8
Structure Analysis by X-Ray Diffraction
8.1
Fundamentals
The wavelength of X-rays is within the same order of mag-
nitude as the distance of atoms or molecules in crystals, i.e.
some tenths of a nanometer. In addition, XR interfere with
electrons, and space in crystals is filled with electrons (and
some nuclei). Thus, XR traversing crystals suffer diffraction
and interference. The interference patterns can be used for
crystal structure elucidation; at the same time they are char-
acteristic for the substance the crystals are made of.
Most organic substances are composed of C,H,N,O and
have few electrons compared with compounds containing
heavy atoms. They are therefore poor scatterers; to obtain XR
diagrams of CHNO crystals using conventional XR sources
demands several hours of exposure times. The availability
of the intense cyclotron radiation yields good diagrams in
reasonably short times.
8.2
Inorganic Pigments and Fillers
All inorganic pigments and fillers contain heavy atoms and
are thus good scatterers. This is advantageous if pigmented
paints or pigmented amorphous polymers (plastics, rubber)
have to be analysed. Several books and publications contain
data on XRD of pigments. A total of 71 XRD patterns (bar
graphs) are found in the book of Scholl (l.c.); unfortunately,
no spacings and intensities are given in numbers. More data
may be found in the powder diffraction file of the Interna-
tional Centre for Diffraction Data (N.N., 10.1). Earlier though
valuable sources are the books of Konig and Kittel (both
10.1). A useful source of reference in XRD data on synthetic
dyes and pigments is the contribution by Whitaker in the
book ofVenkataraman (10.1).
D. O. Hummel, Atlas of Plastics Additives
© Springer-Verlag Berlin Heidelberg 2002
8.3
Organic Pigments
The problems with XRD of organic pigments can be summed
up like this (Curry et aI., 10.2.3; with minor changes):
1. Organic pigments are poor scatterers.
2. Many organic OP, due to their intense coloration, are
applied in low concentrations. Without separation, their
XRD are weak and difficult to interpret.
3. The unit cells of OP are generally much larger than those
of inorganic pigments. Thus, their diffraction lines are
confined to lowe angles. Unfortunately, this region has,
in the Debye-Scherrer technique, the highest background
and may drown weak diffraction lines.
4. OP in paints may be non-crystalline and will then yield no
XRD pattern.
5. Many OP may be derived from one parent compound,
they belong then to a structurally similar family. Changes
in chemical substitutions or inserted metal produce dra-
matic colour changes yet sometimes only subtle changes
in XRD patterns.
Despite these problems the authors were able to produce
valuable data for the identification of organic pigments in
the forensic examination of paints. Debye-Scherrer pow-
der photography was used both for OP and for casework
paint flake specimens. Powdered pigments were loaded into
0.3 mm i.d. glass capillary tubes. The camera had 114.6 mm
i.d., KODIREX or NO-SCREEN film was used. The samples
were exposed for 2 h to iron-filtered Co Ka radiation from
35 kV/34 mA electrons. d-Spacings were measured with
a film-measuring device; maximal errors were ±1O pm
(d>l nm) or ±1 pm (d<l nm). The intensities of the lines
were determined with a recording micro densitometer and
normalised to a scale with maximum 10.
Table 8.1 shows the results of these measurements; inten-
sities are given in italics, the strongest line in bold. Only the
spacings of the three most intense diffraction lines of each
pigment have been recorded. As far as paint flake analysis
is concerned, the minimum size appears to be O.sxO.5 mm 2,
corresponding to an approximate weight of 40 flg.
112 8 Structure Analysis by X-Ray Diffraction

Table 8.1 Table 8.1 Continue

Diffraction data (three strongest peaks), CI pigment numbers
d-spacings/intensities Clnumber Class of colorant
and colorant class for a selection of organic pigments used
in paints (C.J. Curry et al., 10.2.3). The numbers for the 13.6 6.38/5 3.38/4 PV 19 Quinacridone
strongest interferences (intensity 10) are bold, the intensities 13.5 8.56/6 5.01/4 PV37 Dioxazine
on the 1-10 scale are italic. PR=Pigment Red, PY=Pigment 3.72 2.63/3 2.88/2 PV 15 Inorganic
Yellow, PV=Pigment Violet, PB=Pigment Blue, PBR=Pigment 13.1 12.2/7 8.97/2 PB15:2 Phthalocyanine
Brown, PG=Pigment Green, PO=Pigment Orange. The 13.0 11.9/7 5.93/3 PB16 Phthalocyanine
spacings are arranged to suit a Hanawalt-type search (see 12.7 9.71/5 3.75/2 PB15:4 Phthalocyanine
Powder Diffraction File, N.N., 10.1). 12.7 9.67/7 3.74/3 PB15:3 Phthalocyanine
11.6 5.83/5 3.34/4 PB64 Anthraquinone
d-spacings/intensities Clnumber Class of colorant 7.82 3.27/7 7.12/5 PB60 Anthraquinone
3.71 6.44/4 2.62/3 PB29 Inorganic
19.5 8.16/3 3.46/3 PR48:4 Monoazo
11.5 10.0/8 21.2/7 PBR25 Monoazo
19.1 3.40/2 4.09/1 PR52 Monoazo
10.1 6.6417 3.30/5 PBR23 Disazo
18.8 3.72/4 3.42/3 PR48.2 Monoazo
9.67 22/9 11.9/9 PBR32 Monoazo
18.6 3.45/3 4.92/2 PR 48.3 Monoazo
15.2 4.53/3 3.39/1 PG 10 Monoazo
18.4 3.42/3 3.25/2 PR57 Monoazo
15.1 3.34/7 13.0/4 PG7 Phthalocyanine
17.2 6.28/7 3.44/4 PR 149 Anthraquinone
13.5 11.5 8.69/7 PG8 Nitroso
16.8 3.29 3.23/8 PR223 Monoazo
3.40 3.66/7 2.92/5 PG36 Phthalocyanine
16.0 3.27/3 6.32/2 PR 122 Indigoid
3.34 14.8/8 13.2/6 PG7 Phthalocyanine
14.9 3.36 6.11/4 PR5 Monoazo
3.52 6.97/9 11.4/6 P043 Anthraquinone
11.3 5.10/8 3.29/7 PR58 Monoazo
3.37 3.46/6 11.4/5 P052 Pyranthrone
11.2 3.34/5 4.63/3 PR 10 Monoazo
3.36 3.30/6 3.25/5 P05 Monoazo
10.2 3.25/8 20.7/4 PR 144 Disazo
3.24 6.08/3 3.92/2 P036 Monoazo
9.3 3.32/5 3.23/4 PR 166 Azo
3.46 12.2/4 4.87/3 PR 170 Monoazo
3.37 14.7/6 6.88/5 PR209 Quinacridone
3.37 10.6/5 5.63/2 PR 11 Monoazo
3.37 5.92/5 7.41/3 PR 112 Monoazo
3.35 7.27/9 6.50/6 PR 114 Monoazo
3.34 3.51/4 4.84/3 PR 168 Anthraquinone
3.34 2.78/4 3.50/3 PR 168 Anthraquinone
3.33 11.4/7 6.67/3 PR 12 Monoazo
3.31 16.4/5 4.95/4 PR 146 Monoazo
3.31 3.23/8 3.56/5 PR88 Thioindigoid
3.29 8.00/8 3.40/5 PR3 Monoazo
13.5 24.4/3 3.4513 PY 128 Disazo
13.4 3.51 8.76/7 PY83 Disazo
12.6 9.69 8.75 PY 129 Azomethine
10.3 3.28/9 5.69/2 PY 1 Monoazo
8.44 3.50 3.35/2 PY 12 Disazo
8.03 17.1/4 3.41/4 PY 17 Disazo
3.55 7.18/7 4.12/4 PY 110 Isoindolinone
3.41 6.66/4 4.88/3 PY 154 Monoazo
3.40 9.50/4 2.84/4 PY 109 Isoindolinone
3.35 7.24/4 5.31/4 PY 156 Azo
3.32 7.46/9 3.49/3 PY74 Monoazo
3.32 8.06/9 11.7/6 PY 13 Disazo
3.31 7.66/8 10.5/4 PY 14 Disazo
3.31 6.89/3 5.13/2 PY3 Monoazo
3.30 8.08/9 3.40/8 PY24 Anthraquinone
3.25 5.12/3 4.57/2 PY 151 Monoazo
3.25 3.52/8 17.6/7 PY73 Monoazo
15.5 8.69/6 3.45/6 PV23 Dioxazine
15.4 3.29/9 5.55/4 PV 19 Quinacridone