U.S. patent number 3,688,109 [Application Number 05/054,847] was granted by the patent office on 1972-08-29 for x-ray diffraction grating crystals.
This patent grant is currently assigned to Synvar Associates. Invention is credited to Fred R. Gamble.
United States Patent |
3,688,109 |
Gamble |
August 29, 1972 |
X-RAY DIFFRACTION GRATING CRYSTALS
Abstract
The use of structurally layered heavy metal chalcogenides as
diffraction grating crystals in X-ray optical assemblies such as
X-ray fluorescence spectroscopy, the chalcogen being selected from
sulfur, selenium and tellurium, or mixtures thereof. Chalcogenides
intercalated with inorganic and organic materials are
contemplated.
Inventors: |
Gamble; Fred R. (Los Altos,
CA) |
Assignee: |
Synvar Associates (Palo Alto,
CA)
|
Family
ID: |
21993893 |
Appl.
No.: |
05/054,847 |
Filed: |
July 14, 1970 |
Current U.S.
Class: |
378/84; 544/64;
546/2; 359/569; 544/225; 976/DIG.431 |
Current CPC
Class: |
G21K
1/06 (20130101); G21K 2201/062 (20130101); G21K
2201/067 (20130101) |
Current International
Class: |
G21K
1/00 (20060101); G21K 1/06 (20060101); G01n
023/20 () |
Field of
Search: |
;250/51.5,53.1 ;350/162R
;356/79 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Reflection Coefficients of Radiation in the Wavelength Range from
23.6 to 113 A for a Number of Elements and Substances and the
Determination of the Refractive Index and Absorption Coefficient"
by A. P. Lukirskii et al., from Optics and Spectroscopy, Vol. XVI,
No. 2, Feb. 1964, pgs. 168-172..
|
Primary Examiner: Lindquist; William F.
Claims
1. In an X-ray optical assembly comprising at least an X-ray source
and a diffraction grating, the improvement comprising: said
diffraction grating being a structurally layered heavy metal
chalcogenide, the heavy metal being selected from at least one of
those heavy metal elements having an atomic number of 22 to 92,
inclusive, and which is titanium, vanadium, cobalt, nickel, copper,
zinc, gallium, zirconium, niobium, technetium, rhodium, palladium,
silver, indium, tin, hafnium, tantalum, rhenium, iridium, platinum,
gold, lead, bismuth, thorium, and uranium, and the chalcogen being
selected from sulfur, selenium and tellurium, or mixtures
2. The X-ray optical assembly of claim 1, wherein said chalcogenide
is
3. The X-ray optical assembly of claim 2, wherein said chalcogenide
is a
4. The X-ray optical assembly of claim 2, when said chalcogenide
has an
5. The X-ray optical assembly of claim 2, wherein said
intercalated
6. The X-ray optical assembly of claim 5, wherein said organic
compound is
7. The X-ray optical assembly of claim 5, wherein the organic
compound contains an atom selected from nitrogen, sulfur,
phosphorous and oxygen.
8. The X-ray optical assembly of claim 7, wherein the organic
compound
9. The X-ray optical assembly of claim 8, wherein the organic
compound is
10. The X-ray optical assembly of claim 5, wherein the organic
compound is
11. The X-ray optical assembly of claim 5, wherein the organic
compound is
12. The X-ray optical assembly of claim 11, wherein the ionic
compound is a
13. The X-ray optical assembly in accordance with claim 4 wherein
the organic compound is selected from aniline N,N-dimethylaniline,
p-phenylenediamine, 1-aminonapthalene, 1-aminoanthracene,
formamide, butyramide, valeramide, hexanamide, caprylamide,
capramide, lauroylamide, myristamide, palmitamide, stearamide,
cinnamide, benzamide, urea, dimethylformamide, thiobenzamide,
pyridine, quinoline, s-triazine, acridine, pyrimidine, pyridazine,
p-dimethyl-aminopyridine, butylamine, octylamine, hexadecylamine,
octadecylamine, potassium formate, tetrabutyl
14. The X-ray optical assembly of claim 2, wherein the
intercalated
15. The X-ray optical assembly of claim 2, wherein the
intercalated
16. The X-ray optical assembly of claim 2, wherein the
intercalated
17. The X-ray optical assembly of claim 2, wherein the
intercalated
18. The X-ray optical assembly in accordance with claim 1, wherein
the heavy metals are those classified as transition elements in the
Periodic
19. The X-ray optical assembly in accordance with claim 18, wherein
the transition element is selected from Group VB of the Periodic
Table of
20. The X-ray optical assembly in accordance with claim 1, wherein
the
21. The X-ray optical assembly in accordance with claim 20, wherein
said chalcogenide is intercalated with an organic compound selected
from aniline, N,N-dimethylaniline, p-phenylenediamine,
1-amino-naphthalene, 1-aminoanthracene, amides of from one to 18
carbon atoms, urea, pyridine, quinoline, acridine, pyrimidine,
pyridazine, p-dimethylaminopyridine, butylamine, octylamine,
decylamine, octadecylamine, potassium formate,
22. The X-ray optical assembly in accordance with claim 20, wherein
said chalcogenide is intercalated with an organic compound having
a
23. The X-ray optical assembly in accordance with claim 20, wherein
said chalcogenide is intercalated with an organic compound
consisting of an
24. The X-ray optical assembly in accordance with claim 1, wherein
the
25. The X-ray optical assembly in accordance with claim 1, wherein
the
26. The X-ray optical assembly in accordance with claim 1, wherein
the
27. The X-ray optical assembly in accordance with claim 1, wherein
the
28. The X-ray optical assembly in accordance with claim 1, wherein
the
29. The X-ray optical assembly in accordance with claim 1 wherein
the heavy
30. In an X-ray spectroscope assembly of an X-ray source, a
diffracting analyzer, a collimator and detector, the improvement
comprising: said diffracting analyzer being a structurally layered
heavy metal chalcogenide, the heavy metal being selected from at
least one of those heavy metal elements having an atomic number of
22 to 92, inclusive, and which is titanium, vanadium, cobalt,
nickel, copper, zinc, gallium, zirconium, niobium, technetium,
rhodium, palladium, silver, indium, tin, hafnium, tantalum,
rhenium, iridium, platinum, gold, lead, bismuth, thorium, and
uranium, and the chalcogen being selected from sulfur, selenium and
tellurium, or mixtures thereof.
Description
This invention relates to the use of chalcogenides, either per se
or intercalated with various organic and inorganic compounds, as
diffraction grating crystals in X-ray optical assemblies. More
particularly, the invention relates to the novel use of
structurally layered heavy metal chalcogenides where the chalcogen
is selected from sulfur, selenium and tellurium or mixtures
thereof, and where the heavy metal elements have an atomic number
of from 22 to 92, inclusive. The heavy metal elements involved that
form layered chalcogenides are selected from certain of the metals
included in Groups IB, IIB, IVB, VB, VIIB, VIII, IIIA, IVA, and VA
of the Periodic Table of the Elements, or mixtures thereof. In
addition, intercalated metals from Group VIB of the Periodic Table
of the Elements are also useful in this invention.
It is known that the very close and periodic arrangement of atoms
in a small number of crystal structures permit such crystals to act
as a diffraction grating for X-ray spectroscopy. Bragg's law,
governing the ordered structure of crystals with atoms lying on
families of planes that provide a three-dimensional diffraction
grating, is as follows:
n.lambda. = 2d sin .theta.
Where n is an integer indicating the order of the spectrum,
.lambda. is the wavelength, d the crystal lattice spacing of one
set of planes and .theta. the angle between the incident ray and
this set of planes. A more complete description of X-ray
crystallography is found in the McGraw Hill Encyclopedia of Science
and Technology, McGraw Hill, Inc., 1960 Volume 14, at page 567 et
seq.
In conventional X-ray fluorescence spectroscopy such as disclosed
in the aforementioned encyclopedia commencing at page 576 et seq.,
the diffracting analyzer (grating) is an integral component of the
system. This diffracting analyzer is usually a single crystal which
is employed to separate the various wavelengths emitted by the
specimen. The better the resolution of such a crystal, the more
easily the wavelengths from the specimen are separated into
discrete lines characteristic of the elements therein.
One means of improving the resolution of the radiation is to
increase the dispersing capability of the diffracting analyzer. The
angular separation of the incident wavelengths, and, hence the
resolution, is governed by the aforementioned Bragg's law. A broad
selection of crystals with a variety of interplanar spacings allows
one to select a crystal with high dispersing capabilities in the
region of wavelengths of interest.
Because of this requirement for resolution, the choice of
diffracting analyzers has heretofor been somewhat limited. Pure and
perfect crystals of certain materials have been found to be of
little value for this purpose, because many of them cause
extinction of the impinging radiation. Furthermore, it is essential
that the diffracting analyzer be of good quality to produce sharp,
symmetrical peaks representing characteristic wavelengths of the
elements in the sample. Defects tend to decrease intensities,
causing errors in the analysis. For these reasons, the analyzing
crystals of the prior art have been limited to highly purified
materials having the desired physical characteristics. These
include quartz, and the crystals of the alkali metal halides such
as lithium fluoride, sodium chloride, and potassium chloride.
Unfortunately, these materials are subject to certain limitations
and disadvantages including (1) unavailability, (2) fragility, (3 )
poor diffracting efficiency, (4) poor capability of diffracting the
longer wavelengths of incident radiation, (5) high cost and the
difficulty of manufacture, (6) lack of replicability, and (7)
characteristic wavelengths of their own that either interfere with
wavelengths of the sample or contribute to high background or noise
to the analysis. Nearly all of the currently-used analyzing
crystals, whether natural or synthetic, are fragile and can be
irreparably damaged when dropped or bumped.
It has now been found that certain structurally layered heavy metal
chaclogenides can be used as diffraction gratings in X-ray optical
assemblies. More specifically, chalcogenides intercalated with
various organic and inorganic substances, have been found to
possess interplanar spacings heretofor unobtainable in suitable
crystal structures. Thus, the use of the aforementioned
structurally layered heavy metal chalcogenides as diffraction
gratings in X-ray optical assemblies is particularly advantageous
because the chalcogenide crystals provide a range of interplanar
spacing d extending from 6 to 24 angstroms and even higher. In
addition, the crystals are readily prepared in large sizes, are
relatively air stable and exhibit high diffracting power.
Among the specific applications of the aforementioned substances to
X-ray diffraction grating uses is in fluorescent X-ray
spectroscopy, a non-destructive physical method used for the
elemental analysis of heavy metal alloys. In that particular
application, a primary X-ray beam is directed onto a specimen of
interest. Atomic excitations are produced which lead to the
emission of secondary X-rays. The energy spectrum of these is
characteristic of the atoms involved. Therefore, analysis of the
secondary emission will reveal the nature and quantity of
constituents in the alloy. The technique is presently limited to
heavy metals because light metals produce characteristic X-rays
which have much longer wavelengths than the crystal spacings of the
conventional crystals used to analyze a secondary emission. The
present invention enables such conventional testing to be greatly
expanded.
Within the broad concept of the present invention, and as set forth
in copending U.S. Patent Application Ser. No. 884,319, filed Dec.
11, 1969, certain of the intercalated chalcogenides are novel
compounds, i.e., those in which the sum of the atomic numbers of
the heavy metal element and the chalcogen atom are greater than
38.
The compositions useful in this invention include those layered
chalcogenides formed from the heavy metal elements having atomic
numbers of 22--92, inclusive. Intended to be included in this
classification are titanium, vanadium, cobalt, nickel, copper,
zinc, gallium, zirconium, niobium, technetium, rhodium, palladium,
silver, indium, tin, hafnium, tantalum, rhenium, iridium, platinum,
gold, lead, bismuth, thorium, uranium and mixtures thereof. The
preferred grouping includes the transition elements defined by
Groups IB, IIB, IVB, VB, VIIB and VIII of the Periodic Table of the
Elements.
In the preferred embodiment, use of intercalated chalcogenides as
diffraction grating (analyzers) is contemplated. The amount of
organic or inorganic material intercalated with the chalcogenide
can be varied widely and includes weight concentrations of at least
50 percent and higher.
Compounds that are readily intercalated because of their
interaction with the aforementioned chalcogenides include ionic
compounds such as tetrabutyl ammonium chloride, potassium formate,
and sodium chloride and substances that act as Lewis bases. Lewis
base compounds intended to be included are those containing at
least one non-carbon atom selected from Groups VA and VIA of the
Periodic Table of the Elements, preferably oxygen, nitrogen,
phosphorous or sulfur.
Among the organic compounds, it is advantageous that the carbon to
functional group ratio in the aforementioned compounds be no
greater than 50 to 1 and more preferably 15-30 to 1. Although
various polymers are contemplated as being useful, generally those
molecules having chains of less than 50 carbon atoms are preferred.
Nitrogen-containing organic compounds, such as amines, amides,
heterocyclic bases and amidines have been found to be especially
useful for intercalation. Ketones and aldehydes are also
advantageous.
Intercalation of the chalcogenides with various of the compounds
set forth above can be accomplished by a number of procedures, as
set forth in copending application Ser. No. 884,319, supra. Of
these, the most broadly applicable method, when intercalating a
Lewis base or an ionic or highly polar molecule has involved
immersing the chalcogenide crystals in a liquid bath of the
compound for a time sufficient to cause intercalation. Sufficient
prolongation of the residence time creates an equilibrium
condition. Modifications in pressure or temperature also affect the
rate of intercalation, with higher temperatures accelerating the
equilibrium condition.
Alternative procedures that can also be used include:
1. Solution Technique: The organic compound to be intercalated is
dissolved in a solvent which is itself intercalated less rapidly.
The organic crystals to be intercalated are immersed in this
solution at an appropriate temperature, that may be elevated.
2. Cointercalation: The chalcogenide crystals are first
intercalated with an appropriate compound. The crystals are then
treated by one of the above procedures with a second organic
compound which then intercalates along with the first compound.
3. Catalytic Intercalation: The chalcogenide crystals are first
treated with a compound that intercalates readily. They are then
treated with a second organic compound that intercalates at an
accelerated rate due to the presence of the first compound. In this
process, the first compound is displaced by the second
compound.
4. Vapor Phase Intercalation: The chalcogenide crystals to be
intercalated are placed in the vapor of the organic compound to be
intercalated.
5. Solid Phase Intercalation: The calcogenide crystals to be
intercalated are covered and mixed with the compound to be
intercalated at an appropriate, perhaps elevated, temperature.
Each of the aforementioned techniques are similar in that the
intercalation is allowed to proceed a suitable length of time
before the crystals are separated from the excess compound. The
suitable time depends on the amount of material one wishes to place
inside the crystal.
Other compounds can be utilized to displace or co-intercalate with
the Lewis bases or with the aforementioned ionic compounds. Within
this definition of useful secondary intercalating materials are
Lewis acids; charge transfer acceptors or donors; highly
polarizable organic or organometallic substances especially dyes;
and compounds containing sulfur, phorphorous, arsenic and heavy
metal atoms such as mercury that are capable of engaging in
d-orbital bonding.
Other compounds that are suitable for displacement of or
co-intercalation with the Lewis bases can be defined as
follows:
1. A Lewis Acid or Lewis Base, i.e., compounds with lone pair
electrons such as those of nitrogen in amines may donate these in
part to the chalcogen in the chalcogenide. Conversely, compounds
with unoccupied orbitals, such as are present in many boron
compounds, appear to accept electrons from the chalcogen or from
the previously intercalated Lewis base;
2. Charge Transfer donors or acceptors, i.e., certain molecules
such as tetracyanoquinone, chloranil, and tetracyanoethylene which
are very electronegative form charge transfer complexes with the
chalcogenide layers or with the intercalated Lewis bases. These are
stabilized by the high polarizability of the host. Alternatively,
compounds such as tetramethylphenylene-diamine, which have very low
electronegativity, form charge transfer complexes with the host,
but of the opposite kind;
3. Compounds that have large polarization interactions, i.e.,
compounds that interact with the chalcogenides, especially
molecules that are ionic or that are highly conjugated such as dyes
or are highly polar;
4. Compounds capable of d-orbital bonding.
Illustrative examples of the foregoing organic compounds are as
follows: ##SPC1##
Within the broad definition of the compositions that exhibit the
advantageous use as X-ray diffraction gratings, are a series of
intercalated transition metal chalcogenides that include those
formed from sulfur, selenium or tellurium and a transition element
having an atomic number of from 22 to 92, inclusive. More
particularly, those compositions are contemplated where the sum of
the atomic numbers of the transition element and the chalcogen are
greater than 38. Specific chalcogenides within this definition that
have been found particularly useful are the sulfides including
specifically TiS.sub.2, ZrS.sub.2, TaS.sub.2, and NbS.sub.2.
Compounds particularly suitable for intercalation include aniline,
N,N-dimethylaniline, normal aliphatic amines, adamantamine, DABCO,
heterocyclic amines, such as pyridine and pyridazine, ammonia,
hydrazine, dimethyl formamide, normal aliphatic amides from C.sub.1
to C.sub.18, thiobenzamide, cinnamide, and ionic compounds such as
potassium formate, tetrabutylammonium chloride, pyridinium
chloride, and sodium chloride.
By way of summary of the preparation of the chalcogenides suitable
for X-ray optical materials, the following procedure is considered
illustrative. The chalcogenide either in crystal or powder form or
stoichiometric (or near stoichiometric) amounts of the transition
metal and chalcogen were placed inside a quartz tube. A small
amount of elemental halogen, usually iodine, was included to
provide a volatile species. After the contents of the tube were
displaced to one end, the tube was evacuated and then sealed.
The tube was then placed in a furnace constructed to provide a
temperature gradient along the length of the quartz tube. The
temperature of the furnace was raised slowly with the temperature
of the charged end maintained lower than the temperature of the
uncharged end. The gradient was approximately 100.degree. C. When
the uncharged end reached 800.degree. C the gradient was reversed.
Typically the cool end was maintained between 600.degree. and
800.degree. C. The hot end was typically from 50.degree. to
200.degree. C hotter. The temperature gradient produced a driving
force so that the chalcogenide crystals were formed at the
uncharged end of the tube. After completion of crystal growth,
usually several days later, the tube was cooled sometimes slowly,
sometimes rapidly.
Utilizing the foregoing procedure for chalcogenide formation and
the previously described preferred method for intercalation, the
following compositions were formulated and the indicated
interplanar spacings were measured. Each of the compositions
demonstrates highly desirable characteristics when employed as
X-ray diffraction analyzers.
TABLE I
Intercalated TaS.sub.2 *
Organic Compound D Spacing (A)
__________________________________________________________________________
Aniline 18.1 N,N-dimethylaniline 12.4 p-phenylenediamine 12.0
1-aminoaphthalene 21.5 formamide (C.sub.1) 9.2 butyramide (C.sub.4)
11.0 valeramide (C.sub.5) 10.9 hexanamide (C.sub.6) 11.1
caprylamide (C.sub.8) 10.9 stearamide (C.sub.18) 60 cinnamide 12.0,
16.8 benzamide 11.8 urea 9.6, 10.4 dimethylformamide 9.7, 11.8,
12.1 thiobenzamide 11.9 pyridine 11.9 quinoline 12.1
p-dimethylaminopyridine 12.2 ammonia 9.1 hydrazine 9.1
__________________________________________________________________________
TABLE II
NbS.sub.2 Intercalation Compounds*
Compound d (A)
__________________________________________________________________________
benzamide 11.3 aniline 18.0 pyridine 12.0
__________________________________________________________________________
TABLE III
TiS.sub.2 Intercalation Compounds
Compound d (A)
__________________________________________________________________________
formamide 16.1 acetamide 11.5 propionamide 10.5 butyramide 10.5
valeramide 10.5 caproamide 10.5 hydrazine-water 9.6
N-methylformamide 18.4 N, N-dimethylformamide 9.6 N,
N-diethylformamide 9.6 N-methylacetamide 16.3 N,
N-dimethylacetamide 9.6 N-ethylacetamide 9.6 N, N-diethylacetamide
9.6 N-methylpropionamide 9.6 urea 12.3 N, N'-dimethylurea 17.7
N,N-dimethylurea 9.6 N, N'-diethylurea 9.6 N, N-diethylurea 9.6
tetramethylurea 9.6
__________________________________________________________________________
* * * * *