An empirical method for determining the crystallinity of native cellulose was studied with an x-ray diffractometer using the focusing and transmission techniques. The influence of fluctuations in the primary radiation and in the counting and recording processes have been determined. The intensity of the 002 interference and the amor phous scatter at 2θ = 18° was measured. The percent crystalline material in the total cellulose was expressed by an x-ray "crystallinity index." This was done for cotton cellulose decrystallized with aqueous solutions containing from 70% to nominally 100% ethylamine. The x-ray "crystallinity index" was correlated with acid hydrolysis crys tallinity, moisture regain, density, leveling-off degree of polymerization values, and infrared absorbance values for each sample. The results indicate that the crystallinity index is a time-saving empirical measure of relative crystallinity. The precision of the crystallinity index in terms of the several crystallinity criteria is given. Bas...

An Empirical Method for Estimating the Degree of Crystallinity of Native Cellulose Using the X-Ray Diffractometer

We report a synthesis of highly luminescent (CdSe)ZnS composite quantum dots with CdSe cores ranging in diameter from 23 to 55 A. The narrow photoluminescence (fwhm ≤ 40 nm) from these composite dots spans most of the visible spectrum from blue through red with quantum yields of 30−50% at room temperature. We characterize these materials using a range of optical and structural techniques. Optical absorption and photoluminescence spectroscopies probe the effect of ZnS passivation on the electronic structure of the dots. We use a combination of wavelength dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, small and wide angle X-ray scattering, and transmission electron microscopy to analyze the composite dots and determine their chemical composition, average size, size distribution, shape, and internal structure. Using a simple effective mass theory, we model the energy shift for the first excited state for (CdSe)ZnS and (CdSe)CdS dots with varying shell thickness. Finally, we characterize the...

(CdSe)ZnS Core-Shell Quantum Dots - Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites

Existing knowledge about Scherrer constants is reviewed and a summary is given of the interpretation of the broadening arising from small crystallites. Early work involving the half-width as a measure of breadth has been completed and Scherrer constants of simple regular shapes have been determined for all low-angle reflections (h2 + k2 + l2 ≤ 100) for four measures of breadth. The systematic variation of Scherrer constant with hkl is discussed and a convenient representation in the form of contour maps is applied to simple shapes. The relation between the `apparent' crystallite size, as determined by X-ray methods, and the `true' size is considered for crystallites having the same shape. If they are of the same size, then the normal Scherrer constant applies, but if there is a distribution of sizes, a modified Scherrer constant must be used.

Scherrer after sixty years: a survey and some new results in the determination of crystallite size

Monodisperse magnetite nanoparticles have been synthesized by high-temperature solution-phase reaction of Fe(acac)3 in phenyl ether with alcohol, oleic acid, and oleylamine. Seed-mediated growth is used to control Fe3O4 nanoparticle size, and variously sized nanoparticles from 3 to 20 nm have been produced. The as-synthesized Fe3O4 nanoparticles have inverse spinel structure, and their assemblies can be transformed into γ-Fe2O3 or α-Fe nanoparticle assemblies, depending on the annealing conditions. The reported procedure can be used as a general approach to various ferrite nanoparticles and nanoparticle superlattices.

Size-Controlled Synthesis of Magnetite Nanoparticles

Although measurements of crystallinity index (CI) have a long history, it has been found that CI varies significantly depending on the choice of measurement method. In this study, four different techniques incorporating X-ray diffraction and solid-state 13C nuclear magnetic resonance (NMR) were compared using eight different cellulose preparations. We found that the simplest method, which is also the most widely used, and which involves measurement of just two heights in the X-ray diffractogram, produced significantly higher crystallinity values than did the other methods. Data in the literature for the cellulose preparation used (Avicel PH-101) support this observation. We believe that the alternative X-ray diffraction (XRD) and NMR methods presented here, which consider the contributions from amorphous and crystalline cellulose to the entire XRD and NMR spectra, provide a more accurate measure of the crystallinity of cellulose. Although celluloses having a high amorphous content are usually more easily digested by enzymes, it is unclear, based on studies published in the literature, whether CI actually provides a clear indication of the digestibility of a cellulose sample. Cellulose accessibility should be affected by crystallinity, but is also likely to be affected by several other parameters, such as lignin/hemicellulose contents and distribution, porosity, and particle size. Given the methodological dependency of cellulose CI values and the complex nature of cellulase interactions with amorphous and crystalline celluloses, we caution against trying to correlate relatively small changes in CI with changes in cellulose digestibility. In addition, the prediction of cellulase performance based on low levels of cellulose conversion may not include sufficient digestion of the crystalline component to be meaningful.

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Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance

X-ray diffraction procedures for polycrystalline and amorphous materials

X-ray diffraction procedures

The accuracy of the Scherrer crystallite size equation is limited in part by the uncertainty in β, the experimentally deduced pure diffraction broadening. Currently used procedures for estimating β from the observed breadth of a Debye‐Scherrer line are not, in general, applicable to the x‐ray spectrometer.By making use of a scheme of convolution analysis for analyzing the effect of geometrical factors in broadening the pure diffraction contour, a correction curve is developed for determining β from the experimentally measured line breadths b and B (Jones' notation). The degree of reliability of this correction procedure is ascertained by applying Stokes' direct Fourier transform procedure for determining the form of the pure diffraction contour free of instrumental effects.Suggestive procedures are given for crystallite size determination with the x‐ray spectrometer in different size ranges, and several examples are described.

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Determination of Crystallite Size with the X‐Ray Spectrometer

X-Ray Diffraction Procedures: For Polycrystalline and Amorphous Materials, 2nd Edition

The mathematical relationships are developed which are pertinent to the quantitative analysis of powder mixtures for the case of diffraction from the surface of a flat powder specimen. These formulas relate the diffracted intensity to the absorptive properties of the sample. Three important cases are treated: (1) Mixture of n components; absorbing powder of the unknown equal to that of the matrix; concentration proportional to intensity. Direct analysis is permitted. (2) Binary mixture; absorbing powder of the unknown not equal to that of the diluent; concentration not proportional to intensity. Direct analysis is possible by means of calibration curves prepared from synthetic mixtures. (3) Mixture of n components; absorbing power of the unknown not equal to that of the matrix; general case. Analysis is accomplished by the addition of an internal standard. Concentration is proportional to the ratio of the intensity of a selected reflection from the unknown to the intensity of a reflection from the internal standard.

Harold P. Klug

Papers

X-ray diffraction procedures for polycrystalline and amorphous materials

X-ray diffraction procedures

Determination of Crystallite Size with the X‐Ray Spectrometer

X-Ray Diffraction Procedures: For Polycrystalline and Amorphous Materials, 2nd Edition

Basic Aspects of X-Ray Absorption in Quantitative Diffraction Analysis of Powder Mixtures