The variations and climatic significance of D/H ratios in the carbon-bound hydrogen of cellulose in trees

The σD values of nitrated cellulose from a variety of trees covering a wide geographic range have been measured. These measurements have been used to ascertain which factors are likely to cause σD variations in cellulose C-H hydrogen.

It is found that a primary source of tree σD variation is the σD variation of the environmental precipitation. Superimposed on this are isotopic variations caused by the transpiration of the leaf water incorporated by the tree. The magnitude of this transpiration effect appears to be related to relative humidity.

Within a single tree, it is found that the hydrogen isotope variations which occur for a ring sequence in one radial direction may not be exactly the same as those which occur in a different direction. Such heterogeneities appear most likely to occur in trees with asymmetric ring patterns that contain reaction wood. In the absence of reaction wood such heterogeneities do not seem to occur. Thus, hydrogen isotope analyses of tree ring sequences should be performed on trees which do not contain reaction wood.

Comparisons of tree σD variations with variations in local climate are performed on two levels: spatial and temporal. It is found that the σD values of 20 North American trees from a wide geographic range are reasonably well-correlated with the corresponding average annual temperature. The correlation is similar to that observed for a comparison of the σD values of annual precipitation of 11 North American sites with annual temperature. However, it appears that this correlation is significantly disrupted by trees which grew on poorly drained sites such as those in stagnant marshes. Therefore, site selection may be important in choosing trees for climatic interpretation of σD values, although proper sites do not seem to be uncommon.

The measurement of σD values in 5-year samples from the tree ring sequences of 13 trees from 11 North American sites reveals a variety of relationships with local climate. As it was for the spatial σD vs climate comparison, site selection is also apparently important for temporal tree σD vs climate comparisons. Again, it seems that poorly-drained sites are to be avoided. For nine trees from different "well-behaved" sites, it was found that the local climatic variable best related to the σD variations was not the same for all sites.

Two of these trees showed a strong negative correlation with the amount of local summer precipitation. Consideration of factors likely to influence the isotopic composition of summer rain suggests that rainfall intensity may be important. The higher the intensity, the lower the σD value. Such an effect might explain the negative correlation of σD vs summer precipitation amount for these two trees. A third tree also exhibited a strong correlation with summer climate, but in this instance it was a positive correlation of σD with summer temperature.

The remaining six trees exhibited the best correlation between σD values and local annual climate. However, in none of these six cases was it annual temperature that was the most important variable. In fact annual temperature commonly showed no relationship at all with tree σD values. Instead, it was found that a simple mass balance model incorporating two basic assumptions yielded parameters which produced the best relationships with tree σD values. First, it was assumed that the σD values of these six trees reflected the σD values of annual precipitation incorporated by these trees. Second, it was assumed that the σD value of the annual precipitation was a weighted average of two seasonal isotopic components: summer and winter. Mass balance equations derived from these assumptions yielded combinations of variables that commonly showed a relationship with tree σD values where none had previously been discerned.

It was found for these "well-behaved" trees that not all sample intervals in a σD vs local climate plot fell along a well-defined trend. These departures from the local σD VS climate norm were defined as "anomalous". Some of these anomalous intervals were common to trees from different locales. When such widespread commonalty of an anomalous interval occurred, it was observed that the interval corresponded to an interval in which drought had existed in the North American Great Plains.

Consequently, there appears to be a combination of both local and large scale climatic information in the σD variations of tree cellulose C-H hydrogen.

Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels.

Biodeterioration of cellulose materials in Karingote, Nileswaram, Kavvayi and Ramapuram Backwater systems of Kerala

The hydrographic conditions prevailing in an estuarine system along the southwest coast of India are described. The nature of destruction of timber in these backwaters has been examined in detail which revealed the existence of 8 species of shipworms, 2 species each of pholads and isopods. The shipworms are represented by Dicyathifer manni, Lyrodus pedicellatus, Teredo furcifera, T. clappi, Nausitora dunlopei, Bankia carinata, B. campanellata; the pholads by Martesia striata and M. (Purticoma) nairi; and the isopods by Sphaeroma terebrans and S. annandalei. The incidence and relative abundance of these pests are discussed in relation to the salinity profile of the estuary.

High rate deposition of microcrystalline silicon films by high-pressure radio frequency plasma enhanced chemical vapor deposition (PECVD)

Hydrogenated microcrystalline silicon (mu c-Si:H) thin films were prepared by high-pressure radio-frequency (13.56 MHz) plasma enhanced chemical vapor deposition (rf-PECVD) with a screened plasma. The deposition rate and crystallinity varying with the deposition pressure, rf power, hydrogen dilution ratio and electrodes distance were systematically studied. By optimizing the deposition parameters the device quality mu c-Si:H films have been achieved with a high deposition rate of 7.8 angstrom/s at a high pressure. The V-oc of 560 mV and the FF of 0.70 have been achieved for a single-junction mu c-Si:H p-i-n solar cell at a deposition rate of 7.8 angstrom/s.

Gap states and microstructure of microcrystalline silicon thin films

The density of states (DOS) above Fermi level of hydrogenated microcrystalline silicon (mu c-Si H) films is correlated to the material microstructure. We use Raman scattering and infrared absorption spectra to characterize the structure of the films made with different hydrogen dilution ratios. The DOS of the films is examined by modulated photocurrent measurement. The results have been accounted for in the framework of a three-phase model comprised of amorphous and crystalline components, with the grain boundary as the third phase. We observed that the DOS increases monotonically as the grain boundary volume fractions f(gb) is increased, which indicates a positive correlation between the DOS and the grain boundary volume fraction.

The compact microcrystalline Si thin film with structure uniformity in the growth direction by hydrogen dilution profile

The hydrogen dilution profiling (HDP) technique has been developed to improve the quality and the crystalline uniformity in the growth direction of mu c-Si:H thin films prepared by hot-wire chemical-vapor deposition. The high H dilution in the initial growth stage reduces the amorphous transition layer from 30-50 to less than 10 nm. The uniformity of crystalline content X-c in the growth direction was much improved by the proper design of hydrogen dilution profiling which effectively controls the nonuniform transition region of Xc from 300 to less than 30 nm. Furthermore, the HDP approach restrains the formation of microvoids in mu c-Si: H thin films with a high Xc and enhances the compactness of the film. As a result the stability of mu c-Si: H thin films by HDP against the oxygen diffusion, as well as the electrical property, is much improved. (c) 2005 American Institute of Physics.

Structure, stability and photoelectronic properties of transition films from amorphous to microcrystalline silicon

A series of hydrogenated silicon films near the threshold of crystallinity was prepared by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) from a mixture of SiH4 diluted in H, The effect of hydrogen dilution ratios R-H = [H-2]/[SiH4] on microstructure of the films was investigated. Photoelectronic properties and stability of the films were studied as a function of crystalline fraction. The results show that more the crystalline volume fraction in the silicon films, the higher mobility life-time product (mu tau), better the stability and lower the photosensitivity. Those diphasic films contained 8%-31% crystalline volume fraction can gain both the fine photoelectronic properties and high stability. in the diphasic (contained 12% crystalline volume fraction) solar cell, we obtained a much lower light-induced degradation of similar to 2.9%, with a high initial efficiency of 10.01% and a stabilized efficiency of 9.72% (AM1.5, 100 mW/cm(2)). (c) 2005 Elsevier B.V. All rights reserved.

Transition films from amporphous to microcrystalline silicon and solar cells

A series of hydrogenated silicon films near the threshold of crystallinity was prepared by very high frequency plasmaenhanced chemical vapor deposition (VHF-PECVD)from a mixture of SiH4 diluted in H-2. The effect of hydrogen dilution ratios R = [H-2]/[SiH4] on the microstructure of the films was investigated. The photoelectronic properties and stability of the films were studied as a function of crystalline fraction. The results show that the diphasic films gain both the fine photoelectric properties like a-Si: H and high stability like mu w-Si:H. By using the diphasic silicon films as the intrinsic layer, p-i-n junction solar cells were prepared. Current-voltage (J-V) characteristics and stability of the solar cells were measured under an AM1.5 solar simulator. We observed a light-induced increase of 5.2% in the open-circuit voltage (V-oc) and a light-induced degradation of similar to 2.9% inefficiency.

The microstructure of hydrogenated microcrystalline silicon thin films studied by small-angle x-ray scattering

The microstructures of hydrogenated microcrystalline silicon (tic-Si: H) thin films, prepared by plasma-enhanced chemical vapor deposition (PECVD), hot wire CVD(HWCVD) and plasma assisted HWCVD (PE-HWCVD), have been analyzed by the small angle x-ray scattering(SAXS) measurement. The SAXS data show that the microstructures of the μ c-Si: H films display different characteristics for different deposition techniques. For films deposited by PECVD, the volume fraction of micro-voids and mean size are smaller than those in HWCVD sample. Aided by suitable ion-bombardment, PE-HWCVD samples show a more compact structure than the HWCVD sample. The microstructure parameters of the μ c-Si: H thin films deposited by two-steps HWCVD and PE-HWCVD with Ar ions are evidently improved. The result of 45° tilting SAXS measurement indicates that the distribution of micro-voids in the film is anisotropic. The Fouriertransform infrared spectra confirm the SAXS data.

Study on growth mechanism of low-temperature prepared microcrystalline Si thin films

Microcrystalline silicon thin films at different growth stages were prepared by hot wire chemical vapor deposition. Atomic force microscopy has been applied to investigate the evolution of surface topography of these films. According to the fractal analysis I it was found that, the growth of Si film deposited on glass substrate is the zero-diffused stochastic deposition; while for the film on Si substrate, it is the finite diffused deposition on the initial growth stage, and transforms to the zero-diffused stochastic deposition when the film thickness reaches a certain value. The film thickness dependence of island density shows that a maximum of island density appears at the critical film thickness for both substrates. The data of Raman spectra approve that, on the glass substrate, the a-Si: H/mu c-Si:H transition is related to the critical film thickness. Different substrate materials directly affect the surface diffusion ability of radicals, resulting in the difference of growth modes on the earlier growth stage.