4He films on graphite studied by neutron scattering

The properties of ⁴He films adsorbed on graphite have been studied by neutron scattering. In particular excitations of the commensurate phase of the monolayer are discussed. The first two adsorbed layers are solid and the next ones stay liquid. At the boundaries of the superfluid film excitations could be studied. Also the phonons, maxon and rotons of the film are investigated. An explanation of the lower density of the very thin films compared to bulk ⁴He is given.Presented by H. J. Lauter.     

Excitations in Two-Dimensional 4He

We present the study of the ground state and of the low-energy excited states of liquid⁴He in two dimensions (2D) within the Variational Monte Carlo method. As trial wave function a shadow wave function is used. The energies of the maxon and of the roton are close together at the equilibrium density ρ_eq due to the low value of ρ_eq in 2D but at higher densities a well developed roton minimum is present. The short range backflow effects are stronger in 2D than in 3D and close to freezing the roton energy is about 5 K. This value is close to the lowest branch of excitations found from inelastic neutron scattering from thin⁴He film on graphite and interpreted as due to layer rotons. Some strong similarities between the 2D and 3D case are present: the maxon energy close to freezing is about twice the roton energy, the relative strength of the single roton peak in the dynamical structure factor is essentially density independent and very close in value to the 3D case, there is a similar shift between the wave vectors of the roton and of the position of the main maximum of the static structure factor.     

Functionalization of mesoporous MCM-41 for the delivery of curcumin as an anti-inflammatory therapy

In this study, mesoporous silica nanoparticles (MSNs) composed of MCM-41 were synthesized and modified with amine groups (i.e., NH₂) to form NH_2/MCM-41, which was loaded with curcumin (CUR) to form CUR@NH₂/MCM-41 to create an efficient carriers in drug delivery systems (DDSs). The three samples (i.e., pure MCM-41, NH₂/MCM-41, and CUR@NH₂/MCM-41) were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transition electron microscopy (TEM), and a thermogravimetric analyzer (TGA). The study investigated the effect of the carrier dose, CUR concentration, pH, and contact time on the drug loading efficiency (DLE%) by adsorption. The best DLE% for MCM-41 and NH₂/MCM-41 was found to be 15.78 and 80%, respectively. This data demonstrated that the Langmuir isotherm had a greater correlation coefficient (R²) of 0.9840 for MCM-41 and 0.9666 for NH₂/MCM-41 than the Freundlich and Temkin isotherm models. A pseudo-second-order kinetic model seems to fit well with R² = 0.9741 for MCM-41 and R² = 0.9977 for NH₂/MCM-41. A phosphate buffer solution (PBS) with a pH of 7.4 was utilized to study CUR release behavior. As a result, the full release after 72 h was found to have a maximum of 74.1% and 29.95% for pure MCM-41 and NH₂/MCM-41, respectively. The first-order, Weibull, Hixson-Crowell, Korsmeyer-Peppas, and Higuchi kinetic release models were applied to releasing CUR from CUR@MCM-41 and CUR@NH₂/MCM-41. The Weibull kinetic model fit well, with R² = 0.944 and 0.96912 for pure MCM-41 and NH₂/MCM-41, respectively.     

Polarization potentials and elementary excitations in He II at low temperatures

The density fluctuation excitation spectrum of He II is calculated using a generalized polarization potential approach and shown to yield a phonon-roton spectrum for wave vectors less than 2.1 Å^–1 in excellent quantitative agreement with that observed in neutron scattering experiments for pressures ranging fromSVP to 25 bar. The model provides a simple physical explanation for the increase in maxon energy and decrease in roton energy with increasing pressure, and a quantitative account of the pressure variation of the single-phonon energy and probability amplitude in the vicinity of the roton minimum (1.8q2.1 Å^–1).Work supported in part by the National Science Foundation Grant NSF DMR72-03026.     

Synthesis and characterization of V,Mo and Nb incorporated micro–mesoporous MCM-41 materials

Highly microporous metal-MCM-41 ordered mesoporous structure catalysts having different metal/Si (V, Mo, Nb) atomic ratios and combinations of metal sources were hydrothermally synthesized. The structural properties estimated using different techniques were found to be in agreement with each other. Metals were successfully incorporated into MCM-41 without deteriorating the ordered hexagonal structure. The metal ions in the synthesis solutions probably settled on the hydrophilic end of the template hence the metal incorporation resulted improvements in the micropore structure. Low loading of metals caused an increase in the surface area and pore volume values of the catalysts. The highest total (1310 m² g^?1) and micropore surface area values (1083 m² g^?1) were obtained by Nb incorporation. The micro- and mesopore dimensions of MCM-41 increased from 0.5 to 1.1 nm and from 2.5 to 2.8 nm, respectively, with metal incorporation. Low V/Si ratios and presence of Nb in the starting solution enhanced narrow mesopore size distribution. The pore dimension and wall thickness values estimated from nitrogen adsorption and X-ray diffraction methods were consistent with the corresponding values obtained using transmission electron microscopy.     

Silica materials recovered from photonic industrial waste powder: its extraction, modification, characterization and application

This study explored the possibility of recovering waste powder from photonic industry into two useful resources, sodium fluoride (NaF) and the silica precursor solution. An alkali fusion process was utilized to effectively separate silicate supernatant and the sediment. The obtained sediment contains purified NaF (>90%), which provides further reuse possibility since NaF is widely applied in chemical industry. The supernatant is a valuable silicate source for synthesizing mesoporous silica material such as MCM-41. The MCM-41 produced from the photonic waste powder (PWP), namely MCM-41(PWP), possessed high specific surface areas (1082 m²/g), narrow pore size distributions (2.95 nm) and large pore volumes (0.99 cm³/g). The amine-modified MCM-41(PWP) was further applied as an adsorbent for the capture of CO₂ greenhouse gas. Breakthrough experiments demonstrated that the tetraethylenepentamine (TEPA) functionalized MCM-41(PWP) exhibited an adsorption capacity (82 mg CO₂/g adsorbent) of only slightly less than that of the TEPA/MCM-41 manufactured from pure chemical (97 mg CO₂/g adsorbent), and its capacity is higher than that of TEPA/ZSM-5 zeolite (43 mg CO₂/g adsorbent). The results revealed both the high potential of resource recovery from the photonic solid waste and the cost-effective application of waste-derived mesoporous adsorbent for environmental protection.     

Synthesis and characterization of CuO containing mesoporous silica spheres

A new series of mesoporous silica spheres containing nanodispersed copper oxides were synthesized in H₂O/EtOH/ammonia solution at room temperature. The mesoporous structures were characterised using X-ray powder diffraction and N₂ adsorption-desorption techniques. Scanning electron micrograph and transmission electron micrograph revealed that the MCM-41 particles have spherical morphologies. The DTA curve of pure MCM-41 exhibited a sharp single exothermic peak between 290°C and 340°C, while a broad peak with several shoulders in the temperature range between 180°C and 380°C was observed for Cu-MCM-41, indicating the possible complexation of Cu²⁺ with surfactants adhering to the inner surfaces of the mesopores. Electron paramagnetic resonance spectra of uncalcined samples revealed that Cu²⁺ ions are in an octahedral or distorted octahedral coordination with nitrogen ligands of the surfactant while in the calcined samples they are coordinated with oxygen of the MCM-41 framework. The redox properties of samples were examined by a temperature-programmed reduction and N₂O passivation method. The results indicate that CuO with increasing particle size could be formed in the mesoporous materials with increasing Cu contents, and this decreased the reducibility of the resulting CuO.     

Phase Transition of Superfluid 3He in Aerogel

We have studied phase transition of superfluid ³He in 97.5% porosity aerogel by NMR method. Above 1.0 MPa, superfluid phase transition has been observed. The transition temperature T _c ^a is strongly suppressed from its bulk value. The Pressure-Temperature diagram suggests that superfluid phase will not appear below near 0.8 MPa. The A-B phase transition has been observed above 1.3 MPa, below which a state of superfluid phases remains to be identified. The temperature dependence of NMR frequency shifts Δf in the A-like and the B-like phases are almost linear at pressures below 2.4 MPa. We obtained the differential coefficient of NMR frequency shifts ∂(Δf)/∂(T/T _c ^a ) at 0.9T _c ^a as a function of pressure, and it suggests that superfluid phase will not appear below near 0.8 MPa which is the same pressure estimated by P-T diagram.     

He4 State Equation Below 0.8 K

This work develops the Helmholtz potential A(ρ, T) for He⁴ below 0.8 K. Superfluid terms, related to temperature and momentum gradients, are neglected with negligible loss of accuracy in the derived state properties (specific heats, first sound velocity, expansivity, compressibility, etc.). Retained terms are directly related to a bulk fluid compressibility plus phonon and roton excitations in this quantum fluid. The bulk fluid compressibility is found from the empirical equation c₁³ ≈ c₁₀³ + b; P, where c₁ is the velocity of first sound, P is the pressure, and c₁₀ and b are constants; this empirical equation is found to apply also to other helium temperature ranges and to other fluids. The phonon excitations lead to a single temperature-dependent term in A(ρ ,T) up to 0.3 K, with only two more terms added up to 0.8 K. The roton potential, negligible below about 0.3 K, is a single term first derived 60 years ago but little used in more recent work. The final A(ρ ,T) is shown to fit available experimental specific heat data to about ±2% or better. The magnitude of the pressure-independent Gruneisen parameter below 0.3 K is typical of highly compressed normal liquids. Extension of the equation above 0.8 K is hampered by lack of data between 0.8 and 1.2 K     

The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol

Objective: To explore the suitable application of MCM-41 (Mobil Composition of Matter number forty-one)-type and MCM-48-type mesoporous silica in the oral water insoluble drug delivery system.

Methods: Cilostazol (CLT) as a model drug was loaded into synthesized MCM-48 (Mobil Composition of Matter number forty-eight) and commercial MCM-41 by three common methods. The obtained MCM-41, MCM-48 and CLT-loaded samples were characterized by means of nitrogen adsorption, thermogravimetric analysis, ultraviolet-visible spectrophotometry, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and powder X-ray diffractometer.

Results: It was found that solvent evaporation method was preferred according to the drug loading efficiency and the maximum percent cumulative drug dissolution. MCM-48 with 3D cubic pore structure and MCM-41 with 2D long tubular structure are nearly spherical particles in 300–500?nm. Nevertheless, the silica carriers with similar large specific surface areas and concentrating pore size distributions (978.66?m²/g, 3.8?nm for MCM-41 and 1108.04?m²/g, 3.6?nm for MCM-48) exhibited different adsorption behaviors for CLT. The maximum percent cumulative drug release of the two CLT/silica solid dispersion (CLT-MCM-48 and CLT-MCM-41) was 63.41% and 85.78% within 60?min, respectively; while in the subsequent 12?h release experiment, almost 100% cumulative drug release were both obtained. In the pharmacokinetics aspect, the maximum plasma concentrations of CLT-MCM-48 reached 3.63?mg/L by 0.92?h. The AUC_0–∞ values of the CLT-MCM-41 and CLT-MCM-48 were 1.14-fold and 1.73-fold, respectively, compared with the commercial preparation.

Conclusion: Our findings suggest that MCM-41-type and MCM-48-type mesoporous silica have great promise as solid dispersion carriers for sustained and immediate release separately.     

Pressure/current characteristics of a magnetron cold cathode gauge

The gauge characteristics for a magnetron gauge in the pressure range 10⁻⁸-10⁻⁵ mbar with nitrogen as a test gas have been studied. The discharge current versus pressure was measured at different magnetic fields from 0.10 to 0.15 T and anode voltages from 4.0 to 7.0 kV. The results showed that a change of slope appeared at pressures between 5×10⁻⁸ and 5×10⁻⁷ mbar. At higher magnetic fields, a change of slope appeared at lower pressures. The slope of the curve below the inflection was higher than that above the inflection. At the lowest magnetic field (0.10 T), a divergence of the curves was observed at pressures below the inflection. The slope of the curve showed no clear dependence on applied voltage.     

Synthesis and characterization of super-microporous material with enhanced hydrothermal stability

Super-microporouos silicon material with high hydrothermal stability denoted as MCM-41-T has been prepared from mesoporous MCM-41 by high temperature treatment. The structural and chemical property of MCM-41-T has been characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, infrared spectroscopy and ²⁹Si MAS NMR. The characteristic results show that Si-OH groups are forced to condense by high temperature treatment, and the pore size of MCM-41-T is around 1.5 nm in the super-microporous range. Compared with the original material MCM-41, the hydrothermal stability of MCM-41-T has been significantly enhanced.     

TiO2在MCM-41内表面单层及双层分散的结构表征

首次以有机物钛酸丁酯为前驱体,合成了ＴiO2呈单层分散状态（Ｔi/Si=0．２０）或双层分散状态（Ｔi/Si=0．39)的介孔分子筛ＭＣＭ－４１（Si/Al=35）,并以ＸＲＤ,ＦＴＩＲ,Ｎ２吸附－脱附,固体ＵＶ－vis漫反等表征手段对其结构特征的氧化钛分散状态进行了研究,结果表明：ＴiO2在介孔分子筛ＭＣＭ－４１孔道中分散,ＭＣＭ－４１骨架结构结晶度降低,但是附着二层ＴiO2后,仍能保持长程有序结构;ＴiO2与ＭＣＭ－４１骨架结构结果度降低低,但是附着二层ＴiO2后,仍能保持长程有序结构,ＴiO2与ＭＣＭ－４１孔道表面的ＳiO2比化学键连接,生成Ｓi-O-Ti键;无论是单层还是双层分散的ＴiO2在ＭＣＭ－４１内孔壁均匀分散,且由于ＴiO2粒子的减小使其对紫外光的吸收发生明显的蓝移现象。.     

Pressure Dependence of Excitations of Liquid 4He

No Heading Confinement of liquid ⁴He in porous glasses increases its solidification pressure and suppresses the superfluid transition temperature T. It has been reported that a sufficiently high degree of confinement suppresses T to zero at high pressure, signifying a quantum phase transition. We evaluate the behaviour of the excitation spectrum at wave vectors Q < 2.3 Å^–1 at pressures well above 25 bar by calculating the dynamic structure factor, S(Q, E), using the theory of hybridization of one- and two-particle excitations. The aim is to explore whether well-defined excitations exist at high pressures, and whether there is some critical pressure at which they disappear. We find that as the pressure increases, the one-particle excitation energy is well-defined if its energy lies below the two-roton energy, and ceases to exist as a well-defined excitation if its energy lies above the two-roton energy. We relate these findings to potential inelastic neutron scattering measurements.     

Synthesis and characterization of Co-Fe Prussian blue nanoparticles within MCM-41

A Prussian blue analogue, K_0.84Co_1.08[Fe(CN)₆] is prepared by reaction between [Fe(CN)₆]³⁻ in aqueous solution and ion-exchanged Co²⁺ in the channels of MCM-41. Powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, nitrogen adsorption/desorption isotherms, diffuse reflectance UV-vis absorption spectroscopy and magnetic measurements were employed to characterize the product. The results show that the Prussian blue analogue is in nanoparticles within the channels and the hexagonal phase of MCM-41 remains intact during the reactions. A particle size effect on optical and magnetic properties of the nanoparticles was observed.     

Thermo-induced plasmon excitations in the near surface region of ternary Co-Cr-Mo alloy

Electron Energy Loss Spectroscopy has been employed for investigation of the surface and bulk plasmon excitations versus heating in the Co-Cr-Mo alloy surface for the primary electron beam energies Е₀ ranging from 150 to 800 eV. For the annealed alloy the experimental values of the plasmon energy are localized at more energies as compared to the non-annealed alloy. It was established that heating of the alloy promotes to insignificant deviations of the plasmon excitations. Damping of the intensity line of surface plasmon with a increase of heating was established. Physical processes which can influence on the energy displacements of long wavelength plasmon oscillations and damping of surface plasmon in the characteristic loss spectra at heating are considered.     

H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> supported on mesoporous MCM-41 and Al–MCM-41 materials: preparation and characterisation

MCM-41 and Al–MCM-41 has been synthesized using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 °C for 4 h. HPW heteropolyacid supported on the mesoporous were prepared using the incipient wetness method. The characterization of materials was performed by X-ray diffraction, Transmission Electron Microscopy, N₂ adsorption, ²⁹Si Cross Polarization–Magic Angle Spinning and ²⁷Al MAS NMR. Results showed that the hexagonal structure is obtained in both cases. The Aluminium species are located inside an extra-framework. The impregnation reduces the surface area of the mesoporous materials especially of the Al–MCM-41 suggesting a participation of aluminium during the impregnation. HPW is well dispersed in the mesoporous materials and is located inside the pores interacting with the silanol group of the pores wall. ²⁷Al MAS NMR measurements have showed that the impregnation causes the removal of the non-framework aluminium.     

MoO3在介孔分子筛MCM-41上分散和存在状态的研究

在773K加热MoO3和MCM－41的机械混合物，可以实现MoO3分散在介孔分子筛MCM－41表面，用透射电镜和选区电子衍射，配合XRD和液氮温度下氮吸附－脱附曲线和BJH孔径分布，研究了活性组分MoO3在有序介 材料MCM－41上的存在状态，以及MoO3分散到MCM－41表面后MCM－41的结构变化情况。结果表明：当MoO3的含量小于单层分散阈值，加热后MoO3的XRD衍射峰彻底消失，用HRTEM观察不到分散在MCM－41表面或孔道中的MoO3颗粒，而EDS能谱证明在MCM－41的孔道中有呈分散态的MoO3存在。MoO3的含量大于单层分散阈值，通过加热不能使MoO3完全分散在MCM－41表面，而且XRD、HRTEM、氮吸附－脱附等温线和孔径分布都表明由于MoO3的分散量较大，载体MCM－41的有序介孔结构遭到破坏。     

Synthesis and characterization of surface-modified and organic-functionalized MCM-41 type ordered mesoporous materials

A new and efficient method for the preparation of MCM-41 type ordered mesoporous phases using phosphate as promoter under reflux conditions is reported. The various mesoporous materials studied were: silica (Si-MCM-41), alumino-silicate (Al-MCM-41), and titanium-silicate (Ti-MCM-41). Our concept of promoter-assisted synthesis of zeolites and related microporous materials was found to be applicable in the synthesis of ordered mesoporous materials as well. The addition of small catalytic quantity of phosphate ions (PO ₄ ³⁻ ), used as promoters, significantly reduced the synthesis time (by a factor of 3–4) of all these mesoporous materials. The synthesis of new MCM-41 type organic-inorganic composite materials with unique properties is also reported.     

Excitations in liquid4He beyond the roton

The dynamic structure factor S(Q,E) for liquid⁴He at saturated vapor pressure has been measured by inelastic neutron scattering for wave vectors Q between 1.9 and 2.8 Å^–1. The temperature dependence is studied for Q=2.3 Å^–1. The sharp phonon-roton peak gradually disappears with increasing temperature, while the scattering at higher energies is nearly temperature independent. The experimental results are compared with the density-quasiparticle interpretation introduced by Glyde and Griffin, and with a model describing the hybridization with the multiparticle excitations.