Ge–O–Ge) mode occurs at 518 cm⁻¹ in the glass and at 521 cm⁻¹ in the crystalline material. Five-fold coordinated titanium is the majority species present in the Ba₂TiGe₂O₈ glass as revealed by a strong band at 824 cm⁻¹ in the I glass spectrum. The Ba₂TiSi₂O₈ glass spectra are similar to the Ba₂TiSi₂O₈ crystalline spectrum; the strongest band is found at 836 cm⁻¹ in the I glass spectrum. Through comparison with the previous Raman data of other titania silicate glasses, we conclude that the Ba₂TiSi₂O₈ glass has a structure similar to the crystalline phase.     

Effects of metal-support interactions on the hydrogenation of CO over PdSiO2 and PdLa2O3

A study of CO hydrogenation over $\text{Pd}\text{SiO}{}_2$ and $\text{Pd}\text{La}{}_2\text{O}{}_3$ has been carried out for the purpose of identifying the effects of Pd dispersion, Pd morphology, and support composition on the catalytic activity of supported Pd. The specific activity of each catalyst for methanol and methane synthesis was determined from microreactor studies carried out at a fixed set of reaction conditions. Palladium dispersion was measured by H₂O₂ titration, and the morphology of the Pd crystallites, as expressed by the distribution of Pd(100) and Pd(111) planes, was determined from in situ infrared spectra of adsorbed CO. The crystallite morphology of the $\text{Pd}\text{SiO}{}_2$ catalysts is the same, independent of Pd weight loading: 90% of the surface is comprised of Pd(100) planes and 10% of the surface is comprised of Pd(111) planes. By contrast, the crystallite morphology of the $\text{Pd}\text{La}{}_2\text{O}{}_3$ catalysts changes with Pd loading. Primarily Pd(100) planes are exposed at low-weight loadings while Pd(111) planes are exposed at high-weight loadings. The Pd dispersion has little effect on the methanol turnover frequency over both $\text{Pd}\text{SiO}{}_2$ and $\text{Pd}\text{La}{}_2\text{O}{}_3$, for dispersions between 10 and 20%. On the other hand, the methane turnover frequency is independent of Pd dispersion over $\text{Pd}\text{SiO}{}_2$, but increases with decreasing dispersion over $\text{Pd}\text{La}{}_2\text{O}{}_3$. It is further observed that the Pd morphology influences the specific activity of $\text{Pd}\text{La}{}_2\text{O}{}_3$ for methanol synthesis: Pd(100) is nearly threefold more active than Pd(111). For a fixed morphology, the specific methanol synthesis activity of $\text{Pd}\text{La}{}_2\text{O}{}_3$ is a factor of 7.5 greater than that of $\text{Pd}\text{SiO}{}_2$.     

In situ laser raman spectroscopy of the sulfiding of Moγ-Al2O3 catalysts

Raman spectra of sulfided $\text{Mo}\text{γ-}\text{Al}{}_2\text{O}{}_3$ catalysts were obtained using in situ techniques for two sulfiding methods. For samples sulfided by 10% $\text{H}{}_2\text{S}\text{H}{}_2$ at 400 °C, MoS₂ structures were observed. A stepwise sulfiding using 10% $\text{H}{}_2\text{S}\text{H}{}_2$, with spectra recorded at 150, 250, and 350 °C, resulted in observation of molybdenum oxysulfide, reduced molybdate, and surface “MoS₂” phases. Reexposure of these samples to air led to radical modification of the oxysulfide structures as well as transformation of some sulfide phases. A model incorporating terminal and bridging MoS bonding and anion vacancies is proposed. This model is based on the conversion of isolated and aggregated molybdate and MoO₃ species to oxysulfide and reduced molybdenum phases. Conversion of reduced molybdenum phases to sulfides is observed to be slow.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.