“皱、瘦、透、漏”古今谈(下)

二、关于对米芾'相石法'的诠释米芾'相石法'的含义是什么,他本人没有留下片言只语。明朝以前的历代赏石名家,也无人对此作出解说。事隔数百年,直到清朝,园艺家李渔才在《闲情偶寄·居石部》提出了个人的看法:言山石之美者,俱在透、漏、瘦三字。此通于彼,彼通于此,若有道路可行,所谓透也;石上有眼,四面玲珑,所谓漏也;壁立当空,孤峙无倚,所谓瘦也。李渔是第一个对米芾'相石法'作出阐释的人,是值得推崇的。但是他把'透'、'漏'二字作了相同或相似的解说,其负面影响也是值得重视的。至今,没有人对李渔之说提出置疑,而是相反,有的石友以此为依据,怀疑米芾'相石法'的真实性。有多位石友提出,米芾'相石法','透'与'漏'字义相同,'漏'字是多余的。因此断言,在米芾'相石法'中,本来就没有'漏'。

Si-doped diamond films prepared by chemical vapour deposition

The effects of Si doping on morphology, components and structure characteristics of CVD diamond films were studied. Si-doped CVD diamond films were deposited on Si substrate by adding tetraethoxysilane （TEOS） into acetone as source of reactant gas. The morphology and microstructure of diamond films were characterized by scanning electron microcopy （SEM）. The crystalline quality of diamond films was studied by Raman spectroscopy and X-ray diffractometry （XRD）. The surface roughness of the films was evaluated with surface profilometer. The results suggest that Si doping tends to reduce the crystallite size, enhance grain refinement and inhibit the appearance of （11 I） facets. Raman spectra indicate that Si doping can enhance the formation of sp2 phase in diamond films. Moreover, Raman signal of SiC was detected, which suggests the existence of Si in the diamond films. Smooth fine-grained diamond （SFGD） film was synthesized at Si to C ratio of 1%.

EFFECT OF GRID BIAS ON DEPOSITION OF NANOCRYSTALLINE DIAMOND FILMS

A positive grid bias and a negative substrate bias voltages are applied to the self-made hot filament chemical vapor deposited （HFCVD） system. The high quality nanocrystalline diamond （NCD） film is successfully deposited by double bias voltage nucleation and grid bias voltage growth. The Micro-Raman XRD SEM and AFM are used to investigate the diamond grain size, microstructure, surface morphology, and nucleation density. Results show that the obtained NCD has grain size of about 20 nm. The effect of grid bias voltage on the nucleation and the diamond growth is studied. Experimental results and theoretical analysis show that the positive grid bias increases the plasma density near the hot filaments, enhances the diamond nucleation, keeps the nanometer size of the diamond grains, and improves the quality of diamond film.

Amorphous SiO_2 interlayers for deposition of adherent diamond films onto WC-Co inserts

Amorphous Si O2（a-Si O2） films were synthesized on WC-Co substrates with H2 and tetraethoxysilane（TEOS） via pyrolysis of molecular precursor.X-ray diffraction（XRD） pattern shows that silicon-cobalt compounds form at the interface between a-Si O2 films and WC-Co substrates.Moreover,it is observed by transmission electron microscope（TEM） that the a-Si O2 films are composed of hollow mirco-spheroid a-Si O2 particles.Subsequently,the a-Si O2 films are used as intermediate films and chemical vapor deposition（CVD） diamond films are deposited on them.Indentation tests were performed to evaluate the adhesion of bi-layer（a-Si O2 ＋ diamond） films on cemented carbide substrates.And the cutting performance of bi-layer（a-Si O2 ＋ diamond） coated inserts was evaluated by machining the glass fiber reinforced plastic（GFRP）.The results show that a-Si O2 interlayers can greatly improve the adhesive strength of diamond films on cemented carbide inserts;furthermore,thickness of the a-Si O2 interlayers plays a significant role in their effectiveness on adhesion enhancement of diamond films.

Precursor-modified strategy to synthesize thin porous amino-rich graphitic carbon nitride with enhanced photocatalytic degradation of RhB and hydrogen evolution performances

The photocatalytic activity of carbon nitride(CN)materials is mainly limited to small specific surface areas,limited solar absorption,and low separation and mobility of photoinduced carriers.In this study,we developed a precursor-modified strategy for the synthesis of graphitic CN with highly efficient photocatalytic performance.The precursor dicyandiamide reformed by different acids undergoes a basic structural change and transforms into diverse new precursors.The thin porous amino-rich HNO_(3)-CN(5H-CN)was calcined by dicyandiamidine nitrate,formed by concentrated nitric acid modified dicyandiamide,and presented the best photocatalytic degradation rate of Rh B,more than 34 times that of bulk graphitic CN.Moreover,the photocatalytic hydrogen evolution rate of 5H-CN significantly improved.The TG-DSC-FTIR analyses indicated that the distinguishing thermal polymerization process of 5H-CN led to its thin porous amino-rich structure,and the theoretical calculations revealed that the negative conduction band potential of 5H-CN was attributed to its amino-rich structure.It is anticipated that the thin porous structure and the negative conduction band position of 5H-CN play important roles in the improvement of the photocatalytic performance.This study demonstrates that precursor modification is a promising project to induce a new thermal polycondensation process for the synthesis of CN with enhanced photocatalytic performance.

Effect of the Alumosilicate Gels pH on Zeolite Phase Composition for the Co-crystallization of BEA/MOR Zeolites in Na2O-TEABr-Al2O3-SiO2-H2O System

This paper deals with the method of zeolites BEA （beta） and MOR （mordenite） synthesis and the co-crystallization method of zeolites BEA/MOR. Synthesized zeolites were studied based on the SEM （scanning electron microscopy）, XRD （x-ray diffraction） and chemical analysis. The porous structure of these zeolites was investigated by nitrogen low-temperature adsorption. It has been illustrated that regulation of the BEA/MOR co-crystalline zeolites phase composition is possible due to variations of the initial alumosilicate gels composition and hydrogen ions concentration. Zeolites containing the co-crystalline phases of BEA/MOR could to be attractive in the processes using the catalysts, which based on the pure phases BEA or MOR zeolites.

Application of a Step-by-Step Fingerprinting Identification Method on a Spilled Oil Accident in the Bohai Sea Area

In recent years,oil spill accidents occur frequently in the marine area of China.Finding out the spilled oil source is a key step in the relevant investigation.In this paper,a step-by-step fingerprinting identification method was used in a spilled oil accident in the Bohai Sea in 2002.Advanced chemical fingerprinting and data interpretation techniques were used to characterize the chemical composition and determine the possible sources of two spilled oil samples.The original gas chromatography -flame ionization detec-tion (GC-FID) chromatogram of saturated hydrocarbons was compared.The gas chromatography-mass spectrometry (GC/MS) chromatograms of aromatic hydrocarbons terpane and sterane,n-alkane and poly-aromatic hydrocarbons (PAHs) were analyzed.The correlation analysis on diagnostic ratios was performed with Student’s t-test.It is found that the oil fingerprinting of the spilled oil (designated as sz1) from the polluted sand beach was identical with the suspected oil (designated as ky1) from a nearby crude oil refinery factory.They both showed the fingerprinting character of mixed oil.The oil fingerprinting of the spilled oil (designated as ms1) collected from the port was significantly different from oil ky1 and oil sz1 and was with a lubricating oil fingerprint character.The identification result not only gave support for the spilled oil investigation,but also served as an example for studying spilled oil accidents.

Synthesis of Ni-Zn ferrite and its microstructure and magnetic properties

Nanometer Ni0.5Zn0.5Fe2O4 powders with spinel phase were prepared by the hydrothermal method using purified FeSO4 solution from sodium jarosite＇s slag as materials. The results show that the spinel phase of Ni0.5Zn0.5Fe2O4 powders begins to form at a relatively low temperature （130 ℃） and a shorter holding time （1 h） when pH=8. The crystallization kinetics equation at 200℃ is ln[-ln（1-x）] =-0.78＋0.951n t. The growth activation energy of Ni0.5Zn0.5Fe2O4 grains is 41.6 kJ/moL in hydrothermal synthesis process. With the increase of sintering temperature, the density and diameter shrinkage of ferrite circulus increase, whereas its pores decrease. The results of magnetic measurements show that saturation magnetic flux density Bs increases and the coercivity Hc decreases with the increase of their sintering temperature. Magnetic parameters of all the investigated samples satisfy the character demand of high Bs, low Br and low Hc of soft magnetic ferrite materials.

Geochemistry and tectonic significance of volcanic rocks from Qushenla Formation in Gerze area of northern Tibetan Plateau

By using petrological,isotope chronological,and geochemical methods,the authors studied the volcanic rocks in the studied area,mainly including dacites and trachytes. The results show that they formed during the late Early Cretaceous. Geochemically,the volcanic rocks are relatively enriched in large-ion lithophile elements( Rb,K,and Th) and depleted in high field strength elements( Nb,Ta,and Ti),and rich in light rare earth elements,and depleted in heavy rare earth elements. The fact indicates that the main body of the volcanic rocks in the Qushenla Formation was derived from the partial melting of lower crust. The lithological assemblages are characterized by continental high-K calc-alkaline and shoshonitic series,suggesting that the southward-subducting oceanic slab in southern Bangong Lake had break off and that the Bangong Lake-Nujiang Ocean had closed before 107 Ma. The main dynamic mechanisms for the genesis of this set of intermediate-acidic volcanic rocks were upwelling of the asthenosphere and partial melting of the lower crust caused by slab break-off.

Ultrahigh Density Modulation of Aligned Single-Walled Carbon Nanotube Arrays

Controlling the densities of aligned single-walled carbon nanotube arrays （SWNTs） on ST-cut quartz is a critical step in various applications of these materials. However the growth mechanism for tuning SWNT density using the chemical vapor deposition （CVD） method is still not well understood, preventing the development of efficient ways to obtain the desired results. Here we report a general ＂periodic＂ approach that achieves ultrahigh density modulation of SWNT arrays on ST-cut quartz substrates--with densities increased by up to -60 times compared with conventional methods using the same catalyst densities--by varying the CH4 gas ＂off＂ time. This approach is applicable to a wide range of initial catalyst densities, substrates, catalyst types and growth conditions. We propose a general mechanism for the catalyst size-dependent nucleation of SWNTs associated with different free carbon concentrations, which explains all the observations. Moreover, the validity of the model is supported by systematic experiments involving the variation of key parameters in the ＂periodic＂ CVD approach.

Large-area nanopatterned graphene for ultrasensitive gas sensing

Chemical vapor deposited （CVD） graphene is nanopatterned using a spherical block copolymer etch mask. The use of spherical rather than cylindrical block copolymers allows homogeneous patterning of cm-scale areas without any substrate surface treatment. Raman spectroscopy was used to study the con- trolled generation of point defects in the graphene lattice with increasing etching time, confirming that alongside the nanomesh patterning, the nanopatterned CVD graphene presents a high defect density between the mesh holes. The nanopatterned samples showed sensitivities for NO2 of more than one order of magnitude higher than for non-patterned graphene. NO2 concentrations as low as 300 ppt were detected with an ultimate detection limit of tens of ppt. This is the smallest value reported so far for non-UV illuminated graphene chemiresistive NO2 gas sensors. The dramatic improvement in the gas sensitivity is believed to be due to the high adsorption site density, thanks to the combination of edge sites and point defect sites. This work opens the possibility of large area fabrication of nanopatterned graphene with extremely high densities of adsorption sites for sensing applications.

Insight into the rapid growth of graphene single crystals on liquid metal via chemical vapor deposition

Previous reports about the growth of large graphene single crystals on polycrystalline metal substrates usually adopted the strategy of suppressing the nucleation by lowering the concentration of the feedstock, which greatly limited the rate of the nucleation and the sequent growth. The emerging liquid metal catalyst possesses the characteristic of quasi-atomically smooth surface with high diffusion rate. In principle, it should be a naturally ideal platform for the lowdensity nucleation and the fast growth of graphene. However,the rapid growth of large graphene single crystals on liquid metals has not received the due attention. In this paper, we firstly purposed the insight into the rapid growth of large graphene single crystals on liquid metals. We obtained the millimeter-size graphene single crystals on liquid Cu. The rich free-electrons in liquid Cu accelerate the nucleation, and the isotropic smooth surface greatly suppresses the nucleation.Moreover, the fast mass-transfer of carbon atoms due to the excellent fluidity of liquid Cu promotes the fast growth with a rate up to 79 μm s^-1. We hope the research on the growth speed of graphene on liquid Cu can enrich the recognition of the growth behavior of two-dimensional(2 D) materials on the liquid metal. We also believe that the liquid metal strategy for the rapid growth of graphene can be extended to various 2 D materials and thus promote their future applications in the photonics and electronics.

Fast growth of graphene on SiO2/Si substrates by atmospheric pressure chemical vapor deposition with floating metal catalysts

Graphene on dielectric substrates is essential for its electronic applications. Graphene is typically synthesized on the surface of metal and then transferred to an appropriate substrate for fabricating device applications. This post growth transfer process is detrimental to the quality and performance of the as-grown graphene. Therefore, direct growth of graphene films on dielectric substrates without any transfer process is highly desirable. However, fast growth of graphene on dielectric substrates remains challenging. Here, we demonstrate a transfer-free chemical vapor deposition (CVD) method to directly grow graphene films on dielectric substrates at fast growth rate using Cu as floating catalyst. A large area (centimeter level) graphene can be grown within 15 min using this CVD method, which is increased by 500 times compared to other direct CVD growth on dielectric substrate in the literatures. This research presents a significant progress in transfer-free growth of graphene and graphene device applications.