Angular effects in the sputtering of Cr from stainless steel by 10 keV H3

Energy and angular distributions of Cr⁺ sputtered from stainless steel by 1.6 × 10⁻¹⁵ J (10 keV) H⁺₃ are reported as a function of angle of incidence. For more normal incidence, the peak in the energy distribution occurs in the vicinity of 3.2 × 10⁻¹⁹ J (2 eV), the average energy is approximately 1.12 × 10⁻¹⁸ J (7 eV), and the angular distribution is close to cosine. Toward glancing incidence, the peak energy increases to ˜6.4 × 10⁻¹⁹ J (4 eV), the average energy increases to ˜1.28 × 10⁻¹⁸ J (8.0 eV), and the angular distribution shows a distinct maximum in the forward direction. These results are discussed in terms of the increasing role of surface recoils in the sputtering mechanism at glancing incidence.     

ESR法研究Pt催化N2H4分解机制

采用电子自旋共振谱（ESR）法,研究了酸性条件下•NH₂的转化,HClO₄体系下反应时间对溶液中自由基产生的影响、pH值对N₂H₄断键的影响以及HNO₃中N是否对溶液中的•NH₂有贡献,确定了Pt催化N₂H₄分解的反应机理。结果表明：在酸性条件下•NH₂被DMPO捕捉时反应式为•NH⁺₃+HO-H+DMPO=NH⁺₄+DMPO(•OH),硝酸在Pt催化N₂H₄体系中不会发生断键产生•NH₂,所产生的•NH₂是由N₂H₄断键形成的;在HClO₄体系中,随着Pt催化N₂H₄反应时间的延长,N₂H₄中N-N断键的趋势逐渐减小,N-H断键的趋势逐渐增大;随pH值的增大,N₂H₄中N-N断键的速率先快速减小,pH>3后缓慢增大;Pt催化N₂H₄分解反应中N-N断键和N-H断键两种方式共存,但N-N断键占优;反应体系中N₂H₄与H^＋浓度之比决定了N-N断键生成•NH₂的速率,而•NH₂与H^＋的浓度又决定了•NH₂转化成产物的速率,这两方面共同决定了N₂H₄分解的速率。     

Thermodynamic studies on Cs4U5O17(s) and Cs2U2O7(s) by emf and calorimetric measurements

The oxygen potentials over the phase field: Cs₄U₅O₁₇(s)+Cs₂U₂O₇(s)+Cs₂U₄O₁₂(s) was determined by measuring the emf values between 1048 and 1206 K using a solid oxide electrolyte galvanic cell. The oxygen potential existing over the phase field for a given temperature can be represented by: Δμ(O₂) (kJ/mol) (±0.5)=−272.0+0.207T (K). The differential thermal analysis showed that Cs₄U₅O₁₇(s) is stable in air up to 1273 K. The molar Gibbs energy formation of Cs₄U₅O₁₇(s) was calculated from the above oxygen potentials and can be given by, Δ_fG⁰ (kJ/mol)±6=−7729+1.681T (K). The enthalpy measurements on Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were carried out from 368.3 to 905 K and 430 to 852 K respectively, using a high temperature Calvet calorimeter. The enthalpy increments, (H⁰_T−H⁰₂₉₈), in J/mol for Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) can be represented by, H⁰_T−H⁰_298.15 (Cs₄U₅O₁₇) kJ/mol±0.9=−188.221+0.518T (K)+0.433×10⁻³T² (K)−2.052×10⁻⁵T³ (K) (368 to 905 K) and H⁰_T−H⁰_298.15 (Cs₂U₂O₇) kJ/mol±0.5=−164.210+0.390T (K)+0.104×10⁻⁴T² (K)+0.140×10⁵(1/T (K)) (411 to 860 K). The thermal properties of Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were derived from the experimental values. The enthalpy of formation of (Cs₄U₅O₁₇, s) at 298.15 K was calculated by the second law method and is: Δ_fH⁰_298.15=−7645.0±4.2 kJ/mol.     

Electron emission induced by H and H incident on thin carbon foils: influence of charge changing processes

The forward and backward electron emission yields γ_F and γ_B have been calculated by Monte Carlo simulation for protons (H⁺) and hydrogen atoms (H⁰) (with energies between 25 keV and 5 MeV) incident on thin amorphous carbon foils. Direct electron excitations by the incident projectiles as well as electron excitations resulting from charge exchange processes undergone by H⁺ or H⁰ have been taken into account. For the latter, Auger and Shell processes have been considered. Subsequent electron transport has been considered in order to calculate the forward and backward electron emission yields γ_F and γ_B.     

共存离子对时间分辨荧光法测定痕量铀的影响

时间分辨荧光法分析痕量铀具有灵敏度高、操作简便等优点,但是受共存离子的影响很大,准确度评价较低,分析结果误差过大。本工作研究了时间分辨荧光法测定焦磷酸体系中UO2+2时几种干扰离子如H+、Fe3+、NO-3等的影响,为痕量铀样品预处理方法的确定提供重要依据。结果表明:H+对UO2+2的荧光猝灭主要表现为荧光物质的破坏;NO-3对铀络合物荧光体系的影响表现为对激发光的吸收;Fe3+的影响表现为对激发光和荧光的吸收。对于质量浓度为2μg/L的铀溶液,当c(H+)=0.037 5mol/L时,UO2+2的荧光强度下降了44.4%;当ρ(Fe3+)=20mg/L时,UO2+2的荧光强度基本猝灭完全。     

氨基羟基脲与Np(Ⅵ)的还原动力学

研究了氨基羟基脲(HSC)浓度、H~+浓度、NO_3~-浓度、Fe3+浓度、UO2+2浓度、反应温度对氨基羟基脲与Np(Ⅵ)还原反应速率的影响,获得了其动力学方程。实验结果表明:增加氨基羟基脲浓度和提高反应温度,降低H~+浓度和NO_3~-浓度,可以提高氨基羟基脲与Np(Ⅵ)还原速率;在UO2+2存在或Fe3+浓度小于1×10-3 mol/L时,对氨基羟基脲与Np(Ⅵ)的还原没有明显影响。氨基羟基脲还原Np(Ⅵ)的动力学方程式为:-dc(Np(Ⅵ))/dt=kc(Np(Ⅵ))c2.52(HSC)c-0.53(H+)c-0.61(NO_3~-),在4.00℃时k=(1 037±60)(mol/L)-1.40·s-1,活化能Ea=(64.03±6.4)kJ/mol。     

Kinetic electron emission yield induced by H and He ions versus stopping power for Al, Cu, Ag and Au

For H⁺ and He²⁺ ions impinging on Al, Cu, Ag and Au targets we measured simultaneously the yield, γ, of emitted electrons and the electronic energy loss, S_e, in the energy range 0.5 to 4.8 MeV. The targets were prepared under high-vacuum conditions before they were transferred to an ultra-high-vacuum chamber without breaking the vacuum. The targets were sputter cleaned and their composition was examined by Auger electron spectrometry. The values of γ were obtained by current integration and S_e was determined from the energy width of Rutherford backscattering spectra. For H⁺ ions impinging on Cu, Ag or Au and He²⁺ on Al and Cu, the expected proportionality between γ and S_e was found within the experimental errors of 2%. For H⁺ ions on Al and He²⁺ ions on Ag and Au targets, significant deviations were observed.     

The thermal conductivity of UO2 vapor

The thermal conductivity, λ of a saturated vapor over UO_1.96 is calculated in the temperature range 3000–6000 K. The calculation shows that the contribution to λ from the transport of reaction enthalpy dominates all other contributions. All possible reactions of the gaseous species UO₃, UO₂, UO, U, O, and O₂ are included in the calculation. We fit the total thermal conductivity to the empirical equation λ = exp(a+ b/T+cT+dT² + eT³), with λ in cal/(cm s K), T in kelvins, a = 268.90, B = − 3.1919 × 10⁵, C = −8.9673 × 10⁻², d = 1.2861 × 10⁻⁵, and E = −6.7917 × 10⁻¹⁰.     

硝酸体系中铂催化肼还原U(Ⅵ)的反应动力学

开展了硝酸体系中以肼为还原剂、铂黑为催化剂催化还原U(Ⅵ)的动力学研究。通过考察U(Ⅵ)浓度、肼浓度、酸度以及催化剂用量等条件对反应过程的影响，确定了反应的初始动力学速率方程为-dc(UO²⁺₂)dt=kc^0.44(UO²⁺₂)c^0.19(N₂H⁺₅)c^-0.23(H⁺)，在60 ℃、固液比r_S/L=2.0 g/L时，速率常数k=2.6×10^-3 (mol/L)^0.6/min。研究了温度对反应速率的影响，结果表明，在20~75 ℃范围内，随着温度升高，反应速率加快，反应过程由动力学控制转变为扩散控制过程。对比了硝酸体系与高氯酸体系的反应动力学实验数据，发现相同条件下硝酸体系的反应速率明显低于高氯酸体系，并分析了其中的原因。     

硝酸体系中铂催化肼还原U(Ⅵ)的反应动力学

开展了硝酸体系中以肼为还原剂、铂黑为催化剂催化还原U(Ⅵ)的动力学研究。通过考察U(Ⅵ)浓度、肼浓度、酸度以及催化剂用量等条件对反应过程的影响,确定了反应的初始动力学速率方程为-dc(UO²⁺₂)dt=kc^0.44(UO²⁺₂)c^0.19(N₂H⁺₅)c^-0.23(H⁺),在60 ℃、固液比r_S/L=2.0 g/L时,速率常数k=2.6×10^-3 (mol/L)^0.6/min。研究了温度对反应速率的影响,结果表明,在20~75 ℃范围内,随着温度升高,反应速率加快,反应过程由动力学控制转变为扩散控制过程。对比了硝酸体系与高氯酸体系的反应动力学实验数据,发现相同条件下硝酸体系的反应速率明显低于高氯酸体系,并分析了其中的原因。     

三聚磷酸钠交联磁性壳聚糖树脂对铀酰离子的吸附特性

以三聚磷酸钠为交联剂,分别在pH值为3和8条件下制备具有不同交联度的磁性壳聚糖树脂(TPP-MCR)。考察了pH值、吸附时间及初始铀浓度对TPP-MCR吸附UO2+2的影响。结果表明,pH值对两种不同交联度TPP-MCR吸附UO2+2的影响差别较大。FTIR分析表明,TPP-MCR中磷酸根为UO2+2主要吸附位。TPP-MCR吸附UO2+2为吸热自发过程,吸附动力学可用拟二级动力学模型拟合,表明以化学吸附为主。吸附等温线可用Langmuir模型拟合,293K时最大吸附容量为166.7mg/g。吸附UO2+2后的TPP-MCR可用0.1mol/L HNO3-0.1 mol/L EDTA溶液洗脱再生,并可重复使用多次。     

Electron emission in 10–100 keV H and He grazing ion-surface collisions

We have measured energy distributions of electrons ejected during grazing 10–100 keV H⁺ and He⁺ ions scattering from Si surfaces for a broad range of electron observation angles. The distributions have contributions strongly dependent on the directions of incidence and observation. For observation regions around the specular reflection of the ions we have studied the angular dependence of the electron structure resulting from electron transfer to the continuum of the effective ion potential. Far from the ion scattering plane we have observed the Si Auger electron spectrum. We discuss the differences between the Auger peaks obtained by electron and grazing proton bombardment of Si surfaces partially covered with O₂ and Al.     

HNO3介质中U(Ⅳ)还原Np(Ⅴ)的动力学

采用分光光度法研究了HNO₃溶液中U(Ⅳ)还原Np(Ⅴ)的反应,获得了动力学方程-dc (Np(Ⅴ))/dt=kc(Np(Ⅴ))c^0.7 (U(Ⅳ))c^1.9 (H⁺)c (NO^-₃),25℃时反应速率常数k=(6.37±0.49)×10^-3 L^3.6/(mol 3.6•min),反应活化能E_a=60.13 kJ/mol。结果表明,浓度为0~4.2×10^-2mol/L的U(Ⅵ) 对U(Ⅳ)还原Np(Ⅴ)的反应几乎没有影响,并探讨了可能的反应机理。     

Standard Gibbs energy of formation of Cs2CdI4

The vapor pressures of CdI₂ and Cs₂CdI₄ were measured below and above their melting points, employing the transpiration technique. The standard Gibbs energy of formation Δ_fG° of Cs₂CdI₄, derived from the partial pressure of CdI₂ in the vapor phase above and below the melting point of the compound could be represented by the equations Δ_fG°Cs₂CdI₄ (±6.7) kJ mol⁻¹=−1026.9+0.270 T (643 K≤T≤693 K) and Δ_fG°{Cs₂CdI₄} (±6.6) kJ mol⁻¹=−1001.8+0.233 T (713 K≤T≤749 K) respectively. The enthalpy of fusion of the title compound derived from these equations was found to be 25.1±10.0 kJ mol⁻¹ compared to 36.7 kJ mol⁻¹ reported in the literature from differential scanning calorimetry (DSC). The standard enthalpy of formation Δ_fH°_298.15 for Cs₂CdI₄ evaluated from these measurements was found to be −918.0±11.7 kJ mol⁻¹, in good agreement with the values −920.3±1.4 and −917.7±1.5 kJ mol⁻¹ reported in the literature from two independent calorimetric studies.     

热-水-力-化学耦合作用下Ca0.86Nd0.14Ti0.86Al0.14SiO5固溶体的化学稳定性

以CaCO₃、Nd₂O₃、TiO₂、SiO₂、Al₂O₃为原料,用固相法制备掺钕榍石固溶体（Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅）。采用PCT法进行浸泡实验,借助X射线衍射（XRD）、扫描电镜（SEM）、电感耦合等离子体发射光谱（ICP-OES）等分析手段,研究掺钕榍石固溶体在热 水 力 化学（THMC）耦合作用下的化学稳定性。结果表明,在pH值为5～9、温度150～200 ℃、压强0.476～1.554 MPa的耦合作用下,Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅固溶体具有良好的化学稳定性;pH值、温度（压力）对Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅固溶体中Si⁴⁺、Al³⁺、Nd³⁺的归一化浸出率无明显影响;Ca²⁺在200 ℃（1 554 MPa）时的抗浸出性能较150 ℃时的好;在浸泡初期（1～21 d）Ca²⁺在pH值为9时的抗浸出性能优于pH值为5和7时的,浸泡后期（28、42 d）3种溶液中固溶体的Ca²⁺抗浸出性能趋于一致;Ti⁴⁺在pH值为9时的抗浸出性能较pH值为5和7时的好。     

Z variations in yields of multicharged ions scattered and recoiled from a silicon surface

The doubly charged and triply charged ion yields from keV ion-silicon surface scattering are found to have a strong dependence on the atomic number Z₁ of the incident ion. For Z₁ < Z₂ the yield of scattered multicharged ions increases with Z₁, so that these ions dominate the recoiling Si²⁺ and Si³⁺ ions by Z₁ = 9. In contrast, when Z₁ > Z₂, there are large yields of Si²⁺ and Si³⁺ ions, and the multicharged scattered ion yields are too small to detect. The interaction radius at which shell vacancies are produced is also found to change, suggesting that electron promotion occurs at a different level crossing on either side of Z₁ = Z₂.     

Amorphization and recrystallization of the ABO3 oxides

Single crystals of the ABO₃ phases CaTiO₃, SrTiO₃, BaTiO₃, LiNbO₃, KNbO₃, LiTaO₃, and KTaO₃ were irradiated by 800 keV Kr⁺, Xe⁺, or Ne⁺ ions over the temperature range from 20 to 1100 K. The critical amorphization temperature, T_c, above which radiation-induced amorphization does not occur varied from approximately 450 K for the titanate compositions to more than 850 K for the tantalates. While the absolute ranking of increasing critical amorphization temperatures could not be explained by any simple physical parameter associated with the ABO₃ oxides, within each chemical group defined by the B-site cation (i.e., within the titanates, niobates, and tantalates), T_c tends to increase with increasing mass of the A-site cation. T_c was lower for the Ne⁺ irradiations as compared to Kr⁺, but it was approximately the same for the irradiations with Kr⁺ or Xe⁺. Thermal recrystallization experiments were performed on the ion-beam-amorphized thin sections in situ in the transmission electron microscope (TEM). In the high vacuum environment of the microscope, the titanates recrystallized epitaxially from the thick areas of the TEM specimens at temperatures of 800–850 K. The niobates and tantalates did not recrystallize epitaxially, but instead, new crystals nucleated and grew in the amorphous region in the temperature range 825–925 K. These new crystallites apparently retain some ‘memory' of the original crystal orientation prior to ion-beam amorphization.     

Mass spectrometric investigation of the vaporization of li2tio3(s)

The vaporization of Li₂TiO₃(s) has been investigated by the mass spectrometric Knudsen effusion method. Partial pressures of Li(g), LiO(g), Li₂O(g), Li₃O(g) and O₂(g) over Li₂TiO₃(s) have been obtained in the temperature range 1180–1628 K. When the vaporization of Li₂TiO₃(s) proceeds, the content of Li₂O in the Li₂TiO₃(s) sample decreases. The phase of the sample is a disordered Li₂TiO₃ solid solution above 1486 K. The enthalpies of formation and the atomization energies for LiO(g) and Li₃O(g) have been evaluated from the partial pressures to be ΔH^o_f0(LiO, g) = 65.4 ± 17.4 kJ/mol, ΔH^o_f0(Li₃O, g) = − 207.5 ± 56.6 kJ/mol, D^o₀(LiO) = 340.5 ± 17.4 kJ/mol and D^o₀(Li₃O) = 931.6 ± 56.6 kJ/mol, respectively.     

CeO_2/SiO_2吸附剂的制备及其对碘酸根的吸附

以多孔二氧化硅为载体、六水合硝酸铈为原料,采用真空灌注法制备了CeO_2/SiO_2吸附剂,并利用扫描电镜(SEM)、X射线衍射(XRD)、红外光谱(IR)等方法对其进行表征。同时,通过静态和动态吸附实验探究了CeO_2/SiO_2对碘酸根的吸附和脱附行为,考察了pH、反应时间、碘酸根浓度以及共存阴离子等因素对CeO_2/SiO_2吸附性能的影响。研究结果表明:CeO_2/SiO_2在较广的pH值范围内对碘酸根有较高的吸附率,吸附过程符合准二级动力学模型以及Langmuir和Redlich-Peterson模型;共存阴离子对吸附的影响大小为NO_3~-SO_4~(2-)HCO_3~-H_2PO_4~-≈PO_4~(3-);动态吸附实验的柱利用率高达90.96%,且穿透曲线符合Thomas模型;通过IR谱图分析推测CeO_2/SiO_2的吸附机理为阴离子交换。     

Neutralization rate for slow Ar ions in front of KCl(0 0 1)

Charge state distributions of reflected ions are measured when 5 keV Ar^q+(q = 0−2) ions are incident on a clean KCl(0 0 1) surface at grazing angle, θ_i. Although the charge state distribution does not depend on the incident charge state at larger θ_i, significant dependence of the charge state distribution on incident charge state is observed at smaller θ_i. The ionization of Ar⁰ is completely suppressed at θ_i < 20 mrad, while large neutralization probability is observed for Ar⁺ incidence. These features allow us to derive the position-dependent neutralization rate of Ar⁺ in front of KCl(0 0 1). The obtained neutralization rate decreases exponentially with distance from the surface as it is usually assumed.