Previous work presented by the author at these conferences has been summarized by G.N. Ramachandran in “Treatise on Collagen I , 177-8”. Epitactic crystallization of amides and diols in the collagen lattice of formalinized rat tail tendon, with equatorial expansion of the collagen lattice, was used to visualize the core diameter of each coil in the triple spiral at 7A and the vertical repeat of the hydrogen-bonding unit at 5.2A. Expansion of the non - formalinized collagen lattice has been observed as high as 20.1A when 1, 4-trans-(bisamino-methyl) - cyclo-hexane was inserted between the hexagonal array of protein spirals in the collagen lattice, the length of the inserted molecule being 13A. With dimensions based on Fisher - Hirschfelder - Taylor atomic models, with maximum extension of the dihydroxy compounds, the a. parameter of the expanded collagen would be expected to increase from 16.5A in the case of glycol to 20.6A in the case of 1, 5 - pentanediol, but actually the parameter decreases from 18.3A in the case of glycol to 16.2A in the case of 1, 5 - pentanediol. The larger figure in the case of glycol is explained by its hydrogen bonded dimerization. 1,3 propanediol fits in to the collagen lattice as its extended form. In the case of the other compounds, the chains are folded and fit together with Vander Waals bonding, and produce progressively smaller parameters for the a axis in collagen. In this nonaqueous equilibrium the non - formalinized collagen core diameter averages 7.7A ±0.2 and the spacing of hydrogen bond contacts along the collagen fiber axis is 4.8 ±0.2A.

Some branches of structural research could benefit from supplemental information provided by “soft” x-rays. Little use is made of these wavelengths because they are difficult to generate at high intensity, hard to collimate, need vacuum for propagation, and are heavily absorbed in the sample. None of these difficulties is insurmountable, however, and it will be shown that the information to be gained is often worth the extra effort.

A few theoretical and experimental examples with silver L-radiation (λ ≈ 4.15Å) and aluminum K-radiation (λ ≈ 8.34Å) demonstrate that valuable semiquantitative information on the size and number of aperiodic scatterers in solid samples can be extracted. Other examples show the superior sensitivity of these longer wavelengths to dimensional changes in periodic lattices. Applicability of long-wavelength diffraction is restricted to values of interplanar distance d > λ/2. Valuable information about lattice imperfection can be gained from broadening of the reflection at larger glancing angles. It is shown that the heavy absorption of these wavelengths in the sample is not necessarily prohibitive.

The instrumentation used in these studies was designed for routine operation by laboratory personnel without special training. It consists of a demountable high-intensity x-ray source and a multipurpose highvacuum camera. Operation of the x-ray unit resembles that of commercial x-ray diffraction instruments. Because of its greater-flexibility, photographic recording has been practiced so far but could be replaced by electronic readout.

A laboratory has been established with two primary objectives. First it is to permit test and calibration of rocket and satellite x-ray astronomy experiments. Second it is for studies in ultrasoft x-ray physics. The basic units described are a precision x-ray spectrometer, a separate precision spectrograph, direct and fluorescence excitation sources, the rocket payload test chamber, and auxiliary components. Planned applications include measurements of crystal reflection coefficients, rocking curves, light element absorption edge structure, and spectroscopy of solid and high temperature gas sources.

Various electro-optical systems have been reported which permit intensification of X-ray diffraction patterns and thus a decrease in exposure time for recording and display of the X-ray images. Prior to 1966, all such electro-optical systems incorporated a large format X-ray image intensifier of the same type as conventionally used for medical and industrial fluoroscopy. In the past four years, a number of different systems have been reported which are superior to those developed prior to 1966. These systems may be grouped into two main categories, the large format variety for Laue diffraction applications, and the small format variety for topographic applications.

The purpose of the present paper is to describe the particular characteristics of both the large format and small format systems and to discuss the advantages and disadvantages associated with each type. Based on actual performance characteristics it will be shown that:

1. 1. A multiple stage image intensifier system coupled to an external fluorescent screen is the most sensitive and only truly instantaneous system; it can be used with very weak X-ray intensities, the resolution is currently limited by the external fluorescent screen to 42μ the system is extremely versatile in that it can be used both for large format recording of Laue patterns as well as for small format recording of X-ray topographe; the system has a very long lifetime since nothing is altered by X-radiation.

2. 2. An X-ray sensitive vidicon is the least sensitive; it must be used with extremely high intensity X-rays or long exposure times; the resolution is the highest at approximately 15μ and is limited by either bandwidth of the television system, the thickness of the X-ray sensitive target or the size of the electron beam at the target; due to the small size of the X-ray sensitive target the system can only be used for small format recording of X-ray topographs; the lifetime of the system is short since X-radiation causes degradation of the target.

A commercial micro-densitometer is run by an IBM 1800 computer under time sharing. It is used for measuring the transmission of mass spectrometer plates and x-ray powder diffraction films. The x-ray data are processed on the 1800 computer in three steps: First a linear background approximation is performed by least-squares methods, then the data corrected for background are searched for peaks and the position of the peaks is determined. After an optional manual peak selection facilitated by CRT display of the data and results, d-spacings are calculated and printed out together with approximate intensities. The programs are also used for processing data obtained By automated x-ray diffractometers.

In x-ray absorption spectroscopy, the accurate determination of the incident intensity (I0) has long been a difficult problem. Several techniques have been used to collect I0 data, but none have simultaneously obtained both I0 and I (transmitted intensity after absorption). The new technique described herein permits simultaneous determination of I0 and I utilizing a dual detector monitoring of the x-ray beam. With the sample removed, an intensity relationship between the two detectors, arranged in tandem, can be obtained. Knowing this relationship permits determination of I0 in the second detector during an experiment. The effects of voltage, current, and gas flow variations on this relationship are discussed, and an experiment is described where an absorption spectrum is obtained over an emission peak of the x-ray tube target material. The results of the experiment using two methods of obtaining I0 are compared.

A method is described for determining the magnitude and sense of systematic errors in x-ray diffractometer stress measurements produced by focusing aberrations during diffraction from imperfect specimen contours and wide horizontal beam divergences. Corrections for such systematic errors are presently not made. However, if the highest accuracy and/or absolute values of stress are desired, these must be either taken into account or minimized by control of beam geometry. Equations and computer data are presented to indicate the errors in 2θ and stress (σ) resulting from use of flat, various convex and concave curvatures for primary beam divergences of 1° to 3°, Stress errors are calculated for both the parafocus technique of beam focusing and the stationary or non-focusing method.

The results show that convex and flat specimens always produce negative 2θ deviations from the condition of perfect focus and thus a net positive or tensile stress error. The magnitude of this error increases as the radius of the convex shape decreases and/or the ψangle and beam divergence is increased. Concave specimens with curvatures less than the radius of the concave shape required for perfect focus (see body of report) produce positive 2θ deviations and, therefore, negative or com-pressive stress errors.

The stationary or non-focusing technique produced systematic errors which were 1/3 of those produced by focusing aberrations with the parafocus technique. Fortunately, in both cases the actual errors are not very large (less than ±7.5 ksi), even with divergent beams as large as 3° and convex radii as small as 125”.

The measurement of residual stress, using X-ray diffraction techniques, is based on the change in diffraction angle determined for the Intensity maximum of some suitable reflection from the sample when this is placed consecutively with its surface at two different angles to the diffracting planes. These diffraction angles may be obtained in a variety of ways, but are most often calculated from measurements of three X-ray diffraction intensities at angles selected in the immediate vicinity of the peak maximum at each sample angle and fitting each set of data to a parabolic curve. A simple mathematical expression may be derived relating the diffraction angles, and hence the residual stress, to the measured X-ray intensities; there will, however, be statistical errors in the calculated diffraction angles due to random counting errors in the measurement of the X-ray diffraction intensities. From the expression relating the residual stress to the X-ray intensities an equation has been derived giving the standard deviation in the residual stress due to random counting errors. In addition, a simple approximation has been obtained from this equation showing that the standard deviation is decreased by increasing the number of counts accumulated for each X-ray intensity measurement and by increasing the size of the angular increments between the data points. It will also be shown that, using the approximation, it is possible to estimate in advance the number of accumulated counts at each point necessary to attain a desired standard deviation in a residual stress measurement.

Residual elastic stresses have been measured in cold rolled α-brass (30% zinc) using the available x-ray diffractometer methods. Residual stress values obtained by the two exposure and sin2ψ methods of stress analysis are compared with data obtained using Wagner's extrapolation method.

For deformations up to 50% reduction in thickness, tensile surface stresses prevailed, and in most cases could be detected by these methods. Uncertainty of the value of a0, the lattice parameter of the deformed' material, presents a serious limitation to the extrapolation technique. Using the approximation a0 = a0ann, residual stresses appear lower than, and frequently of opposite sign to those given by the two exposure method. In addition, lattice parameter variations in the near surface regions of the rolled sheet were opposite to those expected from the true macrostress distributions shown to exist by the two exposure method and by strain gauge techniques. The distributions of ahkl points in the extrapolation plots were in agreement with theory for a combination of anisotropic elastic stresses and low stacking fault density.

A refined x-ray line profile analysis was used to determine the lattice strain distribution and crystallite domain size in nickel and a series of alloys, Ni-Cr, Ni-ThO2 and Ni-Cr-ThO2 in a wide range of thermo-mechanical conditions. Corrections were made for instrumental broadening and doublet broadening according to Stokes and Rachinger respectively, for errors due to the “hook effect”, for terminal errors in the series arising from Instability of the components, and for the presence of stacking faults and twins on the basis of peak shift and asymmetry. The internal consistency of the x-ray data was reviewed critically and good agreement was found. The values of lattice strain and domain size were used to evaluate the presence of a dislocation substructure and the degree of polygonization of the subgraln boundaries.

It was concluded that the thoria-free materials developed much higher lattice strains during cold rolling than did the Ni-ThO2, due it is thought to the operation of multiple slip in the latter. The Ni-Cr-ThO2 also developed high lattice strains during cold rolling, similar to those of the thoria-free lattices, and this was explained by the influence of chromium on cross-slip. It was postulated that the regions of high lattice strain act as driving forces in the process of recrystallization and promote grain growth during heat treatment following cold rolling.

The x-ray results were correlated with transmission electron microscopy and tensile data in a parallel study in which models for room temperature and high temperature strengthening were proposed.

Lattice constants were measured as a function of temperature by single crystal diffracrometry in the temperature range which includes the Néel temperature of VF2(TN= 7°K). The lattice constants of VF2(D4h14=P42m n m) were measured from room temperature down to 4.2°K. In this range rhe tetragonal c-axis contracts 0.58% from 3.2359 Å (RT) to 3.2170 Å (4.2°K). On the other hand, the a-axes show a net expansion of 0.18% from 4.8023 Å (RT) to 4.8110 Å at 4.2°K. The temperature dependence of the lattice constants can be correlated with anisotropy of exchange forces. Vanadium Ions occupy the center and corner positions of the unit cell. Strong magnetic interactions are directed parallel to the c-axis >001< with considerably weaker interactions parallel to the body diagonals >111< The relative strengths of the two exchange integrals are J >001< = 50 J >111<. As a consequence the magnetic ordering is one-dîmensional along the c-axis and the associated distortions arise from the strong magnetic interactions along this axis.

A least-squares polynomial approximation of the Warren-Averbach Fourier coefficients line broadening analysis has shown flash-evaporated GaAs films to be characterized by De(lll) ≤ 400 Å and >εL2<½ ⋍ 0.002. Though twinning is the dominant faulting mechanism, a considerable amount of single and double deformation stacking faults are also present. Growth under a partial pressure of arsenic and tin has enhanced crystallite size by a factor of four.

The interpretation and use of x-ray photon spectra of substances containing second row elements has utilized a number of theoretical models. These models may be divided into three basic categories, namely, the isolated atom model, various molecular models, and a number of solid state models, it is the purpose of this paper to examine critically the validity and limitations of molecular models for interpreting published x-ray photon spectra and spectra obtained by this group on chlorine and sulfur bearing substances.

Chlorine and sulfur bearing substances were chosen for at least three important reasons. First, a great deal of published experimental data already exists on the Kα, Kβ, and L2, 3 transitions of these substances. Second, motivated in part by the long standing controversy concerning possible 3d orbital participation in the bonding of second row elements, there are extensive quantum mechanical calculations for ions containing sulfur and chlorine via simple molecular orbital concepts. Thirdj the availability of accurate photoelectron spectroscopic data on these substances now permits a detailed quantitative comparison of x-ray photon transitions with quantum mechanical calculations.

Detailed evaluation along these lines indicates that for many substances the theoretically calculated energy values are frequently within a few electron volts (or less) of the experimentally observed energies. This study, therefore, tends to substantiate a viewpoint suggested by some recently; namely, that for many substances the starting point in interpreting most of the basic features of soft x-ray spectra should be based upon molecular bonding approaches.