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 PROCEEDINGS OF THE
INTERNATIONAL CONFERENCE ON
MARTENSITIC TRANSFORMATIONS:
CHICAGO

EDITORS:
Aaron P. Stebner and Gregory B. Olson

CO-EDITORS:
Peter M. Anderson Valery I. Levitas
Mohsen Asle Zaeem Michael J. Mills
Othmane Benafan Peter Müllner
Amy Brice Alan R. Pelton
Emmanuel De Moor David J. Rowenhorst
Ibrahim Karaman Avadh Saxena
Ricardo Komai
The Minerals, Metals & Materials Series
Aaron P. Stebner ⋅ Gregory B. Olson
Editors
Peter M. Anderson ⋅ Mohsen Asle Zaeem ⋅ Othmane Benafan
Amy Brice ⋅ Emmanuel De Moor ⋅ Ibrahim Karaman
Ricardo Komai ⋅ Valery I. Levitas ⋅ Michael J. Mills
Peter Müllner ⋅ Alan R. Pelton ⋅ David J. Rowenhorst
Avadh Saxena
Co-editors

Proceedings of the
International Conference
on Martensitic
Transformations: Chicago

123
Editors
Aaron P. Stebner Gregory B. Olson
Colorado School of Mines Northwestern University
Golden, CO Evanston, IL
USA USA

ISSN 2367-1181 ISSN 2367-1696 (electronic)

The Minerals, Metals & Materials Series
ISBN 978-3-319-76967-7 ISBN 978-3-319-76968-4 (eBook)
https://doi.org/10.1007/978-3-319-76968-4
Library of Congress Control Number: 2018933500

© The Minerals, Metals & Materials Society 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is
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Preface

The International Conference on Martensitic Transformations (ICOMAT) was held on July 9–14,
2017, at the Hyatt Regency in Chicago, Illinois, USA. The event was hosted by the Chicago-based
CHiMaD Center for Hierarchical Materials Design in downtown Chicago.
Located on the shores of Lake Michigan in the heart of the Great Lakes Region of North
America, the city of Chicago is truly an epitome of the “melting pot” reputation of the United
States, evidenced by a diverse array of cultural, economic, and social experiences that draw
tourism, science and technology, arts, and music to its streets year-round. The “Chicago
School” represents a unique tradition of innovation across many fields, notably including
materials, as the birthplace of Materials Science in the 1950s and Materials Design in the
1990s.
ICOMAT 2017 was organized around the central theme of “Martensite by Design.”
Symposia included design for microstructures, properties, advanced manufacturing, and per-
formance. Topics included:

• Theory & Methods for Martensite Design

• Interactions of Phase Transformations and Plasticity
• Quenching and Partitioning of Martensite and Other Advancements in Steels
• Novel Shape Memory Alloys
• Novel Functional Behaviors: Beyond Shape Memory Effect & Superelasticity
• Martensitic Transformations in Non-Metallic Materials
• Size Effects in Martensitic Transformations
• Advanced Characterization of Martensite—3D & High Resolution
• Quasimartensitic Modulations
• Advanced Processing Techniques: Additive, Porous, and Others
• Engineering Applications and Devices
• MSMnet: Magnetomechanics of Magnetic Shape Memory Alloys

The next ICOMAT conference will be held in 2020 in Jeju Island, South Korea.

Aaron P. Stebner
Gregory B. Olson

v
Contents

Part I International Conference on Martensitic Transformations Plenary

Phase Transformations Under High Pressure and Large Plastic Deformations:

Multiscale Theory and Interpretation of Experiments . . . . . . . . . . . . . . . . . . . . . . . 3
Valery I. Levitas

Part II Theory and Methods for Martensite Design

Activation Energy of Time-Dependent Martensite Formation in Steel . . . . . . . . . . 13

Matteo Villa and Marcel A. J. Somers
The Effects of Prior-γ Grain Boundary Segregation of Phosphorus,
Manganese and Molybdenum on Intergranular Fracture Stress in Low
Carbon Martensite Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Masahide Yoshimura, Manabu Hoshino, Masanori Minagawa, and Masaaki Fujioka
Effect of Molybdenum Content on Hardenability of Boron and Molybdenum
Combined Added Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Kyohei Ishikawa, Hirofumi Nakamura, Ryuichi Homma, Masaaki Fujioka,
and Manabu Hoshino
Interaction of Martensitic Microstructures in Adjacent Grains . . . . . . . . . . . . . . . . 29
John M. Ball and Carsten Carstensen
Different Cooling Rates and Their Effect on Morphology and Transformation
Kinetics of Martensite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Annika Eggbauer (Vieweg), Gerald Ressel, Marina Gruber, Petri Prevedel,
Stefan Marsoner, Andreas Stark, and Reinhold Ebner

Part III Interactions of Phase Transformations and Plasticity

TRIP Effect in a Constant Load Creep Test at Room Temperature . . . . . . . . . . . . 43

N. Tsuchida and S. Harjo
Modeling of Strain-Induced Phase Transformations Under High
Pressure and Shear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Mehdi Kamrani, Biao Feng, and Valery I. Levitas
Modeling the Microstructure Evolutions of NiTi Thin Film During
Tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
S. E. Esfahani, I. Ghamarian, V. I. Levitas, and P. C. Collins
Residual Stress and Texture Evolution on Surface of 304L TRIP Steel Sheet
Subjected to FLC Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
I. S. Oliveira, J. M. Alves, R. A. Botelho, A. S. Paula, L. P. M. Brandão,
M. C. Cardoso, L. P. Moreira, and M. C. S. Freitas

vii
viii Contents

An Investigation on the Microstructure and Mechanical Properties of Hot Rolled

Medium Manganese TRIP Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Yu Zhang and Hua Ding
Correlation Between Deformation Texture and Martensitic Transformation in
TWIP/TRIP Steels on Multiscale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Marton Benke, Erzsebet Nagy, Mate Sepsi, Peter Pekker, and Valeria Mertinger
Phase Transitions and Their Interaction with Dislocations in Silicon . . . . . . . . . . . 83
Valery I. Levitas, Hao Chen, and Liming Xiong
Thermal Cycling Induced Instability of Martensitic Transformation and the
Micro-Mechanism in Solution-Treated Ni51Ti49 Alloy . . . . . . . . . . . . . . . . . . . . . . . 89
Cai-You Zeng, Zhong-Xun Zhao, Yuan-Yuan Li, Shanshan Cao, Xiao Ma,
and Xin-Ping Zhang
Influence of Grain Size on Work-Hardening Behavior of Fe-24Ni-0.3C
Metastable Austenitic Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
W. Q. Mao, S. Gao, W. Gong, M. H. Park, Y. Bai, A. Shibata, and N. Tsuji
The Influence of α′ (bcc) Martensite on the Dynamic and Magnetic Response of
Powder Metallurgy FeMnSiCrNi Shape Memory Alloys . . . . . . . . . . . . . . . . . . . . . 99
M. Mocanu, E. Mihalache, B. Pricop, F. Borza, M. Grigoraș, R. I. Comăneci,
B. Özkal, and L. G. Bujoreanu
Critical Analyses on the Instrumented Ultramicrohardness Results on Aging
NiTi Alloy in Distinct Phase Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
R. S. Teixeira, A. S. Paula, F. S. Santos, P. F. Rodrigues, and F. M. Braz Fernandes
Effect of Thermomechanical Treatment on Mechanical Properties of
Ferromagnetic Fe-Ni-Co-Ti Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Anatoliy Titenko, Lesya Demchenko, Larisa Kozlova, and Mustafa Babanli

Part IV Quenching and Partitioning of Martensite and Other Advancements

in Steels

Reversed Austenite for Enhancing Ductility of Martensitic Stainless Steel . . . . . . . 123

Sebastian Dieck, Martin Ecke, Paul Rosemann, and Thorsten Halle
Tough Ductile Ultra High Strength Steels Through Direct Quenching
and Partitioning—An Update . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Mahesh C. Somani, David A. Porter, Jukka I. Kömi, L. P. Karjalainen,
and Devesh K. Misra
Physical Simulation of Press Hardening of TRIP Steel . . . . . . . . . . . . . . . . . . . . . . 135
Hana Jirková, Kateřina Opatová, Martin F.-X. Wagner, and Bohuslav Mašek
Effect of Carbon Content on Bainite Transformation Start Temperature on
Fe–9Ni–C Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Hiroyuki Kawata, Toshiyuki Manabe, Kazuki Fujiwara, and Manabu Takahashi
Influence of Manganese Content and Finish Rolling Temperature on the
Martensitic Transformation of Ultrahigh-Strength Strip Steels . . . . . . . . . . . . . . . . 149
Antti Kaijalainen, Mahesh Somani, Mikko Hemmilä, Tommi Liimatainen,
David A. Porter, and Jukka Kömi
In Situ Neutron Diffraction Study on Microstructure Evolution During
Thermo-Mechanical Processing of Medium Manganese Steel . . . . . . . . . . . . . . . . . 155
Yoshihiko Nakamura, Akinobu Shibata, Wu Gong, Stefanus Harjo,
Takuro Kawasaki, Atsushi Ito, and Nobuhiro Tsuji
Contents ix

Part V Size Effects in Martensitic Transformations

Nanoscale Phase Field Modeling and Simulations of Martensitic Phase

Transformations and Twinning at Finite Strains . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Anup Basak and Valery I. Levitas
Phase Field Study of Lattice Instability and Nanostructure Evolution in Silicon
During Phase Transformation Under Complex Loading . . . . . . . . . . . . . . . . . . . . . 167
H. Babaei and V. I. Levitas

Part VI Novel Functional Behaviors: Beyond Shape Memory Effect &

Superelasticity

Investigation of the Precipitation Processes in NiTi Filaments . . . . . . . . . . . . . . . . . 173

Ondřej Tyc, Jan Pilch, Petr Šittner, and Petr Haušild
Effect of Microstructure on the Low-Cycle Fatigue Properties of a
Fe–15Mn–10Cr–8Ni–4Si Austenitic Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Ilya Nikulin, Takahiro Sawaguchi, and Yuuji Kimura
Martensitic Transformations of Ni–Mn–X Heusler Alloys
with X = Ga, In and Sn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Peter Entel, Markus E. Gruner, Mehmet Acet, Asli Çahır, Raymundo Arroyave,
Thien Duong, Anjana Talapatra, and Ibrahim Karaman
Reversible Negative Thermal Expansion Response and Phase Transformation
Behavior of a Ti-Rich Ti54Ni46 Alloy Prepared by Rapid Solidification . . . . . . . . . 189
Zhong-Xun Zhao, Xiao Ma, Cai-You Zeng, Shanshan Cao, Chang-Bo Ke,
and Xin-Ping Zhang

Part VII Engineering Applications and Devices

Film and Foil-Based Shape Memory Alloy Microactuators for

Fluid Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Hinnerk Ossmer, Marcel Gueltig, Christoph Wessendorf, Manfred Kohl,
and Christof Megnin
Functional Stability of the Ni51Ti49 Two-Way Shape Memory Alloy as
Artificial Anal Sphincter During Thermo-Mechanical Cycling . . . . . . . . . . . . . . . . 201
Yuan-Yuan Li, Cai-You Zeng, Shanshan Cao, Xiao Ma, and Xin-Ping Zhang
Influence of Contact Friction on Force-Deflection of Orthodontic
NiTi Archwire: A Computational Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
M. F. Razali and A. S. Mahmud
Features Cavitation Resistance of Multifunctional Coatings from
Materials with a Shape Memory Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
D. V. Dmitrenko, Zh. M. Blednova, and E. U. Balaev
Microstructure and Mechanical Behaviors of Electron Beam Welded
Ti44Ni47Nb9 Shape Memory Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Dan Yang, Haichang Jiang, Mingjiu Zhao, and Lijian Rong
Relationship Between Applied Stress and Hydrogen-Related Fracture
Behavior in Martensitic Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Yasunari Takeda, Takashi Yonemura, Yuji Momotani, Akinobu Shibata,
and Nobuhiro Tsuji
x Contents

Part VIII Advanced Processing Techniques: Additive, Porous, and Others

Contact Pressure and Residual Strain of Resistance Spot Welding on

Mild Steel Sheet Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Hua Zhong, Xiaodong Wan, Yuanxun Wang, and Yiping Chen

Part IX Advanced Characterization of Martensite—3D and High Resolution

Strain-Induced Martensitic Transformation in a Co-Cr-W-Mo Alloy

Probed by Nanoindentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
Irmgard Weißensteiner, Patrick Voigt, Helmut Clemens, and Verena Maier-Kiener
Estimation of Solute Carbon Concentration by Electrical Resistivity
Method in Low-Carbon Martensitic Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Toshihiro Tsuchiyama, Taiga Taniguchi, Daichi Akama, Setsuo Takaki,
Kenji Kaneko, Masahide Yoshimura, Masaaki Fujioka, and Ryuji Uemori

Part X MSMnet: Magnetomechanics of Magnetic Shape Memory Alloys

Comparison of Highly Mobile Twin Boundaries in Cu–Ni–Al and

Ni–Mn–Ga Shape Memory Single Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
M. Vronka, M. Karlík, Y. Ge, and O. Heczko
Multiphase Microstructure and Extended Martensitic Phase Transformation in
Directionally Solidified and Heat Treated Ni44Co6Mn39Sn11 Metamagnetic
Shape Memory Alloy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
P. Czaja, R. Chulist, M. Szlezynger, M. Fitta, and W. Maziarz

Part XI Novel Shape Memory Alloys

Effect of Heat-treatment Conditions on Microstructure and Shape

Memory Properties of Ti–4.5Al–3V–2Fe–2Mo Alloy . . . . . . . . . . . . . . . . . . . . . . . . 271
Yuichi Matsuki, Hirobumi Tobe, and Eiichi Sato
Porous Ni–Ti–Nb Shape Memory Alloys with Tunable Damping
Performance Controlled by Martensitic Transformation . . . . . . . . . . . . . . . . . . . . . 275
Shanshan Cao, Yuan-Yuan Li, Cai-You Zeng, and Xin-Ping Zhang
Cryogenic Immersion Time Influence on Thermal and Mechanical
Properties of a Ni48-Ti52 Shape Memory Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
Bartholomeu Ferreira da Cruz Filho

Part XII Quasimartensitic Modulations

The Martensitic Transformation in Indium-Thallium Alloys . . . . . . . . . . . . . . . . . . 291

T. R. Finlayson, G. J. McIntyre, and K. C. Rule
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
 Part I
International Conference on Martensitic
Transformations Plenary
 Phase Transformations Under High Pressure
and Large Plastic Deformations: Multiscale
Theory and Interpretation of Experiments
Valery I. Levitas
Abstract
It is known that superposition of large plastic shear at
high pressure in a rotational diamond anvil cell (RDAC)
or high-pressure torsion leads to numerous new phenom-
ena, including drastic reduction in phase transformation
(PT) pressure and appearance of new phases. Here, our
four-scale theory and corresponding simulations are
reviewed. Molecular dynamic simulations were used to
determine lattice instability conditions under six compo-
nents of the stress tensor, which demonstrate strong
reduction of PT pressure under nonhydrostatic loading.
At nanoscale, nucleation at various evolving dislocation
configurations is studied utilizing a developed phase field
approach. The possibility of reduction in PT pressure by
an order of magnitude due to stress concentration at the
shear-generated dislocation pileup is proven. At micro-
scale, a strain-controlled kinetic equation is derived and
utilized in large-strain macroscopic theory for coupled
PTs and plasticity. At macroscale, the behavior of the
sample in DAC and RDAC is studied using a
finite-element approach. A comprehensive computational
study of the effects of different material and geometric
parameters is performed, and various experimental effects
are reproduced. Possible misinterpretation of experimen-
tal PT pressure is demonstrated. The obtained results offer
new methods for controlling PTs and searching for new
high-pressure phases (HPPs), as well as methods for
characterization of high-pressure PTs in traditional DAC
and RDAC.
V. I. Levitas (&)
Departments of Aerospace Engineering, Mechanical Engineering,
and Material Science and Engineering, Iowa State University,
Ames, IA 50011, USA
e-mail: vlevitas@iastate.edu
V. I. Levitas
Ames Laboratory, Division of Materials Science & Engineering,
Ames, IA 50011, USA
© The Minerals, Metals & Materials Society 2018
A. P. Stebner and G. B. Olson (eds.), Proceedings of the International Conference on Martensitic Transformations: Chicago,
The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-319-76968-4_1
Keywords
⋅
⋅
Strain-induced phase transformations High pressure
Four-scale theory Nucleation at dislocation pile-up
Rotational diamond anvil cell
Introduction
In situ studies of material behavior, including phase trans-
formations (PTs), under high pressure up to several hundred
GPa are performed in a diamond anvil cell (DAC). PTs are
usually characterized in terms of pressure for initiation and
completion of direct and reverse PTs, and in some cases for
the concentration of phases versus pressure. It is recognized
that the entire process of producing high pressure is
accompanied by large nonhydrostatic (deviatoric) stresses
and large plastic deformations that drastically affect PTs.
A specially-designed device [1, 2], the RDAC (Fig. 4a), is
utilized to study the strong, multifaceted, and unique effects
of large plastic shear on PTs:
(a) Plastic shear under high pressure leads to the forma-
tion of new phases that may not be producible without
shear [1–7].
(b) Plastic shear under high pressure reduces the trans-
formation pressure by a factor between 2 and 10 for
some PTs [1–4, 6–9], e.g., for transformations from
highly disordered hexagonal hBN into superhard
wurtzitic wBN from 52.5 to 6.7 GPa [8].
(c) The concentration of the high-pressure phase is an
increasing function of plastic shear [1–8]. Plastic strain
is a time-like parameter, so one needs to consider
strain-controlled kinetics instead of time-controlled
kinetics.
Here, we review our results on the development of
four-scale theory and corresponding simulations for under-
standing and description of the reasons for the phenomena
mentioned above in (a)–(c).
3
4 V. I. Levitas
Pressure-Induced Versus Strain-Induced
Phase Transformations Under High Pressure
Note that classical macroscopic thermodynamics fails to
explain a strong reduction in transformation pressure due to
nonhydrostatic stresses. A thermodynamic treatment leads to
a simplified condition in which the transformation work
W reaches some critical value k, given by
W = − pε0t + τγ t = k, where ε0t < 0 and γ t are the volumetric
and shear transformation strains, and p and τ are the pressure
and the shear stress. Under hydrostatic conditions
− ph ε0t = k, which determines k. Then the maximum dif-
ference between transformation pressure under hydrostatic
and nonhydrostatic conditions is ph − p = τy γ t ̸jε0t j, taking
into account that maximum shear stress is limited by the
yield strength in shear τy . Let us assume as a simple estimate
that τy = 1 GPa and γ t ̸ jε0t j = 1 − 5. Then the reduction in
transformation pressure is just 1–5 GPa. If PT pressure under
hydrostatic conditions is 15 or 50 GPa, then maximum
pressure reduction is 33 or 10%, considerably below than
observed in experiments, e.g., in [8].
The first step in understanding the PTs in RDAC was
recognition in [6, 7] that there is a basic difference between
plastic strain-induced PTs under high pressure in RDAC and
pressure- or stress-induced PTs in DAC under
quasi-hydrostatic conditions. Pressure- and stress-tensor-
induced PTs occur predominantly at pre-existing defects
(e.g., dislocations and various tilt boundaries) at stress levels
below the yield strength. These defects represent stress
(pressure) concentrators. The number of nucleation sites is
limited, so one has to increase pressure to activate less potent
defects, i.e., defects with smaller stress concentration.
Strain-induced PTs occur by nucleation at new defects,
e.g., dislocation pileups generated during plastic flow. That
is why it is possible to increase local stresses and promote
PTs near the new defects by increasing plastic shear at
constant pressure. Since concentration of all components of
a stress tensor is proportional to the number of dislocations
in a pileup, which can be as large as 10–100, new defects
may be much stronger than the pre-existing defects. Such
high local pressure and deviatoric stresses may cause
nucleation of the HPP at an external pressure much below
that under hydrostatic conditions. Note that shear stresses
within small nanoscale regions may be limited by the the-
oretical shear strength that could range from one to two
orders of magnitude larger that τy . It was concluded in [6, 7]
that strain-induced PTs require a completely different
experimental characterization as well as new thermodynamic
and kinetic descriptions.
Nanoscale Continuum Treatment: Phase Field
Approach
A simple analytical model of nucleation at the tip of the
dislocation pileup [6, 7] demonstrated that, with a sufficient
number of dislocations, nucleation of HPP can indeed occur
at external pressures an order of magnitude smaller than
under hydrostatic conditions. This model, however, con-
tained a number of simplifying assumptions. For a more
precise and advanced proof of the complex, the first phase
field approach (PFA) for the interaction of PTs and dislo-
cations was developed [10–13], which synergistically com-
bines the most advanced fully geometrically nonlinear
theories for martensitic PTs [14–16] and dislocations [17,
18], with nontrivial interactions and inheritance of disloca-
tions during PTs. This approach combined with the
finite-element method (FEM) was applied for the first sim-
ulation of PT under pressure and shear (Fig. 1) [11–13] in a
nanograined bicrystal. A model material with phase equi-
librium pressure peq = 10 GPa and instability pressure of 20
GPa was considered; transformation strains were ε0t = − 0.1
and γ t = 0.2. Under hydrostatic pressure and single disloca-
tion in the grain, PT occurs at 15.75 GPa. Under a com-
pressive stress σ n = 3.05 GPa (corresponding to an averaged
pressure of 2.0 GPa) and shear, dislocations are generated in
the left grain and pile up against grain boundaries. Strong
concentration of all components of the stress tensor near the
pileup tip leads to a combination of stresses that satisfy local
lattice instability criterion and lead to barrierless nucleation
of a HPP. For the configuration shown in Fig. 1a, HPP is
observed at γ = 0.15 and pressure p̄ = 1.2 GPa averaged over
the transforming grain. When shear increases to 0.2 (Fig. 1
b), a major part of a grain transforms and, in the stationary
state due to volume decrease, pressure drops to 0.8 GPa
(averaged over both grains) and 0.06 GPa averaged over the
transformed grain. Such averaged pressures (rather than σ n)
are usually reported by experimentalists. Thus, a dislocation
pileup can indeed cause a reduction in transformation
pressure more than an order of magnitude below that under
hydrostatic conditions.
The above results have been obtained for neglected
plasticity in the transforming grain. When plasticity is
included (Fig. 1c), the volume fraction of the HPP reduces
in comparison with cases without plasticity. Thus, disloca-
tions play a dual role: they promote PT by producing strong
stress concentrators and also suppress PT by relaxing the
stresses. Some combinations of normal and shear stresses
have been found in [12] where the volume fraction of HPP
either with or without plasticity in the transformed grain
Phase Transformations Under High Pressure …
Fig. 1 Stationary nanostructures for coupled evolution of dislocations
and high-pressure phase (red) in a two-grain sample under pressure and
prescribed shear γ = 0.15 (a), and in the right grain without (b) and with
(c) dislocations for prescribed shear of 0.2. Due to dislocation pileup,
PT occurs at applied pressure more than an order of magnitude lower
than for hydrostatic conditions with one dislocation. Plasticity plays a
does not essentially differ. Figure 1d shows a nanostructure
obtained under compression and shear that includes grain
rotation and switching between slip systems. Major parts of
both grains are transformed despite the fact that dislocations
in the left grain disappeared. Some additional studies with-
out [11] and with normal stress are presented in [13].
Lattice Instability Criteria: PFA Approach
and MD Simulations
Since shear (deviatoric) stresses near the tip of a dislocation
pile are not limited by the macroscopic yield strength but are
limited by the theoretical strength, unique stress states not
achievable in bulk can be produced. Such stresses may cause
PTs into stable or metastable phases that are not or even
could not be achieved in bulk under hydrostatic or nonhy-
drostatic conditions without significant plastic deformation.
The next step is to find the maximum possible effect of
deviatoric stresses, i.e., their effect on PT (lattice instability)
criteria of an ideal (defect-free) single crystal under complex
loading.
A general lattice instability (or PT) criterion was derived
under complex stress states and large strains utilizing PFA
[15]. To test and specify this criterion for silicon (Si),
molecular dynamics (MD) simulations [19, 20] were per-
formed for direct and reverse Si I ↔ Si II PTs (Fig. 2).
Lattice instability criteria are thus linear in terms of normal
to cubic faces stresses σ i and they are independent of shear
stresses, at least below 3 GPa. The effect of nonhydrostatic
stresses is drastic. Thus, under hydrostatic conditions, the
PT pressure is 80 GPa; under uniaxial loading, the stress is
12 GPa, i.e., the mean pressure is 4 GPa, so reduction in PT
pressure is by a factor of 20. While the uniaxial stress of 12
GPa definitely cannot be applied to the real (defective) bulk
sample because it is much higher than the macroscopic
yield strength, it can be obtained at the tip of the dislocation
pileup and drastically reduce the external pressure required
for PT.
5
dual role: it promotes PT by stress concentrators (a, b) but suppresses it
by relaxing these stresses (c). d Complex phase and dislocation
nanostructure obtained under compression and shear, which includes
grain rotation and switching between slip systems. Reproduced with
permission from [12]
Microscale Strain Controlled Kinetic Equations
To produce high pressure in DAC, one must compress a
sample plastically. Thus, not only in RDAC, but in most
cases in DAC without a hydrostatic medium, PTs should be
treated as plastic strain-induced PTs. It was suggested in [6,
7] that strain-induced PTs should be described theoretically
and characterized experimentally with the help of
strain-controlled kinetic equations for concentrations of
high-pressure phases ck and parameters Dm characterizing
the defect structure of the type


dck ̸dq = fk σ, Ep , q, ck , Dm , ð1Þ
where q is the accumulated plastic strain that plays a role of a
time-like parameter and σ and Ep are the stress and plastic
strain tensors. A simplified version of this equation for a
single PT was derived in [6, 7], taking into account con-
ceptually all information learned from the nanoscale model
in [6, 7]:
dc ð1 − cÞp̄d H ðp̄d ÞM − cpr H ðp̄r Þ
=A ;
dq c + ð1 − cÞM
ð2Þ
p − pd p − pr σ y2
p̄d = d εd and p̄r = r εr ; M = .
ph − pε ph − pε σ 1y
Here, four characteristic pressures are utilized: pdε is the
minimum pressure below which a direct plastic
strain-induced PT to HPP does not take place, prε is the
maximum pressure above which a reverse strain-induced PT
to low pressure phase cannot occur, and pdh and prh are the
pressures for direct and reverse PTs under hydrostatic
loading, respectively. These pressures are combined into two
dimensionless characteristic pressures for direct and reverse
PTs, p̄d and p̄r , respectively. In addition, A is the kinetic
parameter, σ 1y and σ 1y are the yield strengths in compres-
sion of low- and high-pressure phases, respectively, and H is
6 V. I. Levitas
Fig. 2 a Crystal lattice instability criterion in space of normal to cubic
faces stresses σ i obtained within phase field approach [15] (plane) and
confirmed by MD simulations [20] (points) for PT Si I → Si II. b The
the Heaviside function (H ð yÞ = 1 for y ≥ 0 and H ð yÞ = 0 for
y < 0). The barrierless character of nucleation at defects
results in time not being a parameter in Eq. (2). Since the
number of pileups and the number of dislocations in each
grow with increasing plastic strain, and when plastic
straining stops, PT stops as well, the accumulated plastic
strain q is a time-like parameter. Defects like dislocation
pileups generate both compressive and tensile stresses of the
same magnitude but in different regions. Consequently,
strain-induced defects simultaneously promote both direct
and reverse PTs, as reflected in the two opposite terms in
Eq. (2). In addition, due to different yield strengths in dif-
ferent phases, plastic strain localizes in the weaker phase,
explaining the ratio of the yield strength of phases in Eq. (2).
Equation (2) was generalized for multiple PTs in [21] and
analysed in [6, 7, 21] for interpretation of experimental
phenomena. Some of the general results are:
(1) If pdε < prε (i.e., direct PT can start at pressure below the
maximum pressure for the reverse PT) and
pdε < p < prε ; for q → ∞ there is a stationary solution
0 < c < 1 of Eq. (2). This explains incomplete PT and
existence of the stationary concentration, see [22].
(2) The solution explains the zero-pressure hysteresis
observed in [1] for B1 to B2 PT in KCl. However, this
PT pressure is not the phase equilibrium pressure that
cannot be determined from a macroscopic plastic
strain-induced experiment because it is not present in
Eq. (2). At the same time, as was found in [11, 12] with
the PFA, the phase equilibrium stress tensor governs the
stationary morphology of the nanostructure, both
locally and in terms of stresses averaged over the
transformed region or grain.
(3) The stationary concentration of the HPP increases with
the ratio σ y2 ̸σ y1 , i.e., a strong HPP is promoted more
by plastic strain than a weak one. Similarly, hard (soft)
inert particles promote (decelerate) plastic
strain-induced chemical reactions [23, 24] that can also
be described by Eq. (2).
same plot but twisted until plane is visible as a line, to demonstrate
closeness of MD and phase field results. Reproduced with permission
from [20]
Fig. 3 Change in volume fraction of Si I (1), Si II (2), and Si III
(3) with plastic straining at pressure of 7 GPa. Reproduced with
permission from [21]
Figure 3 presents a solution for strain-controlled kinetics
for PTs between Si I, Si II, and Si III at a pressure of 7 GPa.
Note that under hydrostatic pressure of 7 GPa, Si I is stable.
For strain-induced PTs, Si III, which is not present on the
equilibrium phase diagram, monotonically increases in
concentration until completion. Si II appears and disappears
with straining. If one assumes that Si II is an unknown phase
to be discovered, then traditional wisdom—the larger the
plastic strain, the larger the promotion for PT—fails. Plastic
strain should be optimal, as also found in [25] for PT in
boron nitride.
Macroscale Modeling Coupled Phase
Transformation and Plastic Flow of a Sample
in DAC and RDAC
Kinetic Eq. (2) was incorporated into macroscale theory for
stress- and plastic strain-induced PTs for the description of
coupled plastic flow and PTs in a sample treated in DAC and
RDAC. An initial simplified version of the theory for small
elastic and transformational strains (but large plastic strains),
linear elasticity, and pressure-independent yield strength was
developed and applied in [26–34]. Strain hardening was
Phase Transformations Under High Pressure …
neglected based on experimental and theoretical results
given in [35]. Even for a model material, the results of a
parametric study changed the fundamental understanding of
the interpretation of experimentally observed effects and
measurements and the extraction of information on material
behavior from sample behavior. Some results for processes
in RDAC both without and with a gasket are presented in
Figs. 4 and 5, respectively. In particular, the results in Fig. 4
reproduce the following experimental phenomena.
(a) A pressure self-multiplication effect [1, 3, 4], i.e.,
pressure growth during PT during torsion at fixed force,
despite the volume reduction due to PT. Even though
this sounds like violation of the Le Shatelie principle, as
mentioned above, strain-induced PTs require
non-traditional thermodynamic treatment. This effect
was automatically reproduced when the yield strength
grew during PTs, similar to that described in a simpli-
fied analytical treatment in [6, 7]. It represents positive
Fig. 4 a Schematics of RDAC; b and c distributions of pressure and
concentration of high-pressure phase, respectively, along the radius of
the contact surface of a sample; d distribution of concentration of
high-pressure phase within a quarter of a sample. Simulations are for
the case without gasket, with the yield strength σ 2y = 5 σ 1y, for
dimensionless applied axial force F = 4.44, and different values of
Fig. 5 Evolution of distributions of a concentration of the
high-pressure phase c, b pressure p, and c accumulated plastic strain
q in the quarter of a sample within a gasket at a fixed compressive force
7
mechanochemical feedback in promotion of PTs by
torsion of an anvil.
(b) Note that even when the pressure exceeds pdε by a factor
of two (line 3 in Fig. 4b and c), PT is not complete.
Experimentalists would say that PT is spread over the
range from pdε to more than 2pdε . However, according to
Eq. (2), this is not kinetic property of the PT, which
could occur until completion at pressure slightly above
pdε under large plastic strains. While not required for PT,
such high pressure appears because of a coupled PT and
plastic flow under such loadings, i.e., as system (sam-
ple) behavior rather than material properties. Pressure
growth can be suppressed by using a sample-gasket
system, see [25, 33] and Fig. 5. Thus, for synthesis of
HPP at minimal pressure, one must design the
sample-gasket system and loading program. The results
shown in Fig. 5 show smaller heterogeneity of all
parameters and a smaller change in pressure during
anvil rotation.
angle of rotation φ. 1: φ = 0.09, 2: φ = 0.38, 3: φ = 0.61, 4: φ = 0.94,
5: φ = 1.10, and 6: φ = 1.30 rad [27]. White lines in the concentration
distribution in (d) correspond to pressure p = pdε . Reproduced with
permission from [27]
F = 6.19 and different values of angle of rotation φ. 1: φ = 0, 2:
φ = 0.1, 3: φ = 0.3, 4: φ = 0.5, 5: φ = 0.8, and 6: φ = 1.0 rad.
Reproduced with permission from [33]
8 V. I. Levitas
(c) Steps (horizontal plateaus) at the experimental pressure
distribution [1, 3, 4]. Since the pressure gradient is
proportional to the frictional stress at the contact surface
between the anvil and a sample, for intense plastic flow
equal to the yield strength in shear [35], these steps led
to the conclusion that the yield strength reduces to zero
in the PT region [1]. This, however, could not be true,
because, e.g., TRIP steels show high strength during
PT. In Fig. 4b, these steps appear automatically as a
result of the solution when PT kinetics is fast enough.
Also, the pressure at the steps lies between two char-
acteristic pressures pdε and prε , allowing experimental
determination of their range.
(d) For relatively large rotations, HPP is detectable in the
region where p < pdε (Fig. 4d), where transformation is
by definition impossible. HPP is brought into this
region by radial plastic flow that occurs due to reduc-
tion of sample thickness during rotation of an anvil.
Since pressure is usually measured after each
rotation-PT increment, an experimentalist may report
pressure where HPP is found as the PT pressure, which
would be a misinterpretation.
In [36], a fully geometrically and physically nonlinear
model for elastoplasticity under high pressure without PTs
was developed, and the problem for compression of a rhe-
nium in DAC was solved, producing results in good corre-
spondence with experiments in [37] for pressures up to 300
GPa. The same model was used in [38, 39] for compression
and torsion in RDAC, revealing a pressure-self-focusing
effect, and suggesting how to utilize it to increase maximum
achievable pressure. In [40], this model was generalized by
including strain-induced PTs and subsequently used to study
PT in BN.
Concluding Remarks
The main mysterious experimental results obtained under
compression and torsion of materials in RDAC are the
reduction in PT pressure by up to an order of magnitude in
comparison with that under quasi-hydrostatic loading, and
appearance of new phases that were not or could not be
obtained under quasi-hydrostatic conditions. Classical
macroscopic thermodynamics fails in explaining these phe-
nomena. In this paper, we review our four-scale theory and
simulations, demonstrating how events at each scale con-
tribute to the explanation of these phenomena. MD simula-
tions demonstrated reduction in PT (lattice instability)
pressure for uniaxial loading of perfect Si by a factor of 20 in
comparison with that from hydrostatic loading. However,
such uniaxial loading cannot be applied to an actual defec-
tive sample because it significantly exceeds the macroscopic
yield strength. At the same time, such stresses can be
obtained at the tip of strong defects as dislocation pileups.
Concentration of all components of the stress tensor is
proportional to the number of dislocations in a pileup that
can be as many as 10–100. Plastic deformation generates
dislocation pileups with high concentration of both pressure
and deviatoric stresses near their tips, satisfying the lattice
instability criterion, and cause barrierless nucleation of an
HPP. Because of the large increase in local stresses, applied
pressure required for nucleation can be significantly reduced.
The possibility of reduction of PT pressure by more than an
order of magnitude was first confirmed by a simple analyt-
ical model and then by advanced PFA. Plasticity plays a dual
role: it promotes PT by producing stress concentrators but
also suppresses PT by relaxing these stresses. Thus, some
combinations of compression and shear were found for
which PT wins this competition. Since such unique stress
states with extremely high deviatoric components, limited by
the theoretical strength (rather than the macroscopic
strength, which is one to two orders of magnitude smaller),
cannot be obtained in a bulk real (defective) material, they
can lead to the appearance of new phases that were not or
even could not be obtained without plastic deformation.
Such an understanding may lead to new directions in
design and synthesis of high-pressure novel phases and
compounds under much lower pressure than under hydrostatic
conditions. Instead of increasing external pressure, succes-
sively filling the material with strain-induced defects causing
unique stress tensor states at the limit of lattice stability and
barrierless PT near their tips is suggested. Classical thermo-
dynamics and kinetics should be conceptually advanced to
multiscale thermodynamics and kinetics in 12 + D parameter
space (six components each of the stress and plastic strain
tensors, and quantitative characteristics of the strain-induced
defect structures). However, nanoscale understanding alone is
not sufficient for achieving this goal. Micro- and macroscale
theories and measurements give important information on
how to characterize PTs in terms of strain-controlled kinetic
equations of the type given in Eqs. (1) and (2) and how to
design a sample-gasket system and loading programs to pro-
duce desired phases at lowest pressure in RDAC or, for larger
scale, during high-pressure torsion. The key points are related
to the heterogeneities of stress and strain fields at both
microscale and macroscale. At microscale, they are caused by
specifics of the stress field of the dislocation pileup that gen-
erate both compressive and tensile stresses of the same mag-
nitude in different regions and thus simultaneously promote
Phase Transformations Under High Pressure …
both direct and reverse PTs. Also, at both scales they are
related to essentially different two- or multiphase system
behaviors depending on the ratio of the yield strength of the
high- and low-pressure phases, as well as that of a gasket.
Acknowledgements The support of ARO (W911NF-12-1-0340), NSF
(DMR-1434613 and CMMI-1536925), and Iowa State University
(Schafer 2050 Challenge Professorship and Vance Coffman Faculty
Chair Professorship) is gratefully acknowledged.
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 Part II
Theory and Methods for Martensite Design
 Activation Energy of Time-Dependent
Martensite Formation in Steel
Matteo Villa and Marcel A. J. Somers
Abstract
The kinetics of f5 5 7gc lath martensite formation in (wt
%) 17Cr-7Ni-1Al-0.09C and 15Cr-7Ni-2Mo-1Al-0.08C
steels was assessed with magnetometry at sub-zero
Celsius temperatures. Samples were cooled to 77 K by
immersion in boiling nitrogen to suppress martensite
formation. Thereafter, thermally activated martensite
formation was monitored during: (i) isochronal (re)
heating at different heating rates; (ii) isothermal holding
at temperatures between 120 and 310 K. The activation
energy, EA , of thermally activated martensite formation
was quantified from the results of both isochronal and
isothermal tests by applying a Kissinger-like method. In
addition, the isothermal data was interpreted applying the
approach presented by Borgenstam and Hillert. The
results of the independent quantification methods were
consistent and indicated an EA in the range 9–13 kJ
mol−1. Thereafter, the two methods were applied to
evaluate the data available in the literature. The overall
analysis showed that EA varies in the range 2–27 kJ
mol−1 and increases logarithmically with the total fraction
of interstitials in the steel.

Keywords
Isothermal martensite Transformation kinetics
Martensitic steel
M. Villa (&)  M. A. J. Somers
Department of Mechanical Engineering, Technical University
of Denmark, 2800 Kongens Lyngby, Denmark
e-mail: matv@mek.dtu.dk
M. A. J. Somers
e-mail: somers@mek.dtu.dk
© The Minerals, Metals & Materials Society 2018
A. P. Stebner and G. B. Olson (eds.), Proceedings of the International Conference on Martensitic Transformations: Chicago,
The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-319-76968-4_2
Introduction
The design of martensitic steels requires models to accu-
rately describe the kinetics of the austenite-to-martensite
transformation in this class of materials. In early work,
martensitic transformations were considered athermal,
meaning that the degree of transformation is determined
exclusively by the lowest temperature reached, independent
of time [1]. This approach has remained [2] and, in the large
majority of cases, allows a consistent description of the
transformation kinetics. Nevertheless, martensite formation
can also proceed isothermally or, rather, time-dependent,
particularly at sub-zero Celsius temperatures.
The first evidence of time-dependent martensite forma-
tion was reported in 1948 [3]. Extensive evidence followed
(see Refs. [4, 5]) and in the 1990s the isothermal behaviour
was brought to a rationalization as a common characteristic
of martensite formation in ferrous alloys [6]. This implies
that martensite formation in steel can be suppressed by
sufficiently fast cooling to a temperature where the trans-
formation proceeds (virtually) infinitely slowly. Consis-
tently, it was shown in several cases (see Refs. [4, 5, 7]) that
martensite formation can be partly suppressed by fast
cooling to temperatures T  77 K, and the transformation
can continue on subsequent (re)heating. Also, the transfor-
mation can be fully suppressed, as firstly demonstrated in
1953 for Fe-Ni-Mn alloys [8], in 1960 for stainless steel [9]
and in 1990 for Fe-Ni alloys [10].
Conversely, the possibility to form martensite at tem-
peratures as low as 4 K was demonstrated already in 1950
[11] and is evidence that the transformation in the investi-
gated alloys is un-suppressible (i.e., intrinsically athermal).
Martensite formation at 4 K also indicates that the growth of
martensite units does not determine the overall rate of the
isothermal process. It was established as early as the 1930–
1950s [12–14] that the duration of an austenite-to-martensite
transformation event can be of the order of a small fraction
of a second and that the growth rate of the martensite units
13
14
can be independent of temperature within a significantly
large temperature interval (i.e., growth is athermal) [14, 15].
Nevertheless, time-dependent growth of martensite has been
observed several times (see Ref. [16]).
To reconcile the above experimental observations, it has
been suggested that the martensite sub-structure controls the
kinetics of martensite formation [13, 17–19]: athermal
martensite is internally twinned and time-dependent marten-
site is internally slipped. This straightforward description is,
unfortunately, not consistent with all experiments. Slow
growth of martensite always involves slipped sub-structures;
however, slipped martensite can also grow instantaneously
[20, 21]. Furthermore, the transformation of austenite into
slipped martensite can be suppressed by fast cooling [22–24];
on the other hand, slipped martensite can form at 4 K (see, for
example, Ref. [11]). Evidently, the kinetics of martensitic
transformations, the roles of nucleation and growth and the
significance of the martensite substructure are incompletely
understood.
Following Huizing and Klostermann [25], we recently
suggested that the products of martensitic transformations in
steel should be classified into two groups [26]:
i. Schiebung, S, martensite corresponds to internally
slipped f5 5 7gc lath martensite and to the internally
slipped product growing on f2 2 5gc plate and f2 5 9gc
lenticular martensites. S martensite is suppressible and
cannot form at an observable rate at temperatures
approaching absolute zero. The growth of S martensite
can be time dependent.
ii. Umklapp, U, martensite corresponds to twinned
f3 10 15gc thin plate martensite, to the twinned parts of
the f2 2 5gc plate and f2 5 9gc lenticular martensites, as
well as to internally slipped strain induced and f1 1 2gc
martensites. U martensite is un-suppressible and can
form at 4 K. The growth of U martensite is
instantaneous.
Additionally, we suggested that the existing kinetics
models, which typically describe the kinetics of martensite
formation in steel as nucleation-controlled (i.e., implicitly
assuming instantaneous growth) and define nucleation as
un-suppressible upon reaching a certain critical driving force
for transformation, DGC (see Ref. [4]), apply to U martensite,
but cannot describe the kinetics of S martensite formation.
For the latter case, a different approach appears necessary.
An alternative approach to describe the kinetics of
isothermal martensite formation was presented by Borgen-
stam and Hillert [27]. They focused on the evolution of the
transformation rate versus temperature and described the
transformation rate in terms of chemical reaction rate theory
as the product of the normalized chemical driving force,
M. Villa and M. A. J. Somers
DG=RT; and the probability for growth, expðEA =RT Þ,
where DG is the chemical driving force for martensite for-
mation, R is the gas constant, T is the temperature and EA is
the activation energy for the formation of isothermal
martensite. This approach can be considered to describe the
kinetics of S martensite formation because it (i) does not
require a priori assumptions on the rate-determining mech-
anism and (ii) indicates that, provided that cooling is suffi-
ciently fast, martensite formation can be suppressed.
However, modelling of the kinetics of transformation
requires information on EA .
Following Borgenstam and Hillert, EA is determined from
the slope of the straight line obtained by plotting isothermal
data in terms of 1=T versus lnðtðMsi =T  1ÞÞ, where T, t,
and Msi are the temperature of isothermal holding, the time
for obtaining a low fraction, say <0.05, of martensite, and
the maximum temperature at which martensite formation can
progress isothermally, respectively. Unfortunately, this
quantification method can be applied only in a very limited
number of cases, where marked isothermal behaviour is
obtained, which makes it suitable only for the case of
Fe-Ni-Mn and Fe-Ni-Cr alloys transforming isothermally at
sub-zero Celsius temperatures.
In recent work [26], EA was determined by applying a
Kissinger-like approach (see Ref. [28]). In a Kissinger-like
analysis, EA is determined either from the time lapse to a
fixed degree of transformation in a series of isothermal tests
at various holding temperatures or from the evolution of the
temperature at which a certain transformed fraction is
reached in a series of isochronal experiments at various
heating/cooling rates. Kissinger-like methods are less robust
than the approach by Borgenstam and Hillert because they
do not take DG into account. Practically, this would imply a
systematic underestimation of EA . The effect is more pro-
nounced for data acquired close to equilibrium conditions
(i.e., at temperatures close to Msi ). An advantage of a
Kissinger-like method is that it can be applied for isochronal
conditions, thus allowing determination of EA in all systems
where martensite formation can be, at least partially, sup-
pressed upon fast cooling to a sufficiently low temperature.
Consistently, in Ref. [26], various Fe-based alloys and
commercial steel grades, developing f5 5 7gc , f2 2 5gc , and
f2 5 9gc martensites, were cooled to 77 K by immersion in
boiling nitrogen. The transformation was then followed
during subsequent isochronal (re)heating and EA was
determined from the slope of the straight line obtained by
plotting lnðTf20 =/Þ versus 1=Tf 0 , where Tf 0 is the temperature
corresponding to a fixed stage of transformation, f 0 , and / is
the heating rate.
In relation to the results of these analyses, Borgenstam
and Hillert [27] suggested that small variations of chemical
composition do not significantly affect the kinetics of the
Activation Energy of Time-Dependent Martensite Formation in Steel
transformation. Under this assumption, isothermal data col-
lected for Fe-Ni-Mn and Fe–Cr-Ni alloys with comparable
total contents of substitutional atoms, but different levels of
interstitial purity, were grouped together. For both series of
alloys, their analysis yielded an approximate value of
EA = 7 kJ mol−1. On the other hand, the Kissinger-like
method applied to a broad range of alloys [26] indicated that
EA increased with the fraction of interstitial atoms and ran-
ges from 8 to 27 kJ mol−1. Extrapolation of this data set to
low interstitial contents showed striking compatibility with
the results obtained according to the approach of Borgen-
stam and Hillert. The present work aims to validate the two
analyses and to obtain reliable information on EA for future
modelling of the transformation kinetics. The following two
steps were taken to arrive at this validation.
Firstly, a new series of experiments was conducted on
(wt%) 17Cr-7Ni-1Al-0.09C (17-7 PH) and 15Cr-7Ni-2Mo-
1Al-0.08C (15-7 PH) stainless steels, wherein f5 5 7gc lath
martensite (i.e., interpreted as pure S martensite) develops at
sub-zero Celsius temperatures. The experiments included
both isothermal and isochronal tests, and the two sets of data
were used to assess EA according to the approach presented
by Borgenstam and Hillert and the Kissinger-like methods
for isothermal and isochronal analysis (cf. Ref. [28]),
respectively. This part of the work aimed at exploring the
importance of the systematic underestimation of EA by
Kissinger-like methods.
Secondly, isothermal data considered in Ref. [27] were
re-evaluated. As suggested in Ref. [26], EA varies with the
logarithm of the interstitial content. Consequently, small
variations in low purity level can significantly affect the
kinetics of the transformation. To verify this, each data set in
Ref. [27] was re-evaluated independently. Additionally, it is
noted that the analysis in Ref. [27] did not distinguish
between f5 5 7gc , f2 2 5gc and f1 1 2gc martensites, which
cannot be reconciled with our interpretation of S martensite.
Data referring to f1 1 2gc martensite were excluded in the
present analysis.
Materials and Methods
The materials chosen for investigation were steels of types
17-7 PH (17Cr-7Ni-1.Al-0.08C) and 15-7 PH (15Cr-7Ni-
2Mo-1Al-009C). In these alloys, the kinetics of the trans-
formation can be adjusted at convenience by varying the
austenitization conditions, and martensite formation on
cooling can be fully suppressed [9]. Samples were Ø 3 mm
disks with a thickness of 0.15 lm (17-7 PH) and 0.25 lm
(15-7 PH) thick, supplied by Goodfellow Inc. in as-rolled
(17-7 PH) and annealed (15-7 PH) condition, respectively.
Samples were electro-plated with a layer of pure Ni (approx.
15
0.5 lm thick) prior to austenitization in order to prevent
preferential formation of martensite at the free surface.
Austenitization was performed in a continuous Ar flow and
consisted in heating at an average rate of 1 K s−1 to the
austenitization temperature, followed by 180 s austenitiza-
tion at temperature and cooling to room temperature at an
average rate of 0.7 K s−1. The austenitization temperatures
chosen were 1253 K (980 °C) for PH 15-7 and 1283 K
(1010 °C) for PH 17-7. In both cases, the microstructure of
the material upon cooling to room temperature consisted of
austenite and a minor (3–5%) presence of delta ferrite situ-
ated at the austenite grain boundaries.
The formation of martensite was followed applying
magnetometry. Details on the experimental setup as well as
on the quantification procedure were given elsewhere [26,
29, 30]. Two types of tests were performed: isothermal and
isochronal. In order to attain identical starting conditions for
the isochronal and isothermal data sets, the samples were
first cooled to 77 K in the vibrating sample magnetometer
before investigation.
Results and Discussion
From Isothermal and Isochronal Transformation
Curves to Sub-zero Celsius Transformation
Diagrams
Examples of the experimentally obtained transformation
curves for 17-7 PH are presented in Fig. 1. Isothermal data
in Fig. 1a indicates that martensite formation is time
dependent in the investigated temperature interval, 120–
270 K. The highest transformation rate was observed at
195 K. The lowest fraction of martensite forms at 270 K,
where less than 0.2% martensite is obtained after 76 ks
isothermal holding. Isochronal data in Fig. 1b shows that
martensite forms during continuous heating starting from
77 K. For the highest heating rate of 0.833 K s−1 (i.e.,
50 K min−1), the transformation barely starts and the pro-
cess stops at approx. 272 K with only 1.5% martensite
formed. This temperature is interpreted as Msi . For the
slowest applied heating rate of 0.00167 K s−1 (i.e., 0.1 K
min−1), the transformation starts at approx. 110 K and sat-
urates at Msi at a maximum value of 74.5% fraction of
martensite, f . In the case of PH 15-7 (not shown), the
investigated temperature interval was 130–310 K, the
highest transformation rate was observed at 230 K and Msi
equalled 315 K.
All data from Fig. 1 for PH 17-7 and the data for PH 15-7 are
presented in Fig. 2a, b, respectively. The isothermal data are
represented by the data arranged along horizontal lines, while
the isochronal data are arranged along the curves with
increasing slope. Interconnecting points of equal transformed
16 M. Villa and M. A. J. Somers

Fig. 1 Fraction of martensite Df formed in 17-7 PH during a isothermal holding at various temperatures and b isochronal heating from 80 K at
various heating rates. The legend refers to a the temperature of isothermal holding in K and b the rate of isochronal heating in K min−1

Fig. 2 Superposition of TTT (full colour) and CHT (faint colour) transformation diagrams for: a 17-7 PH stainless steel austenitized at 1283 K
(1010 °C) and b 15-7 PH stainless steel austenitized at 1253 K (980 °C)

fraction provide Time-Temperature-Transformation (TTT)
and Continuous-Heating-Transformation (CHT) diagrams.
Analogous to Continuous-Cooling-Transformation, (CCT)
diagrams, where the transformation lines are shifted to a lower
temperature as compared to the corresponding TTT diagrams,
the transformation lines for a CHT diagram are shifted to higher
temperature as compared to the lines for the corresponding
TTT diagrams. In the following, the experimental data were
used to quantify EA .
Assessment of Activation Energy for Martensite
Formation
Following the analysis introduced by Borgenstam and Hil-
lert [27], isothermal data in Fig. 2 are presented as 1=T
versus lnðtðMsi =T  1ÞÞ in Fig. 3. At a transformed fraction
of 0.4%, there is good correspondence between data for PH
17-7 (open symbol) and PH 15-5 (closed symbols). For the
higher transformed fractions, the slope of the low tempera-
ture asymptote, which is used to quantify EA , is of compa-
rable magnitude for the two steels and remains virtually
unchanged during transformation. This indicates that the
rate-determining step for time-dependent martensite forma-
tion in the two materials is comparable and remains largely
unaltered during the transformation. Differences in absolute
kinetics are ascribed to the effect of the microstructure on the
evolution of the phase fraction versus time. The activation
energy, EA , was evaluated from the slopes of the low tem-
perature asymptotes. To secure a sufficiently robust analysis,
only data acquired at temperatures equal or lower than the
maximum transformation rate were considered. The analysis
was performed for every increase in f by 0.001 and yielded
EA within the ranges 9.8–14 kJ mol−1 and 8.6–15.3 kJ
mol−1 (mean values 11.3 kJ mol−1 and 12.9 kJ mol−1) for
PH 17-7 and PH 15-7, respectively.
The same data sets were used to estimate EA according to
Kissinger-like isothermal method [28], where EA is evalu-
ated from the slope of the straight line obtained by 1=T
versus lnðtÞ. Additionally, isochronal analysis was per-
formed as previously reported [26] using the second data
set. Isothermal analysis yielded 7.4–12 kJ mol−1 and 7.7–
13 kJ mol−1 (mean values 9.1 kJ mol−1 and 10 kJ mol−1)
for PH 17-7 and PH 15-7, respectively; isochronal analysis
Activation Energy of Time-Dependent Martensite Formation in Steel
Fig. 3 Isothermal data presented in Fig. 2 according to the analysis
proposed by Borgenstam and Hillert [27]. Open symbols connected by
dashed lines and full symbols connected by dotted lines refer to PH
15-7 and PH 15-7 steels, respectively. In this present form, data are
used to quantify EA from the slope of the low temperature asymptote
(schematically presented for 0.4% fraction transformed)
yielded EA within the ranges 7.1–11.9 kJ mol−1 and 9.9–
12.7 kJ mol−1 (mean values 9.8 kJ mol−1 and 11.5 kJ
mol−1) for PH 17-7 and PH 15-7, respectively. Evidently,
isothermal and isochronal analyses yield consistent results.
Moreover, there is a fair agreement between the results of the
Kissinger-like methods and the Borgenstam-Hillert method.
As anticipated, the self-consistent (and driving force omit-
ting) Kissinger-like methods yield systematically lower
values, albeit negligible within experimental accuracy. The
trend is that the Kissinger analysis of the isochronal data set
yields activation energy values in between those obtained
with the Borgenstam-Hillert analysis and the Kissinger-like
analysis of the isothermal data set.
In the following, isothermal data from the literature for
Fe-Ni-Mn and Fe–Cr-Ni and previously used in Ref. [27] are
revisited to determine EA according to the Borgenstam-
Hillert method and the Kissinger-like method. The analysis
considered only those alloys developing f5 5 7gc and
f2 2 5gc martensites and was performed for individual com-
positions to verify the dependence on interstitial content.
Only data sets consisting of at least 3 data points at and below
the maximum transformation temperature were taken into
account, provided that a linear regression coefficient better
than 0.8 was obtained. The results are presented in Fig. 4
along with the values obtained for PH 17-7 and PH 15-7 as
described above and compared with the data in Ref. [26].
Again, a systematic underestimation of EA for the
Kissinger-like method is found as compared to the
Borgenstam-Hillert analysis. Clearly, the data is consistent
with those for the PH steels investigated in this work.
A trend is observed that the activation energy increases with
interstitial content for the data in Refs. [31–35], which
remained unobserved in the evaluation in Ref. [27]. In
17
Fig. 4 Activation energy, EA, for time-dependent martensite formation
as a function of the total atomic fraction of interstitials in the alloy/steel,
C + N. Full symbols refer to data obtained based on the method
presented by Borgenstam and Hillert. Isothermal data: Refs. [32, 33]
extracted at 1 and 5% Df from the reported Figs.; Ref. [31], extracted at
1 and 5% from Fig. 1 present tabulated at 0.2%; Ref. [34], extracted at
20% f from Fig. 2; Ref. [35], data at 1% f extracted from the presented
figure. Isochronal data were reported in previous work by the present
authors [26]. The data is presented such that the error bars in EA are
given as the minimum, maximum and average values taking into
account the standard error of the estimate for linear regression. Dashed
line represent linear fit of data obtained by Kissinger-like methods
comparison with an assessment of the dependence of the
activation energy on interstitial content obtained for a broad
range of iron-based alloys and steels in Ref. [26] (and earlier
in Ref. [7]), excellent correspondence is obtained and the
trend of decreasing activation energy with logarithmic low-
ering of the interstitial content is confirmed (cf. Fig. 4).
A rough quantitative relationship can be obtained by linear
fit of data. Recognizing that the data in Ref. [26] rely on a
Kissinger-like analysis of isochronal data, the linear fit in
Fig. 4 was restricted to this type of analysis, yielding:
EA ¼ ð27:0  1:9Þ þ ð7:0  0:8Þ  LogðC þ N Þ ð1Þ
where C + N represents the total content of C and N atoms
in at. fraction. In line with the above-mentioned omission of
the driving force in Kissinger-like analyses, this equation is
likely to represent an underestimation.
The strong dependence of the activation energy on the
interstitial content would be consistent with solid-solution
strengthening of austenite and with the idea by Ghosh and
Olson [36] that the interaction of solute atoms with the ther-
mally assisted motion of the martensitic interface rate control
the isothermal process. At present it is not clear whether EA
would eventually reach zero for a sufficiently low interstitial
content, or whether the formation of S martensite is intrinsi-
cally time-dependent. In perspective, to fully understand the
nature of martensitic transformation in steel, work should be
initiated to address this fundamental question.
18
Conclusions
The time-dependent formation of martensite in (wt%)
17Cr-7Ni-1Al-0.09C and 15Cr-7Ni-2Mo-1Al-0.08C steels
can be fully suppressed by immersion in boiling nitrogen. The
transformation kinetics were studied in isothermal tests and
isochronal heating experiments and yielded TTT and CHT
(continuous heating transformation) diagrams for martensite
formation in the sub-zero Celsius temperature regime.
The activation energy of time-dependent martensite for-
mation was determined by applying the Borgenstam-Hillert
and Kissinger-like methods for isothermal and isochronal
analysis. The two approaches yield consistent results and
indicated that the activation energy in these steels is 9–
13 kJ mol−1.
The present data were combined with a large number of
partly re-interpreted literature data and establishes a loga-
rithmic dependence on the total fraction of interstitials in the
Fe-based alloys/steels, suggesting that solution strengthening
determines the rate of isothermal martensite formation at
sub-zero Celsius temperature.
Acknowledgements This work was financially supported by the
Danish Council for Independent Research [grant number:
DFF-4005-00223]. The first author acknowledges Otto Mønsted fund
for financially supporting the participation in ICOMAT 2017.
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 The Effects of Prior-γ Grain Boundary
Segregation of Phosphorus, Manganese
and Molybdenum on Intergranular Fracture
Stress in Low Carbon Martensite Steels

Masahide Yoshimura, Manabu Hoshino, Masanori Minagawa,

and Masaaki Fujioka

Abstract
Influence of prior-γ grain boundary segregation of alloy
elements on intergranular fracture stress is important for
the mechanism of temper embrittlement. There are a few
efforts based on pure-iron [1], but no report on low carbon
martensitic steels. In this study, the effect of segregation
of phosphorus (P), manganese (Mn) and molybdenum
(Mo) was investigated. The samples were melted by
changing the amount of P, Mn and Mo based on the base
Fe-0.1%C-3%Mn-90 ppmP. The martensitic steels with
coarse prior-gamma (γ) were made by quenching and
tempering. The segregation was measured by Auger
electron spectroscopy, and the intergranular fracture stress
was regarded as the yield strength at ductile brittle
transition temperature of Charpy V-notch test. This study
revealed that the segregation of P weakened the fracture
stress mostly in the order of P and Mn, and that of Mo
strengthened the fracture stress quantitatively. Mn-P
co-segregation was not observed. The segregation of P
was decreased by the addition of Mo.
Introduction
For conventional low carbon steels, with the increase in
tensile strength, Charpy toughness decreases. Low temper-
ature fractures are normally transgranular. However, tem-
pered martensite shows embrittlement in some cases with
fracture surfaces along prior-gamma (γ) grain boundaries.
Charpy toughness deteriorates significantly. According to
conventional knowledge [2], firstly phosphorus (P) segre-
gates to the grain boundaries during tempering, the mini-
mum energy required for fractures, so-called grain boundary
cohesive energy decrease, intergranular fracture stress
decreases, and finally ductile-brittle transition temperature
(DBTTGB) shifts to a higher temperature.
On the other hand, manganese (Mn) and molybdenum
(Mo) are empirically known as embrittlement and toughness
elements [3], but the mechanisms are not clear especially for
carbon containing martensite. It is required to divide the
direct effect of segregation of itself and the indirect effect
mediated by the segregation of P. That is to say, it is
important to determine whether Mn weakens grain bound-

⋅ ⋅
Keywords aries or Mo strengthens grain boundaries quantitatively. In

⋅ ⋅
Temper-embrittlement Segregation Intergranular addition, it is important to determine whether Mn assists the

⋅ ⋅
fracture Fracture stress Martensite segregation of P and Mo suppresses the segregation of P [4,

⋅
Grain boundary Phosphorus Manganese 5]. The purpose of this work is to clarify the influence of
Molybdenum Steel grain boundary segregations of P, Mn, Mo on intergranular
fracture stress and the influence of Mn, Mo on grain
boundary segregations of P. Therefore, grain boundary
segregations and intergranular fracture stress are measured
independently.

Experiments

M. Yoshimura (&) ⋅ M. Hoshino ⋅ M. Fujioka
Nippon Steel & Sumitomo Metal Corporation, Futtsu, Japan
e-mail: yoshimura.f8c.masahide@jp.nssmc.com
M. Minagawa
Nippon Steel & Sumikin Technology Corporation, Futtsu, Japan
In order to investigate the influence of alloy elements, the
samples were melted by changing the amount of P, Mn, Mo
based on Fe-0.1%C-3%Mn-90 ppmP (see Table 1). The
martensitic steels with coarse prior-γ were made by

© The Minerals, Metals & Materials Society 2018 21

A. P. Stebner and G. B. Olson (eds.), Proceedings of the International Conference on Martensitic Transformations: Chicago,
The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-319-76968-4_3
22 M. Yoshimura et al.

Table 1 Chemical compositions

Ferrous alloys C P* Mn Mo Others mass%, *ppm
3Mn-P 0.095 50 3.0 – Al = 0.025, Si ≤ 0.01,
3Mn 0.094 90 3.0 – S* ≤ 20 N* ≤ 11, O* ≤ 10,
Fe
3Mn + P 0.094 450 3.0 –
5Mn 0.099 100 5.0 –
3Mn + 0.25Mo 0.097 90 3.0 0.25

400μm

Fig. 2 Microstructure of 3Mn with nital eching

Fig. 1 Process

quenching from 1473 K and tempering at 873 K containing

the embrittlement range below Ac1 and subsequently,
quenching (Fig. 1). For the measurement of prior-gamma
grain boundary segregation, Auger electron spectroscopy
was used. Analysis conditions are beam voltage: 10 keV,
beam current:10 nA. Segregation was determined by relative
sensitivity methods. Auger peak values of analysis are P:
120 eV, C: 272 eV, Mn: 542 eV, Mo: 186 eV, Fe: 703 eV.
Relative sensitivity coefficient value was used from JEOL
data set. The samples were broken in a vacuum chamber at
77 K and measurements were performed except for precip-
itates with dispersion.

Experimental Results Fig. 3 Influence of P, Mn, Mo on the relationship between grain

boundary segregation of P and DBTTGB. The range of low concen-
Samples in this work are typical martensitic steels with lath tration of P is shown in the inserted figure
structures (Fig. 2). Prior-gamma size is coarse 360–577 μm.
All samples fracture along prior-γ grain boundaries in low
direct effects of Mo itself (Fig. 3). The results show that Mn
temperature Charpy test. All samples have the almost same
has only the direct effect of segregation of Mn itself, Mo has
yield stress, between 615 and 688 MPa.
the direct effect and the indirect effect mediated by segre-
DBTTGB deteriorated with the increase in segregation of
gation of P.
P (Fig. 3 line). By the addition of Mn, toughness remarkably
deteriorates and the segregation of P was not changed
(Fig. 3). Mn-P co-segregation was not observed. If the Discussion
deterioration by added Mn was only caused by segregation
of P, about 8% of segregation of P was required. On the Intergranular fracture stress was estimated in this study as
other hand, by the addition of Mo, toughness improves and yield stress at DBTTGB temperature. When yield stress
the results show suppression of the segregation of P and the approaches intergranular fracture stress, fracture occurs. That
The Effects of Prior-γ Grain Boundary Segregation of Phosphorus … 23

Intergranular fracture stress (MPa)

200 corresponds to the segregation of P, Mn and Mo itself
3Mn independently (Fig. 4). Influence of alloy elements on
5Mn
Mo +173(MPa/at%) intergranular fracture stress was clarified quantitatively. This
100 3Mn+0.25Mo
3Mn+P study revealed that the segregation of P weakened the
fracture stress mostly in the order of P and Mn, and that of
0
Mo strengthened the fracture stress. The degree of contri-
bution per 1 at % in this work approximately corresponds to
-100 the grain boundary cohesive energy of sigma 3 ab initio
Mn -35(MPa/at%)
calculations based on pure-Fe [7, 8].
-200
P -43(MPa/at%)

-300
0 2 4 6
Grain boundary segregation (at%)
Fig. 4 Influence of grain boundary segregation on intergranular
fracture stress
was calculated by yield stress in a tensile test at room tem-
perature and conversion of the strain rate of the Charpy
impact test from 10−3(/s) to 103(/s) by using the strain rate
temperature effect (Eq 1). Influence of temperature on yield
stress was used by the reference [6] (Eq 2).
R = T × lnð108 ̸ ėÞ
σ YS = − 2.5 × T + Const.
R is the strain rate temperature effect index. T is tem-
perature (K). ė is strain rate (/s). σ YS is yield stress (MPa).
By calculating intergranular fracture stress without the
indirect effect mediated by segregation of P, the influence of
yield stress can be excluded, and intergranular fracture stress
Summary
8 10
This study revealed that the segregation of P weakened the
fracture stress mostly in the order of P and Mn, and that of
Mo strengthened the fracture stress quantitatively. The
results of this work agree with ab initio calculations. As an
indirect effect, the addition of Mo depresses the segregation
of P. Mn-P co-segregation was not observed.
References
1. Lee DY, Barrera EV, Stark JP, Marcus HL (1984) Metall Trans A
ð1Þ 15:1415
2. Mulford RA, McMahon CJ Jr, Pope DP, Feng HC (1976) Metall
ð2Þ Trans A 7:1183
3. McMahon CJ Jr (1989) Mater Sci Forum 46:61
4. Yu J, McMahon CJ Jr (1980) Metall Trans 11A:277
5. Yu J, McMahon CJ Jr (1980) Metall Trans 11A:291
6. Petch NJ (1986) Acta Metall 34:1387
7. Geng WT, Freeman AJ, Olson GB (2001) Phys Rev B 63:165415
8. Yamaguchi M (2011) Metall Trans A 42:319
Another random document with
no related content on Scribd:
hind-side-foremost caricature of what is itself a caricature—an
organ-grinder’s monkey.
When Benny carried the gayly dressed Nanny out to the enclosed
yard, it was hard to tell which exhibition of feeling was the keenest—
poor, unconscious, and absurd Nanny’s delight in her freedom and
her eager desire to take her place with her old companions, or the
consternation and terror of the entire flock at the strange wild beast
which was thus turned loose among them.
They ran from side to side, and crowded each other against the
paling so unceasingly and so wildly, that Benny carried the unwilling
ewe back to the kitchen.
At nightfall, however, Benny again placed Nanny in the open field
with the sheep, thinking that they would gradually, throughout the
darkness, become used to the presence of her little harlequin jacket,
and allow her to graze by their side in peace.
That night two cronies of Benny’s came from a neighboring farm to
talk over that ever-interesting topic, the great snowstorm, and to buy
some of his lambs. The three old men sat by the great fireplace in
the old raftered kitchen in the pleasant glow from the blazing logs,
each sipping with unction a mug of Benny’s famous flip, while Debby
rubbed with tallow the sadly stiffened long-boots that had been worn
in the Christmas snow. Suddenly a loud wail of distress rang in their
ears, the door was thrust violently open, and in stumbled the
breathless form of the tall, gaunt old negress Tuggie Bannocks. She
was a relic of old slavery times, who lived on a small farm near the
old Gilbert Stuart Mill, on Petaquamscut River. They all knew her
well. She had bought many a pound of wool from Benny to wash and
card and spin into yarn, and she always helped Debby in that yearly
trial of patience and skill—her soap-making. The old negro woman
had double qualifications to make her of use in this latter work: her
long, strong arms could stir the soap untiringly for hours, and then
she knew also how to work powerful charms—traditional relics of
Voodooism—to make the soap always turn out a success.
Tuggie Bannocks sank upon the table by the fire, murmuring:
“Tanks be to Praise! Tanks be to Praise!” and closed her eyes in
speechless exhaustion. Debby took a half-crushed basket of eggs
from the old woman’s arm, drew off her red woollen mittens, and
rubbed briskly her long cold claws of hands. Benny had a vague
remembrance of the old-time “emergency” saying, “feathers for
fainters,” and seized a turkey’s wing that was in daily use as a
hearth-brush, thrust it into the flames, and then held the scorching
feathers under the old negress’s nose until all in the room were
coughing and choking with the stifling smoke.
Spluttering and choking at the dense feather-smoke, Tuggie
gasped out: “I ain’t dead yit—I specks I shall be soon, dough—kase I
seen de ole witch a-ridin’—I’se most skeered to death” (then in a
fainter voice)—“gib me a mug of dat flip.” Startled, Benny quickly
drew a great mug of home-brewed beer and gave it a liberal dash of
Jamaica rum and sugar, then seized from the fire the red-hot
“loggerhead” and thrust it seething into the liquid until the flip boiled
and bubbled and acquired that burnt, bitter flavor that he knew
Tuggie dearly loved. The old woman moaned and groaned as she
lay on the table-top, but watched the brewing of the flip with eager
eye, and sat up with alacrity to drink it.
With many a shuddering sigh and many a glance behind her at the
kitchen door, and crossing her fingers to ward off evil spirits she
began: “Ye know, Miss Nickkels, I telled ye I was witch-rid by ole
Mum Amey, an’ dis how I know I was. Ye see I was a-goin’ to wuk a
charm on her first off—not to hurt her none, jess to bodder her a
leetle—an’ I jess put my project on de fire one night, an’ it jess a-
goin’ to boil, an’ in come her ugly, ole grinnin’ black face at de door,
an’ say she a-goin’ to set wid me a spell.” Mum Amey was a wrinkled
half-breed Indian of fabulous age and crabbed temper, a “squaw-
nurse,” who was, of course, not half as black as negro Tuggie. “She
walk ober to de chimbly to light her pipe an’ ask me what I a-cookin’,
an’ I say Ise a-makin’ glue, cause Ise afeard she see de rabbit’s foot
in de pot, an’ I say it all done, an’ yank de pot offen de crane so she
can’t see into it. An’ ob course when I take de project offen de fire
afore it’s wukked, it break de charm; an’ wuss still, I can’t nebber try
no project on her no more. Ole Mum Amey larf, an’ say, a-leerin’ at
me, dat pot ob glue won’t nebber stick nothin’ no more. An’ ebber
sence dat night I ben witch-rid. Mornin’s when I wakes up I sees
marks ob de bit in de corners ob my mouf, where Mum Amey ben a-
ridin’ me all ober Boston Neck an’ up de Ridge Hill till I so tired and
stiff I can’t hardly move. Ise ben pinched in de night an’ hab my ha’r
pulled. An’ my butter won’t come till I drops a red-hot horseshoe in
de cream to dribe her out. One day I jess try her to see ef she a
witch (dough I know she one, ’cause I see her talkin’ to a black cat); I
drop a silber sixpence in her path, an’ jess afore she get to it she
turn an’ go back, jess I know she would. No witch can’t step ober
silber. An’ now, Benny Nickkels, I know for shore she’s a witch, I see
her jess now in de moonlight a-chasin’ an’ ridin’ your sheep; an’,
shore’s yer bawn, yer’ll find some on ’em stone dead in de mornin’—
all on ’em, mebbe!”
Benny looked wretched enough at this statement. Dearly as he
loved his sheep and ready as he was to face physical discomfort and
danger in their behalf, he was too superstitious to dare to go out in
the night to rescue them and brave the witch.
“How did she look, Tuggie? And what did she do?” whispered
awe-struck Debby.
“Oh, she was mons’ous fearsome to see! Witches don’t nebber go
in deir own form when dey goes to deir Sabbaths. She was long an’
low like a snake. She run along de groun’ jess like a derminted yeller
painter, a-boundin’, an’ leapin’, an’ springin’, a-chasin’ dem pore
sheeps—oh, how dey run! Wid her old red an’ blue blanket tied tight
aroun’ her—dat’s how I knowed her. An’ she had big sparklin’ gold
dollars on her back—wages ob de debbil, I ’specks. Sometimes she
jump in de air an’ spread her wings an’ fly awhile. Smoke an’ sparks
come outen her mouf an’ nostrums! Big black horns stick outen her
head! Lash her long black tail jess like de debbil hisself!”
At this dramatic and breathless point in Tuggie’s flip-nourished and
quickly growing tale, credulous Debby, whose slow-working brain
had failed to grasp all the vivid details in the black woman’s fervid
and imaginative description, interjected this gasping comment: “It
must ha’ been the devil or the creeper.”
 Benny jumped from his chair and stamped his foot, and at once
burst into a loud laugh of intense relief, and with cheerful bravado
began to explain animatedly to his open-mouthed cronies that of
course anyone could see that Tuggie’s sheep-chasing witch was
only the creeper sheep in her new fleece, and he offered
swaggeringly to go out alone to the field to bring the ewe in to prove
it.
The old negress sprang to her feet, insulted and enraged at the
jeering laughter and rallying jokes, and advanced threateningly
toward him. Then, as if with a second thought, she stopped with a
most malicious look, and in spite of Debby’s conciliatory
explanations and her soothing expressions “that it might have been
Mum Amey after all,” she thrust aside Benny’s proffered mollification
of a fresh mug of flip, seized her crushed basket, stalked to the door,
and left the house muttering, vindictively: “High time to stop such
unrageous goin’s-on—dressin’ up sheeps like debbils—scarin’ an ole
woman to death an’ breakin’ all her aigs! Ole Tuggie Bannocks ain’t
forgot how to burn a project! Guess dey won’t larf at witches den!”
And surely enough—as days passed it could plainly be seen that
the old negress had carried out her threat—for the chimney was
“conjured”—was “salted.” On windy nights the shepherd and his wife
were sure they could hear Tuggie dancing and stamping on the roof,
and she blew down smoke and threw down soot, and she called
down the chimney in a fine, high, shrieking voice: “I’ll project ye,
Benny; I’ll project ye.” And she burnt the cakes before the fire, and
the roast upon the spit, and thrice she snapped out a blazing coal
and singed a hole in Debby’s best petticoat, though it was worn
wrong side out as a saving-charm. And Benny could see, too, that
the old ram was bewitched. The remainder of the flock soon became
accustomed to the sight of Nanny’s funny false fleece, but he always
fled in terror at her approach. He grew thin and pale (or at any rate
faded), and he would scarcely eat when Nanny was near. Debby
despairingly tried a few feeble counter-charms, or “warders,” but
without avail. When sheep-shearing time came, however, and
Nanny, shorn of her uncanny fleece and clothed in her own half-inch
snowy wool, took her place with the other short-clipped members of
the flock, he ceased to be “witch-rid”—the “project,” the “conjure”
was worked out. He grew fat and fiercely brave, and became once
more the knight of the field, the lord of the domain, the patriarch, the
potestate of his flock.
The story of Tuggie Bannocks’s fright and her revengeful “project”
spread far and wide on every farm from Point Judith to Pottawomat,
and was told in later years by one generation of farmers to another.
And as time rolled on and Nanny reared her lambs and they her
grand-lambs, the creeper sheep were known and sold throughout
Narragansett by the name of witch-sheep.
 THE CRUSOES OF THE NOON-
HOUSE
In a grass-grown graveyard by the side of an old Presbyterian
church in Narragansett, the warm, midday sun shone brightly down
one spring Sabbath in the year 1760 upon two boys twelve years of
age, two cousins, named Elam Noyes and Cotton Fayerweather.
They stood by the side of their grandfather’s grave, which bore a
new blue slate headstone, inscribed with his name and age, and the
verses:

“You children of ye name of Noyes

Make Jesus Christ yo’r oleny choyse.”

The boys had gone into the church-yard with the apparent design
of examining this fine, though misspelled, token of the stone-cutter’s
art, but were really speaking and thinking of a very different subject.
They would never have been allowed to wander in the church-yard
to indulge in idle talk, and even now could spend but a few minutes
in conversation together. It was their only meeting-time during the
week, for they lived at extreme ends of the town, and Elam recited
his lessons to the Baptist minister, who lived near him, while Cotton
attended the village school. They were two well-built, healthy boys,
both dressed in clumsy, homespun suits of clothes, with full knee-
breeches, long-flapped coats and waistcoats, coarse yarn stockings
and buckled shoes, and great gray beaver hats several sizes too
large for them. Elam was as solemn and serious in his appearance
as was his father, but in his brain was a current of keen romance
rarely found in the head of any elderly colonist. As he left the church-
yard with his cousin he said, with much impressiveness, “Remember,
Cotton, if you are not here by candle-light I shall tarry no longer, but
shall go home.”
For several Sundays, as the boys had walked among the graves,
and while they had been busy with the care of their fathers’ horses,
Elam had occupied every moment in telling to Cotton all that he
could remember of a wonderful story he had read in New Haven.
Two months previously he had ridden with his father to that town,
and in the tap-room of the “ordinary” at which they had “put up”
during their stay there had lain a pile of about forty books, which a
sea-captain had left to be sold to any chance traveller, or to
townspeople who might be inclined to purchase them. There were
several copies of Tate and Brady’s new Psalms, which some of the
New England Puritans wished to use instead of the loved old Bay
Psalm-book, two or three Bibles, half a dozen volumes of sermons, a
Dutch Psalm-book, which was not Dutch at all, but a collection of
English songs and ballads, Milton’s “Paradise Lost,” a few prayer-
books, and then there was a wonderful book which Elam did not
have time to finish, though he had not wasted a moment. It thrilled
and filled him with adventurous longings, and was called “Robinson
Crusoe.” This was the first and only story-book he had ever seen,
and as he retold the wonderful tale to Cotton, the desire to run away
out into the great world, to cross the ocean and see some strange
sights and lead a different life from that on a Narragansett farm, grew
strong in both boys’ breasts.
At last Elam, having a fertile though unexercised imagination,
developed a plan of action. They would leave home and meet at the
old meeting-house, where they would spend several weeks of
idleness, roaming the woods by day and sleeping in the noon-house
by night, and when everyone in town was tired of searching for them,
then they would make their way to the sea-shore without fear of
capture, and get on board a ship and sail off somewhere. They could
hide in the wood on the Sabbath days, and as the meeting-house
stood on a lonely road in a great wood on the top of a high hill, there
would be but few passers-by on week-days, and hence few chances
of discovery. And now I must explain about the noon-house, which
was to be their sleeping-place, for none of those queer old buildings
now exist in New England.
By the side of the barn-like church were three long, low, mean,
stable-like log buildings, which could hardly be stables, since at one
end of each hut was a rough stone chimney. These were noon-
houses, or “Sabba-day houses.” One had been built by Elam and
Cotton’s grandfather, and was used by the families of his children.
Until the early years of this century, only two or three meeting-
houses throughout New England contained stoves. All through the
long, bleak, winter weeks, through fierce “nor’-westers” and piercing
frosts, the lonely churches stood, growing colder and colder, until
when they were opened upon the Sabbath the chill and damp
seemed almost unbearable. The women brought to church little iron
foot-stoves filled with hot coals. Upon these stoves they placed their
feet, and around them the shivering children sat at their mothers’ feet
and warmed their chilled hands. But by the time the long service was
over—for often the minister preached two hours and prayed an hour,
and some of the Psalms took half an hour to sing—you can easily
see that the warmth would all have died out of the little foot-stove,
and the mothers and children would be as cold as the fathers, which
is saying a great deal.
Now these half-frozen Baptists and Puritans and Episcopalians
could hardly have remained to attend an afternoon service and lived
through it, so they built houses with chimneys and fireplaces near
the church where they could go and make a fire and get warm and
eat their lunch, and when they asked permission to put up such a
building they said it was to “keep their duds and horses in.”
And, surely enough, at one end of the noon-house were usually
several stalls for the horses, who doubtless also enjoyed the warmth
that came from the fireplace at the end of the room. The “duds” were
the saddles and pillions on which the church attendants had been
seated on their ride to church, and the saddle-bags which were full of
good things to eat. Sometimes a few cooking-utensils to warm the
noonday food were kept in the noon-house, and often hay for the
horses and a great load of logs to burn in the fireplace, and
sometimes a barrel of “cyder,” to drink at the nooning.
 Frequently a large noon-house was built by several farmers in
company, and I am afraid the children did not then enjoy their
Sunday noontimes, for some old deacon or elder usually read a
sermon to them between the morning and afternoon services, and
they had to sit still and listen.
So you see that Elam and Cotton had very comfortable quarters to
sleep in when they ran away to the noon-house on the Monday
following the opening of my story. Each arrived about an hour before
sunset, laden with all the food that he had been able to capture
before leaving home. Cotton had a great piece of salt-pork and a
dozen eggs, some of which had had a rather disastrous journey in
his coat-pockets. Elam had a great crushed mass of dough-nuts and
brown bread. This was not all of their provisions for their sojourn, for
on each successive Sunday for five weeks previously both boys had
crowded their great pockets with russet apples and their saddle-bags
with cold corn-bread and brown bread, and they had starved
themselves at each nooning in order to save their food and thus
provide for the coming day of need; and they had concealed their
treasures in an empty corn-bin at the horses’ end of the house.
Cotton felt sure that they had food enough to last them for three
weeks—rather dry and conglomerated, to be sure, but still good
enough for boys of healthy appetites and simple Puritan tastes. Elam
also had brought a flint and tinder-box with him, and with their aid
and that of some light “candle-wood” he soon had a blazing fire upon
the hearth, the coals of which he carefully covered up to save till
morning, and then the two Robinson Crusoes climbed upon the hay
and fell asleep.
The story of the first day spent by the runaways in their retreat
would be the story of all the days, which were not as pleasure-filled
as they had hoped. They had no hut to build, no goats to tame, no
savages to fight and dread. They rose early in the morning, for the
habits of their daily life were strong, and they did not dare have a fire
much after daybreak, lest the smoke from the chimney should be
discovered by some rare passer-by. They ate their breakfast of
brown bread and cheese and apples and drank a little of the hard
cider. As the weather was fortunately warm, they lolled on the stones
behind the noon-house while Elam told over and over again the story
of Robinson Crusoe and tales of the Indians that he had heard from
his grandfather. They fished, with some success, in a little brook
which ran through the woods, and one day they caught a rabbit in a
trap which Cotton had set, and which he had learned how to make
from old Showacum, a “praying Indian” who lived in the village.
These trophies of their skill they of course skinned and cleaned and
cooked, and though they were hungry—for they were hungry all the
time—the unsalted fish and game did not seem very appetizing to
them. They found a treasure one day in the woods—a store of nuts
which had been forgotten or neglected or reserved until spring by
some kindly squirrels—and with a few cakes of toothsome maple-
sugar they had some variety of diet.
But alas, they also had healthy young appetites, and on Saturday
night Cotton awakened to a fact whose approach had been plainly
looming up before Elam for some time—that their three weeks’
supply of food was all gone. A half-decayed apple was their sole
supper. A drink of the sour cider seemed only to make their hunger
harder to bear, but at last they fell asleep. Perhaps the pangs of his
gnawing stomach made Elam sleep more lightly than on previous
nights, perhaps the equally keen pangs of his awakened conscience
may have made him restless, but at midnight he suddenly sprang to
his feet with an exclamation of horror at a sound which he
recognized at once as the howl of a wolf. He jumped to the fire,
wakening Cotton, who tumbled out of his nest of hay with a
bewildered and wretched expression and an impatient cry of, “Oh,
why did you wake me up when I am so hungry; pray let me sleep if
you do or not,” when nearer and louder still rose the mournful howl of
the wolf. With trembling hand Cotton heaped the light wood on the
blaze which Elam had started with the old leather bellows, and then
threw log after log on the hearth until the blaze roared up the
chimney. Of course, the wolves—for they could hear more than one
—could not get into the noon-house, as window and shutter were
fast, but the boys were so wretched with hunger, so homesick, so
lonesome, that they hardly stopped to reason, and, trembling with
fear, Cotton seized an iron “loggerhead” which his father kept in the
noon-house, and thrust it into the coals to heat to a red-hot pitch,
when it could be used as a weapon. A “loggerhead” was a bar of iron
which was used as a stirring-stick in making “flip.” Deacon
Fayerweather always brought to church each winter Sunday in his
saddle-bags three or four bottles of home-brewed beer and a bottle
of Jamaica rum, from which, with the aid of the loggerhead, he made
a famous jug of flip for the minister and deacons at the nooning.
And now the peaceful loggerhead was the only weapon the two
wretched boys possessed, and, indeed, all they needed, for in a
short time the howls of the wolves grew fainter and fainter and at last
were no longer heard. All thought or power of sleep had, however,
vanished from the brains of the terrified young Crusoes at this
experience of the pleasures of adventure. All wish for final escape to
the sea-shore had also disappeared, and now their only longing was
to return home. All the remaining hours of the night they sat by the
fire, while Elam, romantic in spite of hunger, fright, and
disappointment, made known his plans for the following day. Toward
morning they let the fire die down and expire, and when the sun was
fully risen they left their sheltering noon-house and hid in the woods
not far from the meeting-house, trembling, however, at every sound
as they thought of their dread night-visitors.
As nine o’clock drew near there approached the church on every
side, on foot and on horseback, the members of the congregation. All
knew of the mysterious disappearance of Cotton and Elam, for the
country had been widely and quickly scoured for them. Among the
worshippers came Deacon and Mistress Fayerweather and
Goodman Noyes and his wife, for all felt it a godly duty, even in time
of deep affliction, not to neglect the public worship of God on the
Sabbath. Despairingly did the sad parents hope to hear some news
of their lost boys, who had apparently vanished from the face of the
earth, for neither in farm-house nor in field, neither on the road nor at
the toll-gate, neither by traveller nor by hunter, had they been seen.
The very simplicity of their plan had been its safety. Forty years
previously the whisper of kidnapping by the Indians would have
added terror to the parents’ grief, but those days were happily over.
After sad greetings had been exchanged and the minister had
entered the pulpit, the congregation seated itself for its usual
Sunday-morning service. The opening half-hour prayer was ended,
the church attendants had let down their slamming pew-seats (for
the seats in those old New England meeting-houses always turned
up on hinges to allow the pew occupants to lean against the walls of
the pew during the long prayer), the minister had read with trembling
voice a note which had been sent to him, “desiring the prayers of the
congregation for two families in great inconveniency and distress,”
when a door on the leeward side of the church slowly opened and
two pale, dishevelled, and most wretched-looking youngsters crept
slowly and shamefacedly in. The habit of constant self-repression
and self-control, characteristic of the times, was all-powerful, even in
this intense moment of crisis for the families of Fayerweather and
Noyes. The deacon flushed scarlet, but did not move from his raised
seat in front of the congregation. A faint murmur swept over the
entire assembly at the appearance of Cotton and Elam, but was at
once repressed. The boys walked calmly on to their accustomed
seats on the gallery stairs, under the supervision of the tithingman.
That zealous officer rapped sharply on the head with his long staff
two or three of the occupants of one of the “boys’ pews,” who had
turned around and stared, and whispered noisily at the appearance
of the runaways. The old minister, being slightly deaf, had heard no
ripple of commotion, and, not having glanced at the late comers,
proceeded to offer a pathetic prayer for the lost ones, “whom God
held in the hollow of his hand,” a prayer that brought to Elam and
Cotton a realizing sense of their selfishness and wickedness, and
which worked a lesson that influenced them through life. The parson
then gave out his text: “He will have charge over thee concerning
thee,” and worked his way on in his accustomed and somewhat
monotonous fashion, though with many allusions to the two
wanderers, until at fourteenthly came the long-deferred end. Nor was
there any murmur of feeling heard (though the mothers’ eyes were
filled with tears), when Deacon Fayerweather, in a slightly trembling
voice, lined out the Psalm:

O give yee thanks unto the Lord

because that good is hee,
 Because his loving-kindness lasts
in perpetuitee.

I’th’ desart in a desart way

they wandered: no towne finde
to dwell in. Hungry and thirsty
their Soul within them pinde.

Then did they to Jehovah cry

when they were in distresse
Who did them set at liberty
out of their anguishes.

In such a way as was most right

he led them forth also
That to a citty which they might
inhabit they might go.

I wish I could say that the boys’ parents, being so glad to get the
wanderers home, permitted them to go unpunished, but alas! early
New Englanders believed firmly that “foolishness is bound up in the
heart of a child,” and never spared the rod; and, as “sloathefulnes”
and disobedience to parents were specially abominated, such high-
handed rebellion as this of Elam and Cotton could hardly be allowed
to pass by without being made a public example. Then, too,
unfortunately for the boys, the warmth of joy at recovering the lost
ones had time through the two hours of sermon to cool down and
change into indignation. So at the close of the service Deacon
Fayerweather, after rather coldly greeting his son and nephew,
asked the advice of the minister upon so important a subject, who
gave as his opinion that the gravity of the offence, the necessity of
the lesson to other youths in the congregation, and the conveniency
of circumstances seemed to point out plainly, and was furthermore
upheld by Scripture, that public chastisement should be given upon
the spot, and that Elder Rogers was best fitted, both by age, dignity,
and strength, to administer both rebuke and punishment. And with
promptness and despatch and thoroughness the decree was carried
out; both boys were “whipped with birchen rods” while standing upon
the horse-block before the church.
But though the colonial fathers were stern and righteously
disciplinarian, the colonial mothers were loving and tender, as are
mothers everywhere and in all times, and Mistress Fayerweather
and Mistress Noyes each bore off her weeping boy to the noon-
house and filled his empty stomach well with dough-nuts and pork
and peas and pumpkin-bread, until, with comfort and plenty within,
external woes and past terrors were forgotten.
 THE DOCTOR’S PIE-PLATES
Many of my cherished china treasures, having no historical
association and being of comparatively coarse ware, would be of
little value on the shelves of a collector, and also of little interest to
the general observer; but they are endeared to me by the
remembrance of the circumstances under which they were found, or
by some story connected with their past owner or their past history.
I have a set of dark-blue Staffordshire plates, known as the
“Doctor’s Pie-plates,” which are resplendent with an interest that
does not come from their glorious color, rich as it is, nor from the wit
of the humorous scenes they represent. The plates, named,
respectively, “Dr. Syntax’s Noble Hunting-party,” “Dr. Syntax Upsets
the Beehives,” “Dr. Syntax Painting the Portrait of His Landlady,” “Dr.
Syntax Taking Possession of His Rectory,” and “Dr. Syntax Star-
gazing,” are printed from a set of pictures drawn by Thomas
Rowlandson, one of the most celebrated designers of humorous and
amusing subjects of his day. They were drawn and engraved to
illustrate a book published by William Combe, in 1812, called “Dr.
Syntax’s Tour in Search of the Picturesque.” A second tour, “In
Search of Consolation,” appeared in 1820. This was also illustrated
by Rowlandson. A third tour, “In Search of a Wife,” was printed the
following year. These books had an immense and deserving
popularity. Not only did these blue Staffordshire plates appear,
copying the amusing designs from the Dr. Syntax illustrations, but a
whole set of Derby figures were modelled—Dr. Syntax Walking, In a
Green-room, At York, At the Bookseller’s, Going to Bed, Tied to a
Tree, Scolding the Landlady, Playing the Violin, Attacked by a Bull,
Mounted on Horseback, Crossing the Lake, Landing at Calais, etc.,
and also were sold in large numbers.
The “Doctor’s Pie-plates” did not, however, receive their name on
account of the presence of the laughable figure of Dr. Syntax in their
design, but from a far different and more serious and deeply felt
reason. They were once used as pie-plates; or, rather, I should say
more exactly and truthfully, were used once as pie-plates, and the
story of that solitary pie-episode in their history, with the succeeding
results of their one period of use in that capacity, will explain their
fresh, unused condition, and show why I prize them so highly, and
reveal also the reason why I call them the “Doctor’s Pie-plates.” The
name has a deep significance; the pie-plates are captured trophies
of past war, sad emblems of hopeless rebellion, never-fading
ceramic proofs and emblems of the selfishness, the tyranny of man.
In the latter part of the eighteenth century, an American gentleman
married in England an English lady of some wealth. They brought to
America with them in a sailing-vessel, as part of the bride’s wedding-
outfit, a gayly painted, richly mounted travelling-coach. In this great
coach they rode in grand style with four post-horses from Boston to
Albany, New York, and Philadelphia, and back to the little town in
Narragansett, which was ever after their home. In due time they
died, and left to their only son, a physician, all their worldly goods,
including the old coach, and the far less desirable inheritance of a
high and stubborn temper, and a firm and deep-seated veneration for
English customs, manners, traditions, and productions, which would
be worthy an Anglomaniac of the present day. He, however, made
one unfortunate and incomprehensible deviation from his Anglo-
worship when he married an American wife. As years went on, the
Doctor grew more and more overbearing and dictatorial, especially in
his household (as some English husbands are also said to be), and
in the matter of food and of cooking—those unfortunate hobbies of
an ill-tempered man—he took, perhaps, the most violent stand.
Never did any other wife have to hear so often the words, “as my
mother used to cook it,” and “they don’t do it so in England,” or have
to listen so frequently to acrimonious expressions of dislike of
American cooks and cooking. Pork and beans, “cracker johnny-
cake,” Indian-pudding, even the purely Dutch dough-nuts were
banished from his board; for not only did he refuse to eat these New
England dishes himself, but would not let his wife and daughters,
either. He also became unjust enough bumptiously to denounce as
“American” and “taboo” any food (no matter of what nationality)
which did not suit his fancy or which chanced to disagree with him.
 On an unlucky day, having eaten too greedily of mince-pie (for he
had a fine English appetite), he passed his universal banishing
dictum on that darling of New England hearts and stomachs—the
pie. From thenceforth on feast-days only English plum-pudding was
served for dessert. To the New England wife, accustomed to see at
least four kinds of pie offered to “company,” if one made pretence
even of being truly hospitable and housewifely, the lonely pudding
was a great and almost unbearable source of grief and mortification,
and many a struggle did she make (trying to imitate her forefathers
of old) against the English yoke, but in vain; pieless and barren for
years was her table. But reinforcing troops at last came to her
rescue; for three daughters were grown, and, brave and strong with
youth, they dared to rebel more openly and recklessly than their
browbeaten mother.
In 1830 all the Doctor’s relatives, far and near, were invited to eat
“Thanksgiving dinner” with him and his family; for he was hospitable
enough, in his own fashion; in all, thirty were to sit down at his board.
On the day before Thanksgiving, mother, daughters, and “help” were
all busy at work from early morning in the great pantry and kitchen,
making careful preparation for the coming dinner, and brisk sounds
of chopping and pounding and mixing were heard, and savory smells
and spicy vapors filled the house. Toward the close of the day, when
their work was nearly done, they suddenly heard, to their terror, the
sound of the Doctor’s cane (for he was badly crippled with that
typical English disease, the gout) thump, thumping through the halls
and rooms to the kitchen, an apartment he seldom visited. With
palpitating hearts but firm countenances they stood in a hollow
square for strength, as does any determined band, while he walked
past them to the “buttery,” where were placed in military rows twenty-
six of those hated abominations, pies—mince-pies, pumpkin and
apple and cranberry, and, the crowning dainty of all, “Marlboro’” pies.
Their only hope of salvation was that in the dull, fading November
light the tyrant might not discover the forbidden pastry; and, indeed,
he did not appear to do so, for he merely glanced scowlingly around,
and, without speaking, hobbled back to his office. Once more they
breathed freely, and the eldest daughter said, cheerfully: “Now, girls,
nothing can happen; if he had seen them we should have had to give
them away; but he won’t know anything about it now until they are
brought on the table with the pudding, and he will be most through
his bottle of port then—but oh, what shall we do when the company
goes?”
Poor souls! they slept for one night the happy, unconscious sleep
of the victorious, the hospitable, and awoke on Thanksgiving morn to
find every pie vanished from the pantry-shelf. Every pie? Yes, and
every pie-plate, too!—twenty-six of the new English blue-and-white
stone-ware plates. At first they really believed, in their simplicity, that
a thief must have entered from outside and stolen them; but why
should the marauder take pies, and no other food? Then, too, there
was not a foot-print on the light snow which had fallen early in the
evening. No; the Doctor must have stolen his wife’s pies! But where
could he have hidden the pie-plates? For weeks, yes, for years, they
searched in every nook and corner; through the hay in the barns,
behind the logs of wood in the sheds, in old barrels and boxes in the
cellar, in closets, in trunks, under the eaves in the attic; and they
even peered out on the roof behind the peaks of the gable-windows,
but no pie-plates could they find. The grim old Doctor kept his
silence, until his daughters grew at last to think that some thief must
have entered in spite of apparent impossibility.
Thirty-six years later, in 1866, the aged Doctor died, and went,
doubtless, to an English paradise. His browbeaten wife had given up
the struggle many years before. The daughters, now elderly women,
with a long-concealed but unsubdued hatred born of years of
tyrannical browbeating and oppression, at once made a triumphal
holocaust of many of the cherished treasures of the British tyrant;
and the first victim doomed to destruction was the old English coach
in which their English grandmother had ridden in state through the
country. This broken-down, moth-eaten, rat-nibbled, cobweb and
dirt-filled relic had stood unused for fifty years—an abominable
nuisance, an inconvenient obstruction, a hated eyesore, in the
carriage-house connected with their dwelling. The Doctor had
cherished it on account of its English birthplace; but now its fate was
sealed. As the first heavy blow of the destroying iconoclastic axe
struck the hated coach, a loud rattle as of falling crockery was heard,
and the executioner paused. A careful investigation discovered an
unknown compartment under the driver’s seat which had been
constructed for the purpose of hiding despatch-boxes and, perhaps,
the bride’s jewel-cases—and in this hiding-place were twenty-six dirt-
covered, dark-blue Staffordshire plates. A sudden light of
comprehension and recognition came into the faces of the sisters—
here were the long-lost pie-plates! The cantankerous old Doctor had
craftily arisen in the night, hobbled out silently, in spite of his gout,
thrown the carefully and daintily made Thanksgiving pies to the pigs,
stealthily packed the plates in the old coach, watched maliciously the
unsuccessful plate-search, kept silence throughout the despoiled
Thanksgiving dinner and through nearly forty pieless years, and died
triumphant.
Half of this treasure-trove, which the Doctor could hide, but,
happily, could not take with him, were the Dr. Syntax plates; and
from that half came my share. The other plates were of well-known
English views—Payn’s Hill, the City of Liverpool, Blenheim Castle,
Fulham Church-yard, Windsor Castle—no American views were on
any of his crockery; no landing of Lafayette, no State plates, were
ever allowed to grace that rank old Tory’s pantry.
Thus, one good, one noble result came from this “ugly trick”—the
hidden pie-plates were all saved unscratched, unbroken, for the
Doctor’s kinsfolk to-day, who, in gratitude for his unintentional
posthumous favor, suitably reward him by telling the story of his
spiteful midnight theft whenever we show the plates. And, moreover,
we wantonly and openly insulted and jeered at his memory and his
gastronomic laws by formally and derisively naming the dark-blue
salvage from the coach the Doctor’s Pie-plates.
 MY DELFT APOTHECARY JARS
The circumstances under which I first saw my old Delft apothecary
jars were so painful, so mortifying, that for a long time I could not
bear even to think of them; but now, as years have passed and
softened the sharp lines, I will write account of that unique
adventure.
We were one day, as was our wont, hunting in old Narragansett for
ancient china and colonial furniture, but even on that historic and
early-settled ground had met with scant success. At last, on an out-
of-the-way road, was found a clew.
We were driving slowly along, when the door of a long, low wood-
shed opened, and an elderly man walked out on the single broad
stone step and stood, in the lazy country fashion, staring openly and
sociably at us as we passed by. He had in one hand a piece of dark
wood which he was slowly rubbing with sand-paper. We had driven
past his door when my companion suddenly exclaimed: “That man
had a claw-foot.”
“A claw-foot!” I answered in astonishment; “what do you mean?—a
cloven foot or a club-foot, perhaps?”
“No, you goose; that man had in his hand a claw-foot—the leg of a
chair, I am sure, and I am going back to see to what it belongs.”
So we whisked the pony around and drove to the door where the
claw-footed man still stood, and we then saw in the one dingy
window a small sign bearing the words

ELAM CHADSEY
GENERAL REPAIRER