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Micro-sectoriality in hydrothermally grown ruby

Cite this: DOI: 10.1039/c7ce01520h
crystals: the internal structure of the boundaries
of the growth sectors
Victor G. Thomas, *a Nina Daneu,b Aleksander Rečnik,b Rudolf I. Mashkovtsev,a
Goran Dražić,c Sandra Drev,b Sergey P. Demin,d
Pavel N. Gavryushkin ae and Dmitry A. Fursenkoa

Received 21st August 2017,
Accepted 3rd October 2017
DOI: 10.1039/c7ce01520h
rsc.li/crystengcomm
This study explores the fine structural details of the boundaries between the growth micro-sectors in a
ruby crystal grown hydrothermally on a nonsingularly oriented (011̄2̄) seed. The samples were examined
using IR-spectroscopy and HRTEM-analysis, demonstrating that the interfaces of the micro-sectors serve
as ‘traps’ for OH-groups often observed in grown crystals. Counter to what has previously been reported,
a significant proportion of these OH-groups is incorporated into ruby crystals in an orderly manner,
forming diaspore-like layers growing epitaxially on the corundum (011̄2) lattice planes. The tensions on the
boundaries between the micro-sectors result in local increase of internal pressure, making the diaspore-
like phase stable. The assumption is made that the mechanism discussed in the article can explain the oc-
currence of OH-groups in the structure of nominally anhydrous minerals, such as MgSiO3 (akimotoite)
which is structurally similar to corundum.

Introduction to the regeneration surface {011̄2̄},† and illustrates three types

Seed plates with non-parallel orientation to any of the possi-
ble crystal faces are often used in the hydrothermal (HT)
growth of crystals, such as beryl, corundum and a number of
others. We will call this type of surface the regeneration sur-
face.1 A similar orientation of the seed plate is used for effi-
ciency reasons, in order to produce crystals with satisfactory
quality and sufficiently high growth velocity. The growth front
of the crystals grown on such seeds is macroscopically rough,
representing a combination of a large number of small pyra-
mids (i.e., subindividuals1) grown in parallel (see, for exam-
ple, ref. 2 and 3). This results in specific optical heterogene-
ities in the overgrown layer, which is the main feature
identifying an HT-grown jewelry material.3,4
Fig. 1 shows the optical micrographs of a thin section pre-
pared from a corundum crystal (Al2O3, SG: R3̄c) doped with
Cr3+ ions (ruby) HT-grown on a seed plate oriented in parallel
a
Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy
of Science, pr. Academician Koptyug 3, Novosibirsk 630090, Russia.
E-mail: vithomas@yandex.ru, thomas@igm.nsc.ru
b
Department for Nanostructured Materials, Jožef Stefan Institute, Jamova cesta
39, 1000 Ljubljana, Slovenia
c
Department of Materials Chemistry, National Institute of Chemistry, Hajdrihova
19, 1000 Ljubljana, Slovenia
d ing curved and curl-like optical heterogeneities in the glass, which appear dur-
Tairus Company, pr. Academician Koptyug 3/4, Novosibirsk 630090, Russia
e ing uneven cooling due to increased tension.
Novosibirsk State University, Pirogova St. 2, Novosibirsk 630090, Russia
of optical heterogeneities. One is the color heterogeneity al-
most perpendicular to the seed, representing the alternation
of more and less intensely colored elongated areas (Fig. 1b).
This color intensity alternation pattern probably reflects the
sectorial capture of Cr3+ impurities. This heterogeneity is
present due to the fact that subindividuals are formed from
microfaces, belonging to different crystallographic forms,6
characterized by varying the distribution of chromium. Near
the seed, the thickness of the individual micro-sectors is
small (first few tens of micrometers), making them indistin-
guishable under low magnification. Due to two kinds of geo-
metrical competition (between the microfaces of each
subindividual and also between the neighboring
subindividuals), the thickness of the micro-sectors increases
towards the edge of the crystal.6,7
The second type of optical heterogeneity is the spontane-
ous growth zoning shown in Fig. 1c (see ref. 9 and 10 for the
general overview of growth zoning and ref. 8 for the discus-
sion of this phenomenon in HT-grown crystals). The third
type of heterogeneity is the system of almost vertical lines
(Fig. 1c), or the so-called swirls.‡ According to ref. 6 and 11
† Within this study the indexing of the crystallographic forms is given relative to
the unit cell metrics. Indexing with respect to the single face {112̄1} gives a two-
times smaller Miller index l.5
‡ The term swirls has been adopted from the glass production industry, mean-

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Fig. 1 Thin section of an HT-grown ruby crystal with the seed parallel
to {011̄2̄} and cut perpendicular to the seed's elongation, (a) imaged
with oblique lighting with partially crossed Nicols; (b) thin color zona-
tion near the seed plate part (parallel lighting); (c) the external side of
the crystal (oblique lighting with partially crossed Nicols). Marks: 1,
seed; 2, spontaneous growth zonation in one growth micro-sector; 3,
swirls.
in this type of crystal, swirls indicate the boundaries between
the growth sectors of micro-faces forming subindividuals on
the macroscopically rough growth front. The present paper
focuses on exploring the internal structure of these bound-
aries. A rare case of HT-grown crystals with swirls showing a
quasi one-dimensional defect, which results from a healed
breach on the growth front (e.g., after inclusion),9 will not be
considered in this study.
Since the swirls represent internal crystal defects, under-
standing their nature has important practical applications,
particularly for the jewelry industry. The part of the rays of
the light beam that is passing through the facetted stone un-
dergoes partial or even total internal reflection from the sur-
face of the swirls. Therefore, a portion of the rays does not re-
turn through the table of a gem stone but is lost through its
lower part, making the stone look ‘lifeless’. The higher the
difference between the refractive indices of a crystal in the
swirl region and around it, the stronger the negative impact
of these swirls. Although the possible causes for the appear-
ance of these optical heterogeneities in crystals, as well as
the peculiarities of their constitution and the role of growth
parameters, have long been discussed in the crystal growth
community (see the review in ref. 10), a great number of un-
derlying reasons for the observed phenomena do not allow
resolving the swirling problem in HT-grown crystals.
The present paper explores the fine structure of the
boundaries between the micro-sectors in ruby crystals HT-
grown on the corundum {011̄2̄} regeneration surface. The re-
sults of our experiments allow us to make assumptions about
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the nature of optical heterogeneities in ruby crystals gener-
ated by their micro-sectorial texture.
Experimental methods
The ruby crystals were HT-grown using recrystallization of
polycrystalline synthetic corundum on the seed plate, cut
from a leucosapphire single crystal parallel to {011̄2̄}. The
seed plates were 1 mm thick shaped as an 8 × 2 cm rectangle,
with the long edge set parallel to [12̄10]. A 2 M solution of
KHCO3 was used as a mineralizer.12,13 A 0.25 M K2CrO4 solu-
tion was added to the mineralizer as a source of chromium.
The HT growth process was carried out in sealed 175 ml gold
tubes to prevent the doping of corundum crystals with
unwanted impurities. The tubes were placed in steel auto-
claves with a volume of ∼220 ml. The detailed description of
autoclave loading configuration is given in ref. 14. The tem-
perature of the growth process was governed by two chromel-
alumel thermocouples placed in the autoclave body, 7 mm
below (Tb) and above (Tu) its working chamber, so that Tavg =
(Tb + Tu)/2 = 510 ± 0.1 °C and ΔT = Tb − Tu = 40 ± 0.5 °C. The
pressure was defined using the autoclave filling factor, which
is set to 0.6, resulting in approximately 1.5 kbar. The total du-
ration of the growth process was 21 days.
As opposed to earlier findings,15 the grown ruby crystals
did not contain any optically distinguishable twinning inter-
growths. According to the LA-ICP-MS analysis (using a quad-
rupole mass spectrometer with an inductively coupled
plasma XSERIES2 ICP-MS; Thermo Scientific Company with
the certified NIST 614 standard16), the crystal had the follow-
ing bulk chemical composition (in wt%): Al2O3, 99.435;
Fe2O3, 0.005; Cr2O3, 0.538; TiO2, 0.009; Na2O, 0.004; and K2O,
0.011. It has a low impurity composition, except for Cr that
was captured from the mineralizer solution.
A follow-up analysis was carried out to detect the possible
traces of water (i.e., the main component of the mineralizer)
in the sample, given the earlier reports of its presence in the
corundum structure.17–24 For this purpose we explored the
FTIR spectra of the ruby in the region of stretch vibrations of
OH-groups. The measurements were taken from a polished
plane-parallel 0.8 mm-thick plate oriented perpendicular to
[12̄10], in accordance with the external morphology of the
crystal. The FTIR absorption spectra were measured in the
1000–7500 cm−1 range with a resolution of 2 cm−1. The data
were collected at room temperature using a Bruker Vertex 70
FTIR spectrometer equipped with a Hyperion 2000 micro-
scope. The selected areas of the plates were then examined
under a microscope, and the FTIR spectra were analyzed
using a multiple peak fit option in the Origin 8.5 software.
The internal structure of the growth micro-sectors was
studied using HRTEM-analysis. To prepare the samples for
these analyses, we used the plate previously examined by
FTIR spectroscopy. The sample was cut out from the area
close to the seed crystal with the highest density of the
boundaries between the micro-sectors (Fig. 1). A 2 × 2 mm
block was embedded in a 3 mm copper tube and fixed with
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an epoxy resin before cutting into disks for transmission
electron microscopy (TEM). The disks were mechanically
thinned to about 100 μm and then dimpled down to 20 μm
in the center (Dimple grinder 656, Gatan Inc., Warrendale,
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PA). After polishing, the TEM samples were ion-milled using
4 keV Ar+ ions (PIPS 691, Gatan Inc.) at an 8° angle till perfo-
ration in the disk center containing the growth sectors. Prior
to the analysis, the TEM sample was coated with a thin layer
of amorphous carbon to prevent charging due to the electron
beam. TEM studies were carried out using a 200 kV TEM,
powered with a field-emission gun (FEG) electron source
(JEM-2010F, Jeol Ltd., Tokyo, Japan) with an ultrahigh-
resolution objective pole-piece, achieving a point-to-point res-
olution of 0.19 nm, sufficient for resolving lattice images of
corundum along the selected zone-axes. Electron diffraction
patterns (EDP) and structure models were prepared using the
CrystalMaker® software.
Results and discussion
IR spectroscopy of the hydrothermal ruby
The number of micro-sectors in the overgrown layer of the
ruby decreases towards the periphery of the crystal (see
Fig. 1), which is consistent with the previously proposed
growth model of the regeneration surfaces.6 To explore the
proposed association between the OH-traces,17 and crystal's
structural violations, we carried out IR spectroscopy of the
overgrown layer in two areas: (i) near the seed and (ii) in the
area closer to the edge of the crystal (see Fig. 2). Table 1
shows a comparison between the sharp peaks observed in
the spectra and the previously reported IR spectroscopy anal-
ysis of the ruby and sapphire crystals. The peaks close to
those observed in the IR spectra for natural and synthetic
aluminum hydroxides,24 diaspore, boehmite and gibbsite, are
marked with the symbols D, B, and G, respectively.
The IR-spectra from the areas close to the seed plate are
similar to those towards the crystal edge; however, the region
near the seed plate is characterized by a much higher inten-
Fig. 2 Representative OH infrared absorption spectra (⊥c) normalized
to 1 cm plate thickness for hydrothermally grown ruby, demonstrating
the variability for the areas near the seed (a) and at the crystal edge (b).
The curve (b) is moved up for clarity.
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sity of almost all peaks (see Fig. 2). We, therefore, conclude
that the centers of absorption in both areas are identical,
with their higher concentration near the seed. This is consis-
tent with our proposed assumption about the possible rela-
tionship between the boundaries of the micro-sectors of
growth in the HT-grown ruby and its IR absorption centers.
In other words, these defects may serve as ‘traps’ for the for-
mation of the so-called OH-defects.25
Table 1 highlights two important points. First, almost all
the peaks in the 3186–3420 cm−1 interval, previously reported
for corundum crystals grown by various methods from the
melt ∼2000 °C, correspond to the peaks of the IR-spectrum
of the HT-grown ruby. Therefore, it appears that the corun-
dum crystals grown from the melt contain defects similar to
those of the boundaries between the micro-sectors. Thus,
these defects could be the low-angle boundaries between the
neighboring blocks in the crystals.
Second, the IR-spectra of the HT-grown ruby contain lines
in the 3484–3613 cm−1 interval, which are not common for
corundum grown from the melt but are typical for different
aluminum hydroxides, such as diaspore, boehmite and
gibbsite. This agrees well with the proposal that the broad
absorption bands, combined with several narrow bands in
the OH region (3100–3600 cm−1), result from the presence of
aluminum monohydrates (boehmite and diaspore).17,25 The
accurate mapping of the peaks to a particular phase of alumi-
num hydroxide is problematic due to a considerable variation
in the samples, even in the spectra of the same phase ac-
quired from different areas.24 However, observing the peaks
in the 3484–3613 cm−1 region suggests possible occurrence of
the aluminum hydroxide phase inclusions in the overgrown
layer of HT-grown ruby, which could be detected by HRTEM
analysis.
HRTEM analysis of the growth-sectors in the hydrothermally
grown ruby crystals
The TEM observation at low magnifications reveals that the
region near seed plate contains numerous interfaces of
micro-face growth sectors.§ Only a small fraction of the
micro-faces are oriented edge-on (along the viewing direc-
tion) and are suitable for further TEM investigation. The typi-
cal low-magnification TEM image of an edge-on interface in
the [21̄1̄0] projection is shown in Fig. 3. A small residual tilt
that remained after specimen preparation was adjusted using
a double-tilt specimen holder. The interface is characterized
by a dark spotted line crossing otherwise flawless corundum
matrix. The electron diffraction pattern (EDP) recorded
across the interface (inset in Fig. 3) shows no rotational or
crystal tilt change, suggesting that both crystal domains are
in an identical crystallographic orientation. To index the ex-
perimental EDP, we used a calculated pattern based on
§ In the ‘Experimental methods’ section it was noted that the HT-grown ruby
crystals did not contain any twin intergrowths according to studies under the
optical microscope. TEM also showed the absence of twins in the body of the
crystal.
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Table 1 The IR peak locations (cm−1) of the OH absorption bands for the HT-grown ruby and for corundums of different origins

Verneuil-grown Verneuil-grown Ti-sapphire laser Verneuil-grown Diffussion- doped corundum Verneuil-grown Our
corundum19 corundum20 crystal21 corundum18 with D and H22 corundum23 HT-rubya
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3160 3160 3163

3187 3180 3187 3185 3185 3184 3186D+B
3234 3225 3232 3230 3233 3231 3231D+B+G
3275 3280 3279 3279
3297, 3312 3310 3295, 3309 3290 + 3310 3296 + 3310 3294 + 3308 3304B
3327B
3342D
3371 3367 3382G
3396
3420
3484G+D
3562G+B
3583D
3613G+D
a
Characters to the right of the values of wavelengths in the last column correspond to the peaks fixed in the OH-containing phases of diaspore
(D), boehmite (B), and gibbsite (G).24

crystal structure data for corundum, with a = 0.4757 nm and
c = 1.2988 nm (SG: R3̄c).26 The interface between two corun-
dum domains runs roughly parallel to the {011̄2} planes of
the corundum structure with occasional steps to other lattice
planes. Every change in the interface direction to planes
other than {011̄2} is accompanied by considerable lattice
strain visible as dark contrast in the low-resolution bright-
field TEM image (Fig. 3). This suggests that the {011̄2}cor
planes are the lowest energy planes under the given growth
conditions.
To understand the origin of these contrast features, we
studied the structure of the interfaces under phase-contrast
(HRTEM) imaging conditions. Fig. 4 shows two different
edge-on sections of the interface. Along the interface, as
shown in Fig. 4a, we observe short (Dexp ∼ 7 nm) sections of
the (011̄2) contact area interrupted by sudden slips to low-
index planes, such as (0006), etc. The steps (indicated by ar-
rows) are accompanied by diffuse contrast, whereas the tran-
sition over the (011̄2)cor interfaces appears to be coherent. Of-
Fig. 3 TEM image of the interface between the two domains (micro-
sectors) in the ruby crystal HT-grown on the seed plate {011̄2̄}. The in-
set in the upper-left corner is the experimental EDP recorded over the
two domains, whereas the lower inset shows the corresponding simu-
lated EDP with reflections indexed in the [21̄1̄0] projection.
ten large sections of the interface undulate quite irregularly,
as shown in Fig. 4b.
Under selected imaging conditions, the HRTEM contrast
is dominated by sharp bright dots coinciding with Al–Al dou-
blets viewed along the [21̄1̄0]cor projection. When we ap-
proach the interface, the sharp dots become diffuse and
somewhat dilated. This distinct contrast feature is clearly vis-
ible in magnified section shown in Fig. 5. The dilatation nor-
mal to (011̄2)cor lattice planes is equal to ∼0.13 nm. Accom-
panied by an additional 0.05 nm in-plane shift along the
interface, this produces a net translation corresponding to
½·(0006)C. This shift can be observed when the interface is
glanced at an acute angle along the basal planes of the co-
rundum structure (Fig. 5a). Geometric phase analysis of the
interfacial lattice discontinuities (Fig. 5b) using (011̄2)cor re-
flections demonstrates that the corundum structure in both
domains is continuous, whereas all the relaxation is confined
to only 2–3 lattice planes. It is quite astonishing that identi-
cal translation can be measured on all corundum–corundum
interfaces suggesting that this could be an equilibrium con-
figuration under the given growth conditions.
What could be the source of this unusual lattice dilata-
tion? Given the fact that both crystal domains grew from the
same seed crystal and, except for measured translation, the
two domains show no rotational misalignment with respect
to each other, the expansion must be a result of indepen-
dent¶ growth of two adjacent micro-faces, forming respective
micro-sectors. Under HT conditions, the surface of corundum
is covered by hydroxo- (−OH) and aquo- (−OH2) ligands that
take part in the crystallization process. In principle, two crys-
tal domains (i.e. micro-sectors) that grow from the same seed
crystal would be expected to grow in parallel when there are
no surface interactions between the growing micro-sectors.
¶ When we are talking about the independence of growth of the two neighboring
faces, we mean that the geometrical competition between them is fundamentally
slower than the formation processes of elementary grown layers for each face.

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Fig. 4 HRTEM images of the interfaces in the HT-grown ruby crystals. (a) Low-energy interface following the (011̄2)cor lattice plane of corundum
with occasional steps to (0006)C planes (indicated by red arrows). Each step is accompanied by diffuse strain contrast. (b) Wavy section of the
interface with a coherent (011̄2)cor interface, and undulating segments with a diffuse contact area between the two corundum domains. Sections
of the interface analyzed in more detail in Fig. 5 and 6 are outlined.

Fig. 5 (a) HRTEM image of the coherent (011̄2)cor interface with characteristic dilatation at the contact area of the two corundum domains. The
positions of bright dots correspond to the centroid of Al–Al doublets that are separated by 0.146 nm. (b) Geometric phase analysis using (011̄2)cor
reflection showing dilatation of (011̄2)cor lattice planes near the interface that extends 2–3 lattice planes with a slip to the (0006)cor planes
(indicated by the arrows). The two corundum domains are in an otherwise identical crystallographic orientation.

Here, this is not the case. Under HT growth conditions, the
surfaces are stabilized by –OH ligands that prevent perfect
adhesion of the two domains on the atomic scale. Growing
side-by-side, the two surfaces adopt a semi-equilibrium state
forming stable H-bonds among the ligands that prevent the
formation of oxo-bridges under HT growth conditions.27 If
the ligands covering the surface of the two independently
growing micro-faces will not have time to be removed from
the growing surface, they will be pushed aside to the border
of the junction of two micro-sectors, as a result of the tangen-
tial growth of the faces. In this way, hydroxide layers are
encaptured between the adjacent micro-sectors, giving the
characteristic IR absorption bands. Depending on the respec-
tive growth velocities of the adjacent crystal faces, the inter-
face climbs choosing the lowest energy planes, while the do-
mains continue to grow upwards, normal to the substrate
plane, where they can extend without restraint. Owing to al-
tered surface chemistry, the adjacent crystal domains un-
dergo respective dilatation/compression to satisfy the more
stable local configuration brought by the H-bonds. The strain
induced by the entrapped ligands is so large that it produces
a measurable lattice deformation that can only be compen-
sated by the equivalent compression in the corundum
domains.
Given the fact that (i) dilatation of interfaces suggests the
presence of ligands (Fig. 4 and 5), (ii) IR-spectroscopy data
confirm the presence of OH-groups (Table 1), and (iii) under
given pT-conditions, diaspore is the most stable polymorph
of oxyhydroxide (AlOOH) phases,28 we may presume that the
observed layers between the corundum micro-sectors are dia-
spore-like. The study of diaspore–corundum transformation
showed that the a, b, and c axes of diaspore are transformed
into c, [112̄0] and [11̄00] axes of corundum.29–31 Fig. 6 shows
a close-up image of a coherent section of the equilibrium
(011̄2)cor interface with an overlaid atomic model, involving
the observed translations including one (101)dia ‘wetting
layer’ of diaspore between two adjacent micro-sector domains
of corundum, compensating for their mismatch. Accordingly,

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we can write the crystallographic orientation relationship
(COR) observed between corundum and diaspore as: [21̄1̄0]cor
(011̄2)cor ‖ [010]dia (101)dia.
Our results raise two essential questions about the genesis
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of the diaspore-like layers at the interfaces of the growth
micro-sectors:
[1] What is the reason for the formation of hydroxide
layers within the corundum crystal, and
[2] What causes the observed translational shifts observed
between the micro-sectors?
The first question can be addressed based on the findings
from earlier studies of phase equilibria in the Al2O3–H2O sys-
tem under our pT-conditions.32 Under 1.5 kbar pressure, the
diaspore → corundum transformation takes place at ∼420
°C. The increase of pressure to 13 kbar, however, extends the
field of diaspore stability up to ∼520 °C, i.e., to the average
temperature of our growth process. Locally, such a pressure
increase might be produced by internal tensions at the
boundaries of micro-sectors. Such a strain could be produced
by the repulsion of hydroxylated corundum surfaces forming
H-bonds as the gap between the two sectors is closing-up. Its
extent would be determined by the number of OH-groups
that stabilize the surface of tangentially growing micro-faces.
If this assumption is correct, the diaspore becomes a locally
stable phase, which then grows epitaxially on the (011̄2)cor
surfaces. On the other hand, the diaspore layer might act as
an absorber of tensions at the boundary between the two do-
mains, and the increase of its thickness, therefore, may re-
duce the strain. This, in turn, may trigger the ‘feedback’: the
thicker the diaspore layer, the less the internal pressure due
to the absorbed strain, making the diaspore metastable at a
certain thickness threshold. The latter, therefore, restricts the
terminal thickness of the diaspore layer. The impurity of Cr3+
ions in the corundum may also influence the formation of
the diaspore layers. Specifically, the varying concentration of
Cr3+ in two adjacent sectors (Fig. 1) may result in additional
local heterometric tensions. The latter could both enhance
Fig. 6 HRTEM image of the coherent (011̄2)cor interface with an overlaid model, involving experimentally observed translations and a hypothetical
diaspore layer between the two corundum domains.
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and weaken the tension on the boundaries of the micro-sec-
tors. These questions need to be further explored in future
studies.
To address the second question, we refer to the widely-
known fact that the slope of the boundaries between the
growth sectors is uniquely determined using the angle be-
tween the faces forming these sectors and the ratio of the
growth rates of these faces.33 Specifically, since the set of the
adjacent pairs of micro-faces, which have formed the rough
growth front of the regeneration surface, is very large, espe-
cially in the initial period of the growth process,6 a fairly wide
range of orientations of the boundaries between the micro-
sectors could be expected. Due to the H-bonds, the two do-
mains are likely to be strained along the (011̄2)cor interface,
which may be the reason for the observed lattice shifts.
According to our HRTEM observations, the (011̄2)cor inter-
faces are energetically most stable and form longer coherent
sections. Now, depending on the growth rate of the adjacent
equilibrium crystal faces, the (011̄2)cor sections are making
more or less frequent steps along the resultant interface,
forming an undulating contact area. It is even possible that
in the case of strong tensions in the contact area, the
damping layer at the boundary will include not one but sev-
eral diaspore lattice planes.
To conclude, the collected data on the mechanism of sys-
tematic incorporation of OH-groups in the corundum struc-
ture in the form of two-dimensional diaspore-like layers are
important for future studies not only for gemology purposes,
but also for many open questions related to earth sciences,
especially those dealing with the incorporation of water in
the form of protonated defects such as those observed in our
study. Namely, in geochemistry, the question about the forms
in which the water exists in nominally anhydrous minerals
remains unanswered. At the depths exceeding 650 km, the
spinel-like Mg2SiO4 disproportionates, forming MgSiO3
(akimotoite),34 which is one of the main phases under these
pT conditions. Considering the close structural relationship
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between corundum and akimotoite, one might expect that
the latter relies on a similar mechanism of OH-defect
formation.35
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Summary
The fine structural details of the boundaries between the
growth micro-sectors in the ruby single crystal hydrother-
mally grown on a seed plate oriented in parallel to (011̄2̄)
were examined using IR-spectroscopy and HRTEM-analysis.
This crystallographic form does not correspond to any of the
existing faces of the corundum crystal and therefore grows as
a macroscopically rough regeneration surface with a growth
front formed from a large number of micro-faces, producing
a multitude of interfaces between the adjacent pairs of micro-
scopic growth sectors (domains).
Our IR spectroscopy data shows that the HT-grown ruby
crystals contain the centers of absorption that can be attributed
to the stretch vibrations of OH-groups. The concentration of
these centers could be correlated with the number of bound-
aries between the growth micro-sectors, suggesting that they
‘trap’ the OH-groups within our ruby crystals. Corundum crys-
tals of different compositions, grown from melts, are typically
characterized by similar spectra of IR-absorption. Similarly, in
these crystals, the low angle boundaries between the neighbor-
ing blocks may serve as OH-group ‘traps’.
The investigation of the fine structure of the boundaries
between the adjacent micro-sectors in the hydrothermally
grown ruby crystals using HRTEM-analysis indicated that the
OH-groups are often aggregated in the form of monolayers of
diaspore-like phase, epitaxially growing on corundum (011̄2)
lattice planes. The formation of diaspore-like layers is likely
the result of the local increase of the internal pressure in the
ruby crystal, due to the significant tension in the crystal lat-
tice near the contact area between the micro-sectors. The
diaspore-like layers partially dampen these strains, and the
remaining tension results in optical anomalies in the hydro-
thermally grown ruby crystals forming characteristic swirls.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the state assignment project No.
0330-2016-0016 and by the Slovenian–Russian bilateral pro-
jects BI-RU/14-15-0025 and BI-RU/16-18-004. Hydrothermal ex-
periments were carried out using equipment provided by
TAIRUS Company (Novosibirsk, Russia). We thank Dr. A. L.
Ragozin and O. A. Kozmenko (Sobolev Institute of Geology
and Mineralogy SB RAS, Novosibirsk, Russia) for the bulk
chemical analysis of ruby crystals and Mr. V. V. Poljakov
(TAIRUS Company, Novosibirsk, Russia) for assistance in HT
experiments. We are very grateful to Dr. E. V. Tomas (Higher
School of Economics, Moscow, Russia) for proof-reading the
manuscript and correcting the English.
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