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Energetic Materials
Energetic Materials
Advanced Processing Technologies
for Next-Generation Materials
Edited by
Mark J. Mezger
Kay J. Tindle
Michelle Pantoya
Lori J. Groven
Dilhan M. Kalyon
CRC Press
Taylor & Francis Group
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© 2018 by Taylor & Francis Group, LLC

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Library of Congress Cataloging‑in‑Publication Data
Names: Mezger, Mark J., editor. | Tindle, Kay J., editor. | Pantoya,
Michelle, editor. | Groven, Lori J., editor. | Kalyon, Dilhan M., editor.
Title: Energetic materials : advanced processing technologies for
next-generation materials / [edited by] Mark J. Mezger, Kay J. Tindle,
Michelle Pantoya, Lori J. Groven and Dilhan M. Kalyon.
Other titles: Energetic materials (CRC Press)
Description: Boca Raton : Taylor & Francis, CRC Press, 2017. | Includes
bibliographical references and index.
Identifiers: LCCN 2016059724 | ISBN 9781138032507 (hardback : acid-free paper)
| ISBN 9781315166865 (electronic)
Subjects: LCSH: Explosives. | Chemical processes.
Classification: LCC TP271 .E54 2017 | DDC 662/.2--dc23
LC record available at https://lccn.loc.gov/2016059724
Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com
and the CRC Press Web site at

http://www.crcpress.com
Contents
Preface.......................................................................................................................ix
Editors .......................................................................................................................xi
Contributors ........................................................................................................... xiii
Introduction ............................................................................................................xvii
Section i critical Science and technologies in

the Life cycle of energetic Materials
Chapter 1 Synthetic Methods for High-Energy Organofluorine Compounds ......3

V. Prakash Reddy
Chapter 2 Optical Diagnostics for Characterizing Explosive Performance .......25

Michael J. Hargather
Chapter 3 Solubility Thermodynamics of Organic Energetic Materials .............43

Sanjoy K. Bhattacharia, Nazir Hossain, Brandon L. Weeks,
and Chau-Chyun Chen
Chapter 4 Mathematical Modeling and Experimental Investigations of

Crystallization and Recrystallization Processes to Achieve
Targeted Polymorphs and Crystal Size and Shape Distributions....... 63
Paul Redner, Nebahat Degirmenbasi, Ralph Schefflan,
Eileen Heider, Mark J. Mezger, Steven M. Nicolich,
Suphan Kovenklioglu, and Dilhan M. Kalyon
Chapter 5 Dynamic Characterization of Energetic Materials ............................ 87

Brahmananda Pramanik
Chapter 6 Sustainable High Explosives Development ........................................ 95

Noah Lieb, Neha Mehta, Karl D. Oyler, and
Kimberly Yearick Spangler
v
vi Contents
Chapter 7 Printed Energetics: The Path toward Additive Manufacturing

of Munitions ..................................................................................... 115
Lori J. Groven and Mark J. Mezger
Chapter 8 Rheological Behavior of Energetic Gels and Suspensions ............... 129

Bahadir Karuv, Seda Aktas, Jing He, Hansong Tang,
Constance M. Murphy, Suzanne E. Prickett, and
Dilhan M. Kalyon
Chapter 9 Mixing, Coating, and Shaping ......................................................... 169

Jonghyun Park, Heng Pan, Mark J. Mezger, Steven M. Nicolich,
John M. Centrella, Frank T. Fisher, Nezahat Boz,
Moinuddin Malik, Seda Aktas, Jing He, and Dilhan M. Kalyon
Chapter 10 Continuous Processing and Shaping Using a Fully Intermeshing

Co-Rotating Twin Screw Extruder ................................................... 193
Moinuddin Malik, David F. Fair, Richard S. Muscato,
Michael J. Fair, Mark J. Mezger, Steven M. Nicolich,
Constance M. Murphy, Seda Aktas, Jing He, Bahadir Karuv,
Hansong Tang, and Dilhan M. Kalyon
Section ii the national technology and

industrial Base of the Future
Chapter 11 Transition from Laboratory Innovation to Production and

Military Fielding .............................................................................. 233
Magdy Bichay and Jan A. Puszynski
Chapter 12 Multidisciplinary Teams Required for the Development of

Next-Generation Energetics ............................................................. 257
Kay J. Tindle, Daniel Marangoni, and Nicholas J. Marangoni
Contents vii
Chapter 13 The Nascent National Energetic Materials Initiative ....................... 269

Kay J. Tindle, Robert V. Duncan, Anthony M. Dean,
Steve Tupper, Ronald J. White, Van Romero, Richard A. Yetter,
Stephen D. Tse, Jan A. Puszynski, Dilhan M. Kalyon, and
Michelle Pantoya
Epilogue ................................................................................................................ 279

Index ...................................................................................................................... 281
Preface
Explosives, propellants, and pyrotechnics are energetic materials (EMs) that have
been utilized for the munitions, mining, oil well perforation, construction, and
demolition industries for hundreds of years. In each of these industries, the trend has
been to develop and/or acquire EMs that display greater performance and improved
sensitivity characteristics, that are less expensive and of better quality, and that are
easy and safe to manufacture. Historically, scientists have explored the development
of new materials through organic chemical synthesis that resulted in the identifica-
tion of many EMs with varying properties. Several of these compounds were origi-
nally intended for commercial applications before their energetic properties were
discovered. One such example is trinitrotoluene (TNT) invented in Germany during
the early 1800s as a yellow dye. TNT was found to be an insensitive explosive that
was later used for main charges in munitions by the end of the 1800s.
There was much progress in the development of EMs during World War I and II.
Before and during World War I, EMs for munitions were produced at small arsenals
and ordnance stations, and at a few contractor facilities across the United States.
After World War II, the nation consolidated EM production into large army ammu-
nition plants. The entire complex, termed the National Technology and Industrial
Base (NTIB) for Conventional Munitions, is still utilized for EM manufacturing
today. Constructed in the 1940s and 1950s with the most modern manufacturing
methods of the day, production lines in the NTIB were dedicated single product
lines required to produce materials in extremely high volumes and at the lowest pos-
sible costs. The NTIB had a manufacturing capacity that was designed to supply the
munitions for the United States and its allies through a conflict based on the magni-
tude of World War II. For example, this complex was capable of producing a million
pounds of TNT per day with similar capacities for other legacy EMs.
One of the major conundrums associated with the NTIB is how to right size
a base so that it can efficiently and cost effectively produce ammunition in peacetime
and yet maintain the ability to ramp up the capacity for readiness in the event of a
major war. Since the 1950s, the military has undergone several changes that have
had a significant impact on the NTIB. Several facilities have been closed as a result
of multiple rounds of Base Realignment and Closure actions and in 2010 changes in
the scope of military strategy. No longer is the nation concerned about being ready
at any moment to fight a major conflict on two separate fronts. Military strategy
is now based on short-duration, small-unit operations primarily focused in various
regions of the world. Under this type of strategy, the material requirements between
peacetime and readiness are diminished. The net result of all of these changes is
an NTIB that is operating between 3% and 5% of its total capacity now and for the
foreseeable future.
The military is looking to develop systems that will create leap-ahead advances
in warfighting capabilities. The vision is to transition new technologies to the
warfighter at the speed of development. For EMs, this translates into compounds
with increased power that are more effective and more survivable in a combat
ix
x Preface
environment. Developing new products within the process constraints of the

existing NTIB is a long and arduous endeavor. The immense capacity and inflexi-
bility of these lines form a significant barrier to the transition of many new energetic
products into the field. Retooling and revising line layouts require capital expendi-
tures that make a cost–benefit analysis work against adopting any new technology.
University, commercial, and government laboratories are developing new EMs
that go beyond standard C–H–N–O-type EMs and use processes that are not neces-
sarily traditional organic chemistry methods. These materials include metastable
interstitial compounds, organic–metallic compounds, nanophase and amorphous
phase metallic and organic compounds that are referred to as next-generation EMs.
The nation has a significant capacity within its laboratories to create these materials
using novel processes; however, there is little or no capacity to develop or produce
these innovations. Therefore, potential solutions that could be utilized to create leap-
ahead advances in warfighter capability may never be produced.
Other industries have moved from dedicated production lines and batch processes
to flexible agile manufacturing techniques. The nation is at a point in history where
perhaps the NTIB needs to be rethought to more efficiently meet the challenges and
requirements of the changing military strategy. The scope of this book will be to
look at the development of next-generation EMs that will be developed using new
and novel ingredients and modern manufacturing processes.
Section I focuses on the studies that have been conducted to assess EM physical
and chemical characteristics and the capability to synthesize innovative solutions.
This section will summarize the findings for the purpose of pointing the direction
for the future.
This section will also consider the sciences associated with recent material and
process advances of next-generation EMs. Advances in energetics technology are
making use of new chemical techniques, such as vapor deposition of fine particle
metals as high-density fuels. They look to nanomorphologies of organic crystals,
nontraditional energy release mechanisms, amorphous phases of C–H–N–O com-
pounds, spray coating and drying, acoustic mixing, twin-screw extrusion, and two-
dimensional/three-dimensional printing. This portion of the book will focus on how
basic sciences are being developed and employed to model and design the fabrication
methods to produce inexpensive high-quality EMs. This will include the develop-
ment of these processes for both legacy and next-generation EMs.
Section II examines how to conduct business in a new manner. Forming as a
subgroup in the National Armaments Consortium (NAC), the National Energetic
Materials Initiative (NEMI) is being created to focus and coordinate the develop-
ment efforts for next-generation EMs. Through the NAC, the NEMI will facilitate
the interactions between academia, private organizations, and government agencies
to generate solutions for both the warfighter and commercial industry.
Editors
Mark J. Mezger is a senior technology advisor for Energetics Development
Initiatives at the U.S. Army Armament Research, Development and Engineering
Center at Picatinny Arsenal, Wharton, New Jersey, where he earlier held positions in
the Office of the Director of Technology and the Business Interface Office.
Through the establishment of public–private partnerships, Mezger created a
national nanotechnology network with regional areas of expertise. He also served as the
RDECOM (Research, Development, and Engineering Command) Nanotechnology
Integrated Product Team Chairman. Through his associations with the National
Nanotechnology Manufacturing Center in Swainsboro, Georgia, NanoMaterials
Commercialization Center technical advisory board, Pittsburgh, Pennsylvania, the
Lehigh Valley Nanotechnology Network in Bethlehem, Pennsylvania, the State
University of Missouri at Columbia (MIZZU) in Columbia, Missouri, and the
Greater Garden State Nanotechnology Alliance, he has established for the Army
one of the largest nanoparticle reactor facilities in North America and is currently
involved in applying this technology to explosive and reactive materials.
He earned his ExMT in technology management from the Wharton School at the
University of Pennsylvania–Philadelphia, Pennsylvania, and Bachelor’s of Science
degrees in math–physics and in engineering science are from the State University of
New York at Buffalo, Buffalo, New York.
Kay J. Tindle currently serves as the senior director for the Research Development
Team in the Office of the Vice President for Research at Texas Tech University,
Lubbock, Texas. She earned her BA in teaching English as a foreign language from
Oklahoma Christian University, Edmond, Oklahoma, her MEd in adult and higher
education from the University of Central Oklahoma, Edmond, Oklahoma and her
Ph.D. in higher education research from Texas Tech University, Lubbock, Texas. Her
research focuses on multidisciplinary teams as mechanisms of accountability, com-
munication practices and innovations among multidisciplinary teams, and women
leaders in higher education.
Michelle Pantoya is the J.W. Wright Regents Chair in mechanical engineering

and a professor at Texas Tech University, Lubbock, Texas. Her research focuses on
developing new nanoscale energetic materials used for both industrial and military
applications. Her vision is to promote cleaner, safer, and more effective energetic
composites through an understanding of their basic combustion behavior. Her
advances have been recently aired on a segment of the Discovery Channel’s Daily
Planet entitled Green Ammunition. The news story explains her scientific contri-
butions to remove lead-based materials engrained in most ordnance systems with
environmentally safe and more reactive nanoparticle formulations. She is making
tremendous strides through creating new diagnostic techniques for probing com-
bustion reactions on the nanoscale; and then bridging these findings to describe a
reactive material’s macroscopic behavior. Her ability to establish the link between
xi
xii Editors
how phenomena occurring on the nanoscale affect the energetic performance of a

pyrotechnic on the macroscale is one example of a scientific contribution that has
made her a leader at the frontiers of knowledge in energetic materials combustion.
Another more fundamental impact that broadly advances science is her research to
introduce an entirely new mechanism by which a reaction can occur based on a dis-
persion rather than a classical diffusion process. She received U.S. Presidential rec-
ognition for her work as a recipient of the prestigious National Science Foundation
Presidential Early Career Awards for Scientists and Engineers award in 2004.
Lori J. Groven is an assistant professor of chemical and biological engineering at

South Dakota School of Mines and Technology, Rapid City, South Dakota. Prior
to this appointment, she served as an assistant research faculty in the School of
Mechanical Engineering at Purdue University, West Lafayette, Indiana. She is
an experimentalist focused on the combustion, characterization, processing, and
improvement of materials ranging from traditional materials to the nanoscale for
propulsion and energy storage. Her research has included the study of combustion
of nanosized powders to synthesize intermetallic and ceramic materials, small-scale
propagation of gasless reactions, and direct write of biocidal materials, and most
recently has focused on additive manufacturing routes for energetic materials, to
name a few. She has been the author or coauthor of more than 30 peer-reviewed
publications since 2010.
Dilhan M. Kalyon holds the Institute Professor Chair at Stevens Institute of

Technology, Hoboken, New Jersey, and is affiliated jointly with the Department of
Chemical Engineering and Materials Science and the Departments of Chemistry,
Chemical Biology, and Biomedical Engineering. He has also been the founding direc-
tor of the Highly Filled Materials Center at Stevens since 1989. Professor Kalyon
has received the International Research award of the Society of Plastics Engineers
(2008), the Thomas Baron award in Fluid-Particle Systems of the American Institute
of Chemical Engineers (2008), the Harvey N. Davis Distinguished Teaching
Assistant Professor award (1987), Exemplary Research Award (1992), Henry Morton
Distinguished Teaching Full Professor award (2000), honorary MEng degree
(honoris causa) (1994) and the Davis Memorial award for Research Excellence
(2009) from Stevens Institute of Technology, the Founder’s award of JOCG
Continuous Extrusion and Mixing Group (2004), and various fellowships, includ-
ing DuPont Central Research and Development Fellowship (1997), Exxon Education
Foundation Fellowship (1990), and Unilever Education Fellowship (1991). He was
elected Fellow of the Society of Plastics Engineers (2004) and Fellow of American
Institute of Chemical Engineering (2006).
Contributors
Seda Aktas Robert V. Duncan
Department of Chemical Engineering Department of Strategic Research
and Materials Science Initiatives
Highly Filled Materials Institute and
Stevens Institute of Technology Department of Physics
Hoboken, New Jersey Texas Tech University
Lubbock, Texas
Sanjoy K. Bhattacharia
Department of Chemical Engineering David F. Fair (Retired)
Texas Tech University U.S. Army Armament Research,
Lubbock, Texas Development and Engineering Center
Picatinny Arsenal, New Jersey
Magdy Bichay
Naval Surface Warfare Center Michael J. Fair
Indian Head, Maryland U.S. Army Armament Research,
Development and Engineering Center
Nezahat Boz Picatinny Arsenal, New Jersey
Department of Chemical Engineering
and Materials Science Frank T. Fisher
Highly Filled Materials Institute Department of Mechanical Engineering
Stevens Institute of Technology Stevens Institute of Technology
Hoboken, New Jersey Hoboken, New Jersey
John M. Centrella Lori J. Groven

U.S. Army Armament Research, Department of Chemical and Biological
Development and Engineering Center Engineering
Picatinny Arsenal, New Jersey South Dakota School of Mines
and Technology
Chau-Chyun Chen Rapid City, South Dakota
Texas Tech University Michael J. Hargather
Lubbock, Texas Department of Mechanical Engineering
New Mexico Institute of Mining
Anthony M. Dean and Technology
Colorado School of Mines Socorro, New Mexico
Golden, Colorado
Jing He
Nebahat Degirmenbasi Department of Chemical Engineering
Highly Filled Materials Institute and Materials Science
Stevens Institute of Technology Highly Filled Materials Institute
Hoboken, New Jersey Stevens Institute of Technology
Hoboken, New Jersey
xiii
xiv Contributors
Eileen Heider Daniel Marangoni

Energetics and Warheads Division Research and Sponsored Programs
U.S. Army Armament Research, Rogers State University
Development and Engineering Center Claremore, Oklahoma
Nicholas J. Marangoni
Nazir Hossain Advanced Technology, R&D
Department of Chemical Engineering Rockwell Automation
Texas Tech University Milwaukee, Wisconsin
Lubbock, Texas
Neha Mehta
Dilhan M. Kalyon U.S. Army Armament Research,
Department of Chemical Engineering Development and Engineering Center
and Materials Science Picatinny Arsenal, New Jersey
Highly Filled Materials Institute
Stevens Institute of Technology Mark J. Mezger
and Explosives Technology and Prototyping
Department of Biomedical Division
Engineering, Chemistry U.S. Army RDECOM-Armament
and Biological Sciences Research, Development and
Stevens Institute of Technology Engineering Center
Hoboken, New Jersey Picatinny Arsenal, New Jersey
Bahadir Karuv Constance M. Murphy

Highly Filled Materials Institute Naval Surface Warfare Center
Stevens Institute of Technology Indian Head, Maryland
Hoboken, New Jersey
Richard S. Muscato
Suphan Kovenklioglu Naval Surface Warfare Center
Highly Filled Materials Institute Indian Head, Maryland
Stevens Institute of Technology
Hoboken, New Jersey Steven M. Nicolich
Explosives Technology and Prototyping
Noah Lieb Division
JENSEN HUGHES U.S. Army RDECOM-Armament
Baltimore, Maryland Research, Development and
Engineering Center
Moinuddin Malik Picatinny Arsenal, New Jersey
and Materials Science Karl D. Oyler
Highly Filled Materials Institute U.S. Army Armament Research,
Stevens Institute of Technology Development and Engineering Center
Hoboken, New Jersey Picatinny Arsenal, New Jersey
Contributors xv
Heng Pan Paul Redner

Department of Mechanical Energetics and Warheads Division
and Aerospace Engineering U.S. Army Armament Research,
Missouri University of Science Development and Engineering Center
and Technology Picatinny Arsenal, New Jersey
Rolla, Missouri
Van Romero
Michelle Pantoya Research and Economic Development
Department of Mechanical Engineering New Mexico Tech
Texas Tech University
Lubbock, Texas Ralph Schefflan
Highly Filled Materials Institute
Jonghyun Park Stevens Institute of Technology
Department of Mechanical Hoboken, New Jersey
and Aerospace Engineering
Missouri University of Science Kimberly Yearick Spangler
and Technology U.S. Army Armament Research,
Rolla, Missouri Development and Engineering Center
Brahmananda Pramanik
Department of Mechanical Hansong Tang
Engineering Department of Civil Engineering
Montana Tech of the University City College of New York
of Montana New York, New York
Butte, Montana
Kay J. Tindle
Suzanne E. Prickett Office of the Vice President for
Naval Surface Warfare Center Research
Indian Head, Maryland Texas Tech University
Lubbock, Texas
Jan A. Puszynski
Research Affairs Stephen D. Tse
South Dakota School of Mines Mechanical and Aerospace Engineering
and Technology Rutgers University
Rapid City, South Dakota New Brunswick, New Jersey
V. Prakash Reddy Steve Tupper

Department of Chemistry Office of Sponsored Programs
Missouri University of Science Missouri University of Science
and Technology and Technology
Rolla, Missouri Rolla, Missouri
xvi Contributors
Brandon L. Weeks Richard A. Yetter

Department of Chemical Engineering Mechanical and Nuclear Engineering
Texas Tech University The Pennsylvania State University
Lubbock, Texas State College, Pennsylvania
Ronald J. White
Center for Advanced Mineral and
Metallurgical Processing (CAMP)
and
Department of Materials Science
Montana Tech of the University
of Montana
Butte, Montana
Introduction
DEPARTMENT OF DEFENSE ENERGETIC MATERIALS DOMAIN
Scope
The Department of Defense (DoD) Energetic Materials (EM) mission encompasses
the entire life cycle of the products. As depicted in Figure I.1, the life cycle of prod-
ucts within the DoD is broken out in discrete sections, taking technology from con-
cepts investigated in the laboratory through development to production, operational
sustainment, and removal from service.
Depending on the service and system under consideration, the life cycle ele-
ments of a product are managed by different organizations. In the specific case for
EMs, there is no overarching plan for the complete life cycle between the managing
organizations.
productS
The EM products associated with DoD weapon systems are explosives, gun propel-
lants, rocket propellants, and pyrotechnics. Explosives are generally used for terminal
effects in firing trains and warhead main charges, whereas gun and rocket propel-
lants are used for the propulsion systems of munitions and missiles. Pyrotechnics are
utilized for several purposes: to generate visible light, smoke as obscurants, and heat
as anti-aircraft decoys. Each of these products has its own type of reaction, which
occurs in microseconds in the case of explosives, or in several minutes as in the case
of pyrotechnics.
For each material, the output and its corresponding sensitivity to reaction from
various stimuli are critical to handling safety and weapon system survivability.
For explosives, the goal is to maximize energy output in terms of Gurney energy
(an explosive’s ability to accelerate metal) or its brisance (an explosive’s ability to
move earth), while minimizing its sensitivity to impact, friction, heat, and electro-
static shocks. Gun propellants are different from explosives in that the material devel-
opment seeks to create compounds that maximize a specific impulse (Isp) during
burning with minimal flame temperatures. Gun propellant formulators also have to
be concerned with material sensitivity to external stimuli in order to maximize safety
in service during the product’s usable life. Rocket propellants also try to maximize
Life cycle of energetic materials
System design and Production industrial

Tech base development Sustainment and logistics Demil
development base
Lab to factory Factory to warfighter Beyond
FIGURE I.1 The life cycle of EMs as used by the DoD.
xvii
xviii Introduction
burning characteristics while minimizing their smoke signature along with material
sensitivity concerns.
The processing, storage, and handling of these materials are also uniquely differ-
ent. Certain materials cannot be stored and/or processed in close proximity due to
safety compatibility concerns. This is true not only in case of primary and secondary
explosives, but also with explosives and some pyrotechnic or propellant ingredients.
As a result of these material incompatibilities, safety protocols and material allow-
ances for processing have to be strictly regulated.
MiSSion
The DoD is always looking to identify and employ the best technology that will
provide warfighters with the most effective weaponry possible. To accomplish this
mission, the energetics community within the DoD must monitor advanced technol-
ogy developments nationally and internationally to identify the best technologies to
address issues with military systems. Once unique and innovative technologies are
identified, it is up to the people in the service laboratories to coordinate and facilitate
the linkage between technology providers and people who understand military sys-
tems to realize creative solutions for the warfighter.
NATIONAL CAPABILITIES FOR ENERGETIC

MATERIALS DEVELOPMENT AND PRODUCTION
introduction
EM research and development (R&D) for the DoD stands at a crossroad. In order to
meet the requirements for asymmetrical warfare, more powerful and less-sensitive
energetics are required. To achieve these results, scientists and engineers have had to
break with the traditional means for creating these materials and employ more inno-
vative approaches for new types of materials. However, the nation’s infrastructure
is primarily built around the carbon, hydrogen, nitrogen, oxygen (CHNO) chem-
istry that has been the principal basis for EMs for more than a century. This is a
major limiting factor in the transition and fielding of new materials. This challenge
is how to achieve a disruptive warfighting capability that employs next-generation
EMs (NGEMs) utilizing an industrial complex built upon 1940s’ equipment and
manufacturing processes. There exists little capability to scale technologies being
developed in today’s laboratories, that is, to raise Manufacturing Readiness Levels
(MRLs) so that they are comparable with Technology Readiness Levels (TRLs), and
virtually no capability to produce them in large quantities. The DoD has undertaken
many studies in the previous decade for the purpose of understanding the nation’s
capacity for developing and producing EMs.
congreSS
The House Armed Services Committee in the 2009 Defense Authorization Act
directed the Secretary of Defense to assess the current state of—and future advances
Introduction xix
in—research, development, and manufacturing technology of EM in foreign coun-

tries and the United States. At a minimum, the report was expected to include DoD
programmatic and budgetary recommendations that would ensure advanced EMs,
and equally critical energetic science and technology expertise are available to meet
future national security requirements. Also, the report should have included the risk
to national security if the funding level continues to decline.*
Congress again provided language to the Secretary of the Army in 2016 where it
was stated under the heading of Advanced Energetics: “The House Appropriations
Defense Sub-Committee (HAC-D) urges the Secretary of the Army to demonstrate,
through the application of novel manufacturing pilot processes, next-generation
insensitive energetic materials enabling increased gun-launched munition perfor-
mance to achieve longer ranges and increased terminal effects against a spectrum of
threats.†” The Senate report for the fiscal year 2017 appropriations bill also contained
language to address defense EM manufacturing. This report states, Optimization of
Ammunition Manufacturing. The Committee understands that the Army is the single
manager for conventional ammunition for the DoD and is responsible for ensuring
effective life cycle management of conventional ammunition products. This includes
the development and optimization of ammunition manufacturing processes as well
as development and integration of new materials. The Committee believes that the
manufacturing of conventional ammunition could be assisted by automating and
optimizing propellant production processes and integrating new materials. These
processes and materials may reduce cost, increase ammunition performance, and
enhance soldier safety. Also, the Committee encourages the Secretary of the Army
to equip the national technical industrial base with new and emerging manufacturing
processes and materials in order to achieve these goals.‡
reSponSe to congreSS
In response to the 2009 congressional directive, the Department of Defense, Office
of Research and Engineering (DDR&E) conducted a Life Cycle assessment of EMs
as depicted in Figure I.1. A key point from this study is outlined as follows:
Energetic Materials Is a Department of Defense

Critical Technical Competency
There are virtually no modern defense systems or munition types that do not rely
on EMs. Weapons based on advanced EMs can enhance system performance and
improve tactical survivability. By contrast, there exists no commercial market need
for military EMs at the product level. The commercial mining and construction
industries consume large quantities of EMs; however, these industries use materials
that have very different performance characteristics from the military and therefore
* House Report 110–652, p. 202.
† U.S. Congress. House. Committee on Appropriations. Department of Defense Appropriations Bill, 2017.
114th Congress, 2d session, 2016. House Report 114–577. https://www.congress.gov/congressional-
report/114th-congress/house-report/577/1, p. 216.
‡ U.S. Congress. Senate. Committee on Appropriations. Department of Defense Appropriations Bill, 2017.
114th Congress, 2d session, 2016. Senate Report 114–263. https://www.congress.gov/congressional-
report/114th-congress/senate-report/263, p. 148.
xx Introduction
are not readily interchangeable. To date, there are relatively few industrial and aca-
demic performers that exist in the EM area largely because it is nearly exclusively a
DoD need. The resulting consequence of this is that the DoD laboratories developed
all of the currently fielded tactical and strategic propulsion systems that are produced
by DoD contractors. Advances in EMs tied to achieving specific objectives and solu-
tions will almost surely result from in-house competencies.
Future weapon systems that are based on advanced EM will provide longer stand-
off distances, shorter times to target, greater weapon versatility, and greater effec-
tiveness with smaller payloads. We do need not only new and better EMs, but also a
cost-effective and efficient means to deliver them to the warfighter.
the path Forward

In 2016, the DoD was contemplating substantial modernization efforts required
for its two primary EM production facilities. Recent advances in materials and
manufacturing science have enabled researchers to explore new types of EMs
that go beyond the traditional CHNO technology, which are being referred to as
NGEMs. The national capability to develop these materials so that MRLs can be
matured along with TRLs is lacking. Even where some development capability
exists, there is no production capacity within the NTIB for conventional muni-
tions to produce NGEMs. The challenge to produce new materials results from
capability gaps on either side of the systems design and development phase of
weapon systems. As illustrated in Figure I.2, these gaps represent the valley of
death for NGEMs if the materials cannot be processed as a simple drop in to the
existing production lines.
To accelerate the development of NGEMs and facilitate the transition of these
technologies into the NTIB (i.e., traverse over the valley of death), the U.S. Army
Armament Research, Development and Engineering Center is proposing to develop
a series of Advanced Processing Lines for Energetics (APLE). This program seeks
to bridge the gaps in the current industrial base and provide the capability to mature
MRLs with TRLs for weapon developers. The APLE objectives are to create the
infrastructure that is capable of developing NGEMs and transitioning them into a
modernized NTIB where they can be readily produced in quantities required by the
DoD. The concept is to design, install, and prove out pilot-scale fabrication lines.
Such a capability would enable the DoD to have EMs that have mature MRLs along
with mature TRLs where product changeovers in production can be conducted rou-
tinely. Such pilot lines would facilitate the scale-up to full production and efficiently
transition the technology into the NTIB. The APLE strategy is to develop science-
based, flexible, and agile ingredient and formulation processes to scale up and fabri-
cate promising NGEMs. The approach is to mature technology and MRLs based on
and demonstrated in basic science and technology initiatives from government, aca-
demia, and the commercial defense sectors. The program execution will be through
a series of public–private partnerships between government, academia, and industry.
APLE has three major thrust areas that include next-generation load, assemble, and
pack (LAP) operations, flexible agile ingredient and formulation processing, and nano-
organic energetics or nanoenergetics. The program structure is broken out in Figure I.3.
What is the challenge?
Army S&T provides scientific and engineering services for
the life cycle of SMCA energetic systems
Introduction
System design and Production industrial

S&T Sustainment and logistics Demil
development base
Lab to factory Factory to warfighter Beyond
Gap in manufacturing innovation

Government and Private sector
universities Gap
Investment
Higher performance Reduced sensitivity
Technology readiness level

1 2 3 4 5 6 7 8 9
Eco friendly Efficiently produced
d
d
i
se
h
o
fe
re
a
n
m
Te evel
Te emo
rc
/
p asi
la per
su eve
te sea
c n
ch op
a
ht
s c olo
n
y
Sy bs lop
st,
o
Sy unc atio
Ba chn rch
Re rove bilit
no stra
te d
gy
y
ol men
ste h ns
te yste me
og t
lo tio
gy n
m m nt
FIGURE I.2 Life cycle capability gaps, NGEM valley of death.
xxi
xxii
Advanced processing pilot lines (APPL)
Purpose of the program is to design, install, and prove out advanced process lines for legacy and next generation energetic materials.
• The motivation for this program stems from PEO ammunition’s desire to have energetic materials that are easy to load and easy to manufacture.
• Future materials with disruptive advances cannot be easily produced in the current NTIB. These materials will require modern manufacturing processes in order for the
warfighter to utilize their benefits.
• The APPL capability needs to extend to legacy materials in order to enable and streamline product changeovers as process technologies change in the future with the ability to
go back to traditional materials if needed.
• The Army is currently considering making a large investment for the modernization of Holston and Radford AAPs. This provides an opportunity to incorporate the latest
materials manufacturing processes.
Flexible agile ingredient and

Next gen. LAP Nano energetics
formulation processing
Purpose of this thrust area is to develop process Purpose of this thrust area is to develop Purpose of this thrust area is to develop process
technologies that reduce or eliminate manned manufacturing processes for bulk energetics that technologies that have traditionally been batch
operations associated with the integration of incorporate production technologies from other oriented and transition to continuous ones.
energetics into armament systems. industries that are utilizing nano scale and/or
nano structured components. • The motivation for this thrust is improved safety
• The motivation for this thrust is improved safety and reliability and ease of product changeover.
and reliability and ease of product changeover. • Motivation for this thrust is based on sensitivity
results of nano nitramines. These materials • Continuous processes utilize smaller quantities
• The integration of energetics with electronics have the same energy output of RDX or HMX of materials while in operation which can
and other components to enable highly with half of the observed sensitivity. substantially reduce hazards in operations and
specialized munitions and effects. reduce operational safety arcs.
• Mixing nano scale materials using traditional
• Provide a means to rapidly prototype or mixing processes is difficult at best due to high
remotely manufacture small quantities of viscosities.
sophisticated munition items.
Introduction
FIGURE I.3 APLE program thrust areas.

Introduction xxiii
Each thrust area attempts to look at processes associated with different aspects
of EM product development. The next-generation LAP is concerned with molding,
forming, and shaping, and the interfaces associated with the assembly of EM sub-
components into their intended applications. Flexible agile ingredient and formula-
tion processing is concerned with converting materials made from batch processes
to continuous ones where product flexibility and agile capacity can be maximized.
The nanoenergetics area looks to bring the manufacturing technology from other
industries and adopt them for use with EMs. Of particular interest in this area is
the processing and coating of nano-organic materials while giving consideration
to the hazards associated with the reactivity of small particles.
Many of the processes for EMs are utilized by other industries. In order to adapt
these processes for use with EMs, it is critical that all of the fate and transport phe-
nomena associated with material production be understood. This starts with the
development of robust process models that take into account the reactive nature of
EMs. The successful completion of this modernization effort will produce several
process models for solubility, chemical solubility, chemical and reaction kinetics,
rheological behavior effecting process flows, crystallization, physical properties, and
terminal effects. Once these models are developed and validated, compound cre-
ation, processing, and terminal effects simulations can be conducted. Such simula-
tions should significantly reduce the development cycle times and testing required to
fully qualify new EMs for weapons use, accelerate their transition to the NTIB and
ultimate military fielding. The development of the requisite science and manufactur-
ing technologies associated with EM is the subject of Section I. Establishment of the
partnerships by forming the NEMI and the long-established National Armaments
Consortium is the subject of Section II.
OVERVIEW
Section i: critical Science and technologieS
in the liFe cycle oF energetic MaterialS
Chapter 1: Synthetic Methods for High-Energy Organofluorine Compounds

There is emerging interest in the organofluorine high-energy compounds, in particu-
lar those consisting of the trifluoromethyl, difluoroamine, and pentafluorosulfanyl
moieties. The pentafluorosulfanyl- and gem-difluoroamine-containing high-energy
compounds, in general, exhibit enhanced energy densities and relatively low shock
sensitivities, and often have other favorable characteristics, such as high detonation
velocity and detonation pressure. This review summarizes recent advances in the
synthetic methodologies for fluorinated high-energy compounds, including those
for pentafluorosulfanyl (SF5)- and difluoroamine (NF2)-containing high-energy
compounds.
xxiv Introduction
Chapter 2: Optical Diagnostics for Characterizing Explosive Performance

Optical diagnostics, including schlieren, shadowgraphy, and background-oriented
schlieren (BOS), are used to visualize shock waves and compressible flow phenom-
ena present in energetic and explosive events. These techniques visualize refractive
index variations to obtain a range of qualitative and quantitative information. A one-
dimensional explosively driven shock tube facility is used with schlieren imaging
to measure shock wave propagation speeds from explosive–thermite mixtures. The
schlieren imaging visualizes turbulent flow structures in the expanding product gas
region. An imaging spectrometer is paired with the schlieren imaging to quantify the
mixing of the explosive product gases with the ambient environment. Shadowgraphy
is applied to image field-scale explosive tests. The shadowgraph images reveal shock
waves, fragment motion and speed, and the motion of product gases. BOS is a mod-
ern technique for visualizing refractive fields via their distortion of a background
pattern. Here, the technique is applied to image field-scale explosive events using
the ambient background of the test pad. The BOS images clearly show shock wave
propagation and reflection from surfaces, which are not clearly visible in the raw
high-speed digital images.
Chapter 3: Solubility Thermodynamics of Organic Energetic Materials

Comprehensive thermodynamic solubility modeling of EMs is essential for the devel-
opment of a novel, safe, and efficient process technology, and for predicting the water
solubility upon exposure in the environment. This chapter presents the state-of-the-art
predictive molecular thermodynamic models and test the applicability of these mod-
els for three common organic EMs—PETN, RDX, and HMX—with conductor-like
screening model–segment activity coefficient (COSMO–SAC) model and nonrandom
two-liquid–segment activity coefficient (NRTL–SAC) model. COSMO–SAC gener-
ally overpredicts solubility of EM, and NRTL–SAC can be a practical thermodynamic
model to correlate solubility of EMs in a few representative solvents and to predict
solubility in pure and mixed solvents using up to four molecule-specific parameters.
Also presented are estimated octanol–water partition coefficients for assessing envi-
ronmental impact.
Chapter 4: Mathematical Modeling and Experimental Investigations

of Crystallization and Recrystallization Processes to Achieve Targeted
Polymorphs and Crystal Size and Shape Distributions
In the manufacturing of energetic crystals, including various nitramines, it is a chal-
lenge to obtain the targeted polymorphs and size/shape distributions. Generally,
blending is costly and regrinding of the crystals increases the defect densities to give
rise to increased sensitivity. The ability to predict a priori the polymorph type and
the size and shape distributions of various energetic crystalline materials upon crys-
tallization or recrystallization for different solvents and solvent combinations can
help in the attainment of the desired polymorph type and the desired size and shape
distributions without having to regrind or blend different size populations. Here,
examples of the use of various mathematical models for predictions of the polymorph
type and the dynamics of the fed-batch crystallization processes for two nitramines
Introduction xxv
are presented along with some typical experimental methods. These models include
ab initio and molecular dynamics-based models for the polymorph prediction in
conjunction with various solvent and antisolvent systems and the dynamic material
and energy balance equations, solved in conjunction with population balance models
for the prediction of the number density of crystals as a function of time and size as
functions of the nucleation and growth kinetics for the particles.
Chapter 5: Dynamic Characterization of Energetic Materials

The evaluation of dynamic characteristics of EMs is required for predicting the
deformation behavior, including the failure mechanism and intensity of fragmenta-
tion resulting from high-velocity impact events. These test parameters are significant
for developing and validating physically based material constitutive models that will
ensure the safety and performance of EM.
This chapter describes the importance of dynamic mechanical properties toward
the explosive behavior of EMs and reproduces high-rate mechanical properties
available in recently published research. The safe and efficient experimental techniques,
including split-Hopkinson pressure bars, shock tube, and drop-weight tests, are pre-
sented. The chronological advancement of the experimental and diagnostic techniques
is highlighted, and the future direction of this advancement is investigated. The role
of computer modeling and simulation of EMs under extreme loading conditions and
the contribution of experimental information toward developing improved explosives
are discussed.
Chapter 6: Sustainable High Explosives Development

High explosives continue to play a pivotal role worldwide on the battlefield and in
the commercial sector. Large quantities of these materials are produced on a yearly
basis; the production of military-grade high explosives totals several million pounds
per year in the United States. Overwhelmingly, the explosive compounds and for-
mulations used are not new materials; their development took place decades ago
(or centuries, in some cases), at a time when environmental and toxicity effects were
generally not a primary concern in materials selection. However, with the establish-
ment of increasingly strict environmental regulations from the U.S. Environmental
Protection Agency and the Registration, Evaluation, Authorization, and Restriction
of Chemicals regulation in the European Union, the need for the development of
more sustainable, greener explosives and their formulations has never been greater.
In terms of classification, high explosives are defined as substances capable of under-
going detonation (meaning that they can decompose to generate shock waves travel-
ing at supersonic speeds) when subjected to a stimulus. They can be loosely grouped
into different subcategories, typically as primary or secondary explosives based on
their properties and intended role. Of these, primary explosives are the most sensitive
and typically weaker in power. Their purpose is to convert thermal or mechanical
energy (such as the impact of a firing pin) into shock energy capable of triggering
the much more powerful but less sensitive, secondary explosives. Secondary explo-
sives are intentionally designed to be as insensitive as possible—while maintaining
their explosive performance—in order to minimize unintended initiation from acci-
dents during production or in the field. In fact, an area of heavy R&D in the modern
xxvi Introduction
explosives field is so-called insensitive munitions, which are intended to be highly

resistant to events such as bullet/fragment impact, exposure to fires, and detonation of
other nearby explosives.
Chapter 7: Printed Energetics: The Path toward Additive

Manufacturing of Munitions
In the past few years, additive manufacturing for EM has been an area of increased
interest to the DoD. Picatinny Arsenal has been a leader in this area for a number
of years with efforts focused on fuzing and other small-scale munitions. However,
there are some major barriers, including proper formulation development, process-
ing parameters determination, and print technology readiness. Recent work has
focused on addressing these barriers. For example, printable propellant, pyrotech-
nic, explosive, and biocidal formulations have been developed, and the prerequisite
rheological and other properties are being characterized. As a result, fundamental
knowledge has now been gained that can be translated for the development of vari-
ous print technologies and to fellow researchers at the DoD and elsewhere. In this
chapter, the necessary particle sizes, polymers, viscosity, and print technologies
for printing munitions will be discussed using examples from recent work on high
solid-loaded materials.
Chapter 8: Rheological Behavior of Energetic Gels and Suspensions

The flow and deformation behavior (rheology) of energetic formulations is com-
plex because energetic formulations are typically gels or highly filled suspensions
(i.e., the volume fractions of particles approach their maximum packing fractions).
Viscoplasticity (the development of a yield stress) and wall slip are the important
characteristics of gels and suspensions, and render the characterization of the rhe-
ological material functions a challenge. Furthermore, the viscoplastic nature and
the wall slip behavior are affected by the processing conditions, suggesting that the
development of the microstructure needs to be carefully followed and documented to
enable the collection of reliable and reproducible data. Other factors that can alter the
microstructure include segregation/demixing effects associated with mat formation
and filtration-based segregation of the binder phase under pressure flow, entrainment
of air, the shear-induced migration of the particles, and sedimentation. The methods
that are developed for the characterization of the rheological behavior of energetic
suspensions rely on the use of devices, which allow systematic changes in the surface-
to-volume ratio of the viscometer. For example, steady torsional flow and rectangular
slit dies with changes in gap or capillary rheometers with systematic changes in cap-
illary diameter are suitable to be used. Squeeze flow-based rheometers can also be
utilized. However, in any one of these methods, the analytical methods that are used
to generate the wall slip and material parameters of the energetic material need to be
specially tailored to allow the unambiguous determination of the shear viscosity and
the wall slip velocity versus wall shear stress relationship.
Chapter 9: Mixing, Coating, and Shaping

The distributive and dispersive mixing of the ingredients of energetic formulations
using batch or continuous mixers and the coating of energetic particles using various
Introduction xxvii
solution-based coating methods are the important determinants of the ultimate prop-
erties of energetic particles. Various methods were developed and are available for
the quantitative characterization of the degree of mixedness (mixing indices) of
energetic formulations principally relying on X-ray diffraction or energy-dispersive
X-ray methods. Such mixing indices can differentiate between poor and better mix-
ing conditions and can be correlated with various types of ballistic and other proper-
ties of energetic formulations. Since the 1990s, comprehensive three-dimensional
(3D) finite element method-based solutions have been available that can be used in
conjunction with the determination of Poincaré sections and Lyapunov exponents for
the prediction of scale and intensity of segregation of the ingredients contained in
energetic formulations. A combination of the numerical simulation and experimental
characterization methods can provide better control and optimization of the mixing
operations, thus improving the quality of energetic formulations. Alternatively, EM
can be mixed and coated using solvent or solvent-free methods. Surface properties
of EMs have been studied using experimental and numerical simulation methods to
predict solvent-free mixing behaviors. Actual coating conditions can be identified
using scanning electron microscopy (SEM) and energy dispersive X-Rays (EDX).
Energetic formulations can be placed in a casing upon mixing, and the loading pro-
cess is generally performed through casting, extruding, or pressing. The dynamics
of the loading are closely related to the microstructures of the final form, which
includes porosity, surface area, defects, and uniformity. All of these characteristics
will have an impact on the performance of the EMs.
Chapter 10: Continuous Processing and Shaping Using a Fully

Intermeshing Co-Rotating Twin Screw Extruder
There are a number of continuous processing methods that can be used to process
energetic formulations, that is, convey solids, melt polymer binders, mix the ener-
getic particles into the binder, pressurize, devolatilize, and then shape using a die
flow, all in the confines of the single processor. The most widely used method is the
fully intermeshing and corotating twin-screw extrusion process, which is used in
conjunction with a shaping die. The thermomechanical history of the energetic mate-
rial in such processors is amenable to be mathematically modeled using 3D finite
element method and slip at the wall boundary conditions. Such mathematical models
have been checked against the findings of various experimental investigations, which
have probed the processing mechanisms in such continuous processors. Besides the
convenience of carrying out the typical multiple steps of processing within a single
processing platform, continuous processes also offer inherent safety, that is, rela-
tively large production rates can be achieved with only a small quantity of energetic
material found in the extruder at any given time. Furthermore, the screw elements as
well as the locations at which sensors or feeding ports are placed are interchangeable,
rendering the extrusion platform truly flexible. The integration of the continuous
processor with a shaping die allows the formation of net shapes of energetic grains.
The simulation of the flow and heat transfer occurring in the die needs to be coupled
to the flow and heat transfer occurring in the extruder and is employed to design
the hardware used for the extrusion of the energetic formulations. The stability of
xxviii Introduction
the extrusion process and the formation of extrudate shape distortions emerging out
of the die are the important aspects and can be elucidated using time-dependent
computational source codes in conjunction with detailed rheological behavior of the
energetic formulation.
Section ii: the national technology and induStrial BaSe oF the Future
Chapter 11: Transition from Laboratory Innovation
to Production and Military Fielding
The responsibility of the DoD is the security of our country. The DoD mission
depends on our military and civilian personnel and equipment being in the right
place, at the right time, with the right capabilities, and in the right quantities to pro-
tect our national interests. This has never been more important as the United States
fights terrorists who plan and carry out attacks outside of the traditional boundaries
of the battlefield. This chapter outlines the DoD’s comprehensive strategic plan and
identifies the avenues for readers to learn more about current R&D initiatives among
the federal agencies. Of the many R&D areas of interest to the government and
industry, nanotechnology and additive manufacturing of both EMs and non-EMs are
a priority. This chapter discusses the DoD’s interest in EM research and the undeni-
able need for the transformation of traditional energetic manufacturing processes
and materials into more flexible and agile processes and materials through 2D and
3D printing of energetics and systems. There is a significant need for new technolo-
gies and equipment, which could make possible such transformation with the field
of EM.
Chapter 12: Multidisciplinary Teams Required for the Development

of Next-Generation Energetics
The complexity of the twenty-first century problems and the necessary innovations
needed to solve these problems require a multidisciplinary approach. The focus of
multiple disciplines on a single issue provides the opportunity for a more compre-
hensive understanding of the topic and allows for leaps in advancement rather than
incremental steps. The twenty-first century need for the manufacturing of NGEMs
can only be achieved through a multidisciplinary approach.
As will be discussed in this chapter, federal funding for research is moving away
from funding solo researchers toward multidisciplinary teams. Moreover, the chapter
will discuss types of multidisciplinary teams that are best suited to address the com-
plexities of fast-changing technologies. The federal government recognizes the value
of innovative thinking that develops when research fields intersect. Likewise, research
institutions across the nation try to break down disciplinary silos through internal seed
grant opportunities for multidisciplinary teams. This approach is necessary for more
eureka moments to occur.
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to factions as irreconcilable as Montagues and Capulets, had broken
into civil war on the advent of Queen Joanna as regent; the powerful
family of the Agramonts welcoming her eagerly; while the
Beaumonts, their rivals, out of favour at Court and wild with
jealousy, called hourly upon Charles to avenge their wrongs and his
own. His mother’s will, leaving Navarre to her husband during his
lifetime, had, they declared, been made null and void by the King’s
subsequent remarriage. Not only was it the duty of a son to resist
such unlawful tyranny, but it was folly to refuse with imprisonment
or a poison cup lurking in the background.
The latter argument was convincing; but never was rebellion
undertaken with a heavier heart. The Prince of Viana was a student
and philosopher who, like the Clerk of Oxenford, would have
preferred a shelf of Aristotle’s books at his bed’s head to the richest
robes, or fiddle, or psaltery. The quiet of a monastery library, with its
smell of dust and parchment, thrilled him more than any trumpet-
call; and he would gladly have exchanged his birthright for the
monk’s garb of peace. Fortune willed otherwise, laying on his
shoulders in pitiless mockery the burden of the man of action; and
the result was the defeat that is the usual reward of half-heartedness.
His uncle’s Court at Naples proved a temporary asylum for him in
his subsequent enforced exile; and also the island of Sicily, where he
soon won the affection of the people, and lived in happiness, till
Alfonso’s death awoke him rudely from his day-dreams. He was
overwhelmed by fear for his own future; though, had he been a
different man, he might have wrested away the sceptre of Sicily. In
Aragon itself public opinion had been growing steadily in his favour,
and not only in Navarre were there murmurs at his absence, but up
and down the streets of Barcelona, where the new King was far from
popular, and his haughty Castilian wife an object of dislike.
Prudence dictated to King John a policy of reconciliation; and after
prolonged negotiations the exile returned; but the cold forgiveness
he received from his father and stepmother for the wrongs they had
done him was in marked contrast to the joyous welcome of the
nation. No outward ceremony of a loving father pardoning a prodigal
son could mask the lack of confidence that still denied the Prince his
recognition as rightful heir, and drove him to enter into a secret
alliance with Henry IV. of Castile.
As a result of these negotiations, a marriage was arranged between
Charles and the Infanta Isabel. That the suggested bride was only ten
and the bridegroom nearing forty was a discrepancy not even
considered; and the messengers, who went to Arévalo to report on
the appearance of the Princess, returned to her suitor, as the
chroniclers expressed it, “very well content.” Far different were the
feelings of the King of Aragon, when he learned of the intended
match from his father-in-law, the Admiral of Castile. Isabel had been
destined for his favourite son, and, in spite of the conspiracy to
which he had lent his aid, this alliance still held outwardly good. It
did not need the jealous insinuations of his wife to inflame afresh his
hatred of his first-born; and the Prince of Viana soon found himself
in prison, accused of no less a crime than plotting against his father’s
life.
Unfortunately for King John, popular belief ran in a contrary
direction, and his son’s release was soon demanded by all parts of the
kingdom. In Barcelona, the citizens rose, tore down the royal
standard and took the Governor prisoner. Revolt flamed through the
land; but even more alarming was the sudden declaration of war by
Henry IV., who, taking advantage of the King of Aragon’s
embarrassments, hastily dispatched a force to invade Navarre, where
the Beaumonts were already in the field.
It was a bitter moment for King John. Realizing his critical
position, he agreed to his son’s release; and Charles of Viana passed
in triumph to Barcelona. For once, almost without his intervention,
Fortune had smiled on him; but it proved only a gleam before the
final storm. Three months after he had been publicly proclaimed as
his father’s heir, the news of his sudden illness and death fell on his
supporters with paralysing swiftness.
Nothing, on the other hand, could have been more opportune for
King John and his Queen; and their joy can be gauged by the haste
with which they at once proclaimed the ten-year-old Ferdinand heir
to the throne, demanding from the national Cortes of the three
kingdoms the oath they had so long denied his elder brother. Yet
Queen Joanna’s maternal ambitions were not to be satisfied by this
easy assumption of victory. Charles of Viana dead was to prove an
even more potent foe than Charles of Viana living.
Gentle and unassuming, yet with a melancholy dignity that
accorded well with his misfortunes, he had been accepted as a
national hero by the impulsive Catalans; and after death they
translated the rather negative qualities of his life into the attributes
of a saint. Only the halo of martyrdom was required to fire the
general sympathy into religious fervour; and this rumour supplied
when it maintained that his tragic end had been due to no ordinary
fever, but to poison administered by his stepmother’s orders.
The supposition was not improbable; and the inhabitants of
Barcelona did not trouble to verify the very scanty evidence for the
actual fact. They preferred to rest their accusations on the tales of
those who had seen the Prince’s unhappy spirit, like Hamlet’s father,
walking abroad at midnight demanding revenge. Soon his tomb
became a shrine for pilgrims, and there the last touch of sanctity was
added. He who in life had suffered acutely from ill-health became in
death a worker of miracles, a healer whom no absence of papal
sanction could rob of popular canonization.
The effect upon the public mind was to fan smouldering rebellion
into flames; and when Queen Joanna, having gained the recognition
of her son as heir to the throne by the Aragonese Cortes at Calatayud,
proceeded with the same object to Barcelona, the citizens rose and
drove her from their gates. Only the timely intervention of some
French troops, which Louis XI. had just hired out to King John,
saved her and Ferdinand from falling into the hands of their furious
subjects.
This foreign assistance had contributed not a little to the bitterness
of the Catalans, for the French King had secretly encouraged their
turbulence and disaffection, promising them his support.
“As for peace he could hardly endure the thought of it,” wrote
Philip de Commines of his master, Louis XI. That monarch, like King
John of Aragon, had studied the art of “making trouble,” and in this
truly mediæval pursuit excelled all rivals. It suited his purpose
admirably that his ambitious neighbour should be involved in civil
war, just as it fitted in with his schemes that his troops should
prevent that conflict from going too far. The question was all part
and parcel of his policy of French aggrandizement; the ultimate
object of his design nothing less than the kingdom of Navarre, that
semi-independent state, nominally Spanish, but projecting in a
tantalizing wedge across the Pyrenees.
With Charles of Viana the male line of Evreux had come to an end,
and the claims on Navarre had passed to his sister Blanche. On
Blanche’s death, and Louis in his schemes leapt to the possibility of
such a fortunate accident, the next heir would be Eleanor, her
younger sister, wife of a French Count, Gaston de Foix. It would be
well for France to establish a royal family of her own nationality on
the throne of Navarre. It would be even better for that family to be
closely connected with the House of Valois; and, calculating on the
possibilities, Louis gave his sister Madeleine in marriage to the
young Gaston de Foix, Eleanor’s son and the heir to her ambitions.
It only remained to turn the possible into the certain: to make sure
that Blanche’s claims should not prejudice those of her younger
sister. At this stage in his plans Louis found ready assistance in the
King of Aragon, who included in his hatred of Charles of Viana a still
more unnatural dislike of his gentle elder daughter, whose only sins
were that she had loved her brother in his misfortunes and proved
too good a wife for Henry of Castile.
Thus the tragedy was planned. Blanche must become a nun or pass
into the care of her brother-in-law in some mountain fortress of
Navarre. Then the alternative was whittled away. Nunneries and
vows were not so safe as prison walls and that final silence, whose
only pleading is at God’s judgment-bar. Eleanor, fierce and vindictive
as her father, was determined there should be no loophole of escape,
no half-measures by which she might miss her coveted inheritance.
John of Aragon went himself to fetch his elder daughter to her
fate, assuring her of his intention of marrying her to a French prince,
once they had crossed the Pyrenees; but his victim was not deceived.
Powerless to resist, as she had been in bygone days to help her
brother, Blanche made one last desperate appeal before the gates of
the castle of Orthez closed for ever behind her. On the 30th of April,
1462, she wrote a letter to Henry IV. of Castile, ceding to him her
claims on Navarre, and beseeching him by the closeness of the tie
that had once united them, and by his love for her dead brother, to
accept what she offered and avenge her wrongs.
It was in vain. Even before Charles of Viana’s death, Henry IV.,
repenting of his rash invasion of Navarre, had come to terms with
the Aragonese King, regardless of his ally’s plight; while just at the
climax of Blanche’s misfortunes, an event happened in Castile that
was to make all but domestic affairs slide into the background.
In March, 1462, Queen Joanna gave birth to a daughter in the
palace at Madrid. The King had at last an heir. Great were the
festivities and rejoicings at Court, many the bull-fights and jousts in
honour of the occasion. Below all the sparkle of congratulation and
rejoicing, however, ran an undercurrent of sneering incredulity. It
was nearly seven years since the Queen came a bride to Cordova, and
for thirteen before that had Henry been married to the virtuous
Blanche of Navarre, yet neither by wife nor mistress had he been
known to have child.
“Enrique El Impotente,” his people had nicknamed him, and now,
recalling the levity of the Queen’s life and her avowed leaning
towards the hero of the famous “Passage of Arms,” they dubbed the
little Princess in mockery “Joanna La Beltraneja.”
Was the King blind? or why was the handsome Beltran de La
Cueva created at this moment, almost it seemed in celebration of the
occasion, Count of Ledesma, and received into the innermost royal
councils? There were those who did not hesitate to affirm that Henry
was indifferent to his own honour, so long as his anxiety for an heir
was satisfied.
Whatever the doubts and misgivings as to her parentage, there was
no lack of outward ceremony at the Infanta’s baptism, in the royal
chapel eight days after her birth. The Primate himself, the
Archbishop of Toledo, performed the rites, and Isabel, who with her
brother Alfonso, had been lately brought up to court, was one of the
godmothers, the other, the Marquesa de Villena, wife of the
favourite. Two months later, a Cortes, composed of prelates, nobles,
and representatives of the Third Estate, assembled at Madrid, and, in
response to the King’s command, took an oath to the Infanta Joanna
as heir to the throne; Isabel and her brother being the first to kneel
and kiss the baby’s hand.
The Christmas of 1462 found Henry and his Queen at Almazon;
and thither came messengers from Barcelona with their tale of
rebellion and the fixed resolution they had made never to submit to
King John’s yoke. Instead the citizens offered their allegiance to
Castile, imploring help and support in the struggle before them.
Henry had been unmoved by Blanche’s appeal, for he knew the
difficulties of an invasion of Navarre, but the present project
flattered his vanity. He would merely dispatch a few troops to
Barcelona, as few as he could under the circumstances, and the
Catalans in return would gain him, at best an important harbour on
the Mediterranean, at worst would act as a thorn in the side of his
ambitious neighbour. He graciously consented therefore to send
2500 horse, under the leadership of one of the Beaumonts, as
earnest of his good intentions; but almost before this force had
reached Barcelona, those intentions had already changed, and he had
agreed to the mediation of the King of France in the disputes
between him and the King of Aragon.
Louis XI., “the universal spider,” as Chastellain called him, had
been spreading his web of diplomacy over the southern peninsula. By
the Treaty of Olito, signed by him and King John in April, 1462, he
had promised to lend that monarch seven hundred lances, with
archers, artillery, and ammunition, in return for two hundred
thousand gold crowns to be paid him on the reduction of Barcelona.
Whether he would ever receive this sum was perhaps a doubtful
matter; but Louis had accepted the pledge of the border counties of
Roussillon and Cerdagne, that commanded the eastern Pyrenees,
should the money fail, and would have been more annoyed than
pleased by prompt repayment. According to his own calculations he
stood to gain in either case; and in the meantime he was well content
to increase his influence by posing as the arbiter of Spanish politics.
After a preliminary conference at Bayonne, it was arranged that
the Kings of Castile and France should meet for a final discussion of
the proposed terms of peace on the banks of the Bidassoa, the
boundary between their two territories. It is a scene that Philip de
Commines’ pen has made for ever memorable; for though he himself
was not present he drew his vivid account from distinguished eye-
witnesses on both sides. Through his medium and that of the
Spanish chroniclers we can see the showy luxury of the Castilian
Court, the splendour of the Moorish guards by whom Henry was
surrounded, the favourite Beltran de La Cueva in his boat, with its
sail of cloth-of-gold dipping before the wind, his very boots as he
stepped on shore glittering with precious stones. Such was the model
to whom Castilian chivalry looked, the man, who with the
Archbishop of Toledo and the Marquis of Villena dictated to their
master his every word.
It is small wonder if Louis XI. had for the ruler of Castile “little
value or esteem,” or that Commines himself, summing up the
situation, caustically dismisses Henry as “a person of no great sense.”
There could not have been a stronger contrast between the two
kings: Henry with his pale blue eyes and mass of reddish hair, his
awkwardly-built frame, overdressed and loaded with jewels,
towering above his meagre companion; Louis, sardonic and self-
contained, well aware of the smothered laughter his appearance
excited amongst Castilian courtiers, but secretly conscious that his
badly cut suit of French homespun and queer shaped hat, its sole
ornament an image of the Virgin, snubbed the butterfly throng about
him.
“The convention broke up and they parted,” says Commines, “but
with such scorn and contempt on both sides, that the two kings never
loved one another heartily afterwards.”
The result of the interview, May, 1463, was soon published. In
return for King John’s future friendship, and in compensation for
her expenses as an ally of Charles of Viana, a few years before, Castile
found herself the richer for the town of Estella in Navarre, a gain so
small that it was widely believed the Archbishop of Toledo and his
fellow-politicians had allowed themselves to be bribed.
If the Castilians were bitter at this decision, still more so were the
Catalans, deserted by their ally and offered nothing save the
unpalatable advice that they should return to King John’s allegiance.
The messengers from Barcelona quitted Fuenterrabia as soon as they
heard, openly uttering their contempt for Castile’s treachery.
“It is the hour,” they exclaimed, “of her shame and of her King’s
dishonour!”
They could not realize to the full the truth of their words, nor to
what depths Henry was shortly to fall and drag the fortunes of his
country with him.
CHAPTER III
THE REIGN OF HENRY IV.: CIVIL WAR AND
ANARCHY
1464–1474
Henry IV. had been merely a figurehead at the meeting of

Fuenterrabia, a rôle to which with his habitual lethargy he had no
objection. When, however, he attempted to obtain possession of the
town of Estella and failed to do so in spite of Villena’s outwardly
strenuous efforts, he began at last to suspect that he had been also a
dupe, and that French and Aragonese money had bribed his
ministers to his own undoing.
He could not make up his mind to break openly with the Marquis
and his uncle, the Archbishop of Toledo; but a perceptible coldness
appeared in his manner where they were concerned, in contrast to
the ever-increasing favour that he now bestowed on Beltran de La
Cueva, Count of Ledesma. The latter’s share in the conferences had
been mainly ornamental. Indeed his talents had lain hitherto rather
in the ballroom or the lists than in the world of practical politics; but
success had stirred his ambitions, and especially his marriage with
the daughter of the Marquis de Santillana, head of the powerful
family of Mendoza. With this connection at his back he might hope
to drive Villena and his relations from Court, and with the Queen’s
aid control the destinies of Castile.
In the struggle between the rival favourites, the Princess Isabel
was regarded as a useful pawn on their chess-board. She and her
brother had been summoned to Court at Villena’s suggestion that
“they would be better brought up and learn more virtuous customs
than away from his Majesty’s presence.” Whether irony were
intended or no, Henry had accepted the statement seriously; and
while Alfonso was handed over to a tutor, his sister joined the
Queen’s household.
There were hopes at this time of another heir to the crown; and the
King, foreseeing in the prospect of a son the means to raise his fallen
dignity, was anxious to gratify his wife’s wishes. When she pleaded
therefore for an alliance with her own country, to be cemented by the
marriage of her brother Alfonso, then a widower, with the twelve-
year-old Isabel, he readily agreed. The scheme was the more pleasing
that it ran counter to the union of Isabel and Ferdinand of Aragon,
still strongly advocated by King John. Villena, who had been bribed
into assisting the latter negotiation, received the first real intimation
that his ascendancy was shaken, when he learned that the King and
Court had set off to the south-western province of Estremadura
without consulting him.
Through the medium of the Queen and Count of Ledesma, the
Portuguese alliance was successfully arranged; and Alfonso V. was so
impressed by the young Princess that he gallantly protested his wish
that the betrothal could take place at once. Isabel replied with her
strange unchildlike caution, that she could not be betrothed save
with the consent of the National Cortes, an appeal to Cæsar that
postponed the matter for the time being. Perhaps she knew her
brother well enough to doubt his continued insistence that “she
should marry none save the King of Portugal”; or she may thus early
have formed a shrewd and not altogether flattering estimate of the
volatile and uncertain Alfonso.
In the meantime the Marquis of Villena was plotting secretly with
his brother, the Master of Calatrava, the Archbishop of Toledo, the
Admiral of Castile, and other nobles how he might regain his old
influence. After a series of attempts on his rival’s life, from which
Beltran de La Cueva emerged scatheless with the additional honour
of the coveted Mastership of Santiago, he and his fellow-conspirators
retired to Burgos, where they drew up a schedule of their grievances.
Secret measures having failed they were determined to browbeat
Henry into submission by playing on his well-known fears of civil
war.
The King’s hopes of an undisputed succession had been shattered
by the premature birth of a still-born son; and thus the question of
the Infanta Joanna’s legitimacy remained as a convenient weapon for
those discontented with the Crown. Nor had the gifts and honours
heaped on Beltran de La Cueva encouraged the loyalty of the
principal nobles. The new favourite was rapacious and arrogant,
while even more intolerable to courtiers of good family and wealth
was the rise of an upstart nobility, that threatened to monopolize the
royal favour.
Louis XI. was astute enough to develop such a policy to his own
advantage; but the feeble Henry IV. was no more able to control his
new creations than their rivals. Almost without exception they
betrayed and sold him for their own ends, poisoning his mind
against the few likely to remain faithful, and making his name odious
amongst his poorer subjects by their selfishness and the corruption
of their rule.
The conspirators of Burgos were thus enabled to pose as the
defenders of national liberties; and their insolent letter of censure
took the colouring most likely to appeal to popular prejudice.
Complaints of the King’s laxity in religious matters, of the unchecked
violence of his Moorish guard, of the debasement of the coinage, and
of the incompetence and venality of the royal judges—these were
placed in the foreground, but the real crux of the document came
later. It lay in two petitions that were veiled threats, first that the
King would deprive the Count of Ledesma of the Mastership of
Santiago, since it belonged of right to the Infante Alfonso, and next
that the said Alfonso should be proclaimed as heir to the throne. The
illegitimacy of the Princess Joanna was openly affirmed.
Henry received this letter at Valladolid, and, calling together his
royal council, laid it before them. He expressed neither resentment at
its insolence nor a desire for revenge; and when the aged Bishop of
Cuenca, who had been one of his father’s advisers, bade him have no
dealings with the conspirators save to offer them battle, he replied
with a sneer that “those who need not fight nor lay hands on their
swords were always free with the lives of others.”
Peace at all costs was his cry, and the old Bishop, exasperated,
forgot prudence in his anger. “Henceforth,” he exclaimed, “you will
be thought the most unworthy King Spain ever knew; and you will
repent it, Señor, when it is too late to make amends.”
Already knights and armed men were flocking to the royal
standard, as they heard of the rebels’ ultimatum. Many of them were
genuinely shocked at the attack on the dignity of the Crown, but for
the greater number Henry’s reckless prodigality of money and
estates was not without its attractions.
The King, however, proved deaf alike to warnings and scorn. After
elaborate discussions he and the Marquis of Villena arranged a
temporary peace, known as the Concord of Medina del Campo. Its
terms were entirely favourable to the conspirators, for Henry,
heedless of the implied slur on his honour, agreed to acknowledge
Alfonso as his heir, on the understanding that he should later marry
the Infanta Joanna. With incredible shortsightedness he also
consented to hand his brother over to the Marquis; and on the 30th
of November, 1464, the oath to the new heir to the throne was
publicly taken. This was followed by the elevation of the Count of
Ledesma, who had resigned the Mastership of Santiago in favour of
the young Prince, to the rank of Duke of Alburquerque.
The question of the misgovernment of the country and its cure was
to be referred to a committee of five leading nobles, two to be
selected by either party, while the Prior-General of the Order of San
Geronimo was given a casting vote. This “Junta of Medina del
Campo,” held in January, 1465, proved no lasting settlement, for the
King’s representatives allowed themselves to be won over to the
views of the league, with disastrous results for their own master.
“They straitened the power of the King to such an extent,” says a
chronicler, “that they left him almost nothing of his dominion save
the title of King, without power to command or any pre-eminence.”
Henry was roused at last, but it was only to fall a victim to fresh
treachery.
Two of the most prominent members of the league in its
beginnings had been Don Alonso Carrillo, Archbishop of Toledo,
uncle of the Marquis of Villena, and the Admiral of Castile, Don
Fadrique Enriquez. The former had little of his nephew’s suave
charm and adaptability, and his haughty, irascible nature was more
suited to the camp than the Primacy of the Castilian Church.
“He was a great lover of war,” says Pulgar in his Claros Varones,
“and while he was praised on the one side for his open-handedness
he was blamed on the other for his turbulence, considering the
religious vows by which he was bound.”
At the time of the Concord of Medina del Campo, he and the
Admiral of Castile had professed themselves weary of the consistent
disloyalty of their colleagues, and had returned to Court with the
King. They now denounced the “Junta” and advised their master to
revoke his agreement to the Concord, and to demand that the Infante
Alfonso should be instantly restored to his power. As might be
expected, the league merely laughed at this request. They declared
that they held the young Prince as a guarantee of their safety, and
that, since the King had determined to persecute them, they must
renounce his service.
Not a few of those at Court suspected the Archbishop and Admiral
of a share in this response, but Henry refused to take a lesson from
the ill-results of past credulity. Instead he submitted entirely to his
new advisers, surrendering at their request two important
strongholds. This achieved, Don Fadrique and the Archbishop
deserted to the league without further pretence; and when the royal
messengers discovered the latter in full fighting gear, on his way to
one of his new possessions, and ventured to remind him that the
King awaited him, that warlike prelate replied with an air of fury:
“Go, tell your King that I have had enough of him and his affairs.
Henceforward he shall see who is the true Sovereign of Castile.”
This insult with its cryptic threat was explained almost
immediately by messengers hurrying from Valladolid, who brought
word that the Admiral had raised the standard of revolt, proclaiming
in the market-place, “Long live the King—Don Alfonso!”
From defiance in words the rebel leaders proceeded to show their
scorn of Henry IV. in action. On June 5th of the same year, they
commanded a wooden scaffold to be set up on the plain outside the
city of Avila, so that it could be clearly seen from all the surrounding
neighbourhood. On it was placed an effigy of the King, robed in
heavy black and seated in a chair of state. On his head was a crown,
before him he held a sword, and in his right hand a sceptre—
emblems of the sovereignty he had failed to exercise. Mounting the
scaffold, the chief members of the league read aloud their grievances,
declaring that only necessity had driven them to the step they were
about to take. Then the Archbishop of Toledo removed the crown
and others of the league the sword and sceptre. Having stripped the
effigy of its royal robes, they threw it on the ground, spurning it from
them with their feet.
Immediately it had fallen and their jests and insults had died away,
the eleven-year-old Alfonso ascended the scaffold, and when he had
been invested with the insignia of majesty, the nobles knelt, and
kissed his hand, and took the oath of allegiance. Afterwards they
raised him on their shoulders, shouting, “Castile for the King, Don
Alfonso!”
Messengers soon brought Henry news of his mock dethronement;
and reports of risings in different parts of the land followed in quick
succession. Valladolid and Burgos had risen in the north; there were
factions in the important city of Toledo; a revolt had blazed up in
Andalusia, where Don Pedro Giron, Master of Calatrava, had long
been busy, sowing the seeds of disaffection.
“Naked I came from my mother’s womb, and naked shall the earth
receive me,” exclaimed the King when he was told, and he found a
melancholy satisfaction in quotations from Isaiah concerning the
ingratitude of a chosen people. The tide had, however, turned in his
favour. Even in Avila, amid the shouts of triumph and rejoicing,
when Henry’s effigy was thrown to the ground, some of those present
had sobbed aloud with horror. More practical assistance took the
shape of an army that rapidly collected in response to Henry’s
summons, “eager,” as the chronicler expressed it, “to come to blows
with those tyrants who had thus dishonoured their natural lord.”
Villena who much preferred diplomacy to the shock of warfare had
in the meanwhile induced his master to agree to a personal
interview, with the result that the King broke up his camp,
compensating his troops for their inaction by large gifts of money.
The league, it was understood, would return to Henry’s allegiance
within a certain time; but its leaders had fallen out amongst
themselves, and at length Villena thought it as well that he and his
family should seek advantageous terms on their own account.
He demanded with incredible insolence that Henry should give his
sister Isabel in marriage to Don Pedro Giron, Master of Calatrava. In
return the Master would pay into the impoverished royal treasury an
enormous sum of money, amassed by fraud and violence, besides
entering the royal service with the 3000 lances, with which he was
just then engaged in harrying the fields of Andalusia. By way of
securing future peace, the Infante Alfonso was to be restored to his
brother, and the Duke of Alburquerque and his brother-in-law, the
Bishop of Calahorra, banished.
For all his folly and weakness, it is difficult to believe that Henry
would consent to such terms, but so low were the straits in which he
found himself that he immediately expressed his satisfaction,
sending word to Don Pedro Giron to come as quickly as he could.
Isabel on her part was aghast and, finding entreaties and
remonstrances of no avail, she spent days and nights upon her knees,
praying that God would either remove the man or herself, before
such a marriage should take place. Her favourite lady-in-waiting,
Doña Beatriz de Bobadilla, moved by her distress, assured her that
neither God nor she would permit such a crime, and, showing her a
dagger that she wore hidden, swore to kill the Master, if no other way
of safety should present itself.
Help, indeed, seemed far away, for the bridegroom, having
obtained from Rome a dispensation from his ill-kept vow of celibacy,
was soon on his way to Madrid at the head of a large company of
knights and horsemen. His only reply to those who told him of the
Infanta’s obstinate refusal of his suit was that he would win her, if
not by gentleness then by force.
At Villa Real, where he halted for the night, the unexpected
happened, for, falling ill of an inflammation of the throat, he died a
few days later.
“He was suddenly struck down by the hand of God,” says Enriquez
del Castillo; while Alonso de Palencia describes how at the end “he
blasphemously accused God of cruelty in not permitting him to add
forty days to his forty and three years.”
Both the King and the Marquis of Villena were in consternation at
the news. The latter had begun to lose his influence with the league,
who justly suspected him of caring more for his own interests than
theirs; and, while he bargained and negotiated with a view to
securing for himself the Mastership of Santiago, a position that he no
longer considered belonged to the young Alfonso “of right,” the
Archbishop of Toledo and the Admiral were bent on bringing matters
to an issue by open war.
Henry was forced to collect his loyalists once more; and on the
20th of August, 1467, a battle took place on the plain of Olmedo, just
outside the city. The King’s army had the advantage in numbers;
indeed he had been induced to advance on the belief that the enemy
would not dare to leave the shelter of their walls, and by the time
they appeared it was too late to sound the retreat. Conspicuous
amongst the rebels were the Infante Alfonso clad, notwithstanding
his youth, in full mail armour, and the fiery Archbishop of Toledo in
his surcoat of scarlet emblazoned with a white cross. The latter was
wounded in his left arm early in the fight but not for that ceasing to
urge on his cavalry to the attack. On the other side the hero of the
day was Beltran de La Cueva, whose death forty knights had sworn to
accomplish, but whose skill and courage were to preserve him for
service in a better cause.
Alone, amongst the leading combatants, Henry IV. cut but a poor
figure, for, watching the action from a piece of rising ground, he fled
at the first sign of a reverse, persuaded that the battle was lost. Late
that evening a messenger, primed with the news of victory,
discovered him hiding in a neighbouring village, and he at last
consented to return to the camp.
The royalists succeeded in continuing their march, but since the
enemy remained in possession of the larger number of banners and
prisoners, both armies were able to claim that they had won.
The battle of Olmedo was followed by the treacherous surrender to
the league of the King’s favourite town of Segovia. Here he had left
the Queen and his sister; but while the former sought refuge in the
Alcazar, which still held out for her husband, Isabel preferred to
remain in the palace with her ladies-in-waiting. She had not suffered
such kindness at the hands of Henry IV. as would make her rate
either his love or his power of protection highly; and, when the rebels
entered the town she surrendered to them with a very goodwill.
Henceforward her fortunes were joined to those of Alfonso; but
death which had saved her from marriage with a man she loathed,
was soon to rob her of her younger brother. It is difficult to form a
clear estimate of either Alfonso’s character or abilities from the
scanty references of the chroniclers; but already, at the age of
fourteen, he had proved himself a better soldier than Henry IV.; and
we are told that those who knew him personally judged him more
upright. The news of his death, on July 5, 1468, was therefore
received with general dismay. His death had been ostensibly the
result of swollen glands, but it was widely believed that the real cause
of its seriousness was a dish of poisoned trout prepared for him by a
secret ally of the King.
With his disappearance from the political chess-board, the whole
balance of affairs in Castile was altered; and Isabel emerged from
comparative obscurity into the prominent position she was
afterwards to hold. Would she take Alfonso’s place as puppet of the
league? or would she be reconciled to her elder brother? In the latter
case, how would the King decide between her claims and those of
Joanna “La Beltraneja”? These were the questions on whose answers
depended the future of the land.
The principal members of the league had no doubts at all as to her
complete acquiescence in their plans, and in the town of Avila they
made her a formal offer of the throne, inviting her to assume the title
of Queen of Castile and Leon. Isabel received the suggestion with her
usual caution; for though but a girl of seventeen, she had few
illusions as to the glories of sovereignty. She knew, moreover, that
several prominent insurgents had taken the opportunity of
reconciling themselves at Court, while the Marquis of Villena, now
acknowledged Master of Santiago, was once more hand in glove with
the King. She therefore replied that while her brother lived she could
neither take the government nor call herself Queen, but that she
would use every effort to secure peace in the land.
ALFONSO, BROTHER OF ISABEL OF
CASTILE
FROM “ICONOGRAFIA ESPAÑOLA” BY

VALENTIN CARDERERA Y SOLANO
This answer deprived the league of any legitimate excuse for

rebellion; and they therefore sent letters to the King, declaring their
willingness to return to his service, if he would acknowledge Isabel as
heir to the throne. The Marquis of Villena also pressed the
suggestion, thinking by this means to re-establish his influence
completely; since his enemies, the House of Mendoza, and especially
its cleverest representative Pedro Gonsalez, Bishop of Siguenza, who
had been promoted from the See of Calahorra, had taken up the
cause of Queen Joanna and her daughter.
Henry, anxious for peace, no matter what the price, fell in with
Villena’s schemes. On the 19th of September, 1468, a meeting was
held at the Toros de Guisandos near Avila; and there, in the presence
of the Papal Legate, Henry swore away for a second time the honour
of his so-called daughter, and recognized Isabel as legitimate heir to
the throne and Princess of Asturias. By the terms of an agreement
previously drawn up, he also promised that his sister should not be
compelled to marry against her will, while she in return agreed to
obtain his consent; furthermore he declared that he would divorce
and send back to her own land his wife, whose lax behaviour had
now become a byword.
Isabel’s own position had materially improved; and there were no
lack of suitors for this eligible heiress. Amongst them was a brother
of Edward IV. of England, but whether the Duke of Clarence or
Richard of Gloucester, the chroniclers do not say. The English
alliance was never very seriously considered, whereas a veritable war
of diplomacy was to be waged around the other proposals.
The Infanta’s chief adviser at this time was the Archbishop of
Toledo, though it does not appear that she was as much under his
thumb, as Enriquez de Castillo would have us believe. There is
evidence of considerable independence of judgment both in her
refusal of the crown on Alfonso’s death, and in her willingness to
meet her brother at the Toros de Guisandos, in spite of the
Archbishop’s violent opposition. Throughout the negotiations, the
Archbishop had been on the watch for evidence of some hidden plot,
and only Isabel’s tact and firmness had induced him to accompany
her to the meeting.
Nevertheless it was natural that a girl of her age should rely
considerably on the judgment of a man so well versed in the politics
of the day, especially as the alliance that he urged appealed in every
way to her own inclinations. Ferdinand of Aragon, the Archbishop’s
protégé, was her junior by eleven months; a slight disparity in
comparison with the age of former suitors such as Charles of Viana,
Alfonso of Portugal, and the Master of Calatrava, all her seniors by at
least twenty years.
In modern reckoning, Ferdinand would be called a boy, but his
childhood had been spent amidst surroundings of war and rebellion,
from which he had emerged as his father’s right hand; and John II.,
in token of his love and confidence, had created this son of his old
age King of Sicily to mark his dignity and independence. Shrewd,
practical, and brave, Ferdinand united to a well-set-up, manly,
appearance all those qualities that Henry IV. so conspicuously
lacked. It was little wonder then if he found grace in the Infanta
Isabel’s eyes, not only as an eligible husband, but as a fitting consort
with whose help she might subdue the turbulence of Castile.
It can be imagined that Ferdinand found no grace at all in the eyes
of the Marquis of Villena, to whom opportunities for turbulence were
as the breath of life, and whose affection for the House of Aragon had
never been sincere.
Policy dictated to him a counter-alliance and at first the
importunate Alfonso of Portugal won support. Villena had re-
established his old influence over his master, and at this time formed
an ambitious scheme, by which his son should marry the Infanta
Joanna; the idea being to draw up a new settlement, settling the
crown on his own descendants, if Isabel and her Portuguese husband
had no children.
At Ocaña, where Henry IV. and his sister held a meeting of the
Cortes in 1468, a magnificent embassy appeared from Alfonso V.,
with the Archbishop of Lisbon at its head, seeking the betrothal of
their master to the Infanta Isabel.
“They thought it an easy matter to bring about the marriage,” says
Alonso de Palencia; but they were destined to return to their own
land, with their mission unfulfilled. Isabel had never been attracted
to the Portuguese King; and her coldness was hardened into
antipathy by the Archbishop of Toledo, who sent her secret warnings
that the alliance was a plot to ruin her prospects. Once married, she
would become a foreigner in the eyes of Castile, and while her
children could not hope to succeed to the throne of Portugal, since
Alfonso had already an heir, the Infanta Joanna would be preferred
to her in her own land. Isabel, moved both by these arguments and
her own feelings, thereupon gave a secret promise to marry her
cousin Ferdinand, returning a steady refusal to her brother’s
persuasions and threats.
Henry now made an attempt to capture her, with a view to
imprisoning her in the Alcazar at Madrid; but the attitude of the
principal knights of Ocaña, who loved neither Villena nor the
Portuguese, was so threatening that he quickly changed his manner.
Assuring the Archbishop of Lisbon that some other means would be
found to placate the Princess, whose opposition would only be
increased by violence, he sent him and his fellow-ambassadors away,
not altogether despairing but with their confidence somewhat
shaken.
In the meanwhile the fires of rebellion were alight once more in
Andalusia and burnt so furiously, that it was felt only the King in
person could hope to allay them. With great reluctance he left his
sister in Ocaña, but he dared not risk further unpopularity by using
force. At the Master of Santiago’s suggestion he demanded that she
should promise to take no new steps about her marriage until his
return, thinking in this way to place her in an equivocal position.
Either she would refuse, in which case she would stand self-
convicted of some secret plot, or she would take the oath,
condemning herself as a perjurer if she broke it.
Isabel, appreciating the situation, gave her promise. Even the
Master of Santiago, for all his vigilance, did not know that her
consent to the Aragonese alliance was of previous date, and therefore
arrangements concerned with it could be argued not to fall under the
heading “new.” As soon as Henry IV. and his favourite had gone
southwards, she herself left Ocaña, with the ostensible object of
taking her brother Alfonso’s body to be buried in state at Avila, and
from there went to Madrigal her birthplace, where her mother was
living. It was her hope that here she would be able to complete her
negotiations with King John and his son, undetected; but she found
the Bishop of Burgos, a nephew of the Master of Santiago, in the
town ready to spy on all her actions.
The King had by now planned for his sister a new match, with
Charles, Duke of Berri, brother and heir-presumptive to Louis XI.
Not only would this alliance cement the customary friendship of
Castile and France, but Isabel’s close connection with the French
throne would remove her very thoroughly from the danger zone of
Castilian affairs. When the Cardinal of Arras arrived in Andalusia he
was therefore encouraged by Henry to go to Madrigal in person and
urge the Duke’s suit.
Nothing doubting the success of his mission, for he was a man
famed for his oratory, the Cardinal, having gained admittance to the

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Energetic Materials - Advanced

Processing Technologies for

Advanced processing and manufacturing technologies for

Materials and Processes for Next Generation Lithography

Mesoporous materials for advanced energy storage and

Advanced Processing and Manufacturing Technologies for

Mesoporous Materials for Advanced Energy Storage and

Mechanics for Materials and Technologies Altenbach

Next Generation DNA Led Technologies 1st Edition

Textile Materials for Lightweight Constructions

© 2018 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-1380-3250-7 (Hardback)

Library of Congress Cataloging‑in‑Publication Data

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

Section i critical Science and technologies in

Chapter 1 Synthetic Methods for High-Energy Organofluorine Compounds ......3

Chapter 2 Optical Diagnostics for Characterizing Explosive Performance .......25

Chapter 3 Solubility Thermodynamics of Organic Energetic Materials .............43

Chapter 4 Mathematical Modeling and Experimental Investigations of

Chapter 5 Dynamic Characterization of Energetic Materials ............................ 87

Chapter 6 Sustainable High Explosives Development ........................................ 95

Chapter 7 Printed Energetics: The Path toward Additive Manufacturing

Chapter 8 Rheological Behavior of Energetic Gels and Suspensions ............... 129

Chapter 9 Mixing, Coating, and Shaping ......................................................... 169

Chapter 10 Continuous Processing and Shaping Using a Fully Intermeshing

Section ii the national technology and

Chapter 11 Transition from Laboratory Innovation to Production and

Chapter 12 Multidisciplinary Teams Required for the Development of

Chapter 13 The Nascent National Energetic Materials Initiative ....................... 269

Epilogue ................................................................................................................ 279

environment. Developing new products within the process constraints of the

Michelle Pantoya is the J.W. Wright Regents Chair in mechanical engineering

how phenomena occurring on the nanoscale affect the energetic performance of a

Lori J. Groven is an assistant professor of chemical and biological engineering at

Dilhan M. Kalyon holds the Institute Professor Chair at Stevens Institute of

John M. Centrella Lori J. Groven

Eileen Heider Daniel Marangoni

Bahadir Karuv Constance M. Murphy

Heng Pan Paul Redner

V. Prakash Reddy Steve Tupper

Brandon L. Weeks Richard A. Yetter

Life cycle of energetic materials

System design and Production industrial

Lab to factory Factory to warfighter Beyond

FIGURE I.1 The life cycle of EMs as used by the DoD.

NATIONAL CAPABILITIES FOR ENERGETIC

in—research, development, and manufacturing technology of EM in foreign coun-

Energetic Materials Is a Department of Defense

the path Forward

System design and Production industrial

Lab to factory Factory to warfighter Beyond

Gap in manufacturing innovation

Technology readiness level

Advanced processing pilot lines (APPL)

Flexible agile ingredient and

FIGURE I.3 APLE program thrust areas.