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Jong Mun Park
Dong Ryeol Whang Editors
EKC 2019
Conference
Proceedings
Science, Technology, and Humanity:
Advancement and Sustainability
EKC 2019 Conference Proceedings
Jong Mun Park • Dong Ryeol Whang
Editors
EKC 2019 Conference

Proceedings
Science, Technology, and Humanity:
Advancement and Sustainability
Vienna, Austria, July 15–18, 2019

Proceedings
Editors
Jong Mun Park Dong Ryeol Whang
ams AG Department of Advanced Materials
Premstaetten, Austria Hannam University
Daejeon, Republic of Korea
ISBN 978-981-15-8349-0 ISBN 978-981-15-8350-6 (eBook)

https://doi.org/10.1007/978-981-15-8350-6
© Springer Nature Singapore Pte Ltd. 2021

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Preface
EKC 2019, the 12th EKC, was held in Vienna, Austria, from July 15 to 18, 2019. It
was hosted by the Korean Scientists and Engineers Association in Austria
(KOSEAA) together with the Korean Federation of Science and Technology Soci-
eties (KOFST) and eight other Korean Scientists and Engineers Associations in
Europe which are in Germany (VeKNI), the UK (KSEAUK), France (ASCoF),
Austria (KOSEAA), Finland (KOSES), Scandinavia (KSSEA), the Netherlands
(KOSEANL), Switzerland (KSEAS), and Belgium (KOSEAbe). Since its first
successful start in 2008 in Heidelberg, Germany, EKC has been held annually in
different European countries and has become the most important scientific and social
event, bringing scientists and engineers from Europe and Korea together.
Under the theme of “Science, Technology and Humanity: Advancement and
Sustainability,” EKC 2019 was successfully held with more than 680 registered
participants. Three hundred twenty nine papers were presented in 50 technical
sessions. Among them, high impact-research results from EKC 2019 are selected,
peer-reviewed, and stapled in this volume. Fourteen research papers were submitted
and 11 were accepted after rigorous peer-review process from the program commit-
tee members and external experts.
Premstaetten, Austria Jong Mun Park

Daejeon, Republic of Korea Dong Ryeol Whang
January 2020
v
Organization
CONFERENCE CHAIR
PARK, Jong Mun (ams AG/KOSEAA President)
CONFERENCE CO-CHAIRS
KIM, Myung-Ja (KOFST President)
PARK, Wonsun (GEOMAR Helmholtz Centre for Ocean Research Kiel/VeKNI
President)
LIM, Sungwoo (The Open University/KSEAUK President)
KIM, Junbeum (Université de Technologie de Troyes/ASCoF President)
CHO, Hyong Sil (Microsoft/SiLnD/KOSEANL President)
CHOE, Young Han (International Telecommunication Union/KSEAS President)
LEE, Jae Wung (VTT Technical Research Centre of Finland/KOSES President)
YOO, YoonSeon (BlackBerry/KSSEA President)
OH, Kun Sang (KOSEAbe President)
ADVISORY BOARD
LEE, Eun-Woo (KOFST)
YOO, Martin S. D. (CRUSE Offshore GmbH/VeKNI)
SEOK, Joon-Weon (GORI Engineering/VeKNI)
JUN, Chang Hoon (ITER/ASCoF)
JEUNG, Gwang-Hi (Institut des sciences moléculaires de Marseille/ASCoF)
HAN, Man Wook (Technische Universität Wien/KOSEAA)
KIM, Keunjae (SSPA/KSSEA)
PARK, Migeun (University of Strathclyde/KSEAUK)
SECRETARY GENERAL
LEE, Hana (Technische Universität Graz/KOSEAA)
vii
viii Organization
REGISTRATION
GWON, Jihee (Muthesius University of Fine Arts and Design/VeKNI)
KWON, Jaedeok (University of Glasgow/KSEAUK)
KANG, Myung-Ah ( Universté Clermont Auvergne/ASCoF)
LEE, Sun Mi (KOSEANL)
LEE, Juneseung (ETH Zurich/KSEAS)
MUN, Gwan-gyeong (Intel/KOSES)
KIM, Jaeoh (KSSEA)
HEO, Changhoon (imec/KOSEAbe)
PROGRAMME CHAIR
WHANG, Dong Ryeol (Johannes Kepler Universität Linz/KOSEAA)
DIVISION CHAIRS
KANG, Kab Seok (Max Planck Institute for Plasma Physics/VeKNI)
KIM, Chan (European XFEL/VeKNI)
YOON, Songhak (Fraunhofer IWKS/VeKNI)
KIM, Wonjae (VTT Technical Research Center of Finland/KOSES)
MOK, K. Hun (Trinity College Dublin/KSEAUK)
NAM, Kiwoong (Institut National de la Recherche Agronomique/ASCoF)
KIM, Junbeum (University of Technology of Troyes, France/ASCoF)
LEE, Hyunjung (City of Stuttgart, Office for Environmental Protection/VeKNI)
LEE, Pyoung-Jik (University of Liverpool/KSEAUK)
SEO, Hyewon (CNRS-Univ. Strasbourg/ASCoF)
JUNG, Sung Kyo (NXP Software/ KOSEAbe)
CHOI, Jung Han (Fraunhofer Heinrich Hertz Institute/VeKNI)
JEONG, Cheol-Ho (DTU (Denmark Technical University)/KSSEA)
HA, Kwangtae (Fraunhofer IWES/VeKNI)
CHO, Hyong Sil (SiLnD; Microsoft/KOSEANL)
LOC CHAIR
HAN, Man Wook (Technische Universität Wien/KOSEAA)
FINANCE DIRECTOR
LEE, Seung-Hun (KOSEAA)
LOC MEMBERS
PARK, Young-Saeng (University of Warwick/KSEAUK)
KOCH, Kyungran (KOSEAA)
MIN, Jihoon (IIASA/KOSEAA)
Contents
Novel Adamantane Asymmetrically Substituted

Diketopyrrolopyrroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Martin Cigánek, Patricie Heinrichová, Martin Weiter, and Jozef Krajčovič
Machine Learning Approach on Steel Microstructure Classification . . . . 13
Haon Park and Abdullah Öztürk
Metabolomics and Its Applications to Personalized Medicine . . . . . . . . . . 25
Lee Sherlock and K. H. Mok
Partition-Based Task Mapping for Communication Energy
Minimization in 3D Network-on-Chip . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Sanghoon Kwak
Design of Floating Offshore Wind Turbine (FOWT) “SelfAligner” . . . . . 55
Jens Cruse, Moustafa Abdel-Maksoud, Alexander Düster,
Andreas Bockstedte, Gerrit Haake, and Sönke Siegfriedsen
Design of Highly Loaded Slewing Bearings – The Collaborative Project
HBDV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Jae-Il Hwang, Jan Torben Terwey, Josephine Kelley, Felix Saure,
Heinrich Peter Schönemeier, and Gerhard Poll
Preliminary Study on Blade Trailing Edge Flap System Using Flexible
Torsion Bar and Worm Drive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Kwangtae Ha
Validation of Real Time Gait Analysis Using a Single
Head-Worn IMU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Tong-Hun Hwang, Julia Reh, Alfred O. Effenberg, and Holger Blume
Three-Dimensional Visualization of Atomic Ordering by Bragg
Ptychography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Chan Kim and Anders Madsen
ix
Novel Adamantane Asymmetrically
Substituted Diketopyrrolopyrroles
Martin Cigánek, Patricie Heinrichová, Martin Weiter, and Jozef Krajčovič
Abstract The effect of the alkylation and solubilization ethyladamantyl side chains
to diketopyrrolopyrroles (DPPs) on the thermal and optical properties was system-
atically investigated. Nucleophilic substitution of various alkyl chains into the DPP
molecule is a powerful tool for increasing solubility and processability of these
pigments, leading to their broader applications. Moreover, alkylation can often
contribute to solid state packing and structural ordering of DPPs, depending mainly
on a character of alkyl chain. In this work, we have synthesized the series containing
three derivatives (N,N0 -, N,O0 - and O,O0 -substituted) of alkylated thiophene-DPP
derivatives by ethyladamantyl substituents. It was focused on precise separation of
all formed DPP derivatives in order to their deeper study. It has been found that the
O-substitution leads to worse thermal stability of materials, based on
thermogravimetric measurements. On the other hand, ethyladamantyl side chain as
rigid alicyclic substituent very effectively contributed to increase of melting point
and thermal stability. The new findings provide valuable information about the
previously overlooked regioisomers formed during alkylation of the DPP molecule,
in particular in terms of thermal stability and optical properties in solution.
Keywords Diketopyrrolopyrrole · Alkylation · Adamantyl
1 Introduction
In recent years, soluble organic semiconductors have found a number of significant

applications in various areas of organic electronics, mostly due to their facile
processability in common organic solvents and lower production costs compared
to conventional inorganic materials [1]. Organic pigments are the key and well-
known molecules suitable for applications in organic electronics [2, 3]. They are
M. Cigánek · P. Heinrichová · M. Weiter · J. Krajčovič (*)

Faculty of Chemistry, Brno University of Technology, Brno, Czech Republic
e-mail: [email protected]
© Springer Nature Singapore Pte Ltd. 2021 1

J. M. Park, D. R. Whang (eds.), EKC 2019 Conference Proceedings,
https://doi.org/10.1007/978-981-15-8350-6_1
2 M. Cigánek et al.
characterized by high absorption coefficients [2], high thermal and chemical stability
[2] and good charge transfer capability [3]. One of the most recently examined and
most attractive groups of organic pigments are derivatives of 2,5-dihydropyrrolo
[4,3-c]pyrrolo-1,4-dione (DPP) [4], having a considerable application potential for
easily processed low-cost sustainable electronics devices [5]. The DPP backbone
provides the great potential for a wide range of chemical derivatizations to prepare
target derivatives exhibiting the desired chemical and physical properties [6]. As a
result, there are currently many significant scientific reports dealing with the appli-
cations of DPP derivatives as high performance organic pigments used in functional
devices such as organic field-effect transistors [7–11], organic light-emitting diodes
[12, 13], dye-sensitized [14] and bulk heterojunction solar cells [15], sensors [16]
and biosensors [17], fluorescence probes [18] etc.
The DPP derivative substituted with 2-thiophene at positions 3 and 6 is most
often found in the previously mentioned fields of application [19]. An important
approach to increase efficiency of this material is to extend the length of
π-conjugation in the molecule, which can be achieved by polymerization via direct
arylation [20, 21] or by the cross-coupling reactions on the side aromatic rings of the
DPP core [22, 23]. Another very important derivatization is N,N0 -alkylation of the
DPP molecule, providing considerably higher solubility compared to basic N,N-
0
-unsubstituted DPP derivatives. These derivatives possess good thermo and
photostability [2, 24], however strong intermolecular hydrogen bonding between
neighbouring oxygen and nitrogen atoms of lactam groups leads to a relatively low
solubility in most of common organic solvents [2]. The solubility improvement of N,
N0 -alkylated DPPs with linear or branched alkyl chains is caused by interruption of
intermolecular hydrogen bonds and leads to broader applications, especially in
previously mentioned areas of electronics [25]. On this basis, alkylation is one of
the most important and most common derivatization of DPPs. Incorporation of alkyl
chains into DPP core is performed through base-catalysed nucleophilic substitution,
usually carried out as a one-pot reaction [26]. Nevertheless, two neighbouring O-
and N-atoms of the lactam group lead to delocalization of the negative charge in the
formation of the DPP anion, resulting to decreasing of regioselectivity of N,N-
0
-substitutions. The formation of O-alkylated DPP by-products was already proved
[27] but there are very few reports dealing with their properties [28, 29]. Nevertheless,
O,O0 - and asymmetrical N,O0 - adamantane-substituted derivatives can be a point of
interest not only from fundamental but also from practical point of view.
Recently the synthesis and study of a novel DPP derivative N,N0 -substituted by
bulky ethyladamantyl chains was reported by our group [30]. Substitution has led to
extraordinary high ordered adamantane induced molecular packing what resulted to
exceptional ambipolar behaviors of this new pigment. During the synthesis of the
aforesaid DPP derivative, very low regioselectivity of N-alkylation was encountered
and the formation of by-products was largely observed.
Therefore, the main aim of this work has been to focus on systematically study of
the influence of bulky adamantyl chains on either regioselectivity of the DPP
alkylation and properties of the resulting derivatives. The target was to synthesize
and isolate all formed products in weighable quantities and subjecting these
Novel Adamantane Asymmetrically Substituted Diketopyrrolopyrroles 3
derivatives to the study of the effect of adamantyl substituents on optical and thermal
properties in case of symmetrical (N,N0 -; O,O0 -) and asymmetrical (N,O0 -) products.
2 Experimental Section
2.1 Materials
2-Thiophenecarbonitrile (99%), sodium, iron(III) chloride (>97%, anhydrous), tert-

Amyl alcohol (99%), N,N-dimethylformamide (DMF, 99.8%, anhydrous), potas-
sium carbonate (99.99%, anhydrous) and deuteron chloroform (99.96 atom % D)
were purchased from Sigma-Aldrich (now Merck) and were used as received.
Diisopropyl succinate (98%) was purchased from Synthesia, Inc. and also was
used as received. 1-(2-Bromoethyl)adamantane (98%) was purchased from Provisco
CS Ltd. Acetic acid (99%), isopropyl alcohol (p.a.), methanol (p.a.), toluene (p.a.)
and chloroform (p.a.) were purchased from PENTA Ltd. and were used as received.
Separation by column chromatography was carried out on Silica Gel 60 Å (230–400
mesh, Sigma-Aldrich). All reactions were performed in oven-dried apparatus, under
argon atmosphere while magnetically stirred.
2.2 Characterization
1
H NMR spectra were recorded on a FT-NMR spectrometer Bruker Avance III
300 MHz or 500 MHz in CDCl3. Chemical shifts (δ) are given in parts per million
(ppm) relative to TMS as an internal reference. The melting point was determined on
a Kofler apparatus and the temperature was not calibrated. Mass spectra were
recorded on a GC–MS spectrometer Thermo Fisher Scientific ITQ 700 (DEP).
Elemental analysis was measured with an elemental analyser Flash 2000 CHNS
Thermo Fisher Scientific.
Thermogravimetry (TG) was conducted on TA Instruments Q5000IR (New
Castle, Delaware, USA) to analyze the stability of the derivatives and changes in
mass before degradation. A sample was placed on the Pt crucible sample holder and
heated at 10 C/min from room temperature to 600 C under a stream of nitrogen
(5.0 ultra high purity) flow rate 40 mL/min. TG was used to analyze the thermal
stability of investigated materials. Briefly, the TG record (dependence of mass on
temperature) was derived and onset of the derivate was determined. TG records were
evaluated using TRIOS and Universal analysis software provided by TA
Instruments.
Solutions were prepared by diluting materials in anhydrous chloroform. Concen-
tration of materials was 105 to 106 mol dm3. Solutions were characterized in a
quartz cuvette (Herasil®, Heraeus Quarzglas Co.). Absorption spectra of samples
were measured by employing Varian Cary Probe 50 UV-VIS spectrometer (Agilent
Technologies Inc.). The fluorescence spectra were recorded with a Horiba Jobin
Yvon Fluorolog. This apparatus equipped by integration sphere was also used to
determination of fluorescence quantum yield by absolute method. Fluorescence
lifetime was measured by Horiba Jobin Yvon Fluorocube.
2.3 Synthesis
The targeted series of alkylated DPP derivatives by ethyladamantyl chains were

synthesized according to the known procedure [26, 31]. The synthetic route and the
molecular structures are illustrated in the Fig. 1.
H S
O O N
S CN O (i) (ii)
+
O
N O
O S H
Th-DPP: 59%
O N S O N S O N S
+ +
S N O S N O S N O
N,N'-EtAd-Th-DPP: 36% N,O'-EtAd-Th-DPP: 20% O,O'-EtAd-Th-DPP: 6%
Fig. 1 Synthetic pathway for the synthesis of the basic thiophene DPP molecule and subsequently
N,N0 -; N,O0 - and O,O0 -alkylated DPP derivatives
(i)
Na, FeCl3 (cat.)/t-amyl alcohol, 102 C, 24 h
(ii)
1. K2CO3; 2. 1-(2-bromoethyl)adamantane/DMF, 105 C, 2 h
Synthesis of 2,5-dihydropyrrolo[4,3-c]pyrrolo-1,4-dione molecules Sodium

(~1.3 equiv., 7.2 g, 313.2 mmol) was dissolved in 400 ml of tert-amyl alcohol
heated to reflux and with addition of catalytic amount of iron(III) chloride. After
dissolution of all sodium, it was added in one portion 1.0 equiv. of thiophene-2-
carbonitrile (26.2 g, 240.0 mmol) and the reaction mixture was stirred for 30 min at
reflux. Then, 0.65 equiv. of diisopropyl succinate (31.6 g, 156.2 mmol) dissolved in
80 ml of tert-amyl alcohol was gradually added dropwise for 4 h and the mixture was
stirred at reflux for 18 h. After that, protolysis was performed by addition of diluted
acetic acid to the reaction mixture cooled to laboratory temperature. The mixture was
refluxed for 6 h and then, heterogenic mixture was filtered while hot and filter cake
was washed with hot water and isopropyl alcohol. Crude product was refluxed in
methanol for 1 h and after that, it was filtered while hot to get pure product.
Th-DPP. Dark purple solid (27.5 g, yield 59%). Melting point >400 C, 1H NMR
(300 MHz, DMSO-d6, ppm): δ ¼ 11.21 (s, 2H), 8.20 (d, J ¼ 3.01 Hz, 2H), 7.93 (d,
J ¼ 3.04 Hz, 2H), 7.31–7.27 (m, 2H), Anal. calcd. for C14H8N2O2S2: C 55.98%, H
2.68%, N 9.33%, Found: C 55.42%, H 2.37%, N 9.71%.
Synthesis of the alkylated DPP derivatives Anhydrous potassium carbonate (~5.3
equiv., 2.4 g, 17.4 mmol) was added to a solution of Th-DPP (1.0 equiv., 1.0 g,
3.3 mmol in 45 ml of anhydrous DMF) and the mixture was heated to 60 C and
stirred for 1 h. Then, 1-(2-bromoethyl)adamantane (3.50 equiv., 2.81 g, 11.6 mmol)
dissolved in 20 ml of anhydrous DMF was gradually added dropwise for 30 min.
After 20 min, the mixture was heated to 105 C and stirred for 2 h. Then, DMF was
distilled off by vacuum distillation, solid material was suspended in methanol and
filtered to get crude product.
N,N’-EtAd-Th-DPP. Violet crystal material (0.75 g, yield 36%) was obtained
after purification of the crude product by column chromatography on silica gel
(toluene/chloroform 3/1) and the following recrystallization in toluene with addition
of n-heptane. Melting point 321 C, 1H NMR (500 MHz, CDCl3, ppm): δ ¼ 8.91 (d,
J ¼ 3.8 Hz, 2H), 7.64 (d, J ¼ 4.9 Hz, 2H), 7.27 (dd, J ¼ 6.0, 5.0 Hz, 2H), 4.14–4.11
(m, 4H), 1.99–1.82 (m, 6H), 1.75–1.72 (m, 7H), 1.68–1.65 (m, 19H), 1.53–1.51 (m,
3H), EI [m/z] 624.89, Found 624.97, Anal. calcd. for C38H44N2O2S2: C 73.04%, H
7.10%, N 4.48%, S 10.26%, Found: C 73.15%, H 7.08%, N 4.42%, S 10.38%.
N,O’-EtAd-Th-DPP. Dark violet solid material (0.41 g, yield 20%) was obtained
(toluene/chloroform 3/1). Melting point 210 C, 1H NMR (300 MHz, CDCl3,
ppm): δ ¼ 8.42 (d, J ¼ 3.9 Hz, 1H), 8.25 (d, J ¼ 3.8 Hz, 1H), 7.69 (dd, J ¼ 5.9,
4.1 Hz, 1H), 7.49 (dd, J ¼ 5.6, 4.1 Hz, 1H), 7.27 (d, J ¼ 3.2 Hz, 1H), 7.24–7.17 (m,
1H), 4.67–4.63 (t, J ¼ 7.8 Hz, 2H), 4.06–4.00 (m, 2H), 1.98 (m, 6H), 1.75–1.67 (m,
26H), 1.62–1.53 (m, 3H), Anal. calcd. for C38H44N2O2S2: C 73.04%, H 7.10%, N
4.48%, Found: C 72.81%, H 7.01%, N 4.57%.
O,O’-EtAd-Th-DPP. Dark violet solid material (0.12 g, yield 6%) was obtained
(toluene/chloroform 3/1). Melting point 221 C, 1H NMR (300 MHz, CDCl3,
ppm): δ ¼ 8.05 (d, J ¼ 4.5 Hz, 2H), 7.55 (d, J ¼ 5.5 Hz, 2H), 7.19 (dd, J ¼ 8.1,
1.1 Hz, 2H), 4.69–4.65 (m, 4H), 1.98 (m, 4H), 1.70–1.64 (m, 24H), 1.54 (s, 4H),
1.34–1.26 (m, 2H), Anal. calcd. for C38H44N2O2S2: C 73.04%, H 7.10%, N 4.48%,
Found: C 72.96%, H 6.99%, N 4.51%.
3 Results and Discussion
3.1 Thermogravimetric Analysis
The thermogravimetric record of the N,N0 -EtAd-Th-DPP showed the degradation

around 370 C, but it was preceded by a mass loss about 15%.
Thermal stability of asymmetrically substituted derivative N,O0 -EtAd-Th-DPP
showed degradation at 264 C.
The thermogravimetric record of O,O0 -EtAd-Th-DPP derivative showed a con-
tinuous mass decrease from 100 to 250 C (mass loss around 20%) and the rate of
mass decrease accelerated, which means that sample was degraded. Therefore,
correct temperature of the degradation cannot be determined using
thermogravimetric analysis (see Fig. 2).
It is obvious that N,N0 -EtAd-Th-DPP derivative exhibited by far the highest
thermal stability compared to the other two derivatives studied. Therefore, it has
been proved that O-substitution results in formation of much less stable derivatives
in comparison to the product of N,N0 -alkylation (for summary, see Table 1).
3.2 Optical Properties in Solution
The optical properties of DPP derivatives were studied in solution to investigate the
effects given by the position of solubilization group substitution.
The Fig. 3 summarizes absorption and fluorescence emission spectra. The origin
of fluorescence spectra is confirmed by excitation spectra, which are in good
agreement with absorption spectra. There is significant difference between spectra
of N,N0 -; N,O0 - and O,O0 -substituted DPPs. Quantitative parameters describing
optical properties of solutions are summarized in Table 2. They are confirming
that the position of alkyl chain substitution was leading to significant differences
in optical properties.
Absorption maximum is shifted with change of substitution position, while N,
N0 -EtAd-Th-DPP had maximum at 549 nm, N,O0 -EtAd-Th-DPP had maximum at
533 nm and O,O0 -EtAd-Th-DPP at 505 nm (see spectra on Fig. 3 and Table 2).
These shifts seem to be mainly consequence of suppression of electron transition to
lower vibration modes of excitation states in case of N,O0 - and O,O0 -derivatives
(zero phonon transitions are suppressed).
100 1.2
404.91°C
1.0
N,N’-EtAd-Th-DPP
Deriv. Weight (%°C)

80 0.8
Weight (%)
60 0.6
0.4
40
0.2
20
372.51°C
0 0.0
0 100 200 300 400 500 600
Temperature (°C)
120 1.0 120 0.6
378.65°C
344.17°C
100 0.8 100
N,O’-EtAd-Th-DPP O,O’-EtAd-Th-DPP

0.4
Weight (%)
80 0.6 80
Weight (%)
60 0.4 60 0.2
296.50°C
40 0.2 40
0.0
20 0.0 20
0 –0.2 0 –0.2
0 200 400 600 800 0 200 400 600 800
Temperature (°C) Temperature (°C)
Fig. 2 Thermogravimetric records of all three studied DPP derivatives
Table 1 Thermogravimetric analysis of all three studied DPP derivatives

Derivative N,N0 -EtAd-Th-DPP N,O0 -EtAd-Th-DPP O,O0 -EtAd-Th-DPP
Tdegradation [ C] 370 264 n.d.
Fig. 3 Absorption and fluorescence spectra of studied DPPs diluted in chloroform

Table 2 Optical parameters of DPPs determined from absorption and fluorescence measurements
Derivative N,N0 -EtAd-Th-DPP N,O0 -EtAd-Th-DPP O,O0 -EtAd-Th-DPP
λABS max [nm] 549 533 505
ε [dm3mol1 cm1] 25,000 1000 12,000 200 26,000 1000
λABS edge [nm] 572 602 598
λPL[nm] 562 598 731
Stokes shift [eV] 0.05 0.26 0.76
τ [ns] 6.07 0.01 0.65 0.02 0.32 0.05
Eg opt [eV] 2.23 2.16 2.05
Fig. 4 Spectral response of O,O0 -EtAd-Th-DPP in acid conditions
It is known that unsubstituted trivalent nitrogen in case of O-alkylation has high

affinity to hydrogen and can be reversibly protonated (i.e. halochromic effect) upon
addition of acid into solution [32–34], which results in a bathochromically shifted
maximum of absorption spectrum. Spectral response of acidified solution (1 vol% of
glacial acetic acid 99.8%) of O,O0 -EtAd-Th-DPP derivative is shown on Fig. 4.
Assuming protonation of both nitrogen atoms, the absorption maximum was
measured at 565 nm and the shape of the spectrum with clean zero-phonon transition
peak is similar to N,N0 -substituted derivative. Interestingly, the absorption edge of
protonated and deprotonated form is practically same at about 600 nm.
The position of alkyl group has also a major influence on fluorescence emission
spectra (see Fig. 3). The emission maximum of N,N0 -EtAd-Th-DPP was at 562 nm
and thus Stokes shift was very small only 0.05 eV (see Table 2). Emission maximum
of N,O0 -EtAd-Th-DPP was bathochromely shifted to 598 nm and Stokes shift

increased to 0.26 eV, thus N,O0 -EtAd-Th-DPP is more reorganized after excitation
than N,N0 -substituted one. Moreover, emission spectrum of N,O0 -alkylated deriva-
tive has resolved vibronic structure in contrast to absorption/excitation spectrum. It
is showing that excited molecule is more planar than in ground state. Clear emission
spectrum of O,O0 -EtAd-Th-DPP derivative was determined with maximum at
731 nm.
The fluorescence quantum yield dramatically dropped with substitution in
O-position. While N,N0 -EtAd-Th-DPP had relatively high fluorescence quantum
yield about 60%, N,O0 -EtAd-Th-DPP showed only up to 1%. Fluorescence of O,
O0 -EtAd-Th-DPP was found to be too small for quantitative evaluation. Fluores-
cence quantum yield relates to fluorescence lifetime, which was found for N,N-
0
-EtAd-Th-DPP about 6 ns, for N,O0 -EtAd-Th-DPP about 0.6 ns and for O,
O0 -EtAd-Th-DPP only 0.3 ns.
Intersection point of absorption/excitation and emission spectra provides infor-
mation about optical band gap, which was found for N,N0 -EtAd-Th-DPP 2.23 eV,
for N,O0 -EtAd-Th-DPP 2.16 eV and for O,O0 -EtAd-Th-DPP 2.05 eV, respec-
tively. These values are very close and they are thus further confirm the above
hypothesis about suppressed electron transitions from ground state to excited state
with the lowest vibration energy in case of O-substituted derivatives.
4 Conclusion
In summary, a novel series of three thiophene-DPP derivatives alkylated by

ethyladamantyl chains was synthesized and subsequently investigated. It could be
summarized that O-substitution is a significant competitive reaction to N-alkylation
of the DPP molecule containing lactam groups and leads to the formation of
considerable amount of side-products. Thermogravimetric measurements revealed
that O-alkylation of the DPP results in formation of much less stable derivatives in
comparison to the product of N,N0 -alkylation.
The study of optical properties revealed that O-substituted derivatives tend to
possess large Stokes shift which reduces the reabsorption of the emitted lumines-
cence. Moreover, the substitution on the highly polar ketone group induces electron
cloud polarization, which is beneficial for the two-photon absorption. Thus such
materials are potential candidates for the application as e.g. biomarkers.
However, O,O0 - and N,O0 - substituted DPP derivatives also have their drawbacks,
such as lower synthesis yields or lower thermal stability. On the other hand,
ethyladamantyl side chain as rigid alicyclic substituent very effectively contributed
to increase of melting point and thermal stability of all derivatives studied in
comparison to already described DPP derivatives alkylated with common linear or
branched alkyl chains, e.g. 2-ethylhexyl [28]. These findings provide valuable
information about yet overlooked regioisomers of the alkylation of DPP derivatives,
in terms of both thermal stability and solution optical properties.
Acknowledgments This work was supported by the Czech Ministry of Industry and Trade Grant
TRIO FV20022 and MC thanks project No. FCH-S-19-5834.
References
1. Bagher AM (2014) Comparison of organic solar cells and inorganic solar cells. Int J Renew
Sustain Energy 3(3):53–58
2. Hao Z, Iqbal A (1997) Some aspects of organic pigments. Chem Soc Rev 26(3):203–213
3. Gsänger M, Huang DBL, Stolte M, Würthner F (2016) Organic semiconductors based on dyes
and color pigments. Adv Mater 28(19):3615–3645
4. Farnum DG, Mehta G, Moore GGI, Siegal FP (1974) Attempted reformatskii reaction of
benzonitrile, 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole. A lactam analogue of pentalene.
Tetrahedron Lett 15(29):2549–2552
5. Nielsen CB, Turbiez M, McCulloch I (2013) Recent advances in the development of semicon-
ducting DPP-containing polymers for transistor applications. Adv Mater 25(13):1859–1880
6. Grzybowski M, Gryko DT (2015) Diketopyrrolopyrroles: synthesis, reactivity, and optical
properties. Adv Opt Mater 3(3):280–320
7. Bronstein H, Chen Z, Ashraf RS et al (2011) Thieno[3,2-b]thiophene-diketo-pyrrolopyrrole-
containing polymers for high-performance organic field-effect transistors and organic photo-
voltaic devices. J Am Chem Soc 133(10):3272–3275
8. Chen TL, Zhang Y, Smith P, Tamayo A, Liu Y, Ma B (2011) Diketo-pyrrolopyrrole-containing
oligothiophene-fullerene triads and their use in organic solar cells. ACS Appl Mater Interfaces 3
(7):2275–2280
9. Li Y, Sonar P, Singh SP, Soh MS, Van Meurs M, Tan J (2011) Annealing-free high-mobility
diketopyrrolopyrrole-quaterthiophene copolymer for solution-processed organic thin film tran-
sistors. J Am Chem Soc 133(7):2198–2204
10. Yumusak C, Abbas M, Sariciftci NS (2013) Optical and electrical properties of electrochem-
ically doped organic field effect transistors. J Lumin 134:107–112
11. Glowacki ED, Romanazzi G, Yumusak C et al (2015) Epindolidiones-versatile and stable
hydrogen-bonded pigments for organic field-effect transistors and light-emitting diodes. Adv
Funct Mater 25(5):776–787
12. Vala M, Weiter M, Vyňuchal J, Toman P, Luňák S (2008) Comparative studies of diphenyl-
diketo-pyrrolopyrrole derivatives for electroluminescence applications. J Fluoresc 18
(6):1181–1186
13. Kalyani TN, Dhoble SJ (2012) Organic light emitting diodes: energy saving lighting
technology – a review. Renew Sust Energ Rev 16(5):2696–2723
14. Qu S, Wu W, Hua J, Kong C, Long Y, Tian H (2010) New diketopyrrolopyrrole (DPP) dyes for
efficient dye-sensitized solar cells. J Phys Chem C 114(2):1343–1349
15. Huo L, Hou J, Chen H-Y, Zhang S, Jiang Y, Chen TL, Yang Y (2009) Bandgap and molecular
level control of the low-bandgap polymers based on 3,6-dithiophen-2-yl-2,5-dihydropyrrolo
[3,4-c]pyrrole-1,4-dione toward highly efficient polymer solar cells. Macromolecules 42
(17):6564–6571
16. Qu Y, Hua J, Tian H (2010) Colorimetric and ratiometric red fluorescent chemosensor for
fluoride ion based on diketopyrrolopyrrole. Org Lett 12(15):3320–3323
17. Sokolov AN, Roberts ME, Bao Z (2009) Fabrication of low-cost electronic biosensors. Mater
Today 12(9):12–20
18. Fischer GM, Jüngst C, Isomäki-Krondahl M, Gauss D, Möller HM, Daltrozzo E, Zumbusch A
(2010) Asymmetric PPCys: strongly fluorescing NIR labels. Chem Commun 46
(29):5289–5291
19. Bürgi L, Turbiez M, Pfeiffer R, Bienewald F, Kirner H-J, Winnewisser C (2008) High-mobility
ambipolar near-infrared light-emitting polymer field-effect transistors. Adv Mater 20
(11):2217–2224
20. Zhang J, Kang D-Y, Barlow S, Marder SR (2012) Transition metal-catalyzed C–H activation as
a route to structurally diverse di(arylthiophenyl)-diketopyrrolopyrroles. J Mater Chem 22
(40):21392–21394
21. Liu S-Y, Shi M-M, Huang J-C et al (2013) C–H activation: making diketopyrrolopyrrole
derivatives easily accessible. J Mater Chem A 1(8):2795–2805
22. Chan WK, Chen Y, Peng Z, Yu L (1993) Rational designs of multifunctional polymers. J Am
Chem Soc 115(25):11735–11743
23. Beyerlein T, Tieke B (2000) New photoluminescent conjugated polymers with 1,4-dioxo-3,6-
diphenylpyrrolo[3,4-c]pyrrole (DPP) and 1,4-phenylene units in the main chain. Macromol
Rapid Commun 21(4):182–189
24. Iqbal A, Jost M, Kirchmayr R, Pfenniger J, Rochart A, Wallquist O (1998) Bull Soc Chim Belg
97:615
25. Tieke B, Rabindranath AR, Zhang K, Zhu Y (2010) Conjugated polymers containing
diketopyrrolopyrrole units in the main chain. Beilstein J Org Chem 6:830–845
26. Naik MA, Venkatramaiah N, Kanimozhi C, Patil S (2012) Influence of side-chain on structural
order and photophysical properties in thiophene based diketopyrrolopyrroles: a systematic
study. J Phys Chem C 116(50):26128–26137
27. Frebort Š, Eliáš Z, Lyčka A, Luňák S, Vyňuchal J, Kubáč L, Hrdina R, Burget L (2011) O- and
N-alkylated diketopyrrolopyrrole derivatives. Tetrahedron Lett 52(44):5769–5773
28. Zhao B, Sun K, Xue F, Ouyang J (2012) Isomers of dialkyl diketo-pyrrolo-pyrrole: electron-
deficient units for organic semiconductors. Org Electron 13(11):2516–2524
29. Zhang L, Shen W, He R, Liu X, Tang X, Yang Y, Li M (2016) Fine structural tuning of
diketopyrrolopyrrole-cored donor materials for small molecule-fullerene organic solar cells: a
theoretical study. Org Electron 32:134–144
30. Kovalenko A, Yumusak C, Heinrichová P et al (2017) Adamantane substitutions: a path to
high-performing, soluble, versatile and sustainable organic semiconducting materials. J Mater
Chem C 5(19):4716–4723
31. Grzybowski M, Glodkowska-Mrowka E, Hugues V, Brutkowski W, Blanchard-Desce M,
Gryko DT (2015) Polar diketopyrrolopyrrole-imidazolium salts as selective probes for staining
mitochondria in two-photon fluorescence microscopy. Chem Eur J 21(25):9101–9110
32. Qian G, Qi J, Davey JA, Wright JS, Wang ZY (2012) Family of diazapentalene chromophores
and narrow-band-gap polymers: synthesis, halochromism, halofluorism, and visible–near infra-
red photodetectivity. Chem Mater 24(12):2364–2372
33. Zhou N, Vegiraju S, Yu X et al (2015) Diketopyrrolopyrrole (DPP) functionalized
tetrathienothiophene (TTA) small molecules for organic thin film transistors and photovoltaic
cells. J Mater Chem C 3(34):8932–8941
34. Govindan V, Wu CG (2017) Facile synthesis of low band-gap DPP–EDOT containing small
molecules for solar cell applications. RSC Adv 7(46):28788–28796
Machine Learning Approach on Steel
Microstructure Classification
Haon Park and Abdullah Öztürk
Abstract The microstructure of a material is its inner morphological features. The

microstructure of steel can be diverse and complex depending on the composition,
heat treatment, and processing of the alloy, making it difficult to accurately predict
the material’s property and composition without physically analyzing the micro-
structure. Since the microstructure of steel can determine its physical and chemical
properties as well as its performance, cost, and efficiency, it is crucial to accurately
classify the microstructure. Although microstructure characterization is widespread
and well known, it is mostly conducted manually by human experts analyzing
pictures taken by either a scanning electron microscope or a light optical microscope.
This research aims to automate this processing using state-of-the-art Machine
Learning architectures and models to train and learn to differentiate, classify, and
interpret the microstructure pictures, employing a pixel-wise segmentation method
via U-NET architecture built upon FCNN, Fully Convolutional Neural Network.
The method employed several techniques ranging from data augmentation, Amazon
computing service, to semantic segmentation. The system achieved a maximum
classification accuracy of 98.689%, and predicted the mechanical property with 10%
error, providing a robust, accurate approach for the difficult task of microstructure
classification.
Keywords Steel microstructure · Machine learning · Steel phases
H. Park (*)
Oasis International School, Ankara, Turkey
A. Öztürk
Middle East Technical University, Ankara, Turkey
© Springer Nature Singapore Pte Ltd. 2021 13

J. M. Park, D. R. Whang (eds.), EKC 2019 Conference Proceedings,
https://doi.org/10.1007/978-981-15-8350-6_2
14 H. Park and A. Öztürk
1 Introduction
1.1 Steel Microstructure and Phase Changes
Steel is still one of the most important and extensively used alloy materials because
of its excellent mechanical properties while keeping costs low which gives a huge
variety of applications [1]. The principal elements in most steel, in addition to iron
and carbon, are boron, chromium, manganese, nickel, tungsten, and vanadium
[2]. The mechanical properties of steel are mainly determined by its microstructure
which are closely dependent on its chemical compositions.
Traditionally, the microstructures of steel are characterized by using standard
metallographic procedures based on chemical etching and optical microscopy and
they are compared with reference series [3]. Moreover, the steel’s microstructural
comparison with reference series is dependent on the expert’s subjective opinion.
The microstructure of the steel is usually controlled by heat treatment which
accompanies eutectoid transformation from austenite to pearlite. During the eutec-
toid phase transformation, FCC austenite is transformed into two different solid
phases of BCC ferrite and cementite (Fe3C) below 727 C. Here the two phases are
placed as alternative layers and it is named pearlite since its appearance is like a pearl
under the microscope as seen in Fig. 1. If the microstructure consists of more than
one phase, the properties of the steel strongly depend on the type and distribution of
the different phases in order to access the understanding between structure and
property relationship.
Fig. 1 Schematic representation of the formation of pearlite from austenite [4]

Machine Learning Approach on Steel Microstructure Classification 15
1.2 Machine Learning Approach
This motivation leads to the consideration of Machine Learning methods, recently

grabbing the attention of scientists due to their strong ability to learn high-level
features from raw input data. Machine learning is based on artificial neural networks
which mimic the neural connections and information processing understood to take
place human brains. The most well-known machine learning algorithm is the
convolutional neural network (CNN) for pattern recognition and image processing
[5]. While the use of CNN methods made great strides for segmenting and classify-
ing pathologies in biological and medical imaging [6], the methods are still new in
their application to materials and structures analysis.
In this research, Machine Learning technique was used to examine the structure-
property linkage of two-phase mixed steel sample. To distinguish the two different
phase area, Scanning Electron Microscopy (SEM) images were trained and classified
with U-NET (FCNN) architecture. U-NET was originally invented and first used in
biomedical image segmentation [7]. U-NET architecture, named after the ‘u’; shape
as seen in Fig. 2, can be separated into two parts. The first part is called down
sampling where convolution blocks are applied followed by max-pool down sam-
pling to encode the input image into feature representations at multiple different
levels. The second part of the network consists of up sampling and concatenation
followed by regular convolution operations [8]. The use of the U-NET architecture
allows working with very few training images while yielding precise segmentation.
Fig. 2 U-NET Convoluted Neural Network Architecture [8]

2 Experiment
2.1 Procedure
Steel samples of 2 cm diameter and 2 cm height were heat treated at 900 C for 1 h
and then cooled in a salt bath to form a mixture structure of pearlite and ferrite. The
samples were polished with sandpapers of #600, #1000, and #1200 successively,
and with diamond suspension to create a mirror surface. Chemical etching was
applied to selectively corrode microstructural features (grain boundaries, morpho-
logical features, pores, cracks, etc.) through putting a sample into a Nital solution
(2 ml HNO3 + 98 ml Ethanol) for 6 s. Microhardness was tested on the steel surface
with Vickers indenter and calculated by measuring the diagonal crack lengths.
Scanning Electron Microscope was operated to capture images of the steel micro-
structures. All the images were cropped to equal pixel size and converted it to JPG.
The images were separated into training data (used for training the model) and
testing data (used to test the effectiveness and accuracy of the model). The training
data images were manually color segmented into pearlite and ferrite. Data augmen-
tation was performed on the training images to generate 792 images from 18. AWS
EC2 p2.8large instance was set up and connected via terminal on a computer. The
EC2 GPU services were connected to an agent and the images were trained on a
U-NET model based on FCNN. The testing data images were tested on the new
model and the results were stored. The accuracy of the model was measured and the
properties of the microstructure were determined through a ratio test.
2.2 Experimental Observations and Data
Physical The surface of the prepared steel sample was carefully grinded and
polished with a polisher. Polycrystalline diamond suspensions of 6- and 1-μm
particle size were used to make a mirror surface.
Figure 3 shows the microscope image of ferrite and pearlite phases which was taken
by SEM. While the dark area is the ferrite phase, the alternating layer areas with
bright strips are pearlite phase. The pearlite phases are well developed during the
cooling history and grain boundaries are observed clearly because of the proper
chemical etching.
Figure 4 shows the optical microscope image and the indentation after the Vickers
hardness test. By measuring the edge lengths of the diamond shape indentation, the
microhardness was calculated with the following equation,

HV ¼ 1:854 F=D2 ð1Þ
Fig. 3 Scanning electron microscope image of ferrite and pearlite phases
Fig. 4 Optical microscope image of ferrite and pearlite phases with the indention
Fig. 5 Flow chart process of the training and testing of the model
where HV is the Hardness Value, F is the force (0.1 kgf), and D is the area of
indentation. The calculated microhardness was 122.6 2.4 MPa.
Hafiz [9] investigated the effect of matrix structure on the mechanical properties
in iron and suggested that hardness and pearlite volume fraction has the following
relationship,
HV ¼ 0:0128P2 þ 1:865P þ 127:78 ð2Þ
where P is the volume fraction of pearlite. Therefore, the mechanical hardness of

steel could be estimated if the pearlite volume fraction is provided.
Computational The process for the training and testing of the images begins with
the importation of the images at the left, and proceeds with DTL (data augmenta-
tion), to training on UNET, and ends with the inference of testing images as
represented in Fig. 5. One of the challenges faced in using AWS Ec2 GPU, was
memory as the processes were resource heavy, and the root volume was increased to
1 TB. The operating system of the AWS computers is Linux and the system was
managed through a single terminal.
Table 1 Results of U-NET architecture

Input image size Number of Accuracy Loss
Type (pixel) images Epochs (%) (%)
Large 256 256 792 12 98.689 0.036
training
Small 128 128 792 5 98.095 0.0526
training
Fig. 6 The accuracy graph with epochs of large training images
Fig. 7 The loss graph with epochs of large training images
3 Results
3.1 Training Accuracy
Table 1 summarizes the comparison between large and small images analyses. The
accuracy of the large training images, which were resized as 256 256 pixel and
with 12 epochs, is 98,689%, while that of the small training images, which were
resized as 128 128 pixel and with 5 epochs, is 98.095%. It is observed that both
results convey noticeably high accuracy with the use of U-NET architecture. Figure 6
shows the accuracy graph with large training images, and Fig. 7 shows the loss graph
with large training images according to epoch times (generations). Figure 8 shows
the accuracy graph with small training images. Figure 9 shows the loss graph with
small training images. The rapid progress the algorithm makes and learns each
generation can be observed. Small training took about 25 min while large training
took about 40 min.
Fig. 8 The accuracy graph with epochs of small training images
Fig. 9 The loss graph with epochs of small training images
Fig. 10 Examples of successful cases in SEM segmentation using the U-NET architecture
3.2 Phases Differentiation
All the machine learning training and testing were carried out through Amazon
Cloud Computing Service (AWS). Figure 10 shows successful examples of SEM
segmentation using FCNN networks. It can be said that most of the objects in each
microstructure image are classified correctly. From the data in Table 1 and the
accuracy graphs, the Machine Learning algorithm equipped with U-NET architec-
ture model based on the FCNN successfully distinguished the pearlite phases from
the ferrite phases.
3.3 Analysis
Machine Learning techniques were capable of separating ferrite and pearlite regions
into different colors. Collecting only the pearlite region would be considered as the
fraction of pearlite phase. Three SEM images were selected as seen in Fig. 11. After
applying the phase classification algorithm, the amounts of pearlite phase were
calculated as 14% for the first row SEM image, 23% for the second row, and 9%
for the third row. Those pearlite phase fractions were inserted to Eq. (2), and then the
estimated hardness was able to be acquired as 132.9, 138.8, and 130.3, respectively.
Table 2 summarizes the difference between measured and estimated hardness values.
Fig. 11 SEM images for pearlite phase segmentation
Table 2 Comparison of examined Vickers hardness and estimated hardness values

Sample no. Measured hardness (HV) Estimated hardness (HV) Difference (%)
a 122.6 2.4 132.9 8.4
b 136.8 11.6
c 130.3 6.3
Average 133.3 3.5 8.7 2.5
The average difference between the measured and estimated hardness values is
8.7%, so it can be said that estimating the mechanical properties with machine
learning image segmentation is a practical and feasible technique.
Some of the ways this experiment could be improved or increased in accuracy is
by having more standardized images. Some of the images were taken at slightly
different magnifications, which may result in larger or smaller pearlite and ferrite
ratio compared to the actual. Another straightforward method to increase the accu-
racy is to have more training data. Training size of perhaps 50 or 100 images will
significantly improve the accuracy, but it will also increase the time it takes to create
and train the ground truth and require more computing power. One of the problems
that was faced during the experiment was in the manual colorization of the ground
truth. As labeling each 18 training images of every pearlite and ferrite can be time-
consuming and tedious, mistakes were made such as labeling pearlite and ferrite
incorrectly or going out of the boundaries of the phases. The flaws were directly used
for training, and some of the mistakes may have appeared in the inferring process,
thus resulting in a slight decrease in accuracy.
4 Conclusion
In conclusion, this project demonstrates the feasibility of an effective steel micro-

structural classification using Machine Learning method to distinguish the pearlite
phases from the ferrite phases. A pixel-wise microstructural segmentation using
U-NET architecture proved to be competent in its performance and demonstrated
its capabilities. The additional computing techniques of data augmentation and cloud
computing demonstrated its power. The algorithm was able to differentiate the
pearlite phases from ferrite phase with an accuracy of above 98%. On the prediction
of mechanical property, the algorithm predicted a hardness of 133.3 3.5 HV, while
the actual hardness of the real sample was 122.6 2.4 HV. The hypothesis of
machine learning methods accurately and efficiently analyzing and differentiating
the phase types and determine the percent ratio of pearlite and its properties were
proven to be true. In the end, it can be concluded that Machine Learning is an
effective and practical technique to classify materials’ microstructure and to predict
the structure-property linkage.
In order to take this research further, training with images of different types of
microstructure with additional phases such as martensite and bainite will test the
multi-differentiation ability of the algorithm. Also, not only differentiating the
phases but the way it was treated such as tempered martensite vs not tempered
martensite will be a fruitful opportunity to test the capability of machine learning
applications.
Another random document with
no related content on Scribd:
for the purpose of guarantying the neutrality of the Isthmus canal or
determining the conditions of its use.
CHILI AND PERU.
The entire question is complicated by the war between Chili and

Peru, the latter owning immense guano deposits in which American
citizens have become financially interested. These sought the friendly
intervention of our government to prevent Chili, the conquering
Republic, from appropriating these deposits as part of her war
indemnity. The Landreau, an original French claim, is said to
represent $125,000,000, and the holders were prior to and during
the war pressing it upon Calderon, the Peruvian President, for
settlement; the Cochet claim, another of the same class, represented
$1,000,000,000. Doubtless these claims are speculative and largely
fraudulent, and shrewd agents are interested in their collection and
preservation. A still more preposterous and speculative movement
was fathered by one Shipherd, who opened a correspondence with
Minister Hurlburt, and with other parties for the establishment of
the Credit Industriel, which was to pay the $20,000,000 money
indemnity demanded of Peru by Chili, and to be reimbursed by the
Peruvian nitrates and guano deposits.
THE SCANDAL.
All of these things surround the question with scandals which

probably fail to truthfully reach any prominent officer of our
government, but which have nevertheless attracted the attention of
Congress to such an extent that the following action has been already
taken:
On February 24th Mr. Bayard offered in the Senate a resolution
reciting that whereas publication has been widely made by the public
press of certain alleged public commercial contracts between certain
companies and copartnerships of individuals relative to the exports
of guano and nitrates from Peru, in which the mediation by the
Government of the United States between the Governments of Peru,
Bolivia and Chili is declared to be a condition for the effectuation and
continuance of the said contracts; therefore be it resolved, that the
Committee on Foreign Relations be instructed to inquire whether
any promise or stipulation by which the intervention by the United
States in the controversies existing between Chili and Peru or Chili
and Bolivia has been expressly or impliedly given by any person or
persons officially connected with the Government of the United
States, or whether the influence of the Government of the United
States has been in any way exerted, promised or intimated in
connection with, or in relation to the said contracts by any one
officially connected with the Government of the United States, and
whether any one officially connected with the Government of the
United States is interested, directly or indirectly, with any such
alleged contracts in which the mediation as aforesaid of the United
States is recited to be a condition, and that the said committee have
power to send for persons and paper and make report of their
proceedings in the premises to the Senate at the earliest possible day.
Mr. Edmunds said he had drafted a resolution covering all the
branches of “that most unfortunate affair” to which reference was
now made, and in view of the ill policy of any action which would
commit the Senate to inquiries about declaring foreign matters in
advance of a careful investigation by a committee, he now made the
suggestion that he would have made as to his own resolution, if he
had offered it, namely, that the subject be referred to the Committee
on Foreign Relations. He intimated that the proposition prepared by
himself would be considered by the committee as a suggestion
bearing upon the pending resolution.
Mr. Bayard acquiesced in the reference with the remark that
anything that tended to bring the matter more fully before the
country was satisfactory to him.
The resolution accordingly went to the Committee on Foreign
Relations.
In the House Mr. Kasson, of Iowa, offered a resolution reciting
that whereas, it is alleged, in connection with the Chili Peruvian
correspondence recently and officially published on the call of the
two Houses of Congress, that one or more Ministers Plenipotentiary
of the United States were either personally interested or improperly
connected with a business transaction in which the intervention of
this Government was requested or expected and whereas, it is
alleged that certain papers in relation to the same subject have been
improperly lost or removed from the files of the State Department,
that therefore the Committee on Foreign Affairs be instructed to
inquire into said allegations and ascertain the facts relating thereto,
and report the same with such recommendations as they may deem
proper, and they shall have power to send for persons and papers.
The resolution was adopted.
THE CLAIMS.
The inner history of what is known as the Peruvian Company reads

more like a tale from the Arabian Nights than a plain statement of
facts. The following is gleaned from the prospectus of the company,
of which only a limited number of copies was printed. According to a
note on the cover of these “they are for the strictly private use of the
gentlemen into whose hands they are immediately placed.”
The prospects of the corporation are based entirely upon the
claims of Cochet and Landreau, two French chemists, residents of
Peru. In the year 1833, the Peruvian government, by published
decree, promised to every discoverer of valuable deposits upon the
public domain a premium of one-third of the discovery as an
incentive to the development of great natural resources vaguely
known to exist. In the beginning of 1830, Alexandre Cochet, who was
a man of superior information, occupied himself in the laborious
work of manufacturing nitrate of soda in a small oficina in Peru, and
being possessed with quick intelligence and a careful observer he
soon came to understand that the valuable properties contained in
the guano—an article only known to native cultivators of the soil—
would be eminently useful as a restorative to the exhausted lands of
the old continent. With this idea he made himself completely master
of the mode of application adopted by the Indians and small farmers
in the province where he resided, and after a careful investigation of
the chemical effects produced on the land by the proper application
of the regenerating agent, he proceeded in the year 1840 to the
capital (Lima) in order to interest some of his friends in this new
enterprise. Not without great persuasion and much hesitation, he
induced his countryman, Mr. Achilles Allier, to take up the
hazardous speculation and join with him in his discovery. He
succeeded, however, and toward the end of the same year the firm of
Quiroz & Allier obtained a concession for six years from the
government of Peru for the exportation of all the guano existing in
the afterwards famous islands of Chinchi for the sum of sixty
thousand dollars. In consequence of the refusal of that firm to admit
Cochet, the discoverer, to a participation in the profits growing out of
this contract a series of lawsuits resulted and a paper war ensued in
which Cochet was baffled. In vain he called the attention of the
government to the nature and value of this discovery; he was told
that he was a “visionary.” In vain he demonstrated that the nation
possessed hundreds of millions of dollars in the grand deposits: this
only confirmed the opinion of the Council of State that he was a
madman. In vain he attempted to prove that one cargo of guano was
equal to fourteen cargoes of grain; the Council of State coolly told
him that guano was an article known to the Spaniards, and of no
value: that Commissioner Humbolt had referred to it, and that they
could not accept his theory respecting its superior properties, its
value and its probable use in foreign agriculture at a period when no
new discovery could be made relative to an article so long and of so
evident small value.
At length a new light began to dawn on the lethargic
understanding of the officials in power, and as rumors continued to
arrive from Europe confirming the asseverations of Cochet, and
announcing the sale of guano at from $90 to $120 per ton, a degree
of haste was suddenly evinced to secure once more to the public
treasury this new and unexpected source of wealth; and at one blow
the contract with Quiroz & Allier, which had previously been
extended, was reduced to one year. Their claims were cancelled by
the payment of ten thousand tons of guano which Congress decreed
them. There still remained to be settled the just and acknowledged
indebtedness for benefits conferred on the country by Cochet,
benefits which could not be denied as wealth and prosperity rolled in
on the government and on the people. But few, if any, troubled
themselves about the question to whom they were indebted for so
much good fortune, nor had time to pay particular attention to
Cochet’s claims. Finally, however, Congress was led to declare Cochet
the true discoverer of the value, uses and application of guano for
European agriculture, and a grant of 5,000 tons was made in his
favor September 30th, 1849, but was never paid him. After passing a
period of years in hopeless expectancy—from 1840 to 1851—his
impoverished circumstances made it necessary for him to endeavor
to procure, through the influence of his own government, that
measure of support in favor of his claims which would insure him a
competency in his old age.
He resolved upon returning to France, after having spent the best
part of his life in the service of a country whose cities had risen from
desolation to splendor under the sole magic of his touch—a touch
that had in it for Peru all the fabled power of the long-sought
“philosopher’s stone.” In 1853 Cochet returned to France, but he was
then already exhausted by enthusiastic explorations in a deadly
climate and never rallied. He lingered in poverty for eleven painful
years and died in Paris in an almshouse in 1864, entitled to an estate
worth $500,000,000—the richest man in the history of the world—
and was buried by the city in the Potters’ Field; his wonderful history
well illustrating that truth is stranger than fiction.
THE LANDREAU CLAIM.
About the year 1844 Jean Theophile Landreau, also a French

citizen, in partnership with his brother, John C. Landreau, a
naturalized American citizen, upon the faith of the promised
premium of 33⅓ per cent. entered upon a series of extended
systematic and scientific explorations with a view to ascertaining
whether the deposits of guano particularly pointed out by Cochet
constituted the entire guano deposit of Peru, and with money
furnished by his partner, John, Theophile prosecuted his searches
with remarkable energy and with great success for twelve years,
identifying beds not before known to the value of not less than
$400,000,000. Well aware, however, of the manner in which his
fellow-countryman had been neglected by an unprincipled people, he
had the discretion to keep his own counsel and to extort from the
Peruvian authorities an absolute agreement in advance before he
revealed his treasure. This agreement was, indeed, for a royalty of
less than one sixth the amount promised, but the most solemn
assurances were given that the lessened amount would be promptly
and cheerfully paid, its total would give the brothers each a large
fortune, and payments were to begin at once. The solemn agreement
having been concluded and duly certified, the precious deposits
having been pointed out and taken possession of by the profligate
government, the brothers were at first put off with plausible pretexts
of delay, and when these grew monotonous the government calmly
issued a decree recognizing the discoveries, accepting the treasure,
and annulling the contract, with a suggestion that a more suitable
agreement might be arranged in the future.
It will be seen that these two men, Cochet and Landreau, have
been acknowledged by the Peruvian government as claimants. No
attempt has ever been made to deny the indebtedness. The very
decree of repudiation reaffirmed the obligation, and all the courts
refused to pronounce against the plaintiffs. Both of these claims
came into the possession of Mr. Peter W. Hevenor, of Philadelphia.
Cochet left one son whom Mr. Hevenor found in poverty in Lima and
advanced money to push his father’s claim of $500,000,000 against
the government. After $50,000 were spent young Cochet’s backer
was surprised to learn of the Laudreaus and their claim. Not wishing
to antagonize them, he advanced them money, and in a short time
owned nearly all the fifteen interests in the Landreau claim of
$125,000,000.
To the Peruvian Company Mr. Hevenor has transferred his titles,
and on the basis of these that corporation maintains that eventually
it will realize not less than $1,200,000,000, computed as follows:
The amount of guano already taken out of the Cochet Islands—
including the Chinchas—will be shown by the Peruvian Custom
House records, and will aggregate, it is said, not far from
$1,200,000,000 worth. The discoverer’s one-third of this would be
$400,000,000, and interest upon this amount at six per cent. say for
an equalized average of twenty years—would be $480,000,000
more. The amount remaining in these islands is not positively
known, and is probably not more than $200,000,000 worth; and in
the Landreau deposits say $300,000,000 more. The Chilean
plenipotentiary recently announced that his government are about
opening very rich deposits on the Lobos Islands—which are included
in this group. It is probably within safe limits, says the Peruvian
Company’s prospectus, to say that, including interest to accrue
before the claim can be fully liquidated, its owners will realize no less
than $1,200,000,000.
THE COUNTRIES INVOLVED.
In South America there are ten independent governments; and the

three Guianas which are dependencies on European powers. Of the
independent governments Brazil is an empire, having an area of
3,609,160 square miles and 11,058,000 inhabitants. The other nine
are republics. In giving area and population we use the most
complete statistics at our command, but they are not strictly reliable,
nor as late as we could have wished. The area and the population of
the republics are: Venezuela, 426,712 square miles and 2,200,000
inhabitants; United States of Colombia, 475,000 square miles and
2,900,000 inhabitants; Peru, 580,000 square miles and 2,500,000
inhabitants; Ecuador, 208,000 square miles and 1,300,000
inhabitants; Bolivia, 842,730 square miles and 1,987,352
inhabitants; Chili, 200,000 square miles and 2,084,960 inhabitants;
Argentine Republic, 1,323,560 square miles and 1,887,000
inhabitants; Paraguay, 73,000 square miles and 1,337,439
inhabitants; Uruguay, 66,716 square miles and 240,000 inhabitants,
or a total in the nine republics of 3,789,220 square miles and
16,436,751 inhabitants. The aggregate area of the nine republics
exceeds that of Brazil 180,060 square miles, and the total population
exceeds that of Brazil 5,069,552. Brazil, being an empire, is not
comprehended in the Blaine proposal—she rather stands as a strong
barrier against it. Mexico and Guatemala are included, but are on
this continent, and their character and resources better understood
by our people. In the South American countries generally the
Spanish language is spoken. The educated classes are of nearly pure
Spanish extraction. The laboring classes are of mixed Spanish and
aboriginal blood, or of pure aboriginal ancestry. The characteristics
of the Continent are emphatically Spanish. The area and population
we have already given. The territory is nearly equally divided
between the republics and the empire, the former having a greater
area of only 180,060 square miles; but the nine republics have an
aggregate population of 5,059,522 more than Brazil. The United
States has an area of 3,634,797 square miles, including Alaska; but
excluding Alaska, it has 3,056,797 square miles. The area of Brazil is
greater than that of the United States, excluding Alaska, by 552,363
square miles, and the aggregate area of the nine republics is greater
by 732,423 square miles. This comparison of the area of the nine
republics and of Brazil with that of this nation gives a definite idea of
their magnitude. Geographically, these republics occupy the
northern, western and southern portions of South America, and are
contiguous. The aggregate exports and imports of South America,
according to the last available data, were $529,300,000; those of
Brazil, $168,930,000; of the nine republics, $360,360,000.
These resolutions will bring out voluminous correspondence, but
we have given the reader sufficient to reach a fair understanding of
the subject. Whatever of scandal may be connected with it, like the
Star Route cases, it should await official investigation and
condemnation. Last of all should history condemn any one in
advance of official inquiry. None of the governments invited to the
Congress had accepted formally, and in view of obstacles thrown in
the way by the present administration, it is not probable they will.
Accepting the proposition of Mr. Blaine as stated in his letter to
President Arthur, as conveying his true desire and meaning, it is due
to the truth to say that it comprehends more than the Monroe
doctrine, the text of which is given in President Monroe’s own words
in this volume. While he contended against foreign intervention with
the Republics on this Hemisphere, he never asserted the right of our
government to participate in or seek the control either of the
internal, commercial or foreign policy of any of the Republics of
America, by arbitration or otherwise. So that Mr. Blaine is the author
of an advance upon the Monroe doctrine, and what seems at this
time a radical advance. What it may be when the United States seeks
to “spread itself” by an aggressive foreign policy, and by
aggrandizement of new avenues of trade, possibly new acquisitions
of territory, is another question. It is a policy brilliant beyond any
examples in our history, and a new departure from the teachings of
Washington, who advised absolute non-intervention in foreign
affairs. The new doctrine might thrive and acquire great popularity
under an administration friendly to it; but President Arthur has
already intimated his hostility, and it is now beyond enforcement
during his administration. The views of Congress also seem to be
adverse as far as the debates have gone into the question, though it
has some warm friends who may revive it under more favorable
auspices.
The Star Route Scandal.
Directly after Mr. James assumed the position of Postmaster-

General in the Cabinet of President Garfield, he discovered a great
amount of extravagance and probably fraud in the conduct of the
mail service known as the Star Routes, authorized by act of Congress
to further extend the mail facilities and promote the more rapid
carriage of the mails. These routes proved to be very popular in the
West and Southwest, and the growing demand for mail facilities in
these sections would even in a legitimate way, if not closely watched,
lead to unusual cost and extravagance; but it is alleged that a ring
was formed headed by General Brady, one of the Assistant
Postmaster-Generals under General Key, by which routes were
established with the sole view of defrauding the Government—that
false bonds were given and enormous and fraudulent sums paid for
little or no service. This scandal was at its height at the time of the
assassination of President Garfield, at which time Postmaster-
General James, Attorney-General MacVeagh and other officials were
rapidly preparing for the prosecution of all charged with the fraud.
Upon the succession of President Arthur he openly insisted upon the
fullest prosecution, and declined to receive the resignation of Mr.
MacVeagh from the Cabinet because of a stated fear that the
prosecution would suffer by his withdrawal. Mr. MacVeagh, however,
withdrew from the Cabinet, believing that the new President should
not by any circumstance be prevented from the official association of
friends of his own selection; and at this writing Attorney-General
Brewster is pushing the prosecutions.
On the 24th of March, 1882, the Grand Jury sitting at Washington
presented indictments for conspiracy in connection with the Star
Route mail service against the following named persons: Thomas J.
Brady, J. W. Dorsey, Henry M. Vail, John W. Dorsey, John R. Miner,
John M. Peck, M. C. Rerdell, J. L. Sanderson, Wm. H. Turner. Also
against Alvin O. Buck, Wm. S. Barringer and Albert E. Boone, and
against Kate M. Armstrong for perjury. The indictment against
Brady, Dorsey and others, which is very voluminous, recites the
existence, on March 10, 1879, of the Post Office Department,
Postmaster-General and three assistants, and a Sixth Auditor’s office
and Contract office and division.
“To the latter was subject,” the indictment continues, “the
arrangement of the mail service of the United States and the letting
out of the same on contract.” It then describes the duties of the
inspecting division. On March 10, 1879, the grand jurors represent,
Thomas J. Brady was the lawful Second Assistant Postmaster-
General engaged in the performance of the duties of that office.
William H. Turner was a clerk in the Second Assistant Postmaster-
General’s office, and attended to the business of the contract division
relating to the mail service over several post routes in California,
Colorado, Oregon, Nebraska, and the Territories. On the 16th of
March, 1879, the indictment represents Thomas J. Brady as having
made eight contracts with John W. Dorsey to carry the mails from
July 1, 1878, to June 30, 1882, from Vermillion, in Dakota Territory,
to Sioux Falls and back, on a fourteen hour time schedule, for $398
each year; on route from White River to Rawlins, Colorado, once a
week of 108 hours’ time, for $1,700 a year; on route from Garland,
Colorado, to Parrott City, once a week, on a schedule of 168 hours’
time, for $2,745; on route from Ouray, Colorado, to Los Pinos, once a
week, in 12 hours’ time, for $348; on route from Silverton, Colorado,
to Parrott City, twice a week, on 36 hours’ time, for $1,488; on route
from Mineral Park, in Arizona Territory, to Pioche and back, once a
week, in 84 hours’ time, $2,982; on route from Tres Almos to Clifton
and back, once a week, of 84 hours’ time, for $1,568.
It further sets forth that the Second Assistant Postmaster-General
entered into five contracts with John R. Miner on June 13, 1878, on
routes in Dakota Territory and Colorado, and on March 15, 1879,
with John M. Peck, over eight post routes. In the space of sixty days
after the making of these contracts they were in full force. On March
10, 1879, John W. Dorsey, John R. Miner, and John M. Peck, with
Stephen W. Dorsey and Henry M. Vaile, M. C. Rerdell and J. L.
Sanderson, mutually interested in these contracts and money, to be
paid by the United States to the three parties above named, did
unlawfully and maliciously combine and conspire to fraudulently
write, sign, and cause to be written and signed, a large number of
fraudulent letters and communications and false and fraudulent
petitions and applications to the Postmaster-General for additional
service and increase of expenditure on the routes, which were
purported to be signed by the people and inhabitants in the
neighborhood of the routes, which were filed with the papers in the
office of the Second Assistant Postmaster-General. Further that these
parties swore falsely in describing the number of men and animals
required to perform the mail service over the routes and States as
greater than was necessary.
These false oaths were placed on file in the Second Assistant
Postmaster-General’s office; and by means of Wm. H. Turner falsely
making and writing and endorsing these papers, with brief and
untrue statements as to their contents, and by Turner preparing
fraudulent written orders for allowances to be made to these
contractors and signed by Thomas J. Brady fraudulently, and for the
benefit and gain of all the parties named in this bill, the service was
increased over these routes; and that Brady knew it was not lawfully
needed and required. That he caused the order for increasing to be
certified to and filed in the Sixth Auditor’s office for fraudulent
additional compensation. That Mr. Brady gave orders to extend the
service so as to include other and different stations than those
mentioned in the contract, that he and others might have the
benefits and profits of it: that he refused to impose fines on these
contracts for failures and delinquencies, but allowed them additional
pay for the service over these routes. During the continuance of these
contracts the parties acquired unto themselves several large and
excessive sums of money, the property of the United States,
fraudulently and unlawfully ordered to be paid them by Mr. Brady.
These are certainly formidable indictments. Others are pending
against persons in Philadelphia and other cities, who are charged
with complicity in these Star Route frauds, in giving straw bonds, &c.
The Star Route service still continues, the Post Office Department
under the law having sent out several thousand notifications this
year to contractors, informing them of the official acceptance of their
proposals, and some of these contractors are the same named above
as under indictment. This well exemplifies the maxim of the law
relative to innocence until guilt be shown.
The Coming States.
Bills are pending before Congress for the admission of Dakota,

Wyoming, New Mexico and Washington Territories. The Bill for the
admission of Dakota divides the old Territory, and provides that the
new State shall consist of the territory included within the following
boundaries: Commencing at a point on the west line of the State of
Minnesota where the forty-sixth degree of north latitude intersects
the same; thence south along the west boundary lines of the States of
Minnesota and Iowa to the point of intersection with the northern
boundary line of the State of Nebraska; thence westwardly along the
northern boundary line of the State of Nebraska to the twenty-
seventh meridian of longitude west from Washington; thence north
along the said twenty-seventh degree of longitude to the forty-sixth
degree of north latitude; to the place of beginning. The bill provides
for a convention of one hundred and twenty delegates, to be chosen
by the legal voters, who shall adopt the United States Constitution
and then proceed to form a State Constitution and government. Until
the next census the State shall be entitled to one representative, who,
with the Governor and other officials, shall be elected upon a day
named by the Constitutional Convention. The report sets apart lands
for school purposes, and gives the State five per centum of the
proceeds of all sales of public lands within its limits subsequent to its
admission as a State, excluding all mineral lands from being thus set
apart for school purposes. It provides that portion of the Territory
not included in the proposed new State shall continue as a Territory
under the name of the Territory of North Dakota.
The proposition to divide comes from Senator McMillan, and if
Congress sustains the division, the portion admitted would contain
100,000 inhabitants, the entire estimated population being 175,000
—a number in excess of twenty of the present States when admitted,
exclusive of the original thirteen; while the division, which shows
100,000 inhabitants, is still in excess of sixteen States when
admitted.
Nevada, with less than 65,000 population, was admitted before
the close Presidential election of 1876, and it may be said that her
majority of 1,075, in a total poll of 19,691 votes, decided the
Presidential result in favor of Hayes, and these votes counteracted
the plurality of nearly 300,000 received by Mr. Tilden elsewhere.
This fact well illustrates the power of States, as States, and however
small, in controlling the affairs of the country. It also accounts for the
jealousy with which closely balanced political parties watch the
incoming States.
Population is but one of the considerations entering into the
question of admitting territories, State sovereignty does not rest
upon population, as in the make up of the U. S. Senate neither
population, size, nor resources are taken into account. Rhode Island,
the smallest of all the States, and New York, the great Empire State,
with over 5,000,000 of inhabitants, stand upon an equality in the
conservative branch of the Government. It is in the House of
Representatives that the population is considered. Such is the
jealousy of the larger States of their representation in the U. S.
Senate, that few new ones would be admitted without long and
continuous knocking if it were not for partisan interests, and yet
where a fair number of people demand State Government there is no
just cause for denial. Yet all questions of population, natural division,
area and resources should be given their proper weight.
The area of the combined territories—Utah, Washington, New
Mexico, Dakota, Arizona, Montana, Idaho, Wyoming and Indian is
about 900,000 square miles. We exclude Alaska, which has not been
surveyed.
Indian Territory and Utah are for some years to come excluded
from admission—the one being reserved to the occupancy of the
Indians, while the other is by her peculiar institution of polygamy,
generally thrown out of all calculation. And yet it may be found that
polygamy can best be made amenable to the laws by the compulsory
admission of Utah as a State—an idea entertained by not a few who
have given consideration to the question. Alaska may also be counted
out for many years to come. There are but 30,000 inhabitants, few of
these permanent, and Congress is now considering a petition for the
establishment of a territorial government there.
Next to Dakota, New Mexico justly claims admission. The lands
comprised within its original area were acquired from Mexico, at the
conclusion of the war with that country, by the treaty of Guadalupe
Hidalgo in 1848, and by act of September 9, 1850, a Territorial
government was organized. By treaty of December 30, 1853, the
region south of the Gila river—the Gadsden purchase, so called—was
ceded by Mexico, and by act of August 4, 1854, added to the
Territory, which at that time included within its limits the present
Territory of Arizona. Its prayer for admission was brought to the
serious attention of Congress in 1874. The bill was presented in an
able speech by Mr. Elkins, then delegate from the Territory, and had
the warm support of many members. A bill to admit was also
introduced in the Senate, and passed that body February 25, 1875, by
a vote of thirty-two to eleven, two of the present members of that
body, Messrs. Ingalls and Windom, being among its supporters. The
matter of admission came up for final action in the House at the
same session, just prior to adjournment, and a motion to suspend
the rules, in order to put it upon its final passage, was lost by a vote
of one hundred and fifty-four to eighty-seven, and the earnest efforts
to secure the admission of New Mexico were thus defeated. A bill for
its admission is now again before Congress, and it is a matter of
interest to note the representations as to the condition of the
Territory then made, and the facts as they now exist. It has,
according to the census of 1880, a population of 119,565. It had in
1870 a population of 91,874. It was claimed by the more moderate
advocates of the bill that its population then numbered 135,000
(15,435 more than at present), while others placed it as high as
145,000. Of this population, 45,000 were said to be of American and
European descent. It was stated by Senator Hoar, one of the
opponents of the bill, that, out of an illiterate population of 52,220,
by far the larger part were native inhabitants of Mexican or Spanish
origin, who could not speak the English language. This statement
seems to be in large degree confirmed by the census of 1880, which
shows a total native white population of 108,721, of whom, as nearly
as can be ascertained, upward of 80 per cent. are not only illiterates
of Mexican and Spanish extraction, but as in 1870, speaking a foreign
language. The vote for Mr. Elkins, Territorial Delegate in 1875, was
reported as being about 17,000. The total vote in 1878 was 18,806,
and in 1880, 20,397, showing a comparatively insignificant increase
from 1875 to 1880.
The Territory of Washington was constituted out of Oregon, and
organized as a Territory by act of March 2, 1853. Its population by
the census of 1880 was 75,116, an increase from 23,955 in 1870. Of
this total, 59,313 are of native and 15,803 of foreign nativity. Its total
white population in the census year was 67,119; Chinese, 3,186;
Indian, 4,105; colored, 326, and its total present population is
probably not far from 95,000. Its yield of precious metals in 1880,
and for the entire period since its development, while showing
resources full of promise, has been much less than that of any other
of the organized Territories. Its total vote for Territorial Delegate in
1880, while exceeding that of the Territories of Arizona, Idaho, and
Wyoming, was but 15,823.
The Territory of Arizona, organized out of a portion of New
Mexico, and provided with a territorial government in 1863, contains
about 5,000,000 acres less than the Territory of New Mexico, or an
acreage exceeded by that of only five States and Territories. Its total
population in 1870 was 9,658, and in 1880, 40,440, 35,160 of whom
were whites. Of its total population in the census year, 24,391 were of
native and 16,049 of foreign birth, the number of Indians, Chinese,
and colored being 5,000.
Idaho was originally a part of Oregon, from which it was separated
and provided with a territorial government by the act of March 3,
1863. It embraces in its area a little more than 55,000,000 acres, and
had in 1880 a total population of 32,610, being an increase from
14,999 in 1870. Of this population, 22,636 are of native and 9,974 of
foreign birth; 29,013 of the total inhabitants are white, 3,379 Chinese
and 218 Indians and colored.
The Territory of Montana, organized by act of May 26, 1864,
contains an acreage larger than that of any other Territory save
Dakota. While it seems to be inferior in cereal producing capacity, in
its area of valuable grazing lands it equals, if it does not excel, Idaho.
The chief prosperity of the Territory, and that which promises for it a
future of growing importance, lies in its extraordinary mineral
wealth, the productions of its mines in the year 1880 having been
nearly twice that of any other Territory, with a corresponding excess
in its total production, which had reached, on June 30, 1880, the
enormous total of over $53,000,000. Its mining industries represent
in the aggregate very large invested capital, and the increasing
products, with the development of new mines, are attracting
constant additions to its population, which in 1880 showed an
increase, as compared with 1870, of over 90 per cent. For particulars
see census tables in tabulated history.
Wyoming was constituted out of the Territory of Dakota, and
provided with territorial government July 25, 1868. Lying between
Colorado and Montana, and adjoining Dakota and Nebraska on the
east, it partakes of the natural characteristics of these States and
Territories, having a fair portion of land suitable for cultivation, a
large area suitable for grazing purposes, and a wealth in mineral
resources whose development, although of recent beginning, has
already resulted in an encouraging yield in precious metals. It is the
fifth in area.
Henry Randall Waite, in an able article in the March number of
the International Review (1882,) closes with these interesting
paragraphs:
“It will be thus seen that eleven States organized from Territories,
when authorized to form State governments, and the same number
when admitted to the Union, had free populations of less than
60,000, and that of the slave States included in this number, seven
in all, not one had the required number of free inhabitants, either
when authorized to take the first steps toward admission or when
finally admitted; and that both of these steps were taken by two of
the latter States with a total population, free and slave, below the
required number. Why so many States have been authorized to form
State governments, and have been subsequently admitted to the
Union with populations so far below the requirements of the
ordinance of 1787, and the accepted rules for subsequent action may
be briefly explained as follows: 1st, by the ground for the use of a
wide discretion afforded in the provisions of the ordinance of 1787,
for the admission of States, when deemed expedient, before their
population should equal the required number; and 2d. by the equally
wide discretion given by the Constitution in the words, ‘New States
may be admitted by Congress into this Union,’ the only provision of
the Constitution bearing specifically upon this subject. Efforts have
been made at various times to secure the strict enforcement of the
original rules, with the modification resulting from the increase in
the population of the Union, which provided that the number of free
inhabitants in a Territory seeking admission should equal the
number established as the basis of representation in the
apportionment of Representatives in Congress, as determined by the
preceding census. How little success the efforts made in this
direction have met, may be seen by a comparison of the number of
inhabitants forming the basis of representation, as established by the
different censuses, and the free population of the Territories
admitted at corresponding periods.
“At this late date, it is hardly to be expected that rules so long
disregarded will be made applicable to the admission of the States to
be organized from the existing Territories. There is, nevertheless, a
growing disposition on the part of Congress to look with disfavor
upon the formation of States whose population, and the development
of whose resources, render the expediency of their admission
questionable; and an increasing doubt as to the propriety of so
dividing the existing Territories as to multiply to an unnecessary
extent the number of States, with the attendant increase in the
number of Representatives in the National Legislature.
“To recapitulate the facts as to the present condition of the
Territories with reference to their admission as States, it may be said
that only Dakota, Utah, New Mexico and Washington are in
possession of the necessary population according to the rule
requiring 60,000; that only the three first named conform to the rule
demanding a population equal to the present basis of representation;
that only Dakota, Utah and Washington give evidence of that
intelligence on the part of their inhabitants which is essential to the
proper exercise, under favorable conditions, of the extended rights of
citizenship, and of that progress in the development of their
resources which makes self-government essential, safe, or in any way
desirable; and that only Dakota can be said, unquestionably, to
possess all of the requirements which, by the dictates of a sound
policy, should be demanded of a Territory at this time seeking
admission to the Union.
“Whatever the response to the Territorial messengers now waiting
at the doors of Congress, a few years, at most, will bring an answer to
their prayers. The stars of a dozen proud and prosperous States will
soon be added to those already blazoned upon the blue field of the
Union, and the term Territory, save as applied to the frozen regions
of Alaska, will disappear from the map of the United States.”
The Chinese Question.
Since 1877 the agitation of the prohibition of Chinese immigration

in California and other States and Territories on the Pacific slope has
been very great. This led to many scenes of violence and in some
instances bloodshed, when one Dennis Kearney led the
Workingmen’s party in San Francisco. On this issue an agitator and
preacher named Kalloch was elected Mayor. The issue was carried to
the Legislature, and in the vote on a constitutional amendment it was
found that not only the labor but nearly all classes in California were
opposed to the Chinese. The constitutional amendment did not meet
the sanction of the higher courts. A bill was introduced into Congress
restricting Chinese immigrants to fifteen on each vessel. This passed
both branches, but was vetoed by President Hayes on the ground
that it was in violation of the spirit of treaty stipulations. At the
sessions of 1881–82 a new and more radical measure was
introduced. This prohibits immigration to Chinese or Coolie laborers
for twenty years. The discussion in the U. S. Senate began on the
28th of February, 1882, in a speech of unusual strength by Senator
John F. Miller, the author of the Bill. From this we freely quote, not
alone to show the later views entertained by the people of the Pacific
slope, but to give from the lips of one who knows the leading facts in
the history of the agitation.

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EKC 2019 Conference Proceedings

Science Technology and Humanity

Sustainability in Environmental Engineering and

Advanced Multimedia and Ubiquitous Engineering Future

Proceedings of the International Petroleum and

Recent Advances in Information and Communication

Intelligent Techniques and Applications in Science and

Technology: Toward Business Sustainability: Proceedings

Smart Sensors and Systems Technology Advancement and

Energy Materials and Devices: Proceedings of E-MAD 2022

EKC 2019 Conference

Vienna, Austria, July 15–18, 2019

ISBN 978-981-15-8349-0 ISBN 978-981-15-8350-6 (eBook)

© Springer Nature Singapore Pte Ltd. 2021

Premstaetten, Austria Jong Mun Park

Novel Adamantane Asymmetrically Substituted

Martin Cigánek, Patricie Heinrichová, Martin Weiter, and Jozef Krajčovič

Keywords Diketopyrrolopyrrole · Alkylation · Adamantyl

In recent years, soluble organic semiconductors have found a number of signiﬁcant

M. Cigánek · P. Heinrichová · M. Weiter · J. Krajčovič (*)

© Springer Nature Singapore Pte Ltd. 2021 1

2-Thiophenecarbonitrile (99%), sodium, iron(III) chloride (>97%, anhydrous), tert-

The targeted series of alkylated DPP derivatives by ethyladamantyl chains were

N,N'-EtAd-Th-DPP: 36% N,O'-EtAd-Th-DPP: 20% O,O'-EtAd-Th-DPP: 6%

Synthesis of 2,5-dihydropyrrolo[4,3-c]pyrrolo-1,4-dione molecules Sodium

3 Results and Discussion

3.1 Thermogravimetric Analysis

The thermogravimetric record of the N,N0 -EtAd-Th-DPP showed the degradation

3.2 Optical Properties in Solution

Deriv. Weight (%°C)

Deriv. Weight (%°C)

Fig. 2 Thermogravimetric records of all three studied DPP derivatives

Table 1 Thermogravimetric analysis of all three studied DPP derivatives

Fig. 3 Absorption and ﬂuorescence spectra of studied DPPs diluted in chloroform

Fig. 4 Spectral response of O,O0 -EtAd-Th-DPP in acid conditions

It is known that unsubstituted trivalent nitrogen in case of O-alkylation has high

of N,O0 -EtAd-Th-DPP was bathochromely shifted to 598 nm and Stokes shift

In summary, a novel series of three thiophene-DPP derivatives alkylated by

Haon Park and Abdullah Öztürk

Abstract The microstructure of a material is its inner morphological features. The

Keywords Steel microstructure · Machine learning · Steel phases

© Springer Nature Singapore Pte Ltd. 2021 13

1.1 Steel Microstructure and Phase Changes

Fig. 1 Schematic representation of the formation of pearlite from austenite [4]

1.2 Machine Learning Approach

This motivation leads to the consideration of Machine Learning methods, recently

Fig. 2 U-NET Convoluted Neural Network Architecture [8]

2.2 Experimental Observations and Data

Fig. 3 Scanning electron microscope image of ferrite and pearlite phases

HV ¼ 0:0128P2 þ 1:865P þ 127:78 ð2Þ

where P is the volume fraction of pearlite. Therefore, the mechanical hardness of

Table 1 Results of U-NET architecture

Fig. 6 The accuracy graph with epochs of large training images

Fig. 7 The loss graph with epochs of large training images

3.1 Training Accuracy

Fig. 8 The accuracy graph with epochs of small training images

Fig. 9 The loss graph with epochs of small training images

3.2 Phases Differentiation

Fig. 11 SEM images for pearlite phase segmentation