新时代，以创新思维审议磷矿加工方法

地球已进入以人类为中心的“人类纪元”。为使全球可持续发展,应考虑今后几十代人对磷资源的需求。介绍了世界磷资源现况及国内外最新磷矿储量数据,分析了我国磷肥产品结构;提出高品位、易加工磷资源用于磷化工、磷化学品合成,低品位、难选磷矿用于含磷肥料生产的新思路,并认为生产过磷酸钙、钙镁磷肥比生产磷铵类肥料对磷资源利用更合理。提出了磷肥产业结构调整新战略,以使我国磷资源的可采寿命从目前的100—200年延长至500年。     

Continuous solvent extraction of sunflower,seed, groundnuts,palmkernels, rapeseed,and copra

In principle, the oil milling process is straightforward. The wide variety of equipment in use reflects, however, a multiparametric process. The main limiting parameters are kind of seed, oil content, particle strength, particle structure, temperature, moisture, particle size, residence time, mechanical forces, etc. Additionally, the seed specific parameters vary not only between kinds of seed but also for the same seed, due to different conditions in climate, soil, and harvesting. Therefore, equipment design must be widely based on statistical averages of the limiting parameters. In other words, exact precalculation of the single technological steps is impossible. As a consequence, for more than 5,000 years, the oil milling process has been in the stage of being optimized. The acutal technical standard is very satisfying, but there is still a strong need for further research and development. Currently, as in the past, the oil milling process seems to be not so much a science as an art.     

微波消解ICP-AES法测定润滑油中的铁,镍,铜,锌,硼,磷

通过微波消解处理润滑油,ICP法测定润滑油中铁,镍,铜,锌,硼等元素,通过正交实验进行微波消解条件优化,并进行了精密度实验,标准样品的回收率为98%以上,相对标准偏差小于1%。     

The introduction of alkyl,ester, carboxylate,amino, hydroxyl,and phosphate functional groups to the surface of polyethylene

The surface of polyethylene was derivatized with ester, carboxylate, amino, hydroxyl, and phosphate functional groups. α, ω bifunctional alkanes, containing on one end a primary amine, were coupled to oxidized polyethylene through an amide linkage. Polyethylene was first oxidized with chromic acid, the carboxylate groups were converted to the acyl chloride with phosphorus pentachloride, and then reacted with a primary amine to give the covalently bound amide. The copposing ends of the bifunctional alkanes were the methyl, tertiary amine, ester, and hydroxyl groups. The ester was converted to the carboxylate by acid cleavage and the hydroxyl group converted to the phosphate by treatment first with phosphorus oxychloride and then aqueous base. Attenuated total reflection FTIR, XPS, and pH-dependent contact angle wetting were used to characterize the surfaces. The FTIR data were used to confirm the formation of the amide and to detect an undesired carboxylate/ammonium ion complex formed in the presence of trace amounts of water. XPS data were used to confirm expected changes in elemental composition and to provide quantitative estimates of the yields. Oxidation of the polyethylene introduced 5 × 10¹⁴ carboxylate groups/cm² in the 25 Å XPS sampling depth. Of these, up to 98% could be converted to the amide. The advancing contact angle data confirmed the acid/base behavior of the functional groups.     

Characterization of crystalline cellulose in biomass: Basic principles, applications, and limitations of XRD, NMR, IR, Raman, and SFG

Cellulose is among the most important and abundant biopolymers in biosphere. It is the main structural component of a vast number of plants that carries vital functions for plant growth. Cellulose-based materials have been used in a variety of human activities ranging from papers and fabrics to engineering applications including production of biofuels. However, our understanding of the cellulose structure in its native form is quite limited because the current experimental methods often require separation or purification processes and provide only partial information of the cellulose structure. This paper aims at providing a brief background of the cellulose structure and reviewing the basic principles, capabilities and limitations of the cellulose characterization methods that are widely used by engineers dealing with biomass. The analytical techniques covered in this paper include x-ray diffraction, nuclear magnetic resonance, and vibrational spectroscopy (infrared, Raman, and sum-frequency-generation). The scope of the paper is restricted to the application of these techniques to the structural analysis of cellulose.     

Adsorption of dimer,trimer, stearic,oleic, linoleic,nonanoic and azelaic acids on ferric oxide

The adsorption isotherms of solutions of dimer, trimer, stearic, oleic, linoleic, nonanoic and azelaic acids in organic solvents, (mostly hexane) have been determined on an alpha ferric oxide with a surface area (B.E.T. N₂ adsorption) of 99 m² (99 × 10²⁰ A²) per gram. They all showed limiting adsorption as grams adsorbed per gram of iron oxide beyond a concentration of about 1 g/100 cc, analagous to the Langmuir type monolayer isotherm. Areas per molecule were calculated and compared with areas of close-packed models in positions parallel to and perpendicular to the surface. The calculated areas corresponded more closely to the flat or parallel positions. Heats of adsorption were determined and were in the range of 27–71 kcal/eq, suggesting chemisorption of the COOH group at the surface. The value of dimer acid suggests that both COOH groups are chemisorbed. Models show that the parallel position permits both COOH groups to touch the surface. The perpendicular position generally does not permit both COOH groups to touch the surface. Dimer acid showed a value (71 kcal/eq) higher than the monobasic acids (44–55 kcal/eq), possibly due to interaction of the ring structure (partly aromatic) with the surface. Azelaic acid from an 80–20t-butanol-hexane solvent showed a lower value of 27 kcal/eq, possibly due to adsorption of a hydrogenbonded alcohol-acid moiety as such. Journal Series No. 547, General Mills, Inc. Research Laboratories.     

Synthesis,mechanical, and thermophysical properties of high-entropy (Zr,Ti,Nb,Ta,Hf)C0.8 ceramic

Two high-entropy carbides, including stoichiometric (Zr,Ti,Nb,Ta,Hf)C and nonstoichiometric (Zr,Ti,Nb,Ta,Hf)C_0.8, were prepared from monocarbides and ZrH₂. Their sinterability, microstructures, mechanical properties, thermophysical properties, and oxidation behaviors were systematically compared. With the introduction of carbon vacancy, the sintering temperature was lowered up to 300°C, Vickers hardness was almost unaffected, whereas the strength decreased significantly generally due to the decrease of covalent bonds. The thermal conductivity shows a 50% decrease for nonstoichiometry high-entropy carbide, which is a major consequence of the lower electrical conductivity. The oxidation resistance in high temperature water vapor was not sensitive to carbon stoichiometry.     

Preparations,optical, structural,conductive and magnetic evaluations of RE's (Pr,Y, Gd,Ho, Yb) doped spinel nanoferrites

Rare earths RE's (Pr, Y, Gd, Ho, Yb) substituted MnZn spinel ferrites with composition of Mn_0.5Zn_0.5M_0.02Fe_1.98O₄ (M = Pr, Y, Gd, Ho, Yb) are prepared by sol gel combustion approach. Low sintering temperature (500 °C) is used to sinter the RE's doped MnZn samples. MnZn samples are further characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) to measure the cubic crystalline structure, particle size, morphology, porosity and grain size. Cubic crystalline phase of prepared RE's doped MnZn ferrites is confirmed by x-ray diffraction (XRD). The morphology, porosity and grain size are observed using FESEM. The magnetic properties of RE's doped MnZn nanoferrites are analyzed by vibrating sample magnetometer (VSM). Coercivity (H_c), remanence (M_r) and saturation magnetization (M_s) are calculated from the magnetic loops. The saturation and remanence of the nanoferrites are increased by the substitution of RE's metal ions and varies from 14.76 to 26.36 emu/g and 9.98–22.48 emu/g respectively. Bohr magneton and anisotropy constant are calculated from the recorded magnetic data. The conductive analysis of the prepared samples is studied at 40 °C −300 °C temperature, leading to the conductivity measurements from 1.12 × 10^-2 Ω^-1-cm^-1 to 9.52 × 10^-2 Ω^-1-cm^-1. UV–Vis spectroscopy is used to determine the semi conducting nature of RE's doped MnZn spinel ferrite samples. The magnetic, conductive and optical study of the RE's doped MnZn nanoferrites sintered at low temperature suggests the use of these materials for microwave absorption, supercapacitor, lithium ion batteries and nanoelectronics industrial applications.     

ICP-AES分析低合金钢中的Mn、Mo、V、Ni、Al、Cu、Cr元素

用等离子发射光谱法测定低合金钢中的Mn、Mo、V、Ni、Al、Cu、Cr元素,试样用HNO3和HCl在加热条件下分解,经过系列试验,选择仪器的工作条件,进行测定,建立了一套分析方法,经对照分析,分析结果令人满意。本方法快速准确,精密度良好,完全可以满足生产需要。     

Photochemical degradation of acetylated,methylated, phenylhydrazine-modified,and ACC-treated wood

If wood under clear, ultraviolet-transparent coatings could be protected from photodegradation, the performance of clear finishes would be greatly enhanced. The objective of this study was to determine whether acetylation or methylation of the wood and whether reaction with phenylhydrazine or treatment with acid copper chromate would impart resistance to photodegradation by longwave UV light. Infrared (IR) and ultraviolet (UV) spectra, analysis of wood before and after irradiation, and quantitative determination of volatile degradation products were used to measure degradation. Acetylation did not protect wood, although acetyl groups themselves were resistant to photodegradation. Methylation did not protect wood either, and methylated wood yielded more methanol and formaldehyde during photodegradation. Phenylhydrazine-modified wood lost the newly introduced nitrogen and failed to protect wood also. Acid copper chromate treatment allowed some demethoxylation, but severely curtailed the photooxidation process.     

Breaking, making, and twisting of chemical bonds in gas, liquid, and nanocavities

In this Account, we recount on our studies of 1'-hydroxy-2'-acetonaphthone (HAN, a proton transfer prototype molecule) in gas, solutions, and nanocavities. The internal H-bond photoreaction in HAN leads to a keto type structure, and following its formation, an internal twisting motion gives birth to keto rotamers. Theory, temperature, and solvent effects on its photodynamics show the involvement of efficient radiationless processes in both keto structures. When HAN is caged in a cyclodextrin nanocavity, the spectroscopy, photodynamics, and issues of twisting motion are strongly affected and could be tuned: a behavior relevant to those of many chemical and biological systems.     

Morphological,structural, surface,thermal, chemical,and magnetic properties of Al-doped nanostructured copper ferrites

Aluminum-doped copper ferrite nanoparticles synthesized via thermal decomposition were analyzed for Al³⁺ substitution effects. Nanocrystalline doped copper ferrite with a crystallite size <9 nm was characterized using several advanced techniques, including X-ray diffractometry (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). The degree of thermal decomposition used for doping copper ferrite at the nanoparticle level correlates well with the quantitative, dimensional, and structural characterizations. The Scherrer equation and Williamson–Hall method were employed to determine the general lattice strain and constants. Structural properties, such as the oxygen positional parameters, radii of the octahedral and tetrahedral sites, hopping lengths, bond lengths and angles, site bonds, and edge lengths, were determined using XRD patterns. The improved A–B super-exchange interaction was demonstrated by the discrepancy in the theoretically anticipated bond angles. The analysis of magnetic hysteresis (M − H) using a vibrating sample magnetometer (VSM) and XPS confirmed the improvement in the super-exchange interaction. XPS results suggest that Fe and Cu in the crystal lattice are in the form of Fe^III and Cu^II, respectively. The investigation of the degree of inversion, state, and composition using XPS aids to understand the properties of the nanostructured copper ferrites. The saturation and remnant magnetization were determined from hysteresis loops at 1.8 T obtained using the VSM at room temperature. The noncollinear spin and efficient sublattice interactions are responsible for the decrease in M_s and M_r.     

Creep, Strength, Expansion, and Elastic Moduli of Sintered BeO As a Function of Grain Size, Porosity, and Grain Orientation

Physical properties are presented for extruded and sintered BeO from 25° to 1400° C as a function of porosity (0 to 15%), grain size (5 to 100μ), and grain orientation (random to 80% preferred). The elastic constants and linear thermal expansion are sensitive to the degree of preferred grain orientation. Measurements on polycrystalline specimens permitted calculation of the anisotropy in single crystals of BeO for these properties. Modulus of rupture data are treated in terms of the Knudsen equation, and compressive creep data have been used to estimate the diffusion coefficient controlling strain rate at 1200°C.     

Design,Synthesis, and Self-Assembly Studies of a Suite of Monodisperse,Facially Amphiphilic,Protein–Dendron Conjugates

The custom design of protein–dendron amphiphilic macromolecules is at the forefront of macromolecular engineering. Macromolecules with this architecture are very interesting because of their ability to self-assemble into various biomimetic nanoscopic structures. However, to date, there are no reports on this concept due to technical challenges associated with the chemical synthesis. Towards that end, herein, a new chemical methodology for the modular synthesis of a suite of monodisperse, facially amphiphilic, protein–dendron bioconjugates is reported. Benzyl ether dendrons of different generations (G1–G4) are coupled to monodisperse cetyl ethylene glycol to form macromolecular amphiphilic activity-based probes (AABPs) with a single protein reactive functionality. Micelle-assisted protein labeling technology is utilized for site-specific conjugation of macromolecular AABPs to globular proteins to make monodisperse, facially amphiphilic, protein–dendron bioconjugates. These biohybrid conjugates have the ability to self-assemble into supramolecular protein nanoassemblies. Self-assembly is primarily mediated by strong hydrophobic interactions of the benzyl ether dendron domain. The size, surface charge, and oligomeric state of protein nanoassemblies could be systematically tuned by choosing an appropriate dendron or protein of interest. This chemical method discloses a new way to custom-make monodisperse, facially amphiphilic, protein–dendron bioconjugates.     

Deformation, Recrystallization, Strength, and Fracture of Press-Forged Ceramic Crystals

Sapphire and ruby were very difficult to press-forge because they deformed without cracking only in a limited temperature range before they melted. Spinel crystals were somewhat easier and MgO, CaO, and TiC crystals much easier to forge. The degree of recrystallization that occurred during forging (which was related to the ease and type of slip intersections) varied from essentially zero in Al₂O₃ to complete (i.e. random polycrystalline bodies were produced) in CaO. Forging of bi-and polycrystalline bodies produced incoherent bodies as a result of grain-boundary sliding. Strengths of the forged crystals were comparable to those of dense polycrystalline bodies of similar grain size. However, forged and recrystallized CaO crystals were ductile at lower temperatures than dense hot-pressed CaO. This behavior is attributed to reduced grain-boundary impurities and porosity. Fracture origins could be located, indicating that fracture in the CaO occurs internally as a result of surface work hardening caused by machining.     

Microcalorimetric studies of interactions of ethene, isobutene, and isobutane with silica-supported Pd, Pt, and PtSn

Microcalorimetric measurements were made of the interaction of hydrogen, ethene, isobutene and isobutane at 300 K with silica- supported Pt, Pd, and PtSn catalysts. The initial heats of hydrogen adsorption on silica-supported Pd and Pt are 104 and 95 kJ/mol, respectively. The presence of Sn decreases the saturation uptake of hydrogen on the PtSn sample. The initial heats of ethene interaction with Pd/silica and Pt/silica are 170 and 145 kJ/mol, respectively. The presence of Sn decreases the initial heat to 115 kJ/mol on the PtSn sample. The initial heats of isobutene interaction with silica-supported Pd and Pt are 160 and 190 kJ/mol, respectively. The presence of Sn decreases the initial heat to 125 kJ/mol on the PtSn sample. It appears that ethene and isobutene adsorb dissociatively on silica-supported Pd and Pt to form alkylidyne species at 300 K, with an average strength of carbon-metal bonds for these species near 230 kJ/mol. Ethene and isobutene adsorb on silica-supported PtSn to form di- σ- and π-bonded alkene species at 300 K, with an average strength of carbon-metal bonds for these species near 190 and 130 kJ/mol, respectively. Isobutane appears to adsorb dissociatively on a small number of sites on silica-supported Pd and Pt, and this dissociation is also inhibited by Sn on PtSn samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

ICP—AES法测定镍铁中Si、Co、Cu、P、Mn、Cr

研究了用ICP—AES法测定镍铁中Si、Co、Cu、P、Mn、Cr元素含量的分析方法。分析了镍基和铁基效应对某些元素强度影响情况,采用基体匹配法消除镍基和铁基的干扰效应。采用信倍比和净强度为仪器测量的选择条件,用多元素混合标准溶液绘制工作曲线。测出镍铁中的Si、Co、Cu、P、Mn、Cr元素分析方法检出限。此方法有较高准确度和精密度。     

Effect of shipping on quality of seeds,meals, fats,and oils

Although few studies have been conducted relative to quality preservation of oilseeds and their products while in transportation containers, there are known causative factors of quality degradation which are applicable from long experience of storage in ordinary land-based containers. Often the success of quality retention is a function of the basic level of quality negotiated by the buyer and seller and the inherent idiosyncrasies of the commodity when handled and when exposed to the ambient conditions of the air and container.     

Synthesis of methyl,propyl, butyl,isobutyl, hexyl,cyclohexyl, octyl,and 2-ethylhexyl esters of epoxyoleic acid

A series of esters of 12,13-epoxyoleic acid were prepared by means of alcoholysis of triepoxyolein (trivernolin). The procedure for the alcoholysis, and isolation and purification of the esters are described. Analytical characteristics of the esters are reported. E. Util. Res. Devel. Div., ARS, USDA.     

对羧基苯甲醛、对甲基苯甲酸、苯甲酸、对苯二甲酸和间苯二甲酸在N,N-二甲基甲酰胺中的溶解度

采用激光监视技术由合成法实验测定了对羧基苯甲醛、对甲基苯甲酸、苯甲酸、对苯二甲酸和间苯二甲酸在N,N－二甲基甲酰胺中的溶解度。实验数据用多项式方程进行关联,计算的溶解度与实验值符合良好。