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1.
戊酸甲酯是生物柴油和长链脂类燃烧过程中的中间产物之一。迄今为止,文献中还没有戊酸甲酯点火延迟的实验结果,因此对其点火特性的研究是必要的。在本文工作中,于反射激波后测量了戊酸甲酯/空气和戊酸甲酯/4%氧气/氩气的点火延迟时间。实验条件为:戊酸甲酯/空气点火温度1050–1350 K,点火压力1.5 × 105和16 × 105 Pa,当量比0.5、1和2;戊酸甲酯/4%氧气/氩气点火温度1210–1410 K,点火压力3.5 × 105和7 × 105 Pa,当量比0.75和1.25。点火延迟时间由在距离激波管端面15毫米处的测量点测到的反射激波到达信号和CH自由基信号所决定。所得实验结果显示:对于戊酸甲酯/空气和戊酸甲酯/4%氧气/氩气,温度或压力的增加都一定会使它们的点火延迟时间变短,但对于戊酸甲酯/空气,当量比对其点火延迟时间的影响在高低压下却是不同的(16 × 105 Pa: τign = 5.43 × 10−6Ф−0.411exp(1.73 × 102/RT),1.5 × 105 Pa: τign = 7.58 × 10−7Ф0.193exp(2.11 × 102/RT)。当压力为3.5 × 105–7 × 105 Pa时,还获得了戊酸甲酯/4%氧气/氩气点火延迟时间随点火条件的变化关系:τign = 2.80 × 10−5(10−5P)−0.446±0.032Ф0.246±0.044exp((1.88 ± 0.03) × 102/RT)。这些关系式反映了点火延迟时间对温度、压力和当量比的依赖关系,且有助于将实验数据归一到特定条件下进行比较。在本文实验条件下,由于戊酸甲酯/空气的燃料浓度远大于戊酸甲酯/4%氧气/氩气的燃料浓度,所测戊酸甲酯/空气的点火延迟时间远短于戊酸甲酯/4%氧气/氩气的点火延迟时间。通过对戊酸甲酯和其它长链脂类的点火特性比较,发现在相对低温时(空气中1200 K以下,氩气中1280 K以下),戊酸甲酯的点火延迟时间要长于其它长链脂类的点火延迟时间。已有的两个戊酸甲酯化学动力学机理都不能很好地预测本文实验结果,对戊酸甲酯机理的进一步完善是需要的。敏感度分析结果表明,支链反应H + O2 = O + OH对戊酸甲酯的高温点火起着最强的促进作用。据我们所知,本文首次报道了戊酸甲酯的高温点火延迟实验数据,研究结果对了解戊酸甲酯的点火特性非常重要,并且为完善戊酸甲酯的化学动力学机理提供了实验依据。  相似文献   

2.
新型非线性光学杂化材料结构与性能的研究   总被引:3,自引:0,他引:3  
由硅烷染料ASD与钛酸四正丁酯在酸性条件下共水解、缩合得到杂化材料,利用透射电镜(TEM)和X射线能量色散谱仪(EDS)进行分析,结果表明,杂化溶胶粒子是由硅和钛的化合物组成的球形纳米粒子.由一维刚性取向气体模型计算杂化材料膜再极化后的二阶非线性光学系数χ(2)为1.43×10-7esu.差示扫描量热法(DSC)测得杂化材料的玻璃化温度可达469K;用紫外-可见光谱对杂化膜在极化前后的取向及取向稳定性进行了研究.用原子力显微镜(AFM)和X射线衍射(XRD)研究了材料在极化过程中的结晶行为和微观结构对生色团取向稳定性的影响,初次在这种极化后的膜中观察到了介观结构.  相似文献   

3.
中红外非线性光学晶体可以实现中红外激光频率转换、拓展激光波长,在民用和军用领域中有至关重要的应用价值。其中,硅酸镓镧族晶体具有透过范围宽、激光损伤阈值高、晶体质量好等优势,引起了国内外同行的广泛关注。在这篇综述中,我们基于现有的实验数据,研究和分析了三种重要的硅酸镓镧族晶体La_3Ga_5Si O_(14)(LGS)、La_3Ga_(5.5)Nb_(0.5)O_(14)(LGN)、La_3Ga_(5.5)Ta_(0.5)O_(14)(LGT)的综合性能,详细总结了它们在电光调Q开关和中红外光参量振荡以及差频激光输出方面的应用。最后,本文还讨论了今后硅酸镓镧族中红外非线性光学晶体的重点发展方向。  相似文献   

4.
A novel copper(II) thiocyanate complex [Cu(im)2(NCS)2] 1 (im=imidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. This supramolecular compound exhibits a three-dimensional solid state structure constituted by N–HS hydrogen bonds and π–π stacking interactions. The compound in DMF solutions has a very strong third-order non-linear optical (NLO) behavior with absorption coefficient and refractive index 2=1.18×10−11 mw−1, n2=−9.00×10−16 m2w−1, respectively, and third-order NLO susceptibility χ(3) of 7.00×10−10 esu.  相似文献   

5.
Recently, ferroelectric materials have attracted considerable research attention. In particular, two dimensional (2D) ferroelectric materials have been considered as most crucial for next-generation circuit designs because of their application as novel electric memory devices. However, a 2D ferroelectric material is very rare. The ferroelectric materials with the form ABP2X6 (A = Ag, Cu; B = Bi, In; X = S, Se) are of interest because of their ferroelectric property maintained in their ultrathin structures. Within the ABP2X6 monolayer, the P―P bonds form the pillars that hold the top and bottom X planes, while the off-center A―B atoms between the X layers induce a spontaneous ferroelectric polarization. If the two off-center A―B sites are equally aligned, this would lead to the appearance of the paraelectric state. Such intriguing structures must impart novel mechanical properties to the materials. Until now, there has been no report on the mechanical properties of monolayer ABP2X6. Based on first-principles calculations, we studied the structural, electronic, mechanical as well as the electromechanical coupling properties of monolayer ABP2X6 (A = Ag, Cu; B = Bi, In; X = S, Se). We found that they are all semiconductors with wide bandgaps of 2.73, 2.17, 3.00, and 2.31 eV for CuInP2Se6, CuBiP2Se6, AgBiP2S6, and AgBiP2Se6, respectively, which are calculated based on the Heyd-Scuseria-Ernzerhof (HSE) exchange correlation functional model. The conduction band minimum is mainly from p orbitals of X and B atoms, whereas the valence band maximum is due to the hybridization of the p orbital of X atoms and the d orbital of A atoms. Moreover, there are three short and three long A/B―X bonds due to the A―B off-center displacement. Together with the d-p orbital hybridization, the main reason for the distorted ferroelectric structure in ABP2X6 monolayers is the Jahn-Teller effect. ABP2X6 monolayers are predicted to be a new class of auxetic materials with an out-of-plane negative Poisson's ratio, i.e., the values of the negative Poisson's ratio are in the order AgBiP2S6 (−0.805) < AgBiP2Se6 (−0.778) < CuBiP2Se6 (−0.670) < CuInP2S6 (−0.060). This is mainly due to the tensile strain applied in the x/y direction enlarging the angle between P―P bonds and top layer X atoms, thereby enhancing the bucking height of monolayer ABP2X6. Moreover, external strain has a significant impact on the A―B off-center displacement, rendering an out-of-plane piezoelectric polarization. The values of e13 for CuInP2S6, CuBiP2Se6, AgBiP2S6, AgBiP2Se6 monolayers are calculated to be −3.95 × 10−12, −5.68 × 10−12, −3.94 × 10−12, −2.71 × 10−12 C∙m−1, respectively, which are comparable to the only experimentally confirmed 2D out-of-plane piezoelectric Janus system (piezoelectric coefficient = −3.8 × 10−12 C∙m−1). This unusual auxetic behavior, ferroelectric polarization, and the electromechanical coupling in monolayer ABP2X6 could potentially lead to enormous technologically important applications in nanoelectronics, nanomechanics, and piezoelectrics.  相似文献   

6.
Novel chromophores Ch1–8 based verbenone bridge with various strong donors and acceptors were designed for applications in nonlinear optics, and the nonlinear optical (NLO) properties of those verbenone-type chromophores were systematically investigated using the bond length alteration (BLA) theory, two states model (TSM) and sum-over-states (SOS) model. The results show that several verbenone-based chromophores possess remarkably large molecular second-order hyperpolarizabilities, which is due to its electron distribution close to the cyanine limit, the appropriate strength of acceptor, rather large change in dipole moment and low excitation energy. Computed hyperpolarizability (βtot) of Ch6 also approach an outstanding 2922 × 10−30 esu in TFE. The hyperpolarizability density analyses and two states model (TSM) were carried out to make a further insight into the origination of molecular nonlinearity of this unique system, suggesting that tuning structure of acceptor and polarity of the medium have great influence on the second-order nonlinear optical properties. More importantly, chromophores Ch1–Ch8 exhibited distinct features in two-dimensional second order NLO responses, and the strong electro-optical Pockels effect and optical rectification responses. The excellent electronic sum frequency generations (SFG) and difference frequency generations (DFG) effect are observed in these verbenone-type chromophores. These chromophores have a possibility to be appealing second-order nonlinear optical (NLO) materials, data storage materials and DSSCs materials from the standpoint of large β values, high LHE, and excellent two-dimensional second order NLO responses.  相似文献   

7.
In this paper, we have calculated the third-order nonlinear optical polarizabilities corresponding to three optical processes: third-harmonic generation (THG), electric-field-induced second-harmonic generation (EFISHG) and degenerate four-wave mixing (DFWM) for B12N12, B24N24 and B36N36 clusters. The calculations have been performed by employing ab initio time-dependent density functional theory combined with sum-over-states method (SOS//TDDFT). We obtained the similar dynamic behavior of third-order NLO polarizabilities for three BN clusters. At input photon energy below 1.25 eV, the resonance enhancements of response haven't occurred. This is due to the fact that the calculated BN clusters have the large transition energy. B24N24 cluster has the larger transition dipole moments and the third-order polarizabilities of B24N24 are much larger than those of B12N12 and B36N36. We also estimate the static third-order optical susceptibility χ(3) for BN fullerene materials from the average static third-order polarizability <γ>. The static χ(3) of B24N24 fullerene materials are 1.36×10−14 esu for three NLO processes.  相似文献   

8.
合成了2种新的具有潜在应用价值的非线性光学(NLO)有机材料芳香查尔酮衍生物1-(呋喃-2-基)-3-(4-甲氧基苯基)丙烯酮(1)和1-(噻吩-2-基)-3-(4-甲氧基苯基)丙烯酮(2),并对其进行了NMR、IR和HR-MS结构表征。 采用4f相位相干成像技术测定了化合物1和2的三阶NLO性质并确定了相关参数:脉冲宽度4 nm,激光波长440 nm,化合物1:非线性吸收系数β=5.5×10-10 m/W,非线性折射系数n2=-2.1×10-17 m2/W,三阶非线性极化率χ(3)=1.58×10-11 esu;化合物2:β=-2.4×10-10 m/W,n2=0.3×10-17 m2/W,χ(3)=0.50×10-11 esu;并测定了紫外光谱和DSC曲线。 采用密度泛函方法计算了化合物1和2的轨道能量和极化率,结果表明电子转移能在分子内部进行,说明比较易于极化,展示了良好的非线性光学性质。  相似文献   

9.
孙金鱼  石玉芳  王桂林  赵明根 《应用化学》2015,32(10):1134-1138
合成了一种新的具有潜在应用价值的非线性光学(NLO)有机材料1-(芘-1-基)-3-(4-二甲氨基苯基)丙烯酮(PMAK),并通过 NMR、IR、MS和元素分析等技术手段进行了表征。 采用溶液Nd:YAG激光技术测定了PMAK的三阶非线性光学性质并确定了相关参数。 纳秒实验结果:折射率n2=-3.5×10-17 m2/W,吸收系数β=7.0×10-10 m/W,极化率χ(3)=2.54×10-11 esu,分子超极化率γ=3.44×10-30 esu;皮秒实验结果:n2=-2.8×10-18 m2/W,β=8.3×10-11 m/W,χ(3)=2.49×10-12 esu,γ=3.33×10-31 esu。  相似文献   

10.
采用密度泛函理论(DFT)方法对双环金属Ir(III)异腈配合物的非线性光学(NLO)性质进行计算研究。用B3PW91(UB3PW91)(金属原子采用LANL2DZ基组,非金属原子采用6-31G*基组)方法对配合物进行几何结构优化。在优化构型基础上,采用B3PW91(UB3PW91)和B3LYP(UB3LYP)方法计算了配合物的第一超极化率(βtot),并用CAM-B3LYP(UCAM-B3LYP)(金属原子采用LANL2DZ基组,非金属原子采用6-31G**基组)方法模拟配合物的吸收光谱。结果表明,主配体的取代基(R1)和副配体的取代基(R2)对第一超极化率值贡献不大。配合物发生氧化还原反应,电荷转移方式增多,电荷转移程度增大,使βtot值显著增加,其中1a+([(C∧N)2Ir(CNR)2]+(R=CH3))发生氧化反应和还原反应的βtot值分别增大了75倍和144倍。因此,这类双环金属铱(III)异腈配合物的氧化还原反应可以有效地调节其二阶NLO性质。  相似文献   

11.
合成了一个新的非线性光学(NLO)有机材料1-二茂铁基-3-[(9-乙基)咔唑-3-基]丙烯酮(FCAK),并通过NMR、IR、MS和元素分析等技术手段进行了表征。 采用粉末Nd∶YAG激光技术测定了标题化合物的三阶非线性光学性质并确定了相关参数。 激光脉冲为4 ns时,非线性折射率n2=-3.5×10-18 m2/W,非线性吸收系数β=-2.7×10-11 m/W,三阶非线性极化率χ(3)=2.04×10-12 esu,三阶非线性分子超极化率γ=1.1×10-30 esu。 激光脉冲为21 ps时,n2=0.55×10-18 m2/W,β=-0.6×10-11 m/W,χ(3)=3.4×10-13 esu,γ=0.13×10-30 esu。  相似文献   

12.
聚羟基丁酸-戊酸的非等温热分解反应动力学   总被引:4,自引:0,他引:4  
用非等温TG-DTA技术, 在5.0、10.0、15.0和20.0 K•min-1线性升温条件下, 研究聚羟基丁酸-戊酸(PHBV)的热分解反应动力学. 结果表明, 分解过程分三个阶段:分解初期、分解中期和分解后期. 分解初期的机理函数为Avrami-Erofeev方程(n=1/2), 对应随机成核和随后生长机理, 表观活化能Ea(β→0)为69.44 kJ•mol-1, 指前因子A(β→0)为106.27 s-1;分解中期的机理函数为Avrami-Erofeev方程(n =2/5), 对应随机成核和随后生长机理, 表观活化能Ea(β→0)为117.64 kJ•mol-1, 指前因子A(β→0)为1011.48 s-1;分解后期的机理函数为Mampel Power法则(n=1/3), 对应机理为幂函数法则, 表观活化能Ea(β→0)为116.64 kJ•mol-1, 指前因子A(β→0)为108.68 s-1.  相似文献   

13.
The current study has obtained excellent potential nonlinear optical(NLO) materials by combining density functional theory methods with sum-over-states model to predict the second order NLO properties of helical graphene nanoribbons(HGNs) through introducing azulene defects or/and BN units. The introduction of these functional groups deforms the pristine HGN (compression or tension) and enhances obviously the static first hyperpolarizability(<b0>) of system by up to two orders of magnitude. The tensor components along the helical axis of HGNs play a dominant role in the total <b0>. The azulene defects and the BN units polarize the pristine HGN to different degrees, and the azulenes and contiguous benzenes are involved in the major electron excitations with significant contributions to <b0> but the BN units are not. The BN-doped chiral HGNs have good kinetic stability and strong second order NLO properties(6.84×105×10-30 esu), and can be a potential candidate of high-performance second order NLO materials. The predicted two-dimensional second order NLO spectra provide useful information for further exploration of those helicenes for electro-optic applications.  相似文献   

14.
合成了一种新的有机非线性光学(NLO)材料1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮(PMPAK),通过1H NMR、IR、HR-MS和元素分析表征其结构。 以Nd:YAG-Laser System作为光源,激光波长450 nm,脉冲宽度4 ns(FWHM),采用4f相位相干成像技术测定了PMPAK的三阶NLO性质并确定了相关参数:非线性折射率n2=-1.84×10-16 m2/W,非线性吸收系数β=2.53×10-9 m/W,非线性极化率χ(3)=1.137×10-10 esu。  相似文献   

15.
Langmuir-Blodgett (LB) film of a hemicyanine derivative, (E)-N-hexadecyl-4-[2-(4-dimethylaminophenyl)ethenyl]pyridinium bromide (Hc) was fabricated. The Langmuir film of Hc exhibited good transfer behaviour. Optical second harmonic generation from the LB film was measured. Macroscopic second-order susceptibilily, molecular hyperpolarizability and tilt angle for the molecules on a substrate were estimated to be 7.06×10-6 esu, 6.47×10-27 esu,and 31.6° respectively.  相似文献   

16.
The solute polarization due to solvent is a an electrostatic quantum effect that impacts diverse molecular properties, including the nonlinear optical response of a material. An iterative procedure that allows updating the solute charge distribution in the presence of the solvent is combined with a sequential Monte Carlo/Quantum Mechanics methodology and Density Functional Theory methods to evaluate the nonlinear optical (NLO) response using the hyper Rayleigh scattering (HRS) of a series of chromones recently identified in Chamaecrista diphylla, an herbaceous plant abundant throughout the Americas and used in folk medicine. From this study, it is determined that from gas to solvent environment, the systems acquire low refractive index (n) and an improvement of the first hyperpolarizability (βHRS), signaling potential NLO uses. It is shown that the octupolar contributions (βJ=3) superate the dipolar ones (βJ=1) and dominate the second-order optical response in both gas and liquid phases, which indicate nontrivial optical materials. Moreover, the solvent environment and structural changes in the periphery can tune significantly the dipolar/octupolar balance, showing a key to control the decoupling between these contributions.  相似文献   

17.
分别采用热解法和溶胶-凝胶-碳热还原法合成了石墨相氮化碳(g-C3N4)和纳米级碳化硅(β-SiC), 通过浸渍-热处理法将两者复合并通过浓盐酸质子化, 分别制备了g-C3N4/β-SiC和质子化g-C3N4/β-SiC(P-g-C3N4/β-SiC)复合光催化剂. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 高分辨透射电子显微镜(HRTEM)、 傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、 紫外-可见漫反射光谱(UV-Vis-DRS)和光致发光光谱(PL)等对样品进行了表征. 结果表明, P-g-C3N4/β-SiC复合材料的比表面积增大, 光生电子-空穴对的复合几率降低, 光催化性能明显提高. 在光催化降解染料茜素红(ARS)研究中, 样品的可见光催化活性顺序为P-g-C3N4/β-SiC>g-C3N4/β-SiC>P-g-C3N4>g-C3N4>β-SiC. 其中P-g-C3N4/β-SiC在60 min内对ARS的降解效率高达99.9%, 符合准一阶动力学模型, 速率常数为0.0967 min -1, 且循环使用9次后, 光催化降解效率仍保持97.5%以上.  相似文献   

18.
采用共沉淀法制备了高比表面积的MnxCo3−xO4球形催化剂,研究了NH3选择性催化还原NOx性能。Mn-Co金属氧化物具有尖晶石结构,随着Co含量的增加,晶体结构由四方相转变为立方相。高浓度的表面活性氧物种和变价元素的强有效电子转移(Co3+ + Mn3+ ↔ Co2+ + Mn4+)有利于提高MnxCo3−xO4 (x = 1.0、1.5、2.0)尖晶型石催化剂的氧化还原能力,催化剂表面的Mn富集作用形成了氧缺陷结构和丰富的表面活性位点,进一步促进SCR脱硝反应,呈现出优异的催化性能。Cotet(CoMn)octO4晶体结构中,Mn离子(Mn3+和Mn4+,以三价锰为主)和部分Co离子被配置到八面体中心,这些物种作为活性位点存在着较强的电子转移交互作用,该构型对促进低温脱硝活性和保护活性位点耐受SO2毒害具有重要的意义。Mn-Co尖晶石表面的NH3-SCR脱硝反应过程主要遵循Eley-Rideal反应机理,即吸附态NH3与气态NO (或NO2)的反应路径。随着反应温度的增加,反应生成的NH4NO3中间体很可能转化为NH4NO2物种,进而分解为N2,提高了催化剂的氮气选择性。  相似文献   

19.
采用密度泛函理论(DFT)方法对卟啉-碳硼烷-硼亚甲基二吡咯(BODIPY)三元化合物的几何结构、 吸收光谱及二阶非线性光学(NLO)特性进行计算分析. 结果表明, V型化合物的静态第一超极化率(βtot)大于相应直线型化合物, 且延长共轭链可提高体系的βtot. 分析体系的电子密度差分图得出, 化合物氧化还原态的电荷转移方式与本征态相比发生了改变, 从而使其二阶NLO性质发生明显变化. 含频第一超极化率计算结果表明, 在一定范围内频率对化合物有较小的色散效应. 因此, 通过延长二维化合物的共轭链及氧化还原反应, 可以有效调控其二阶NLO响应.  相似文献   

20.
A series of D3 (Fe(II), Ru(II), Zn(II), Hg(II)) and D2d (Cu(I), Ag(I), Zn(II)) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 microm, and the molecular hyperpolarizability (beta0) values are in the range of 200-657 x 10(-30) esu for octahedral complexes and 70-157 x 10(-30) esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4'-oligophenylenevinylene-functionalized 2,2'-bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (lambdamax=482 nm, beta1.91(1 e)=870 x 10(-30) esu, beta0(1 e)=657 x 10(-30) esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and pi linkers), and the nature of the metallic centers. For example, the length of the pi-conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand-to-metal ratio result in a substantial enhancement of beta. The contribution of the metal-to-ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).  相似文献   

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