CaF_2单晶体应用研究

氟化钙晶体具有良好的光学性能、机械性能及物化稳定性 ,有透光范围宽广 ( 0 .1 2 5～1 0 μm)、透过率高 ,折射率低 ,相对色散大等优点。自真空紫外至中红外波段被广泛地用作窗口、透镜、棱镜、分束器、基板等材料。高纯度的CaF2 单晶体是真空紫外波段准分子激光器良好的窗口材料 ,单晶或热锻单晶CaF2 材料是一氧化碳及化学激光器的窗口材料。大尺寸、完整性好的CaF2 晶体更是紫外与可见波段优秀的镜头材料。CaF2 晶体亦可作为激光晶体和无机闪烁晶体材料。迄今为止 ,碱土氟化物晶体真空紫外波段的良好透光性能是其它材料无法相比的。此外 ,用于真空紫外波段的CaF2 单晶材料还具有抗辐射、臭氧阻高、损伤阈值高、抗氟气腐蚀和成本低的优点。近期研究表明 ,CaF2 晶体真空紫外波段主要性能已达到MgF2 晶体同等水平。在紫外和可见波段 ,CaF2 晶体由于特殊的折射指数与相对色散值 ,使其成为复消色差透镜理想的光学材料。晶体完整性好 ,光学均匀性好于 1 0 -5 ,应力双折射通常在 5～ 1 5nm/cm范围内。用于高倍显微镜镜头的CaF2 只有几个毫米大小 ,而用于侦察、天文、紫外光刻的CaF2晶体 ,其直径最大已接近 30 0mm。长春光机所的CaF2 晶体已被用于这些方面 ,最大镜头尺寸1 90mm。人工CaF2

直径200毫米CaF_2单晶体生长

我们采用一种特定设计的Bridgman Stockbarger炉 ,已经稳定地生长出直径 2 0 0mm ,高1 70mm的CaF2 晶体 ,晶体初端与终端有时出现较明显的光散射、亮点及包裹体。晶体初始端主要缺陷是零星分布散射亮点 ,而散射光柱则很轻 ;晶体终端出现 30mm左右的指向终端逐渐变重的散射光柱。进一步试验表明 ,通过改进工艺 ,端部效应影响可以得到有效地改进。大尺寸CaF2 单晶体生长工艺技术的成熟主要表现在晶体结构完整性好 ,其次是低角度晶界处的光学连续性好。大尺寸单晶体的制做中 ,结构完整性无论对晶体光学性能还是对元件制做都是至关重要的。决定结构完整性的关键因素是炉内温场分布 ,其次是工艺参数的选取及合理匹配。在低角度晶界界面上 ,应该不存在杂质沉积或者说杂质沉积甚微 ,无微气泡层出现。界面光学连续性好 ,光波通过此处无明显的波前畸变发生。结构完整性好的晶体 ,通过精密退火 ,应力可达到 5～ 8nm/cm ,保证各种光学元件的加工制做及材料性能的要求。目前这些晶体已经进入国内外市场 ,被加工成1 90mm、1 5 7mm以及98mm光学透镜及窗口。

基于ASP-SERes2Net的说话人识别算法

为提升说话人识别的特征提取能力,解决在噪声环境下识别率低的问题,提出一种基于残差网络的说话人识别算法——ASP-SERes2Net。首先,采用梅尔语谱图作为神经网络的输入;其次,改进Res2Net网络的残差块,并且在每个残差块后引入压缩激活(squeeze-and-excitation,SE)注意力模块;然后,用注意力统计池化(attention statistics pooling,ASP)代替原来的平均池化;最后,采用附加角裕度的Softmax(additive angular margin Softmax,AAM-Softmax)对说话人身份进行分类。通过实验,将ASP-SERes2Net算法与时延神经网络(time delay neural network,TDNN)、ResNet34和Res2Net进行对比,ASP-SERes2Net算法的最小检测代价函数(minimum detection cost function,MinDCF)值为0.0401,等误率(equal error rate,EER)为0.52%,明显优于其他3个模型。结果表明,ASP-SERes2Net算法性能更优,适合应用于噪声环境下的说话人识别。

B_2O_3替代CaF_2铁水预处理脱磷的热力学研究

通过MoSi管式高温炉在1450℃下研究了用0～8%B_2O_3替代40%CaO-52%Fe_2O_3铁水预处理渣中0～8%CaF_2的含量,对初始硅含量为0.61%,初始磷含量0.06%～0.09%的铁水脱磷效果。实验结果表明,B_2O_3替换CaF_2后,预处理脱磷渣氧化性增加,铁水的脱磷率大于80%,渣的磷容量略有降低,从9.35×10^(21)变化到7.48×10^(21),可以满足预处理脱磷的要求。

Can trastuzumab emtansine be replaced by additional chemotherapy plus targeted therapy for HER2-overexpressing breast cancer patients with residual disease after neoadjuvant chemotherapy?

Human epidermal growth factor receptor 2(HER2)-overexpressing breast cancer is an aggressive phenotype with a poor prognosis,and can easily metastasize and recur.Currently,chemotherapy plus HER2-targeted therapy is the standard systemic treatment for most of these patients.Given that neoadjuvant chemotherapy(NAC)has an efficacy equivalent to that of adjuvant chemotherapy and some additional benefits,many patients,especially those with more advanced tumors,prefer NAC and generally will not receive additional chemotherapy after surgery,irrespective of the pathological response.However,achieving pathological complete response to NAC is strongly correlated with prognosis,especially in triple-negative and HER2-overexpressing breast cancer.Therefore,postoperative treatment of these patients with residual diseases should be optimized to achieve favorable outcomes.The CREATE-X study has confirmed that additional chemotherapy can improve the outcomes of patients with HER2-negative residual disease after NAC.In addition,chemotherapy plays an indispensable role in the treatment of patients who receive surgery directly or who have recurrent lesions.Therefore,can additional chemotherapy improve prognosis of patients with HER2-overexpressing residual breast cancer?At present,no studies have compared the efficacy of additional chemotherapy plus trastuzumab with that of anti-HER2 therapy alone in residual cancer.The KATHERINE study revealed that trastuzumab emtansine(T-DM1)can reduce the risk of recurrence or death by 50%compared with trastuzumab in patients with HER2-positive residual invasive breast cancer after neoadjuvant therapy.T-DM1 is an antibody-drug conjugate of trastuzumab and the cytotoxic agent emtansine,and thus,to an extent,T-DM1 is equivalent to simultaneous application of chemotherapy and targeted therapy.However,high cost and low accessibility limit its use especially in low-and middle-income countries and regions.Hence,we proposed this perspective that additional chemotherapy plus trastuzumab should be given to HER2-overexpressing breast cancer patients with residual disease after NAC to improve their prognosis by discussing that the efficacy of additional chemotherapy plus trastuzumab is superior to that of anti-HER2 therapy alone and not inferior to T-DM1.Additional chemotherapy plus trastuzumab-based HER2-targeted therapy can be used as an alternative regimen to T-DM1 when T-DM1 is unavailable.However,further clinical research on the selection of chemotherapeutic agents is warranted.

EFFECTS OF WATER TABLE AND NITROGEN ADDITION ON CO_2 EMISSION FROM WETLAND SOIL

Soil respiration is a main dynamic process of carbon cycle in wetland. It is important to contribute to global climate changes. Water table and nutritious availability are significant impact factors to influence responses of CO2 emission from wetland soil to climate changes. Twenty-four wetland soil monoliths at 4 water-table positions and in 3 nitrogen status have been incubated to measure rates of CO2 emission from wetland soils in this study. Three static water-table controls and a fluctuant water-table control, with 3 nitrogen additions in every water-table control, were carried out. In no nitrogen addition treatment, high CO2 emissions were found at a static low water table (Ⅰ) and a fluctuant water table (Ⅳ), averaging 306.7mg/(m2·h) and 307.89mg/(m2·h), respectively, which were 51%-57% higher than that at static high water table (Ⅱ and Ⅲ). After nitrogen addition, however, highest CO2 emission was found at Ⅱ and lowest emission at Ⅲ. The results suggested that nutritious availability of wetland soil might be important to influence the effect of water table on the CO2 emission from the wetland soil. Nitrogen addition led to enhancing CO2 emissions from wetland soil, while the highest emission was found in 1N treatments other than in 2N treatments. In 3 nutritious treatments, low CO2 emissions at high water tables and high CO2 emissions at low water tables were also observed when water table fluctuated. Our results suggested that both water table changes and nutritious imports would effect the CO2 emission from wetland.

Catalytic nucleophilic addition of terminal alkynes to α,β-unsaturated-γ-lactams

A novel catalytic reaction has been developed for the nucleophilic addition of terminal alkynes toα,β‐unsaturated‐γ‐lactams via a cyclic N‐acyliminium ion intermediate. This simple reaction pro‐ceeds rapidly under mild conditions, and provided a practical approach for the synthesis of a wide range of 5‐alkynyl‐2‐pyrrolidinones in moderate to good yields （45%–76%）.

Crystallization and dielectric properties of lead-free glass-ceramic composites with Gd_2O_3 addition

Lead-free glass-ceramic composites in barium sodium niobate silica system with Gd2O3 addition were synthesized through melt-casting fol-lowed by controlled crystallization technique. Crystallization and dielectric properties of the Gd2O3 adding glass-ceramic composites were investigated. With the increase in the concentration of Gd2O3, the glass transition temperature and the crystallization temperature of the pre-cursor glass shift towards the higher temperature. The crystallization behavior that occurred during the heat treatment procedure leads to the enhancement of dielectric constant. All the three compositions of glass-ceramic composites exhibit ferroelectricity when tested at room tem-perature. Both the values of the remanent polarization and coercive field are enhanced regularly with the gradual increase in the concentration of Gd2O3 additive under the same testing field.

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba(N_3)_2

Additive Ba（N3）2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure （about 6.0 GPa） by employing the temperature gradient method. Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus. The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated. It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets. The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra. The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form, and the aggregated nitrogen concentration in diamond increases with temperature and duration. In addition, it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature. Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy. Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress, whereas diamond crystals heavily doped with the addition of Ba（N3）2 display the tensile stress.

Influence of Li2O Addition on the Performance of Vitrified Bond and Vitrified Diamond Composites

In order to develop high-performance diamond wheels,the vitrified bond with different contents of Li2O addition and corresponding diamond composites were prepared.The experimental results show that the addition of a small content of Li2O leads the formation of the mullite phase in vitrified bond.When the Li2O content is 3wt%,the mullite content in the vitrified bond reaches the maximum.Whereas,the vitrified bond turns into a pure glass phase when the Li2O content further increases to 5wt%.The softening temperature of vitrified bond,wetting angle between the vitrified bond and the diamond film decrease with the increasing of the Li2O content.The softening point of the vitrified bond with 5wt% Li2O is 537 ℃ and the contact angle is 32°,which are 44 ℃ and 44° lower than those of the sample without Li2O.The CTE (coefficient of thermal expansion),the flexural strength and hardness of the diamond composite sample first increase and then decrease with the increasing of the Li2O content.When the Li2O addition is 3wt%,the flexural strength and hardness of the composites reaches the maximum values of 93 MPa and 98 HRB,respectively,which are 43.1% and 12.6% higher than those of the sample without Li2O.

Ameliorating the re/dehydrogenation behaviour of MgH2 by zinc titanate addition

Magnesium hydride(MgH_(2))is the most feasible and effective solid-state hydrogen storage material,which has excellent reversibility but initiates decomposing at high temperatures and has slow kinetics performance.Here,zinc titanate(Zn_(2)TiO_(4))synthesised by the solid-state method was used as an additive to lower the initial temperature for dehydrogenation and enhance the re/dehydrogenation behaviour of MgH_(2).With the presence of Zn_(2)TiO_(4),the starting temperature for the dehydrogenation of MgH_(2)was remarkably lowered to around 290℃–305℃.In addition,within 300 s,the MgH_(2)–Zn_(2)TiO_(4)sample absorbed 5.0 wt.%of H_(2)and 2.2–3.6 wt.%H_(2)was liberated from the composite sample in 30 min,which is faster by 22–36 times than as-milled MgH_(2).The activation energy of the MgH_(2)for the dehydrogenation process was also downshifted to 105.5 k J/mol with the addition of Zn_(2)TiO_(4)indicating a decrease of 22%than as-milled MgH_(2).The superior behaviour of MgH_(2)was due to the formation of Mg Zn_(2),MgO and MgTiO_(3),which are responsible for ameliorating the re/dehydrogenation behaviour of MgH_(2).These findings provide a new understanding of the hydrogen storage behaviour of the catalysed-MgH_(2)system.

Effects of Sintering Additives on Preparation of CaF_2 Transparent Ceramics

The effects of different sintering addictives on the preparation of CaF2 transparent ceramics were studied. Transparent CaF2 ceramics were fabricated by vacuum sintering and hot isostatic pressing （HIP） method, using CaF2 nanopowders synthesized by chemical precipitation method as raw materials. The nanopowders and transparent ceramics were studied using X-ray diffraction, transmission electron microscopy （TEM）, scanning electron microscopy （SEM） and spectrophotometer. The experimental results indicated that the obtained nanopowders presented normal distribution with grain size about 30 nm; transmittance of CaF2 transparent ceramics was 39% and 26% at 1100 nm for LiF and NaF as sintering addictives, respectively, with corresponding mean grain size 188 μm and 44 μm. Loss of transmission could be attributed to the residual closed porosity. Sintering mechanism was liquid-phase sintering at pre-stage, then solid-phase sintering at later stage, as well as solid solution of lithium ions and sodium ions in the CaF2 lattice structure.

Curtailing Carbon Usage with Addition of Functionalized NiFe2O4 Quantum Dots:Toward More Practical S Cathodes for Li-S Cells

Smartcombination of manifold carbonaceous materials with admirable functionalities(like full of pores/functional groups,high specific surface area) is still a mainstream/preferential way to address knotty issues of polysulfides dissolution/shuttling and poor electrical conductivity for S-based cathodes.However,extensive use of conductive carbon fillers in cell designs/technology would induce electrolytic overconsumption and thereby shelve high-energy-density promise of Li-S cells.To cut down carbon usage,we propose the incorporation of multi-functionalized NiFe2O4 quantum dots(QDs) as affordable additive substitutes.The total carbon content can be greatly curtailed from 26%(in traditional S/C cathodes) to a low/commercial mass ratio(~5%).Particularly,note that NiFe2O4 QDs additives own superb chemisorption interactions with soluble Li2Sn molecules and proper catalytic features facilitating polysulfide phase conversions and can also strengthen charge-transfer capability/redox kinetics of overall cathode systems.Benefiting from these intrinsic properties,such hybrid cathodes demonstrate prominent rate behaviors(decent capacity retention with ~526 mAh g^-1 even at 5 A g^-1) and stable cyclic performance in LiNO3-free electrolytes(only ~0.08% capacity decay per cycle in 500 cycles at 0.2 A g^-1).This work may arouse tremendous research interest in seeking other alternative QDs and offer an economical/more applicable methodology to construct low-carbon-content electrodes for practical usage.

MICHAEL ADDITION OF NITROALKANE TO α,β-UNSATURATED CARBONYL COMPOUNDS ON KF / Al_2O_3/ PEG4000

Michael addition of nitroalkanes to α,β-unsaturated carbonyl compounds occurs in the presence of KF/AI_2O_3/PEG4000 without solvent.Yields are fair to good and work-ups are easy.

Michael Addition of Nitroalkanes to CF_3CCl_2COCH=CHPh: A Facile Route to Fluorine-containing γ-Nitro Ketones

Nitroalkanes react smoothly with CF_3CCl_2COCH=CHPh via Michael addition in the presence of inorganic bases such as KF/Al2O3 or K2CO3, giving fluorinecontaining γ-nitro ketones in good yields.

Addition Reactivity of C_(36) Cage Controlled by the Curvature and the Electronic Factors:A DFT Study

The molecular geometries and electronic structures of the fullerene derivatives C36（OH）n（n = 1～2） have been investigated on the basis of density functional theory calculation at the B3LYP/6-31＋＋G＊ level.The geometry optimization results indicate that the location of C2 atom is the most active site in the three potential adding patterns,and the C1 or C2 site has a larger binding energy than C3 for the addition reactions of C36（D6h） cage and OH radicals resulting from the larger curvature.The electronic structure calculation results disclose that the C2 site has larger electronic population in HOMO and larger spin density,and the addition reaction on the C2 site need overcome a lesser energy gap than that on the C1 or C3 site.Thus,the addition is controlled jointly by the curvature and the electronic factors.Besides,when two hydroxyls are added to the C36 surface,the C2 sites are also the most active locations.The most stable addition adduct of C36（OH）2 is the isomer which holds Ci symmetry,and the spin multiplicity seriously affects the stabilities of the adducts.

BrCo (dmgh)_2Py/Zn Promoted Addition of BrCF_2CF_2CH=CHCH_2X to Alkynes: Direct Synthesis of 4,4,5,5-Tetrafluorocyclopentene Derivatives

BrCF2CF2CH=CHCH2X(x=Cl, OAc, OH) reacted smoothly with alkynes in the presence of BrCo(dmgh)2Py/Zn, giving 4,4,5,5-tetrafluorocyclopentene derivatives in moderate yields.

Regioselective Addition of Silyl Enolates to α, β-Unsaturated Aldehyde and its Acetal Catalyzed by MgI2 Etherate

Regioselective addition reactions of silyl enolates to a, b-unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This unique regioselectivity is distinctly different with other Lewis acidic promoters and may be attributed to the high oxyphilicity of IMg+.

STUDY ON Cp_2TiCl_2/Fe-INITIATED ADDITION OF 2-HALOTETRAFLUOROETHYL IODIDES TO ALKYNES AND ALKENES

Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.

Effect of Li and Ti Additions on Lα(Al)+Mg_2Si Pseudobinary Eutectic Reaction

Effect of Li and Ti additions on Lα(AI)+Mg2Si pseudobinary eutectic reaction in ternary Al-Mg-Si system has been investigated by thermoanalysis, directional solidification and metallographic techniques in this study. It has been found that Li addition causes decreasing of the volume fraction of Mg2Si, while a little amount of Ti causes to increasing, which is of a great importance to the adjustment of phase constitution and alloy properties. Doping components have little influence on the eutectic temperature.