Stagno et al. Progress in Earth and Planetary Science
https://doi.org/10.1186/s40645-021-00421-y(2021) 8:27

Progress in Earth andPlanetary Science

RESEARCH ARTICLE

Open Access

Can quasicrystals survive in planetary
collisions?
Vincenzo Stagno1, Luca Bindi2* , Sota Takagi3 and Atsushi Kyono4

Abstract
We investigated the compressional behavior of i-AlCuFe quasicrystal using diamond anvil cell under quasi-hydrostatic
conditions by in situ angle-dispersive X-ray powder diffraction measurements (in both compression and decompression) up
to 76 GPa at ambient temperature using neon as pressure medium. These data were compared with those collected up to
104 GPa using KCl as pressure medium available in literature. In general, both sets of data indicate that individual d-spacingshows a continuous decrease with pressure with no drastic changes associated to structural phase transformations oramorphization. The d/d0, where d0 is the d-spacing at ambient pressure, showed a general isotropic compression behavior.
The zero-pressure bulk modulus and its pressure derivative were calculated fitting the volume data to both the Murnaghanand Birch-Murnaghan equation of state models. Results from this study extend our knowledge on the stability of
icosahedrite at very high pressure and reinforce the evidence that natural quasicrystals formed during a shock event inasteroidal collisions and survived for eons in the history of the Solar System.
Keywords: Icosahedrite, Quasicrystal, CV3 chondrite, Khatyrkite, In situ angle-dispersive X-ray diffraction

1 Introduction
Textural and chemical studies of shocked veins and mineral assemblages observed in meteorites over the last decades have been widely interpreted in light of dynamic(e.g., shock experiments) and static (e.g., multi anvil anddiamond anvil cell experiments) compression investigations of diverse minerals and their stability at high (H)pressure (P) and temperature (T) (Tomioka and Miyahara2017). Some of the early studies were pioneer in order tolink the coexistence of various minerals with shockimpact events that have led to the formation of HP polymorphs in chondritic meteorites either by solid-solid reaction (Gillet et al. 2000; Beck et al. 2004; El Goresy et al.
2008, 2010; Bindi et al. 2017, 2020) or by crystallization ofmelts in shock veins (Miyahara et al. 2008, 2009). In somecases, static experiments were preferred to shock experiments to account for collisions of large asteroidal bodies
or the passage of multiple shock waves through such bodies during multi-stage collisional events (Chen et al. 1996).
* Correspondence: luca.bindi@unifi.it
2
Dipartimento di Scienze della Terra, Università di Firenze, Via La Pira 4,
I-50121 Florence, Italy
Full list of author information is available at the end of the article

Among the several studies reporting the observation ofhigh-pressure minerals in meteorites (e.g., El Goresy et al.
2000, 2001a, b, 2008, 2010; Tomioka and Miyahara 2017;
Bindi et al. 2017, 2020; Tomioka et al. 2021), the discovery
of metallic alloys has been of particular interest as theseprovide (1) direct information on differently O2-depriveted portions of the Solar Nebula where alloys condensated, (2) a snapshot of the cooling history of the pristinechondritic material, and (3) a valid comparative model ofcore formation and chemical composition (McDonoughand Sun 1995). Due to the different chemical compositions of the observed metallic particles found in meteorites, their relation with the bulk chemistry of the hosting
meteorite along with textural observations has required adifferent interpretation. For instance, El Goresy and Chao
(1976, 1977) reported the discovery of Fe-Ni-Cr particles
in the basement rocks of Ries crater (Germany) that were
attributed to a condensation process after vaporization of
the impacting (carbonaceous) stony meteorite. This finding of metal particles was anticipated by the description of
Co-, Cu-, and Ni-rich spheroids within impactites fromthe Barringer Meteorite Crater in Arizona by Kelly et al.
(1974) explained on the basis of extensive chemical© The Author(s). 2021 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License,
which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give
appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate ifchanges were made. The images or other third party material in this article are included in the article's Creative Commonslicence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commonslicence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain
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(2021) 8:27

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reactions with the impacted target as well as Fe removalby oxidation and vaporization processes when meteorites
pass through the terrestrial atmosphere. Palme andWlotzka (1976) and El Goresy et al. (1978) reported thefinding of a metal particle from the Ca, Al-rich inclusionof the Allende and Leoville meteorites markedly enrichedin platinum group elements (PGE) and explained as resultof condensation process from the Solar Nebula when not
representative of pre-solar grains (i.e., Fremdlinge). Several
studies have focused on the different Fe/Ni ratios of kamacite and taenite from stony meteorites referred to the different cooling histories (Reed 1964). More recently, thefinding of metallic Fe coexisting with Fe-rich bridgmanite(hiroseite) in a shock vein of Suizhou meteorite (Bindi
et al. 2020) has been reported as the first direct evidence
in nature of redox-driven disproportionation reactions(Frost et al. 2004). Such discovery highlights the fact that(HP) mineral assemblages found in shocked meteorites
can either have inherited the redox conditions of the portion of Solar Nebula where chondritic material formed(Stagno and Aulbach 2021) or have reached equilibrium
within 10−1–100 seconds during the impact event (Ohtani
et al. 2007; Beck et al. 2005; Xie and Sharp 2007) whose P,
T, and chemical composition are influenced by the locallybuffered oxygen fugacity (fo2). On the other hand,studies conducted through molecular dynamic simulations have established a relation between the heliocentric distance and the redox conditions of theaccreting bodies with the latter being more oxidized
beyond 1.1-1.7 AU (Rubie et al. 2015).
Over this last decade, fundamental questions havebeen raised by the finding of metallic inclusions in the
Khatyrka meteorite, a CV3 carbonaceous chondrite discovered in the Koryak mountains of Chukotka in Eastern
Russia (Bindi et al. 2012; MacPherson et al. 2013). These
particles were found to be Al-Cu(Ni)-Fe alloys with aquasiperiodic atomic arrangement, materials well studied
for the last 35 years in the laboratory but exceedingly
rare in nature (Shechtman et al. 1984; Levine and Steinhardt 1984; Bindi et al. 2009). The natural quasicrystals
were then named icosahedrite (Al63Cu24Fe13) and decagonite (Al71Ni24Fe5; Bindi et al. 2011, 2015b), and recently, a first model of formation has been reported on
the basis of their trace element contents (Tommasini
et al. 2021).
The presence of stishovite, ahrensite, and a spinelloid
phase reported in Khatyrka fragments (Hollister et al.
2014) as well as the presence of (redox) reaction rims
(Lin et al. 2017) in the proximity of these particles wereinterpreted as evidence that the meteorite formed as result of a multi-stage process that started with the (1)condensation of Al-Cu-Fe from reduced portions of the
Solar Nebula about 4.56 Gya and (2) experienced shock
metamorphism induced by a hypervelocity impact withpressures exceeding at least 10 GPa and temperatures
up to 1500 °C about < 600 Ma before (3) being ejectedfrom its parent (K-type) asteroid 2–3 Ma ago (Meieret al. 2018). Moreover, the recent discovery of a COtype chondritic spherule from the Nubian Desert, Sudan,containing the same assemblage of aluminum, iron, andcopper and with a morphology remarkably similar to
Khatyrka, provided further support and independent evidence that these samples were formed in outer space(Suttle et al. 2019).
Figure 1 is a cartoon summarizing the state of art forthe metallic inclusions in Khatyrka meteorite. Several experimental studies were conducted at the aim both toreproduce shock-impact events to verify whether extraterrestrial quasicrystals would form and to test the stability of Al-Cu-Fe quasicrystal as function of pressure
and temperature (see Table 1).
The first set of dynamic compression experiments successfully resulted in the formation of both icosahedral
Al-Cu-Fe QC (Asimow et al. 2016; Oppenheim et al.
2017a; Hu et al. 2020) and decagonal QC (Oppenheim
et al. 2017b) by performing shock experiments.
Studies aimed to test the stability of icosahedrite werecarried out by Stagno et al. (2014, 2015, 2017) using bothin situ multi anvil (MA) and diamond anvil cell (DAC)
techniques assisted by synchrotron radiation X-ray diffraction (XRD) at room/high temperature. The results fromthese studies showed that (1) synthetic icosahedrite remains stable without any transformation to approximant
phases over a wide P range from 3 to 42 GPa and T up to1600 °C, (2) it exhibits a negligible effect of pressure on
the volumetric thermal expansion properties, and (3) the
quasiperiodic order of icosahedrite is retained up to 51.3
GPa. Importantly, it has been shown that pressure acts tostabilize the icosahedral symmetry at temperatures muchhigher than previously reported and that direct solidification of AlCuFe QCs from an unusually Al-Cu-rich melt ispossible but it is limited to a narrow temperature range(Stagno et al. 2017). However, the possibility that icosahedrite could form in nature and survived at elevated pressures and temperature conditions cannot be excluded as
this relies on the experimental investigation of its structural behavior and potential decomposition products athigh pressures.
As motivation of this study, there is evidence that heavily shocked ordinary chondrites, classified into shock stage
S6, have experienced pressures up to ~ 75 GPa as confirmed by the presence of high-pressure minerals (Stöffler
et al. 2018). Hence, the extension of pressure ranges up to~ 70 GPa and beyond is important to understand the icosahedrite stability in shocked meteorites.
Therefore, we report in situ angle-dispersive X-ray powder diffraction (XRD) measurements on synthetic icosahedrite to extend the investigation of the interplanar

Stagno et al. Progress in Earth and Planetary ScienceStagno et al. Progress in Earth and Planetary Science(2021) 8:27

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Fig. 1 Cartoon summarizing details of the Khatyrka meteorite. Top-left: schematic sketch of an asteroidal collision in outer space; top-right: SEMBSE image of Grain 126A of the Khatyrka meteorite. Brighter phases indicate Cu-Al-alloys and Fe-droplets, while darker phases are silicates andoxides (see Lin et al. 2017 for more explanations); bottom: TEM image of Grain 125 of the Khatyrka meteorite showing “ladders” composed byringwoodite and amorphous silica (see Hollister et al. 2014 for more explanations)distances at pressures up to about 75 GPa at ambient
temperature. Our results are integrated with data by
Takagi et al. (2015) on the compression behavior of icosahedral Al65Cu22Fe13 to better understand the possible evolution of icosahedrite at megabar pressures adopting a
univocal compression model.

2 Materials and methods
The synthetic quasicrystal used as starting material inthis study is the same as that used by Stagno et al.
(2015), and it was previously characterized by SEM and
XRD measurements and showed to have the formula

Al63Cu24Fe13 (Bancel 1999) plus minor amounts ofcupalite, (Cu, Fe)Al. The advantage of using this starting
material is that its composition can be considered theanalog of icosahedrite (Bindi et al. 2011). After extracting a small fragment from the synthetic single crystal, asmall chip was crushed to form a platelet. A small platelet with a diameter of approximately 60 μm was loaded
into the sample chamber of a symmetric diamond anvil
cell with flat anvils of 300-μm size culet and rhenium
gasket as sample chamber with a 150-μm diameter hole.
In situ angle-dispersive X-ray diffraction (ADXRD) measurements were performed at high pressure at the 13ID-

Stagno et al. Progress in Earth and Planetary Science(2021) 8:27

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Table 1 Bulk modulus (B0) and its pressure derivative (B’0) for Al-Cu-Fe alloys and end-members
0Composition

TechniqueP (GPa)B0

B0

References

i-Al62Cu25.5Fe12.5

EDXD

35

139 (6)

2.7

Sadoc et al. (1994)

i-Al62Cu25.5Fe12.5

EDXD

33.6

155 (10)2

Lefebvre et al. (1995)

p-Al62.8Cu26Fe11.2

EDXD

29.8

175 (16)

2

Lefebvre et al. (1995)

r-Al64Cu24Fe12

EDXD

35

175 (16)

2

Lefebvre et al. (1995)

i-Al65Cu22Fe13

ADXD

72

131 (7)4 (fixed)

Takagi et al. (2015)

i-Al63Cu24Fe12

ADXD

75.8

121 (8)3.68 (4)This study

Al

ADXD

144.3

76.3 (1.1)

4.16 (5)Dewaele et al. (2004)

Cu

ADXD

144.3

135.1 (1.1)

4.91 (5)Dewaele et al. (2004)

Fe

EDXD

300

165 (4)5.33 (9)Mao et al. (1990)

EDXD stays for energy-dispersive X-ray diffraction, while ADXD stays for angle-dispersive X-ray diffraction

D beamline (GSECARS) of the Advanced Photon Sourcein Argonne (Illinois). Neon was loaded as the pressure
medium, and the DAC was mounted on a motor-driven
stage with the tungsten carbide (WC) seat on the downstream side and the cubic boron nitride (c-BN) seat on
the upstream side. A focused monochromatic 30-keV Xray beam with a wavelength of 0.4133 Å and a sampleto-detector distance of ~ 296 mm was used. Diffraction
patterns were collected on a MarCCD-165 detector with
exposure time of 15 s. Pressure was measured using thethermal equation of state (EoS) of Ne used as pressure
medium (Hemley et al. 1989). The collected data were

processed using FIT2D software (Hammersley 1998),
and the d-spacing relative to each reflection was accurately determined using PeakFit software.

3 Results and discussion
The collected most representative diffraction data ofsynthetic icosahedrite are shown in Fig. 2 as function ofpressure, while Table 2 shows the d-spacing at differentpressures using the two-integer indices (Janot 1994; Lu
et al. 2001) along with the estimated pressures from theequation of state of Ne. The peaks were indexed according to Bindi et al. (2011), and the d-spacing wasFig. 2 Pressure effect on selected interplanar spacings (Å-angstrom) of the synthetic icosahedrite under quasi-hydrostatic conditions (Ne pressure
medium). Symbols: diamonds and triangles indicate previous runs (Stagno et al. 2015). Squares are experiments from this studyStagno et al. Progress in Earth and Planetary Science(2021) 8:27

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Table 2 Pressure dependences of d-spacings (Å) and a6D (Å) from the characteristic peaks
PNe (GPa)

V (Å3)

a6d(8,4)(12,16)(24,36)(28,44)(32,48)(44,64)(56,84)(60,92)(72,116)(80,128)

0.0

2020.96

12.6431

8.94

5.53

3.750

3.410

3.240

2.799

2.451

2.350

2.108

2.006

5.0

1938.85

12.4695

8.82

5.44

3.698

3.368

3.201

2.760

2.420

2.319

2.080

1.979

5.6

1929.35

12.4491

8.80

5.45

3.696

3.366

3.203

2.759

2.420

2.319

2.081

1.979

21.8

1746.67

12.0431

8.52

5.26

3.566

3.252

3.092

2.669

2.339

2.239

2.009

1.912

22.7

1747.89

12.0459

8.52

5.27

3.571

3.251

3.094

2.665

2.338

2.241

2.012

1.912

35.4

1637.86

11.7876

8.33

5.16

3.495

3.181

3.021

2.609

2.326

2.194

1.971

1.872

37.0

1611.29

11.7235

8.29

5.14

3.478

3.164

3.007

2.593

2.320

2.185

1.952

1.862

42.8

1617.61

11.7388

8.30

5.13

3.479

3.161

3.009

2.593

2.321

2.180

1.954

1.858

40.0

1608.28

11.7162

8.28

5.13

3.476

3.163

3.007

2.594

2.320

2.183

1.953

1.858

40.0

1606.81

11.7126

8.28

5.14

3.477

3.168

3.007

2.593

2.320

2.183

1.954

1.862

51.0

1571.3111.6257

8.22

5.07

3.447

3.133

2.986

2.573

2.305

2.158

1.941

1.846

53.8

1562.72

11.6045

8.21

5.05

3.437

3.127

2.977

2.562

2.303

2.153

1.935

1.840

56.8

1556.76

11.5897

8.19

5.04

3.427

3.118

2.968

2.558

2.296

2.147

1.930

1.835

60.5

1528.91

11.5202

8.15

5.04

3.414

3.113

2.956

2.550

2.287

2.140

1.921

1.829

63.5

1520.63

11.4994

8.13

5.02

3.406

3.106

2.949

2.541

2.278

2.137

1.916

1.824

66.5

1507.03

11.4650

8.11

5.01

3.397

3.098

2.940

2.533

2.280

2.129

1.911

1.819

68.0

1501.0911.4499

8.10

4.99

3.396

3.093

2.936

2.533

2.281

2.128

1.908

1.816

71.0

1484.92

11.4087

8.07

4.98

3.386

3.085

2.926

2.526

2.277

2.119

1.901

1.811

71.5

1481.15

11.3990

8.06

4.97

3.391

3.095

2.935

–

2.281

2.120

1.906

1.815

75.8

1453.00

11.3263

8.01

4.95

3.380

3.075

2.925

–

2.277

2.116

1.897

1.812

74.5

1452.88

11.3260

8.01

4.96

3.375

3.076

2.920

2.515

2.271

2.115

1.897

1.806

74.5

1449.65

11.3176

8.00

4.97

3.375

3.073

2.916

2.516

2.278

2.119

1.902

1.805

54.0

1570.54

11.6238

8.22

5.08

3.453

3.141

2.986

2.575

–

–

1.944

1.846

27.8

1712.36

11.9637

8.46

–

3.565

3.237

3.077

–

–

–

–

–

determined by fitting each diffraction peak using a
Gaussian formula within an uncertainty of less than 0.01
Å. The effect of pressure on the d-spacing is shown in
Fig. 3 with P determined by the EoS of Ne. According toour results, seven out of eight interplanar distances show
a similar linear compression behavior, unlike (8,4) thatappears more compressible over the P range of investigation. This is more evident in Fig. 4 where the pressure
dependence of the lattice parameter a6D is plotted up to
the maximum pressure of ~ 76 GPa defined as,sﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ
N þ Mτ
a6D ¼ dð1Þ2ð2 þ τ Þ
where d is the d-spacing in Å, N and M are the Cahn
indices for which the d-spacing is experimentally determined (i.e., (8,4) in this case), and τ is the golden ratio,(1+√5)/2 (Steurer and Deloudi 2009). The sixdimensional lattice parameter, with respect to the zero-Pparameter by Bindi et al. (2011), is shown to gradually
decrease with increasing pressure (Fig. 4) well in agreement with data by Stagno et al. (2015) providing,therefore, a significant evidence of reproducibility of theobtained results that reflects also the accuracy of theperformed experiments in both compression and decompression. The estimated reduction of the lattice parameter from the ambient pressure value of 12.64 Å to
75.8 GPa is about 10.4% implying a constant compressibility behavior as previously observed up to 50 GPa. No
clear evidences of either structural phase transitions oramorphization were observed within the investigatedpressure range as it can be also seen in Fig. 2. Figure 4
also shows data by Takagi et al. (2015) collected by insitu ADXRD but on synthetic Al65Cu22Fe13. In theirstudy, these authors reported no substantial changes in
the XRD profile relative to five characteristic peaks up to
104 GPa. These are the (24,36), (28,44), (32,48), (72,116),and (80,128) for which the least anisotropy was also observed in our measurements in case of the synthetic analog of icosahedrite, Al63Cu24Fe13. No information wasderived for the most anisotropic (8,4) reflection, which islikely the reason of the little difference with respect tothe study by Stagno et al. (2015).
The data were fitted to both Murnaghan and BirchMurnaghan EoS (Angel et al. 2014). The former modelStagno et al. Progress in Earth and Planetary Science(2021) 8:27

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Fig. 3 Representative powder X-ray diffraction patterns of i-QC collected at room temperature in angle-dispersive mode (wavelength of 0.4133 Å)
as function of pressure. Filled gray circles refer to Au used as a pressure marker. The diffraction peaks are indexed using Cahn indices (N, M)
following the scheme proposed by Janot (1994)

allows a direct comparison with the previous experimental
data from literature (see Table 1) and results in a bulk
0
modulus of 121(8) GPa ( B0 of 3.68 ± 4), which is close0with the 113.7 GPa (B0 of 4.22) obtained for the same QC
compressed to 50 GPa (Stagno et al. 2015). As a consequence of the observed consistency between the present
data and those by Stagno et al. (2015), we can fit successfully all of them to the same EoS and obtain a B0 of 120(2)0GPa and B0 of 3.87(14). These EoS parameters are slightly
0
smaller than 139 GPa ( B0 of 2.7) in case of icosahedral
0
Al62Cu25.5Fe12.5 by Sadoc et al. (1994), 155 GPa (B0 of 2.0)0
by Lefebvre et al. (1995), and close to 120 GPa (B0 of 5)
for decagonal Al72Ni20Co8 (Hasegawa et al. 1999). A fit ofour data to the third-order Birch-Murnaghan EoS pro0
duces little negligible differences (B0 116 ± 3, B0 of 4.39 ±17). Noteworthy, we refer to the decagonal phase since, atpresent, this is the only available data on the physicalproperties of decagonal QC with composition very close
to that found in nature, Al71Ni24Fe5, for which a HP origin
has been proposed (Bindi et al. 2015a, b).
Interestingly, Takagi et al. (2015) noted a slightly volume
shift between 72 and 75 GPa beyond which they claimed
that the QC would transform to an approximant phase.
This consideration is supported, in their opinion, by theappearance of small unknown peaks at 2θ of ~ 8.5° and
10.6° for (λ = 0.41441 Å). Therefore, their data were fitted
to 72 GPa using a third-order Birch-Murnaghan EoS toStagno et al. Progress in Earth and Planetary Science(2021) 8:27

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Fig. 4 Variation of the lattice parameter as function of pressure compared with similar studies on Al63Cu24Fe13 (Stagno et al. 2015) and Al65Cu22Fe13(Takagi et al. 2015). The zero-P volume is from Bindi et al. (2011)

0give a bulk modulus of 131(7) GPa (B0 of 4 as fixed value).
A second EoS fit for volume-P data collected from 74 to
104 GPa provided a higher bulk modulus like 170(40) GPa0(B0 of 4 as fixed value). Such difference was proposed tobe caused by the different compressional behavior of i-QC
and an approximant phase, although no sufficient evidence exists that such phase transformation could occur.
For instance, it cannot be excluded that the peaks reported as unknown could be representative of weak reflections of the i-QC that appears visible as result of preferredorientation upon compression (similar peaks also were observed within a lower P range for similar compositions by
Lefebvre et al. 1995). The unknown peak that Takagi et al.
(2015) noted at 10.6° = ~ 2.24 Å would correspond to thereflection (56,84) of the i-QC (Bindi et al. 2009, 2011).
Further, it is not surprising that the compressibility reported by Stagno et al. (2015) is slightly higher than thatobtained by Takagi et al. (2015) as the latter determined
the EoS from the least compressible d-spacings of i-QC;
on the contrary, Stagno et al. (2015) performed a highresolution investigation of the icosahedral structure bymonitoring the behavior in the high d-spacing region that
included peaks (12,16) at 5.53 Å and (8,4) at 8.94 Å. The
d-spacing referred to this latter reflection manifested amore evident anisotropic compressional behavior

resulting, therefore, in a lower bulk modulus. On the other
hand, first-order phase transitions would appear visible
through the variation of the d-spacing as function of P.
Figure 3 shows a continuous decrease of d-spacing as P
increases up to 75.8 GPa. Therefore, we fit the data by
Stagno et al. (2015) up to 72 GPa along with those by
Takagi et al. (2015) up to 104 GPa with only a unique
0
EoS. The obtained bulk modulus of 121(3) GPa ( B0 of
3.87 ± 12) using a Murnaghan EoS fitting model is consistent with the EoS parameters used to fit our data up to
75 GPa. Fitted to a third-order Birch-Murnaghan EoS, we
0obtain a bulk modulus of 117(3) GPa ( B0 of 4.45 ± 15),
which is again consistent with the previous fit by Stagno
et al. (2015). Both fitting models are showed in Fig. 5 with
an imperceptible difference between them. Data from literature are also shown by comparison. In particular, thecompressibility of icosahedral Al62Cu25.5Fe12.5 determinedby Sadoc et al. (1994) and Lefebvre et al. (1995) has been
extrapolated up to 104 GPa assuming that no phase transition occurs for this composition by analogy with thoseinvestigated here. Both curves are quite consistent withthe experimental measurements although a little shift islikely due to, again, the fact that the lattice parameter wasdetermined by the less compressible d-spacing. In
addition, loss of hydrostaticity could have occurredStagno et al. Progress in Earth and Planetary Science(2021) 8:27

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Fig. 5 Pressure-volume data for i-Al64Cu23Fe13 from this study (black circles) and Takagi et al. (2015; empty circles) fitted using both a Murnaghan(black dotted line) and Birch-Murnaghan EOS (dashed green line). Our fit is compared with previous studies by Sadoc et al. (1994) and Lefebvre
et al. (1995) both for icosahedral Al62Cu25.5Fe12.5 and for one approximant phase with composition Al64Cu24Fe12 (Lefebvre et al. 1995). The curves
obtained from these previous studies are extrapolated up to 104 GPa assuming that no structural phase transformation occurs

because of the use of silicon oil as pressure medium. Importantly, the extrapolated V/V0 is shown also for therhombohedral and pentagonal approximant phases by Lefebvre et al. (1995) where periodic approximant refers to a
crystalline solid with similar chemical composition to aquasicrystal, but whose atomic arrangement is slightly distorted so that the symmetry conforms to the conventionallaws of three-dimensional crystallography. These phases,
although described to have a slightly different chemicalcomposition, resulted to have the same physical behavior
at high P reflected by the same EoS parameters. Interestingly, these approximant phases are shown to undergo avolumetric reduction under compression that is apparently lower than the QC phase. Therefore, we areconfident that no phase transition occurred at P > 72 GPa
within the Al-Cu-Fe system investigated to date. This evidence raises important questions on the stability also of
approximant phases on extraterrestrial bodies that experienced shock-impact events. The recent findings of aquasicrystal with 10-fold symmetry, decagonite, with composition Al71Ni24Fe5 (Bindi et al. 2015a, b) and its approximant, proxidecagonite (Bindi et al. 2018), in the same
Khatyrka meteorite suggest the possibility that P-T conditions might play a key role in determining the most energetically stable atomic configuration. To date, however, noapproximant to icosahedrite has been found that support
the possibility that this phase transition might require extremely high P-T conditions never explored so far inexperiments.

At the present, both dynamic and static compression experiments have revealed the structural stability of i-QC.
Both icosahedral Al-Cu-Fe quasicrystals (Asimow et al.
2016; Oppenheim et al. 2017a; Hu et al. 2020) anddecagonal quasicrystals (Oppenheim et al. 2017b) were reported as run products of shock experiments during
which shock pressures up to 35 GPa were generated withT as high as 400 °C within less than 1 μs. These experiments succeeded in reproducing both the textural contacts between the quasicrystalline phases and the Al-CuFe alloys as well as their chemical composition as in the
Khatyrka meteorite. More importantly, the finding of quasicrystals incorporating additional elements like Cr and Ni
to the known Al-Cu-Fe, as well as the variability of the Al/
Cu and Cu/Fe atomic ratios, represent an important evidence that quasicrystals do form during impact and keep
their structural stability under more complex chemical environments than previously thought.
Static experiments carried out in the diamond anvil
cell, in particular, have extended our knowledge of the
behavior of synthetic icosahedrite up to megabar pressures. The effect of temperature has been investigatedthrough either laser heating in DAC or multi anvil experiments. While the former helped to verify the structural stability of the i-QC during heating up to ~ 1850
°C and upon cooling/quench, experiments performed
with the large volume press helped to shed light on the
kinetics versus thermodynamic stability of the QC.
Stagno et al. (2017) showed experimentally that

Stagno et al. Progress in Earth and Planetary Science(2021) 8:27

icosahedrite can be stable for hours under hydrostatic
compression at HT in the presence of additional minerals like cupalite, khatyrkite, and stolperite, similarly towhat are found in nature. The experimental observationof the coexistence of synthetic icosahedrite along withan Al-Cu-Fe melt (plus additional phases) proves that
icosahedrite can survive at those high P-T conditions at
which shock glassy veins containing high-P polymorphs
were proposed to form. We are confident that important
steps forward have been done through experimental
studies that demonstrate both the kinetics and thermodynamic stability of Al-Cu-Fe QCs, expanding, therefore,
their potential occurrence through space and time.

Page 9 of 11

Availability of data and materials
The dataset supporting the conclusions of this article is included within thearticle and its additional file.

Declarations
Competing interests
The authors declare that they have no competing interest.
Author details
1
Dipartimento di Scienze della Terra, Università La Sapienza, P.zle Aldo Moro5, I-00185 Rome, Italy. 2Dipartimento di Scienze della Terra, Università diFirenze, Via La Pira 4, I-50121 Florence, Italy. 3Institute of Materials Structure
Science, High Energy Accelerator Research Organization (KEK), Ibaraki, Japan.
4
Division of Earth Evolution Sciences, Graduate School of Life andEnvironmental Sciences, University of Tsukuba, Ibaraki, Japan.
Received: 13 January 2021 Accepted: 25 March 2021

4 Conclusions
We presented the results of experiments conducted at P up
to ~ 76 GPa using the DAC technique that confirms the stability of icosahedrite at high P. Our results appear consistent
with previous data collected up to 50 GPa and show a linear
decrease of the d-spacing with the exception for the (8,4) reflection, as never observed to the present, for which the calculated volume reduction is about 10% with respect to the
V0. Our data were, therefore, integrated with those previously
published by Takagi et al. (2015), who claimed for the transition of the i-QC to an approximant phase at 72–75 GPa.
Based on a re-fit of these data along with those by Stagno
et al. (2015) to a unique EoS fit model, we propose that icosahedrite can retain its structure up to megabar pressures.
This extended P range, further accompanied by the stabilityof i-QC at elevated T representative of shock impacts, rulesout the possibility to find Al-Cu-Fe approximant phases in
the Khatyrka meteorite.
Acknowledgements
Portions of this work were performed at GeoSoilEnviroCARS (The Universityof Chicago, Sector 13), Advanced Photon Source (APS), Argonne National
Laboratory. GeoSoilEnviroCARS is supported by the National Science
Foundation – Earth Sciences (EAR – 1634415) and Department of EnergyGeoSciences (DE-FG02-94ER14466). This research used resources of theAdvanced Photon Source, a U.S. Department of Energy (DOE) Office of
Science User Facility operated for the DOE Office of Science by Argonne
National Laboratory under Contract No. DE-AC02-06CH11357. We are gratefulto Sergey Tkachev and Vitali Prakapenka (GSECARS) for their help during theexperiments. We are particularly delighted to participate to the special issue
honoring Ahmed El Goresy. His numerous discoveries of shock-induced
high-pressure phases in meteorites and samples from terrestrial impact craters made possible to detect several unusual mineral assemblages. With his
work, Ahmed significantly contributed to a better understanding of cosmochemical processes in the early solar system.
Authors’ contributions
VS and LB proposed the topic, conceived, and designed the study. VS carriedout the experimental study. VS and LB analyzed the data and helped in theirinterpretation. ST and AK collaborated with the corresponding author in theconstruction of manuscript. All authors read and approved the final manuscript.
Funding
This work benefited from partial support by “Fondi di Ateneo 2019” of the
Sapienza University, Italy to V.S. The research was also in part funded by MIURPRIN2017, project “TEOREM deciphering geological processes using Terrestrial
and Extraterrestrial ORE Minerals,” prot. 2017AK8C32 (PI: Luca Bindi).

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