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 ADVANCED MATERIALS,
POLYMERS, AND COMPOSITES
New Research on Properties,
Techniques, and Applications
 ADVANCED MATERIALS,
POLYMERS, AND COMPOSITES
New Research on Properties,
Techniques, and Applications

Edited by
Omari V. Mukbaniani, DSc
Tamara Tatrishvili, DSc
Marc J. M. Abadie, DSc
First edition published 2022
Apple Academic Press Inc. CRC Press
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Library and Archives Canada Cataloguing in Publication
Title: Advanced materials, polymers and composites : new research on properties, techniques, and applications / edited
by Omari V. Mukbaniani, DSc, Tamara Tatrishvili, DSc, Marc J.M. Abadie, DSc
Names: Mukbaniani, O. V. (Omar V.), editor. | Tatrishvili, Tamara, editor. | Abadie, Marc J. M., editor.
Description: First edition. | Includes bibliographical references and index.
Identifiers: Canadiana (print) 20210101989 | Canadiana (ebook) 20210101997 | ISBN 9781771889513 (hardcover) |
ISBN 9781774638200 (softcover) | ISBN 9781003105015 (ebook)
Subjects: LCSH: Polymers. | LCSH: Polymerization. | LCSH: Composite materials. | LCSH: Nanocomposites (Materials)
Classification: LCC TA455.P58 A35 2021 | DDC 620.1/92—dc23
Library of Congress Cataloging‑in‑Publication Data
Names: Mukbaniani, O. V. (Omar V.), editor. | Tatrishvili, Tamara, editor. | Abadie, Marc J. M., editor.
Title: Advanced materials, polymers, and composites : new research on properties, techniques, and applications / Omari V.
Mukbaniani, Tamara Tatrishvili, Marc J.M. Abadie.
Description: First edition. | Palm Bay, FL : Apple Academic Press, 2021. | Includes bibliographical references and index. |
Summary: "This new book reviews several domains of polymer science, especially new trends in polymerization
synthesis, physical-chemical properties, and inorganic systems. Composites and nanocomposites are also covered in
this book, emphasizing nanotechnologies and their impact on the enhancement of physical and mechanical properties
of these new materials. Kinetics and simulation are discussed and also considered as promising techniques for achieving
chemistry and predicting physical property goals. This book presents a selection of interdisciplinary papers on the state
of knowledge of each topic under consideration through a combination of overviews and original unpublished research.
Advanced Materials, Polymers, and Composites: New Research on Properties, Techniques, and Applications is addressed
to all those working in the field of polymers and composites, including academics, institutes, research centers, as well as
engineers working in the industry"-- Provided by publisher.
Identifiers: LCCN 2020058327 (print) | LCCN 2020058328 (ebook) | ISBN 9781771889513 (hardcover) |
ISBN 9781774638200 (softcover) | ISBN 9781003105015 (ebook)
Subjects: LCSH: Polymerization. | Polymers.
Classification: LCC TP156.P6 A36 2021 (print) | LCC TP156.P6 (ebook) | DDC 547/.28--dc23
LC record available at https://lccn.loc.gov/2020058327
LC ebook record available at https://lccn.loc.gov/2020058328
ISBN: 978-1-77188-951-3 (hbk)
ISBN: 978-1-77463-820-0 (pbk)
ISBN: 978-1-00310-501-5 (ebk)
DOI: 10.4324/9781006105015
About the Editors

Omari V. Mukbaniani, DSc

Professor, Ivane Javakhishvili Tbilisi State University,
Faculty of Exact and Natural Sciences, Department of Chemistry; Chair,
Macromolecular Chemistry; Director of the Institute of Macromolecular
Chemistry and Polymeric Materials at TSU, Tbilisi, Georgia
Omari Vasilii Mukbaniani, DSc, is a Professor and Director of the Macromo­
lecular Chemistry, Department of Ivane Javakhishvili Tbilisi State University,
Tbilisi, Georgia. He is also the Director of the Institute of Macromolecular
Chemistry and Polymeric Materials. For several years he was a member
of the advisory board of the Journal Proceedings of Ivane Javakhishvili
Tbilisi State University (Chemical Series), contributing editor of the journals
Polymer News and the Polymers Research Journal. His research interests
include polymer chemistry, polymeric materials, and the chemistry of
organosilicon compounds. He is an author of more than 480 publications, 27
books, monographs, and 10 inventions. He created in 2007 the International
Caucasian Symposium on Polymers and Advanced Materials, which takes
place every other two years in Georgia. The next symposium, ICSP&AM7,
will be in July 2021.

Tamara Tatrishvili, DSc

Senior Specialist, Unite of Academic Process Management
(Faculty of Exact and Natural Sciences), Ivane Javakhishvili Tbilisi State
University; Senior Researcher of the Institute of Macromolecular
Chemistry and Polymeric Materials at TSU, Georgia
Tamara Tatrishvili, PhD, is a Senior Specialist at the Unite of Academic Process
Management (Faculty of Exact and Natural Sciences) at Ivane Javakhishvili
Tbilisi State University as well as a Head of the Department of the Institute of
Macromolecular Chemistry and Polymeric Materials in Tbilisi, Georgia.
vi About the Editors

Marc J. M. Abadie, DSc

Professor Emeritus, Institute Charles Gerhardt of Montpelier—Aggregates,
Interfaces, and Materials for Energy (ICGM-AIME, UMR CNRS 5253),
University Montpelier, France
Professor Marc J. M. Abadie is an Emeritus Professor at the University
Montpellier, France. He was the head of the Laboratory of Polymer Science
and Advanced Organic Materials-LEMP/MAO. He is currently a “Michael
Fam” Visiting Professor at the School of Materials Sciences and Engineering,
Nanyang Technological University NTU, Singapore. His present activity
concerns high-performance polymers for PEMFCs, composites and nano­
composites, UV/EB coatings, and biomaterials. He has published 11 books
and 11 patents. He has advised nearly 95 MS and 52 PhD students with whom
he has published over 400 papers. He has more than 40 years of experience
in polymer science with 10 years in the industry (IBM, USA; Ministry of
Defence, UK; and SNPA/Total, France). In the 1980s, he created the Inter­
national Symposium on Polyimides and High-Temperature Polymers, a.k.a.
STEPI, which takes place every other three years in Montpellier, France. The
next symposium, STEPI 12, will be in June 2021.
Contents

Contributors.............................................................................................................xi
Abbreviations ......................................................................................................... xxi
Preface .................................................................................................................. xxv

PART I: Composites and Nanomaterials..................................................1

1. Correlation Between Chemical Structure and Photoreactivity in
UV Curing Formulation .................................................................................3
Marc J. M. Abadie, Iulian Manole, and Cătălin Fetecău

2. The Modified Natural Zeolites in Ion-Exchange Adsorption of

Some Heavy Metals.......................................................................................23
L. Akhalbedashvili, N. Gagniashvili, S. Jalaghania, N. Janashvili, R. Kvatashidze,
G. Todradze, and N. Loria

3. Properties of the Magnetic Polymer Nanocomposites in

Magnetic Fields .............................................................................................33
Jimsher Aneli and Grigor Mamniashvili

4. Physical‑Chemical Studies of M2I·MII·L2·nH2O Type

Heteronuclear Citrates .................................................................................43
I. Beshkenadze, M. Gogaladze, N. Klarjeishvili, L. Gogua, and O. Lomtadze

5. Coumarone‑Indene Resins with Functional Groups .................................53

Mariia Shved, Olena Shyshchak, Olena Astakhova, and Michael Bratychak

6. Oxidation and Exfoliation of Powdered Graphite Foil and

Its Wastes: Preparation of Graphene and Its Oxides ................................93
T. Dundua, V. Ugrekhelidze, L. Nadaraia, N. Nonikashvili, V. Gabunia,
M. Japaridze, N. Barbakadze, and R. Chedia

7. Liquid Crystal Microspheres Based Light and pH

Controlled Smart Drug Delivery Systems ................................................ 111
K. Chubinidze, D. Dzidziguri, O. Mukbaniani, M. Chubinidze, A. Petriashvili,
G. Petriashvili, M. P. De Santo, M. D. Luigi Bruno, and R. Barberi

8. Coating of Cordierite Monolith Substrate by Washcoat and

Hybrid Nanocomposite...............................................................................129
N. Makhaldiani, M. Donadze, and M. Gabrichidze
viii Contents

9. Negative Photoresists on the Basis of Copolymers of

2‑Chloromethyl‑1‑(p‑Vinyl Phenyl)Cyclopropane with
Glycidyl Methacrylate ................................................................................141
K. G. Guliyev, A. I. Sadygova, Ts. D. Gulverdashvili, and D. B. Tagiyev

10. Possibilities of Synthesis of Monodispersed Latex...................................153

A. A. Hovhannisyan, G. K. Grigoryan, A. G. Nadaryan, and N. H. Grigoryan

11. Biodegradable Polymer Packaging Materials in

Seawater Environment ...............................................................................163
Helena Janik, Justyna Kucińska-Lipka, Maciej Sienkiewicz, and Alicja Kosakowska

12. Water Sorption in Polyester/Dust/Glass Polyester

Recyclate Composites with Nanofillers .....................................................183
M. Jastrzębska and M. Rutkowska

13. Sorption Properties of Hydrogels of Rare‑Crosslinked Functional

Polyacids and Polybases in Relation to Rare Earth Metal Ions .............193
T. K. Jumadilov, R. G. Kondaurov, and A. M. Imangazy

14. Change in Rheological Properties of Pitch‑Thermoplastic

Under the Effect of Polar Polymers...........................................................209
I. Krutko, V. Kaulin, I. Danylo, K. Yavir, and K. Satsyuk

15. Investigation of Complex Formation Process of Zinc with

Fulvic Acids, Isolated from Natural Waters at pH = 9 ............................221
T. Makharadze

16. Effects of Dysprosium Addition on the Superconducting

Properties of Hg‑1223 HTS ........................................................................231
I. R. Metskhvarishvili, T. E. Lobzhanidze, G. N. Dgebuadze, B. G. Bendeliani,
M. R. Metskhvarishvili, and V. M. Gabunia

17. Hot Shock Wave Fabrication of Nanostructured Superconductive

MgB2 and MgB2‑Fe Composites.................................................................239
Akaki Peikrishvili, Giorgi Tavadze, Bagrat Godibadze, Grigor Mamniashvili,
and Alexander Shengelaya

PART II: Polymer Synthesis and Application ......................................253

18. Condensed Phosphates: New Inorganic Polymers with a
Variety of Applications and Improvement of Their Gravimetric
Determination Methods..............................................................................255
M. Avaliani, E. Shapakidze, V. Chagelishvili, N. Barnovi, and N. Esakia
Contents ix

19. New Cationic Polymers Composed of Non‑Proteinogenic

α-Amino Acids .............................................................................................277
Nino Zavradashvili, Giuli Otinashvili, Temur Kantaria, Nino Kupatadze, David Tugushi,
Ashot Saghyan, Anna Mkrtchyan, Sergey Poghosyan, and Ramaz Katsarava

20. Investigation of the Causes of Stability Violation of

Propagating Polymerization Heat Waves in the Process of
Frontal Polymerization...............................................................................289
Anahit O. Tonoyan, Aram H. Minasyan, Anahit Z. Varderesyan,
Armenuhi G. Ketyan, and Sevan P. Davtyan

21. Synthesis and Investigation of Properties of Comb‑Type

Methylsiloxane Copolymers with Pendant Diphenylsiloxane Groups...297
Tamara Tatrishvili, Kaloian Koynov, and Omari Mukbaniani

22. Reaction Hydrosilylation of Allyl-2,3,4-Tri-O-Acetyl-β-D-

Ramnopyranose with Methyl‑ and Phenylcyclodisilazanes ....................319
N. N. Sidamonidze, R. O. Vardiashvili, and M. O. Nutsubidze

23. Synthesis and Characterization of Novel Star‑Type Triarm Block

Copolymers Including Poly(Β-Methyl Β-Alanine) by
Raft Polymerization ....................................................................................327
B. Savaş, E. Çatiker, T. Öztürk, E. Meyvaci, M. Atakay, and B. Salih

24. Using of Polymers Technologies in the Industry ......................................341

L. V. Tabatadze, V. V. Shvelidze, E. J. Churgulia, and N. G. Shengelia

PART III: Materials and Properties......................................................349

25. Geopolymers Based on Local Rocks as a Future Alternative to
Portland Cement .........................................................................................351
E. Shapakidze, M. Avaliani, M. Nadirashvili, V. Maisuradze,
I. Gejadze, and T. Petriashvili

26. Investigation of Free Volume of Oriented Electrical Conducting

Polymer Composites by Spin Probe Method............................................359
Jimsher Aneli and Levan Nadareishvili

27. Comparison of Modified Polyethylene Incubation Effects in

Seawater and Composting Natural Environment....................................367
M. Rutkowska, A. Heimowska, K. Krasowska, and M. Jastrzębska
28. Obtaining of Biodegradable Polymers by Targeted
Polycondensation Reaction ........................................................................377
Givi Papava, Nora Dokhturishvili, Marina Gurgenishvili, Ia Chitrekashvili,
Eter Gavashelidze, Nazi Gelashvili, Riva Liparteliani, and Ketevan Archvadze
x Contents

29. Enhancing of the Properties of Polymer Composites with

Mineral Fillers Modified by Tetraethoxysilane ........................................383
O. Mukbaniani, J. Aneli, and E. Markarashvili

30. Peculiarities of Copolymerization of Vinyloxycyclopropanes with

Maleic Anhydride and Synthesis of Photosensitive Polymers.................393
Rita Shahnazarli

31. About the Rotation Mechanisms of the Molecular “Motors”.................407

N. S. Vassilieva-Vashakmadze, R. A. Gakhokidze, T. S. Vashakmadze,
M. Z. Gorgoshidze, and P. L. Toidze

Index .....................................................................................................................419
Contributors

Marc J. M. Abadie
Institute Charles Gerhardt Montpellier/AIME CNRS, University of Montpellier, France;
“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania,
E-mails: marc.abadie@umontpellier.fr; marc@icmpp.ro
L. Akhalbedashvili
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia, E-mail: aklali@yahoo.com

Jimsher Aneli
Institute of Macromolecular Chemistry and Polymeric Materials, Ivane Javakhishvili Tbilisi State
University, Ilia Chavchavadze Blvd. 13, Tbilisi–0179, Georgia; R. Dvali Institute of Machine
Mechanics, 10 Mindeli Str. Tbilisi–0186, Georgia, E-mail: janeli@yahoo.com
Ketevan Archvadze
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia

Olena Astakhova
Lviv Polytechnic National University, 12, S. Bandery St., 79013 Lviv, Ukraine

M. Atakay
Hacettepe University, Department of Chemistry, 06800 Ankara, Turkey

M. Avaliani
Iv. Javahishvili Tbilisi State University, Raphiel Agladze Institute of Inorganic Chemistry and
Electrochemistry, Mindeli Street 11, Tbilisi–0186, Georgia,
E-mails: avaliani21@hotmail.com; marine.avaliani@tsu.ge

N. Barbakadze
Laboratory of Problems of Chemical Ecology, Petre Melikishvili Institute of Physical and Organic
Chemistry, Iv. Javakhishvili Tbilisi State University, 31, Ana Politkovskaia Str., Tbilisi–0186, Georgia,
Phone: (+995 599) 76-53-15, E-mail: chemicalnatia@yahoo.de

R. Barberi
CNR-IPCF, UOS Cosenza, Physics Department, University of Calabria, Rende (Cs), Italy

N. Barnovi
Iv. Javahishvili Tbilisi State University, Raphiel Agladze Institute of Inorganic Chemistry and
Electrochemistry, Mindeli Street 11, Tbilisi–0186, Georgia

B. G. Bendeliani
Ilia Vekua Sukhumi Institute of Physics and Technology, Department of Cryogenic Technique and
Technologies, Tbilisi–0186, Georgia

I. Beshkenadze
Petre Melikishvili Institute of Physical and Organic Chemistry, Ivane Javakhishvili Tbilisi State
University, 31 A. Politkovskaia str. Tbilisi 0186 Georgia
xii Contributors

Michael Bratychak
Lviv Polytechnic National University, 12, S. Bandery St., 79013 Lviv, Ukraine,
E-mail: mbratychak@gmail.com

M. D. Luigi Bruno
CNR-IPCF, UOS Cosenza, Physics Department, University of Calabria, Rende (Cs), Italy
E. Çatiker
Ordu University, Department of Chemistry, 52200 Ordu, Turkey, E-mail: ecatiker@gmail.com

V. Chagelishvili
Iv. Javahishvili Tbilisi State University, Raphiel Agladze Institute of Inorganic Chemistry and
Electrochemistry, Mindeli Street 11, Tbilisi–0186, Georgia

R. Chedia
Laboratory of Problems of Chemical Ecology, Petre Melikishvili Institute of Physical and Organic
Chemistry, Iv. Javakhishvili Tbilisi State University, 31, Ana Politkovskaia Str., Tbilisi–0186, Georgia

Ia Chitrekashvili
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia
K. Chubinidze
Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze 1,
Tbilisi, Georgia; Institute of Cybernetics of Georgian Technical University, Tbilisi, Georgia,
E-mail: chubinidzeketino@yahoo.com

M. Chubinidze
Tbilisi Medical State University, Tbilisi, Georgia

E. J. Churgulia
Department of Chemistry, Sokhumi State University, A. Politkovskaya, St., 12, Tbilisi–0186, Georgia

I. Danylo
Donetsk National Technical University, Department of Chemical Technologies, 85300 Pokrovsk, Ukraine

Sevan P. Davtyan
National Polytechnic University of Armenia, Department of General Chemistry,
and Chemical Processes, Teryan Str., 105, Yerevan–0009, Armenia

G. N. Dgebuadze
Ilia Vekua Sukhumi Institute of Physics and Technology, Department of Cryogenic Technique and
Technologies, Tbilisi–0186, Georgia

Nora Dokhturishvili
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia

M. Donadze
Faculty of Chemistry and Metallurgy, Georgian Technical University, Kostava Ave., 69, 0171, Tbilisi,
Georgia

T. Dundua
Department of Agricultural Sciences and Biosystems Engineering, Georgian Technical University,
17, D. Guramishvili Str. Tbilisi–0192, Georgia

D. Dzidziguri
Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze 1,
Tbilisi, Georgia
Contributors xiii

N. Esakia
Iv. Javahishvili Tbilisi State University, Institute of Exact and Natural Sciences,
Department of Chemistry, 0179, I. Chavchavadze Ave 3, Tbilisi, Georgia

Cătălin Fetecău
ReForm UDJG Interdisciplinary Research Platform, Center of Excellence Polymer Processing,
“Dunărea de Jos” University of Galați, Galați, Romania
M. Gabrichidze
Faculty of Chemistry and Metallurgy, Georgian Technical University, Kostava Ave., 69, 0171,
Tbilisi, Georgia

V. Gabunia
Laboratory of Problems of Chemical Ecology, Petre Melikishvili Institute of Physical and Organic
Chemistry, Iv. Javakhishvili Tbilisi State University, 31, Ana Politkovskaia Str., Tbilisi–0186, Georgia

V. M. Gabunia
Ilia Vekua Sukhumi Institute of Physics and Technology, Department of Cryogenic Technique and
Technologies, Tbilisi – 0186, Georgia; Petre Melikishvili Institute of Physical and Organic Chemistry of
the Iv. Javakhishvili Tbilisi State University, Jikia Str., 5, Tbilisi–0186, Georgia

N. Gagniashvili
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia

R. A. Gakhokidze
Iv. Javakhishvili Tbilisi State University, Department of Bioorganic Chemistry, Tbilisi, Georgia

Eter Gavashelidze
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia

I. Gejadze
Iv. Javakhishvili Tbilisi State University, Al. Tvalchrelidze Caucasian Institute of Mineral Resources,
11 Mindeli Street, Tbilisi–0186, Georgia

Nazi Gelashvili
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia

Bagrat Godibadze
Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave., 1, 0179 Tbilisi, Georgia

M. Gogaladze
Petre Melikishvili Institute of Physical and Organic Chemistry, Ivane Javakhishvili Tbilisi State
University, 31 A. Politkovskaia, Tbilisi–0186, Georgia

L. Gogua
Tbilisi State Medical University, 33, Vaja-Pshavela Ave.0186, Tbilisi, Georgia

M. Z. Gorgoshidze
E. Andronikashvili Institute of Physics, Iv. Javakhishvili Tbilisi State University, Tbilisi, Georgia

G. K. Grigoryan
Scientific-Technological Center of Organic and Pharmaceutic Chemistry NAS
Republic of Armenia, 0014, Yerevan, 26 Azatutyan Av., Armenia
xiv Contributors

N. H. Grigoryan
Scientific-Technological Center of Organic and Pharmaceutic Chemistry NAS
Republic of Armenia, 0014, Yerevan, 26 Azatutyan Av., Armenia

K. G. Guliyev
Institute of Polymer Materials of Azerbaijan National Academy of Sciences, Az5004, Sumgait,
S. Vurgun Str.124, Azerbaijan, E-mail: ipoma@science.az, kazim_pm@mail.ru
Ts. D. Gulverdashvili
Azerbaijan Medical University, Biophysical, and Bioorganic Chemistry (Sub)Department, Az1022,
Baku, Bakikhanov Str., 23, Azerbaijan

Marina Gurgenishvili
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia, E-mail: marina.gurgenishvili@yahoo.com

A. Heimowska
Department of Industrial Commodity Science and Chemistry, Faculty of Entrepreneurship and Quality
Science, Gdynia Maritime University, 83 Morska Str., 81-225 Gdynia, Poland
A. A. Hovhannisyan
Scientific-Technological Center of Organic and Pharmaceutic Chemistry NAS Republic of Armenia,
0014, Yerevan, 26 Azatutyan Av., Armenia, E-mail: hovarnos@gmail.com
A. M. Imangazy
JSC “Institute of Chemical Sciences after A.B. Bekturov,” Almaty, the Republic of Kazakhstan

S. Jalaghania
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia
N. Janashvili
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia
Helena Janik
Gdansk University of Technology, Chemical Faculty, Polymer Technology Department, Gdansk,
Poland, E-mail: helena.janik@pg.edu.pl

M. Japaridze
Laboratory of Problems of Chemical Ecology, Petre Melikishvili Institute of Physical and Organic
Chemistry, Iv. Javakhishvili Tbilisi State University, 31, Ana Politkovskaia Str., Tbilisi–0186, Georgia

M. Jastrzębska
Department of Industrial Commodity Science and Chemistry, Faculty of Entrepreneurship and Quality
Science, Gdynia Maritime University, 83 Morska Str., 81–225 Gdynia, Poland,
E-mail: m.jastrzebska@wpit.umg.edu.pl

T. K. Jumadilov
JSC “Institute of Chemical Sciences after A.B. Bekturov,” Almaty, the Republic of Kazakhstan,
E-mail: jumadilov@mail.ru

Temur Kantaria
Institute of Chemistry and Molecular Engineering, Agricultural University of Georgia, Tbilisi, Georgia

Ramaz Katsarava
Institute of Chemistry and Molecular Engineering, Agricultural University of Georgia, Tbilisi, Georgia,
E-mail: r.katsarava@agruni.edu.ge
Contributors xv

V. Kaulin
Donetsk National Technical University, Department of Chemical Technologies, 85300 Pokrovsk, Ukraine

Armenuhi G. Ketyan
National Polytechnic University of Armenia, Department of General Chemistry,
and Chemical Processes, Teryan Str., 105, Yerevan–0009, Armenia
N. Klarjeishvili
Petre Melikishvili Institute of Physical and Organic Chemistry, Ivane Javakhishvili Tbilisi State
University, 31 A. Politkovskaia str., Tbilisi 0186, Georgia
R. G. Kondaurov
JSC “Institute of Chemical Sciences after A.B. Bekturov,” Almaty, the Republic of Kazakhstan

Alicja Kosakowska
The Institute of Oceanology of the Polish Academy of Sciences, Sopot, Poland

Kaloian Koynov
Max Planck Institute for Polymer Research, Department of Physics of Interfaces, Ackermannweg 10,
D-55128 Mainz, Germany

K. Krasowska
Department of Industrial Commodity Science and Chemistry, Faculty of Entrepreneurship and Quality
Science, Gdynia Maritime University, 83 Morska Str., 81-225 Gdynia, Poland

I. Krutko
Donetsk National Technical University, Department of Chemical Technologies, 85300 Pokrovsk,
Ukraine, E-mail: poshukdoc@gmail.com

Justyna Kucińska-Lipka
Gdansk University of Technology, Chemical Faculty, Polymer Technology Department, Gdansk, Poland

Nino Kupatadze
Institute of Chemistry and Molecular Engineering, Agricultural University of Georgia, Tbilisi, Georgia

R. Kvatashidze
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia

Riva Liparteliani
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia

T. E. Lobzhanidze
Ivane Javakhishvili Tbilisi State University, Department of Chemistry, Faculty of Exact and Natural
Sciences, 0179 Tbilisi, Georgia

O. Lomtadze
Petre Melikishvili Institute of Physical and Organic Chemistry, Ivane Javakhishvili Tbilisi State
University, 31 A. Politkovskaia str. Tbilisi 0186, Georgia

N. Loria
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia

V. Maisuradze
Iv. Javakhishvili Tbilisi State University, Al. Tvalchrelidze Caucasian Institute of Mineral Resources,
11 Mindeli Street, Tbilisi–0186, Georgia
xvi Contributors

N. Makhaldiani
Faculty of Chemistry and Metallurgy, Georgian Technical University, Kostava Ave., 69, 0171, Tbilisi,
Georgia, E-mail: makhaldianinino@gmail.com

T. Makharadze
Ivane Javakhishvili Tbilisi State University, Tbilisi, Georgia, E-mail: makharadze_tako@yahoo.com
Grigor Mamniashvili
Andronikashvili Institute of Physics of Ivane Javakhishvili Tbilisi State University, 6, Tamarashvili str.,
0177, Tbilisi, Georgia; G. Tsulukidze Mining Institute, 7 E. Mindeli St. Tbilisi–0186, Georgia
Iulian Manole
ReForm UDJG Interdisciplinary Research Platform, Center of Excellence Polymer Processing,
“Dunărea de Jos” University of Galați, Galați, Romania
E. Markarashvili
I. Javakhishvili Tbilisi State University, I. Chavchavadze Ave., 1 Tbilisi–0127, Georgia;
Institute of Macromolecular Chemistry and Polymeric Materials, Ivane Javakhishvili University,
Ilia Chavchavadze Blvd. 13, Tbilisi–0179, Georgia

I. R. Metskhvarishvili
Ilia Vekua Sukhumi Institute of Physics and Technology, Department of Cryogenic Technique and
Technologies, Tbilisi–0186, Georgia; Georgian Technical University, Faculty of Informatics and
Control Systems, 0175 Tbilisi, Georgia

M. R. Metskhvarishvili
Georgian Technical University, Faculty of Informatics and Control Systems, 0175 Tbilisi, Georgia

E. Meyvaci
Giresun University, Department of Chemistry, 28200 Giresun, Turkey

Aram H. Minasyan
National Polytechnic University of Armenia, Department of General Chemistry, and Chemical
Processes, Teryan Str., 105, Yerevan–0009, Armenia
Anna Mkrtchyan
Institute of Pharmacy, Yerevan State University, Yerevan, Republic of Armenia

Omar Mukbaniani
Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave.,
1 Tbilisi – 0127, Georgia; Institute of Macromolecular Chemistry and Polymeric Materials,
Ivane Javakhishvili University, Ilia Chavchavadze Blvd. 13, Tbilisi–0179, Georgia,
E-mail: omarimu@yahoo.com

L. Nadaraia
Department of Agricultural Sciences and Biosystems Engineering, Georgian Technical University, 17,
D. Guramishvili Str. Tbilisi–0192, Georgia

Levan Nadareishvili
V. Chavchanidze Institute of Cybernetics, Georgian Technical University, Georgia

A. G. Nadaryan
Scientific-Technological Center of Organic and Pharmaceutic Chemistry NAS Republic of Armenia, 0014,
Yerevan, 26 Azatutyan Av., Armenia

M. Nadirashvili
Iv. Javakhishvili Tbilisi State University, Al. Tvalchrelidze Caucasian Institute of Mineral Resources, 11
Mindeli Street, Tbilisi–0186, Georgia
Contributors xvii

N. Nonikashvili
Laboratory of Problems of Chemical Ecology, Petre Melikishvili Institute of Physical and Organic
Chemistry, Iv. Javakhishvili Tbilisi State University, 31, Ana Politkovskaia Str., Tbilisi–0186, Georgia

M. O. Nutsubidze
Iv. Javakhishvili State University, Department of Chemistry, I. Chavchavadze Ave., 1, 0179, Tbilisi, Georgia
Giuli Otinashvili
Institute of Chemistry and Molecular Engineering, Agricultural University of Georgia, Tbilisi, Georgia

T. Öztürk
Giresun University, Department of Chemistry, 28200 Giresun, Turkey

Givi Papava
TSU Petre Melikishvili Institute of Physical and Organic Chemistry 31, A. Politkovskaia Str.,
Tbilisi–0186, Georgia
Akaki Peikrishvili
F. Tavadze Institute of Metallurgy and Materials Science, 10 E. Mindeli St. Tbilisi–0186, Georgia,
E-mail: akaki.peikrishvili@yahoo.com

A. Petriashvili
Tbilisi Medical State University, Tbilisi, Georgia

G. Petriashvili
Institute of Cybernetics of Georgian Technical University, Tbilisi, Georgia

T. Petriashvili
Iv. Javakhishvili Tbilisi State University, Al. Tvalchrelidze Caucasian Institute of Mineral Resources,
11 Mindeli Street, Tbilisi–0186, Georgia

Sergey Poghosyan
Institute of Pharmacy, Yerevan State University, Yerevan, Republic of Armenia

M. Rutkowska
Department of Industrial Commodity Science and Chemistry, Faculty of Entrepreneurship and Quality
Science, Gdynia Maritime University, 83 Morska Str., 81–225 Gdynia, Poland

A. I. Sadygova
Azerbaijan Medical University, Biophysical, and Bioorganic Chemistry (Sub)Department, Az1022,
Baku, Bakikhanov Str., 23, Azerbaijan

Ashot Saghyan
Institute of Pharmacy, Yerevan State University, Yerevan, Republic of Armenia

B. Salih
Hacettepe University, Department of Chemistry, 06800 Ankara, Turkey

M. P. De Santo
CNR-IPCF, UOS Cosenza, Physics Department, University of Calabria, Rende (Cs), Italy
K. Satsyuk
Donetsk National Technical University, Department of Chemical Technologies, 85300 Pokrovsk, Ukraine

B. Savaş
Kafkas University, Kars Vocational School, 36100 Kars, Turkey

Rita Shahnazarli
Institute of Polymer Materials of Azerbaijan National Academy of Sciences,
S. Vurgun Str., 124, AZ5004, Azerbaijan, E-mail: shahnazarli@mail.ru
xviii Contributors

E. Shapakidze
Iv. Javakhishvili Tbilisi State University, Alexander Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Street 11, Tbilisi–0186, Georgia, E-mail: elena.shapakidze@tsu.ge

Alexander Shengelaya
G. Tsulukidze Mining Institute, 7 E. Mindeli St., Tbilisi–0186, Georgia
N. G. Shengelia
Department of Chemistry, Sokhumi State University, A. Politkovskaya, St., 12, Tbilisi–0186, Georgia

Mariia Shved
Lviv Polytechnic National University, 12, S. Bandery St., 79013 Lviv, Ukraine

V. V. Shvelidze
Department of Physics, Tbilisi State University, I. Chavchavadze Ave., 1, 0179 Tbilisi, Georgia

Olena Shyshchak
Lviv Polytechnic National University, 12, S. Bandery St., 79013 Lviv, Ukraine

N. N. Sidamonidze
Iv. Javakhishvili State University, Department of Chemistry, I. Chavchavadze Ave., 1, 0179, Tbilisi,
Georgia, E-mail: neli.sidamonidze@tsu.ge

Maciej Sienkiewicz
Gdansk University of Technology, Chemical Faculty, Polymer Technology Department, Gdansk, Poland

L. V. Tabatadze
Department of Chemistry, Sokhumi State University, A. Politkovskaya, St., 12, Tbilisi–0186, Georgia

D. B. Tagiyev
Azerbaijan Medical University, Biophysical, and Bioorganic Chemistry (Sub)Department, Az1022,
Baku, Bakikhanov Str. 23, Azerbaijan

Tamara Tatrishvili
Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State University, I. ChavchavadzeAve.,
1 Tbilisi–0127, Georgia; Institute of Macromolecular Chemistry and Polymeric Materials, Ivane
Javakhishvili University, Ilia Chavchavadze Blvd. 13, Tbilisi–0179, Georgia,
E-mail:omarimu@yahoo.com

Giorgi Tavadze
F. Tavadze Institute of Metallurgy and Materials Science, 10 E. Mindeli St., Tbilisi–0186, Georgia

G. Todradze
Ivane Javakhishvili Tbilisi State University, Alexandre Tvalchrelidze Caucasian Institute of Mineral
Resources, Mindeli Str., 11, Tbilisi–0186, Georgia

P. L. Toidze
Georgian Technical University, Department of Chemical and Biological Technologies, Tbilisi, Georgia

Anahit O. Tonoyan
National Polytechnic University of Armenia, Department of General Chemistry, and Chemical
Processes, Teryan Str., 105, Yerevan–0009, Armenia, E-mail: atonoyan@mail.ru

David Tugushi
Institute of Chemistry and Molecular Engineering, Agricultural University of Georgia, Tbilisi, Georgia

V. Ugrekhelidze
Department of Agricultural Sciences and Biosystems Engineering, Georgian Technical University,
17, D. Guramishvili Str. Tbilisi–0192, Georgia
Contributors xix

Anahit Z. Varderesyan
National Polytechnic University of Armenia, Department of General Chemistry, and Chemical
Processes, Teryan Str., 105, Yerevan–0009, Armenia

R. O. Vardiashvili
Iv. Javakhishvili State University, Department of Chemistry, I. Chavchavadze Ave., 1, 0179, Tbilisi, Georgia
T. S. Vashakmadze
Iv. Javakhishvili Tbilisi State University, Vekua Institute of Applied Mathematics, Tbilisi, Georgia

N. S. Vassilieva‑Vashakmadze
Georgian Academy of Engineering, Tbilisi, Georgia, E-mail: nonavas@rambler.ru

K. Yavir
Donetsk National Technical University, Department of Chemical Technologies, 85300 Pokrovsk, Ukraine

Nino Zavradashvili
Institute of Chemistry and Molecular Engineering, Agricultural University of Georgia, Tbilisi, Georgia
Abbreviations

AA α-amino acid
AAm acrylamide
AIBN α,α’-azoisobutyronitrile
AlG allylglycine
AlG12 bis-(allyl-glycine)-1,12-dodecylen
AlG6 bis-(allyl-glycine)-1,6-hexylen
a-PHB amorphous poly[(R,S)-3-hydroxybutyrate]
BAPO bis acyl phosphine oxide
BCP block-copolymers
BPM bitumen-polymer mixtures
BS bentonite special
C coal
C/O carbon to oxygen
CIF coumarone-indene fraction
CIR coumarone-indene resins
CIRC coumarone-indene resins with carboxy groups
CIRM coumarone-indene resins with methacrylic fragments
CLCs cholesteric liquid crystals
CMCP 2-chloromethyl-1-(p-vinyl phenyl)cyclopropane
CPs cationic polymers
CTP coal tar pitch
CVD chemical vapor deposition
DCP dicumyl peroxide
DHB dihydroxybenzoic acid
DLS dynamic light scattering
DMA dimethylacetamide
DMF dimethylformamide
DPC differential photocalorimeter
DSC differential scanning calorimetry
EB electron beam
ER epoxy resin
ESR electron spin resonance
FA fulvic acids
FC field-cooled
xxii Abbreviations

FD fluorescent dye
FGM functional gradient materials
FP frontal polymerization
FTIR Fourier transform infrared spectroscopy
GMA glycidyl methacrylate
GO graphene oxide
GPC gel-permeation chromatography
HAP hydroxyacetophenone
HDPE high density polyethylene
HLB hydrophilic-lipophilic balance
HPs hybrid-polymers
HTP hydrogen transfer polymerization
LB Langmuir-Blodgett
LDPE low-density polyethylene
LFCT light fraction of coal tar
MA maleic anhydride
MAA methacrylic acid
MB masterbatch
MC merocyanine
MEK methyl ethyl ketone
MEVA maleized ethylene-vinyl acetate
MF membrane filtration
MFR melt flow rate
MM molecular mechanics
MMA methyl methacrylate
MOR mordenite
MotA motility protein A
MotB motility protein B
MS-Ring symmetry mismatch
Na2CO3 sodium carbonate
NaN3 sodium azide
NaOH sodium alkali
NIR near-infrared light
NPAAs non-proteinogenic amino acids
NPs nanoparticles
OPC ordinary Portland cement
poly(MBA-b-MMA) poly(β-methyl β-alanine-b-methyl methacrylate)
PBS poly(butylene succinate)
PCL poly(ε-caprolactone)
Abbreviations xxiii

PE polyethylene
PEAs poly(ester amides)
PECH poly(epichlorohydrin)
PEGs polyethylenglycols
PGF powdered graphite foil
pGFW powdered graphite foil wastes
PHA polyhydroxyalkanoates
PHB poly(3-hydroxybutyrate)
PHB/V poly(b-hydroxybutyrate/valerate)
PI photo initiator
PLA poly(D,L-lactide)
PLLA poly(L-lactide)
PMBA-diBr poly(β-methyl β-alanine)
PMFCs polymer matrix fibrous composites
PMHS polymethylhydrosiloxane
PMMA polymethyl methacrylate
PNC polymer nanocomposites
PP polypropylene
PRs petroleum resins
PVA polyvinyl alcohol
PVB polyvinylbutyral
PVC polyvinyl chloride
RAFT reversible addition-fragmentation chain transfer
REMs rare earth metals
rGO reduced graphene oxide
ROP ring-opening polymerization
SAcP solution active polycondensation method
SEI secondary electron images
SEM scanning electron microscopy
SPS spark-plasma sintering technology
SRB selective reflection band
SW seawater
Td decomposition temperatures
TEOS tetraethoxysilane
TG/DTA thermogravimetric and differential thermal analyzer
Tg glass-transition temperatures
TGA thermogravimetric analysis
THF tetrahydrofuran
TMPTA trimethylolpropane triacrylate
xxiv Abbreviations

TPS thermoplastic starch

UV ultraviolet
UVT ultraviolet light
VOC volatile organic compounds
VOCP vinyloxycyclopropanes
VSM vibrating sample magnetometer
XRD x-ray diffraction
ZFC zero-field-cooled
Preface

Polymers, a word that we hear about it a lot, are very vital, and one cannot
imagine life without them. Polymers, a large class of materials, consist of
many small molecules, named monomers, that are linked together to form long
chains and are used in a lot of products and goods that we use in daily life.
There were relatively few materials available for the manufacture of
the article needed for a civilized life. Steel, glass, wood, stone, brick, and
concrete for most of the construction, and cotton, wood, jute, and a few other
agricultural products for clothing or fabric manufacture were used.
The rapid increase in demand for manufactured products introduces new
materials. These new materials are polymers, and their impact on the present
way of life is almost incalculable. Products made from polymers are all around
us: clothing made from synthetic fibers, polyethylene (PE) cups, fiberglass,
nylon bearings, plastic bags, polymer-based paints, epoxy glue, polyurethane
foam cushion, silicone heart valves, and Teflon-coated cookware.
In modern technologies, new organic materials and tools have been
developed to fulfill the strong demand of innovative chemical structures. For
the last three decades, increasing need in the high technology industries (space,
micro, and nanoelectronics, membranes, fuel cells, etc.) has been the driving
force for the development of new polymeric systems that combine thermal
stability with specific functional properties, and also others such as lightweight,
high corrosion resistance, good wear properties, dimensional stability, low
flammability, separation properties, moisture resistance, insulating properties,
and ability to be transformed with conventional equipment.
This book reviews several domains of polymer science, especially new
trends in polymerization synthesis, physical-chemical properties, and inorganic
systems. Composites and nanocomposites are also covered in this book,
emphasizing nanotechnologies and their impact on the enhancement of physical
and mechanical properties of these new materials. Kinetics and simulation are
discussed and also considered as promising techniques for achieving chemistry
and predicting physical property goals. This book presents interdisciplinary
papers on the state of knowledge of each topic under consideration through a
combination of overviews and original unpublished research.
xxvi Preface

This book is addressed to all those working in the field of polymers and
composites, i.e., academics, institutes, research centers, as well as engineers
working in the industry.
—Omar Mukbaniani, DSc
Ivane Javakhishvili Tbilisi State University,
Faculty of Exact and Natural Sciences,
Institute of Chemistry, Department of Macromolecular Chemistry,
Director of the Institute of Macromolecular Chemistry and
Polymeric Materials at TSU, Georgia
—Tamara Tatrishvili, DSc
Ivane Javakhishvili Tbilisi State University,
Faculty of Exact and Natural Sciences,
Institute of Chemistry, Senior Specialist at the Office of
Academic Process Management;
Head of the Department of the Institute of Macromolecular
Chemistry and Polymeric Materials at TSU, Georgia
—Marc J. M. Abadie, DSc
Professor Emeritus, Doctor Honoris Causa
Institut Charles Gerhardt de Montpellier-Agrégats, Interfaces et
Matériaux pour l’Energie (IGCM AIME UMR CNRS 5253)
STEPI General Chairman, Expert près la Cour d’Appel
“Michael Fam” Visiting Professor @ NTU/MSE, Singapore
 PART I
Composites and Nanomaterials
CHAPTER 1

Correlation Between Chemical Structure

and Photoreactivity in UV Curing
Formulation
MARC J. M. ABADIE,1,2 IULIAN MANOLE,3 and CĂTĂLIN FETECĂU3
Institute Charles Gerhardt Montpellier/AIME CNRS, University of
1

Montpellier, France, E-mails: marc.abadie@umontpellier.fr;

marc@icmpp.ro
2
“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania
3
ReForm UDJG Interdisciplinary Research Platform, Center of Excellence
Polymer Processing, “Dunărea de Jos” University of Galați, Galați, Romania

ABSTRACT

Ultraviolet (UV) curing is a light-induced polymerization of multifunc­

tional monomers/oligomers. It is a very eco-efficient and energy saving
crosslinking method that has been extensively used as a coating for wood,
paper, walls, and thin-film technology in microelectronic via a photoli­
thography process.
To get a 3D network, most of the formulation uses multifunctional
monomers/oligomers or a mixture of them that crosslink under exposure to
UV radiations in a free radical or anionic process, depending on the chemical
functionality engaged in the monomers/oligomers formulation.
According to the formulation used, Mc and crosslink density Xc are
determined and correlated to the photoreactivity of the system considered.
Some examples are given covering cationic UV curing and radical thermal
curing systems as well.
4 Advanced Materials, Polymers, and Composites

1.1 INTRODUCTION

Photochemistry through ultraviolet (UV) or electron beam (EB) radiation

has been used for more than 40 years, specifically for coatings, adhesives,
inks, electronics, and 3D printing in recent years [1]. Fast curing (usually less
than 1 second), excellent film properties, and essentially nonvolatile organic
compounds (VOC) are the major benefits among many other advantages
compared with conventional solvent-borne thermal curing process, which
is under increasing pressure from regulatory agencies to limit the number of
solvents emitted into the environment.
In the curing process, UV is generally used to cure coatings 200–500
μm thick. For thicker composite structures such as polymer matrix fibrous
composites (PMFCs) used in aerospace and automotive applications, EB is
a more suitable technique for curing parts up to 10–20 cm thick, depending
on the power of the EB [2]. In recent years, major advances have been made
in raw materials and equipment designs that make this unique technology
available for more and new industrial applications.
In this chapter, we analyze some formulation based on acrylates, epoxies,
and/or vinyl ethers that have been published [3], their respective photosensi­
tivity, and photoreactivity [4] compared to Mc and the crosslink density Xc
of the formulations considered.

1.2 UV CURING SYSTEM

1.2.1 UV BASIC

The electromagnetic spectrum (Figure 1.1.) goes from low energy (radio
waves) to high energy (electron beam). According to the Planck’s equation
each radiation is associated to energy: E = AN.hc/λ = 119.705×10–6/λ kJ/mol.
Among UV rays, only visible rays [400 nm (299 kJ/mol) ≤ λ ≥ 700 nm (171
kJ/mol)] and UVA rays [315 nm (380 kJ/mol) ≤ λ ≥ 400 nm (299 kJ/mol)]
require the presence of a photoinitiator to initiate polymerization. Indeed, the
energy developed by the radiation is not sufficient to break the C-C or C-O
bonds (≈ 350 kJ/mol). However, in the case of UVB [280 nm (427 kJ/mol)
≤ λ ≥ 315 nm (380 kJ/mol)] and UVC [100 nm (1196 kJ/mol) ≤ λ ≥ 280 nm
(427 kJ/mol)] and especially for lower wavelengths such as EB, the energy
of the radiation developed is higher than the bond energies and therefore the
resin can be cured without the presence of a photo initiator.
Correlation Between Chemical Structure and Photoreactivity 5

FIGURE 1.1 The electromagnetic spectrum.

In the polymerization of the double bond, only the π bond is a concern in

the propagation reaction. The energy to cut C=C corresponds to π and σ bonds
equivalent to EC=C = 615 kJ/mol. To break the σ bond C-C, the energy needed
is EC-C = 347 kJ/mol. Therefore, the energy to provide for opening the π bond
will be: (615–347) kJ/mol = 268 kJ/mol, corresponding to a wavelength λ =
446.7 nm. In other words, for λ < 446.7 nm, we need to use a photoinitiator.
Using the Hesse law vz. “the bond energy of a reaction ΔH is the total
number of bonds broken minus the total number of bonds formed”:
ΔH = ΣΔH(bonds broken) – ΣΔH(bonds formed) = n(C = C) – 2n(-C-C-)
= ΔH = (615 – 2 × 347) kJ/mol = 79 kJ/mol
that corresponds to a wavelength λ < 1515.3 nm. According to Hesse law,
even in the visible, we could make a polymerization without any photoini­
tiator, which makes no sense if we consider the time depending. For example,
if we leave styrene in the sunlight for a year, it will polymerize alone without
a photoinitiator.

1.2.2 RADICAL PHOTOINITIATOR

A photosensitive formulation for UV curing contains photoinitiator, monomer/

oligomer multifunctional, and some additives [4]:
1. Photoinitiator for radical polymerization (acrylates, methacrylates)
is classified as [5]:
i. Cleavage (Type 1): HAP (hydroxyacetophenone).

Examples of photoinitiators class 1 are Irgacure® 651, Darocur®1173

(liquid), or bis-acyl phosphine oxide (BAPO) [a mixture of 75 wt.%
Darocur®1173 and 25 wt.% BAPO (liquid)], to cite some of them.
6 Advanced Materials, Polymers, and Composites

ii. H‑Abstraction (Type 2): BP + RNH2 (benzophenone + amine).

1.2.3 CATIONIC PHOTO INITIATOR

2. Photoinitiators for cationic polymerization (epoxy and vinyl ether

resins), upon exposure to UV light, produce strong acid [6, 7]
according to the following scheme:

Epoxy polymerize by cationic process [8], initiated by a proton H+

(HMtXn). Sulfonium or iodonium salts exposed to UV produce not only
strong acid but also radicals, making the polymerization of acrylates (meth­
acrylates) also possible.
The photoinitiator (PI) Cyracure® UVI-6976, largely used, consist of
a mixture 40/60 of hexafluoroantimonate of S,S,S,‘S’-tetraphenylthiobis
(4,1-phenylene) disulfonium and hexafluoroantimonate of diphenyl (4-phen­
ylthiophenyl) sulfonium (CAS no. 89452-32-9 and 71449-78-0) at 50% by
weight in propylene carbonate (Figure 1.2).

FIGURE 1.2 Cyracure® UVI 6976.

Correlation Between Chemical Structure and Photoreactivity 7

Note that recently a new cationic photoinitiator has been proposed viz.
iodonium and sulfonium salt-containing tetrakis (perfluorotbutyloxy) alumi­
nate anion sulfonium/iodonium salt (Figure 1.3) [9, 10].

FIGURE 1.3 Tetrakis aluminate anion.

It should be noted that, while radical polymerizations are sensitive to

oxygen (chain peroxidation reaction leading to degradation of the polymer),
this is not the case for cationic polymerizations, however moisture-
sensitive. This remark is important because it does not require working in
the absence of oxygen when using epoxy resins (ERs), but the environment
should be dry. Using additive with chlorinated anhydride may improve
the UV irradiation stability of the ER. The photopolymerization process is
represented in Figure 1.4.

FIGURE 1.4 Scheme of photopolymerization.

8 Advanced Materials, Polymers, and Composites

1.3 CALCULATION OF MC AND XC

1.3.1 AVERAGE FUNCTIONALITY F

The main group of polymers belongs to the class of thermoplastics and fibers,
which are linear or branched, uncrosslinked polymers, semi-crystalline,
or amorphous, and that can be processed into different shapes by thermal
treatment, can be remolded, and are recyclable. Besides other classification,
one classification of the polymer types can be done by the increasing
degree of crosslinking, whereof the elastomers are slightly or moderated
crosslinked, occurring very often as rubber-like flexible materials, and
thermosets or duromers, which are highly crosslinked with the formation of
the 3D network, amorphous, cannot be remolded and recycled, and available
as hard materials.
• Since the networks consist of infinite molecular mass molecules (Mw
approaches infinity, whereas Mn stays finite), virtually insoluble, the
characterization of crosslinked polymers cannot be done by molecular
mass determination, but rather by dynamic thermal-mechanical
analysis technique or by crosslink density and molecular mass between
X-links.
• DTMA applies an oscillatory force at a set frequency to the sample
and reports changes in stiffness and damping. Young modulus E is
determined by deformation under stress [Elastic (Storage) Modulus E’
and Viscous (Lost) Modulus E”] whereas rigidity and shear modulus
G by deformation under shearing stress [G’ & G”].
The functionality of the monomer f used is defined as the ratio of the
number of bonds formed to the number of monomer molecules used during
the polymerization process:
Number of Link Formed per Monomer
f =
Number of Molecule Monomer

If the monomer is monofunctional (having one double bond), the func­

tionality f = 2, and the structure of the polymer obtained are linear, therefore
a thermoplastic. In the case of monomer difunctional, the functionality f
= 4, or multifunctional, the structure of the polymer is crosslinked, f > 2,
therefore a thermoset.
Correlation Between Chemical Structure and Photoreactivity 9

The calculation of the average functionality f of the monomer makes

it possible to determine to which category the polymer obtained after
polymerization belongs. The average functionality f0 of a mixture of ni
monomer of fi functionality is given by:
n1 f1 + n2 f 2 + ........ + ni f i
f0 =
n1 + n2 + ........ + ni

For example for monofunctional monomer (acrylate, styrene, epoxy, vinyl

ether) f = 2 (two possibilities to form a bond), for difunctional monomer
(acrylate, styrene, epoxy, vinyl ether) f = 4 (four directions to form a link),
for trifunctional monomer f = 6, etc.

1.3.2 MC AND DEGREE OF CROSSLINK XC

The crosslinking density is expressed by ν (mol/g-ν ≥ 0) or by the degree of

crosslinking Xc-0 ≤ Xc ≤ 1. If several components are used, the molar mass
M is calculated by the medium molecular mass M0:
n1 M 1 + n2 M 2 + ........ + ni M i
M0 =
n1 + n2 + ........ + ni

Resulting in Mc vz. molar mass between two crosslinks (thee directions or

more) [11]:
M0 M0
Mc = Mc =
f0 − 2 pf 0 − 2

where; p is the fraction of double bonds converted (p ≤ 1).

10 Advanced Materials, Polymers, and Composites

fav = f0 = 2 → Mc is infinite
→ The polymer is linear

Then the resulting in a crosslink density Xc of:

1
Xc =
Mc
The calculation of the network quantities can also be done according to
the theories developed by Macosco and Miller [12]. The prerequisites of this
theory are:
• Equal reactivity of all functional groups. It is obvious that this condi­
tion is not respected when the reaction is engaged as the increasing
viscosity during the reaction will reduce the reactivity of the func­
tional groups.
• The reactivity of the groups being independent from each other.
• Cyclization is not considered.
The network characterizing values can be experimentally determined by
DTMA, based on the theory of rubber elasticity [13] where the crosslinking
density Xc is:
E′
Xc =
3ρ RT
where; E’ is the modulus in the rubber elastic region, R is the gas constant, ρ
is the density, and T is the absolute temperature.

1.3.3 MESH SIZE

The mesh size of a 3D network can be derived from the rubber-elasticity

theory using the following equation [14, 15]:
1
−
⎛ G ′N A ⎞ 3
ξ =⎜ ⎟
⎝ RT ⎠
where; G’ is the storage modulus in Pa, NA is the Avogadro constant in mol–1,
R is the molar gas constant in J.(mol.K)–1, and T is the temperature in K.
Correlation Between Chemical Structure and Photoreactivity 11

1.4 MATERIALS AND EXPERIMENTAL METHODS

1.4.1 RESINS

We have investigated formulation based on multifunctional ERs UV cured

and multifunctional acrylate resins cured thermally for 3D printing applica­
tions [3].

1.4.1.1 EPOXY

Multifunctional epoxy polymers/monomers considered are based on dicy­

clopentadiene DCPD (Figure 1.5a), on naphthalene (Figures 1.5b and 1.5c),
on benzene (Figure 1.5d).

FIGURE 1.5a Hepiclon™ HP 720.

FIGURE 1.5b Hepiclon™ HP 4710, f = 8.

FIGURE 1.5c Hepiclon™ HP 4032, f = 4.

12 Advanced Materials, Polymers, and Composites

FIGURE 1.5d Hepiclon™ HP 820, f = 4.

1.4.1.2 ACRYLATES

Two multifunctional acrylates such as trimethylolpropane triacrylate (TMPTA-

Figure 1.6a) and ethoxylated (3) trimethylolpropane triacrylate (ETPTA-
Figure 1.6b) have been crossling by thermal effect in the presence of benzoyl
peroxide BPO.

FIGURE 1.6a Trimethylolpropane triacrylate, f = 6.

FIGURE 1.6b Ethoxylated (3) trimethylolpropane triacrylate, f = 6.

1.4.2 CO-SOLVENTS

As all the ERs are solid except Epolam® 515, co-monomers used in all
systems will play the role of solvent in view to get liquid formulation and
Correlation Between Chemical Structure and Photoreactivity 13

also will participate in the crosslinking reaction once this reaction is initi­
ated. As already mentioned for Epolam® 515 (Figure 1.7a), other liquid
epoxies such as Bis(3,4-epoxycyclohexylmthyl) adipate (Figure 1.7b) have
been used.

FIGURE 1.7a Epolam® 515, f = 4.

FIGURE 1.7b Epoxy adipate Cyracure® UVR 6128, f = 4.

We also have considered as a co-reactive solvent, the vinyl ethers (Figure

1.8), that polymerize by the cationic mechanism.

FIGURE 1.8 Rapid-Cure® DVE-3 tri(ethylene glycol) divinyl ether.

1.4.3 KINETICS

UV photopolymerization kinetics has been performed by differential scan­

ning photocalorimetry (Figure 1.9), monitoring the photopolymerization that
determines the photosensibility of any thin films (Figure 1.10) [16].
Kinetics parameters of the epoxy systems have been studied using a TA
instrument #912 based on DSC #2920 model differential photocalorimeter
(DPC), equipped with a 200 W high-pressure mercury lamp, giving an
optical range from 285 to 440 nm with an intensity of 45 mW/cm2 on the
single DSC head (one sample and fully cured reference) [17].
14 Advanced Materials, Polymers, and Composites

FIGURE 1.9 Schematic of DPC.

FIGURE 1.10 DPC photogram.

Correlation Between Chemical Structure and Photoreactivity 15

The pan, filled fully cured under 20 min of the UV exposure sample of
resin, was used as a reference. The samples weighting (2.0 ± 0.2) mg were
placed in aluminum pans covered by PET film and subjected to 1 min of
isothermal conditioning before and 5 minutes after UV exposure.
As any polymerization reaction is an exothermic process, DPC allows
doing kinetics according to the DPC curve (Figure 1.10). Calculations of the
kinetics of photopolymerization of the considered formulation are based on
the general Šesták and Berggren’s equation [18].

d α ( t ,T )
= k(T )α m (1− α ) [ −ln(1 − α ) ]
n p
R p(T ) =
dt

where; α is the degree of conversion, k is the rate coefficient, m, and n are the
reaction order of initiation and propagation, respectively, and p is the order
of termination reaction.
In order to simplify this equation, we consider only the outset of the
polymerization process. In so doing, the value of p in Eq. (1) can be taken
as 0. A simplified autocatalytic kinetic equation can thus be obtained, which
gives us the following rate equation [19]:

d α ( t ,T )
= k(T )α m (1− α )
n
R p(T ) =
dt
dα
The values of k are determined from a ln curve-ln plot of vs. [αm/n(1–α)]:
dt
⎛ dα ⎞
⎟ = ln k + n ln α (1− α )
mn
ln ⎜
⎝ dt ⎠

The reactions are conducted at different ratio monomer/co-monomer

solvent to determine the rate coefficient k of the photopolymerization. Plotting
k at different temperature allow to reach the activation energy Ea of the
considered system for each ratio [3].
Ea
−( )
k(T ) = A exp RT

where; A is the frequency factor or collision factor, Ea is the activation

energy, R is the ideal gas constant (8.314 J/mol.K), and T is the temperature
measured in Kelvin.
16 Advanced Materials, Polymers, and Composites

1.5 RESULTS AND DISCUSSION

1.5.1 UV CATIONIC CROSSLINKING REACTION OF EPOXY

Experiments have been performed using the photoinitiator UVI-6976 at a

concentration of 3 wt.% with a UV light intensity of 45 mW/cm2.
We have analyzed the following couple epoxy polymer-monomer/
co-reactive solvent crosslink by UV radiation:
• Hepiclon™ HP 4710/Epoxy adipate Cyracure® UVR 6128 (Table 1.1).
• Hepiclon™ HP 4032/Epolam® 515 (Table 1.2).
• Hepiclon™ HP 720/DVE di-vinyl ether (Table 1.3).
• Hepiclon™ HP 820/Epolam® 515 (Table 1.2) although Epolam® 515
is the worst solvent for photoreactivity according to our precedent
study at different ratio polymer or monomer/co-reactive solvent [3].
We have also compared these epoxies to acrylate systems crosslink by
thermal effect in the presence of benzoyl peroxide BPO. The ratio polymer/
co-reactive solvent given in weight is recalculated in a mole that can be used
to determine the values of f0, M0, Mc, and Xc.

TABLE 1.1 Hepiclon™ HP 4710/Epoxy Adipate

HP 4710/Adipate 0/100 20/80 30/70 40/60
Ea (kJ.mol )–1
4.0 ± 0.2 10.3 ± 1.7 21.5 ± 1.5 29.4 ± 2.1
f0 4 4.57 4.88 5.22
M0 366 392.85 407.64 423.95
Mc 183 153.14 141.54 131.66
Xc 5.5×10 –3
6.5×10 –3
7.1×10 –3
7.6×10–3
Molar mass of Hepiclon™ HP 4710, Mm = 556 g.mol–1, f0 = 8; Epoxy adipate Cyracure®
UVR 6128, Mm = 366 g.mol–1, f0 = 4.

The monomer Hepiclon™ HP 4710 has a high functionality f0, double

of the co-reactive solvent. This induces a greater difference in the values of
f0, going from 4.57 for 20/80 to 5.22 for 40/60, which impact Mc and make
it decreasing. Therefore, the density of crosslinking Xc will increase up to
the ratio of 40/60 with Xc = 7.6×10–3. Therefore, when the percentage of
the oligomer increases going from 20 wt.% to 40 wt.%, it is normal that
the crosslink density increases too due to its high functionality. For high
Correlation Between Chemical Structure and Photoreactivity 17

density, we need higher energy for low crosslink density. More compact is
the system; more energy has to be provided.

TABLE 1.2 Hepiclon™ HP 4032/Epolam® 515

HP 4032/Epolam® 515 0/100 40/60 60/40 90/10
Ea (kJ.mol )–1
44.9 ± 3.2 37.3 ± 2.5 37.4 ± 1.5 38.9 ± 2.8
f0 4 4 4 4
M0 312 292.93 286.70 275.53
Mc 156 146.47 143.35 137.77
Xc 6.4×10 –3
6.8×10 –3
7.0×10 –3
7.3×10–3
Molar mass of Hepiclon™ HP 4032, Mm = 272 g.mol–1, f0 = 4; for Epolam® 515, Mm = 312
g.mol–1, f0 = 4.

In this example, the molar masses values for Hepiclon™ HP 4032 and
Epolam® 515 are of the same order of magnitude-272 g/mol and 312 g/mol,
respectively, and the same average functionality for both. We do observe that
M0 and Mc are decreasing. Therefore, the crosslinking density is increasing
up to 7.3×10–3 for the ratio 90/10, a result that conforms to our expectations.

TABLE 1.3 Hepiclon™ HP 720/DVE Di-Vinyl Ether

HP 720/DVE 0/100 40/60 60/40 70/30
Ea (kJ.mol )–1
3.6 ± 0.4 10.6 ± 1.1 22.8 ± 1.8 29.4 ± 2.0
f0 4 4.37 4.59 4.79
M0 202 283.62 355.42 406.94
Mc 101 119.49 137.10 145.79
Xc 9.9×10–3 8.4×10–3 7.3×10–3 6.9×10–3
Molar mass of Hepiclon™ HP 720, Mm = 720 g.mol–1 for n ≈ 1, f0 = 6; for DVE Di-vinyl ether
Mm = 202 g.mol–1, f0 = 4.

Considering the energy of activation Ea, we observe that it is increasing

when the quantity of Hepiclon™ HP 720 is increasing, which is normal as
the activation energy of the co-reactive solvent is low, and its percentage is
decreasing. The values of the average functionality f0 are increasing when the
concentration of Hepiclon™ HP 720 is increasing as its f0 is higher than the
co-reactive solvent. As a result, M0 and Mc are increasing, and therefore the
18 Advanced Materials, Polymers, and Composites

crosslinking density decreases due to the higher molar mass of the monomer,
720 g/mol compared to 202 g/mol of the co-reactive solvent. In that case, the
degree of crosslink is the highest for the lower percentage of the oligomer
that can be explained by the low viscosity and the high reactivity of the
co-reactive solvent. Therefore, in this system, the solvent may play a major
role in the formation of the network; the higher is the concentration of the
co-reactive solvent, the higher is the degree of crosslink. Therefore, in that
case, the more expanded the network is, the more difficult is the crosslinking
reaction. The highest degree of crosslinking is obtained for the ratio polymer/
co-reactive solvent 40/60 (Table 1.4).

TABLE 1.4 Hepiclon™ HP 820/Epolam® 515

HP 820/Epolam® 515 0/100 20/80 30/70 40/60
Ea (kJ.mol )–1
44.9 ± 3.2 51.1 ± 4.5 57.6 ± 2.5 65.1 ± 3.1
f0 4 4 4 4
M0 312 326.12 383.22 414.79
Mc 156 178.06 191.61 207.39
Xc 6.4×10–3 5.6×10–3 5.2×10–3 4.8×10–3
Molar mass of Hepiclon™ HP 820, Mm = 820 g.mol–1 for n ≈ 1, f0 = 4; for Epolam® 515, Mm
= 312 g.mol–1, f0 = 4.

In that case, as both the monomer-Hepiclon™ HP 820 and the co-reactive

solvent-Epolam® 515 have the same f0, the average functionality of the system
will not change and f0 = 4 whatever the mixture considered. For the activation
energy Ea, M0 and Mc, we do observe the same phenomena as Hepiclon™ HP
720. The higher crosslinking degree is obtained for the ratio of 20/80. This
surprising result may be explained by the low reactivity of both oligomer, and
co-reactive solvent, observed by the high activation energy compare to the
precedent system Hepiclon™ HP 720/DVE Di-vinyl ether.

1.5.2 THERMAL RADICAL CROSSLINKING REACTION OF

MULTIFUNCTIONAL ACRYLATES

We have considered two triacrylates monomers, the trimethylolpropane

triacrylate (TMPTA) and the ethoxylated (3) trimethylolpropane triacrylate
(ETPTA) polymerized by the benzoyl peroxide for [BPO] = 0.5, 1, 1.5, and 2
wt.% (Table 1.5).
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" Skurfa, 204, 205.
Kalfadal in Caithness (Calder), 182, 183.
Kalfadalsá (Calder Water), 187.
Kali, Kol’s son (Earl Rögnvald II.), xxxv, 58, 75-79, 83.
" Hundason; see Karl.
" Snæbiorn’s son, 54, 55, 57.
Kari, xxviii.
Karl Hundason, xxx, 17, 18.
Karston, 157.
Katanes; see Caithness.
Katharina, Countess of Caithness, lv.
Ketil Flatnef, xxii.
Kiarval, King of Dublin, xxvi, 209.
Kintradwell, Sutherlandshire, 197.
Kintyre (Satiri), xxxiv, cxii, 21, 56, 195.
Kirkiboll, Sutherlandshire, 18.
Kirkiuvag; see Kirkwall.
Kirk o’ Taing, Caithness, 33.
Kirkwall (Kirkiuvag), lxxxvii, lxxxix, 37, 39, 41, 99, 110, 155, 157,
158, 163, 170, 171, 179.
Kjárekstadir, 157, 160.
Kjölen Mountains, 23, 25.
Klifland, 47.
Kol of Halland, 128.
" Isak’s son, 47.
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100, 111.
Kolbein Hruga, lxxv, xcvii, cxxiii, 46, 126, 177.
" Karl, 126.
Konufogr (Conchobhar), King, 7.
Kormak, Archdeacon of Sudreyar, lxxvi.
Knut (Canute) the Great, King, 16.
" the Wealthy, 161.
Kristín, Sigurd’s daughter, 151.
Kugi of Westrey, 73, 91, 96, 101, 102-104.
Kunnaktir (Connaught), 57, 58.
Kyle Scow, Sutherlandshire, 182.
" of Sutherland (Ekkialsbakki), xxiii, lxxix, cxii, 21, 107, 115.
" of Tongue, 18.
Kyrpinga Orm, 80.
Ladoga (Aldeigiuborg), 24.
Lanfranc, Archbishop of Canterbury, lxxii.
Largs, battle of, xlviii.
Larne, Lough (Ulfreksfiord), 7.
Lambaborg, 122, 125, 155, 159, 160.
Laufandaness, 5.
Laurentius, priest, xlii.
" Bishop of Hole, lxxvii.
Leif, xii.
Lewis (Liodhus), xxxiv, 54, 118, 154, 155, 177.
Lifolf Skalli, 193, 194.
Liodhus; see Lewis.
Liot, Earl, xxv, 209, 211.
" Níding, 69, 70.
Liotolf, 106, 154, 159.
Lingrow, 74.
Linlithgow, palace of, lxxi.
Lisbon, 140.
Lochloy, xli.
Lodbrok, cvi.
Logierait, xxxvi.
Lögman Gudrodson, 54.
Lödver; see Hlödver.
Lomberd, xliii.
Lopness, in Sanday, 5.
Lubeck, lii.
Lundy island, 117, 118.
Lybster, in Caithness, 91.
" in Reay, Caithness, church of, xcvii.
Macbeth, xxv, 43, 209.
Macgarvey, battle of, xxxix.
Maddad, Earl of Athole, xxxvi, cxi, 86, 105, 108, 113, 115, 153.
Moddan, 69.
" Eindridi, 69.
Maeshow, ci, cv, 159.
Maeyar (Isle of May), 123.
Magbiód, xxv, 209.
Magnus Barelegs, King, xxxiii, 52-55, 58, 66, 75.
 " Erlend’s son, Earl (St. Magnus), xxiv, 47, 48, 52, 54, 55, 58, 59-
66, 71, 83, 95, 99, 105.
" Erlingson, King, xxxix, 151, 193, 199.
" Eyvind’s son, 95.
" Gilbride’s son, Earl, xlvi, xlvii, xlix.
" Harald’s son, King, 48.
" Havard’s son, 47, 73, 91, 131, 134, 185.
" John’s son, Earl, liv.
" Magnusson, Earl, xlix.
" Mangi, 188, 193.
" Olaf’s son, King (the Good), xxxi, 24-26, 30-32, 34-36, 39-41,
43, 48.
" Orfi, 72.
" Orm, 69.
" Sigurd’s son, King (the Blind), 83, 84.
Mainland (Meginland) of Orkney (Hrossey), xxviii, 5, 36, 49, 60, 67,
74, 89, 102, 104, 105, 106, 107, 159, 164, 175, 178.
Malbrigd, xxiii, 107, 203, 204.
Malcolm, Bishop of Caithness, lxxxvi.
" Scottish Earl, xxvii.
" II. (Melkolf), King of Scots, xxix, xxxiii, 3, 16, 44, 212.
" Canmore (Langhals), 46, 55, 71, 86.
" the Maiden, 108, 153, 154, 155, 180, 181, 192.
" M’Heth, Earl of Moray, xxxviii, xlii, 181, 192.
Malise, Earl of Stratherne, lv.
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" Sperra, lx.
Malvoisin, Bishop of St. Andrews, lxxxi.
Man, Isle of, 116, 118, 203.
Mani, Olaf’s son, 196.
Manuel I., Emperor, 150.
Margad, Grim’s son, 74, 91, 92, 122, 124, 125, 169, 170.
Margaret, Hakon’s daughter, xxxvii, cxi, 72, 86, 105, 108, 109, 153,
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" Moddan’s daughter, 69.
" the Maiden of Norway, xlix, l, xci.
" the false Maiden of Norway, l, lii.
Maria, Harald’s daughter, 47.
Mariuhofn, 179.
Marseilles (Marselia), 142.
Maurice de Moravia, lvii.
May, Isle of, 123, 124, 163.
" Monastery of, 124.
Medalland’s hofn (Midland harbour), in Orkney, 159.
Melbrigd; see Malbrigd.
Melkolf; see Malcolm.
Melsnati, xxvi.
Menelaus, Emperor, 150.
Menteith, Johanna de, lvii.
" Sir John de, lvii.
Menzies, Sir David, lxviii.
Mikligard (Constantinople), 24, 127, 148-150, 163.
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" Sir John de, lvii.
Moray (Mærhæfi), 21, 204.
" Firth (Breidafiord), 20, 21.
Morukari (Morkere), 47.
Moseyarborg; see Mousa.
Moslems, 141.
Moulhead of Deerness, 88, 156.
Mousa, Borg of (Moseyarborg), cix, cxi, 113, 161.
Mowat of Bucholly, 122.
Murcadh, son of Brian Borumha, xxviii.
Muirceartach, xxxiv.
Murdoch, Duke of Albany, lxx.
Munkalif, monastery of, lxxv.
Myrkhol (Murkle), in Caithness, xxv, 195, 207.
Mýrkiartan, 56.
Myrkvifiörd, 124, 181.
Navidale, xiv.
Nennius, x.
Ness (Caithness), 8, 37, 87, 116, 121, 122, 155, 158, 160, 164, 166,
169, 180, 195, 209.
" river, x.
Nicolas, Abbot of Scone, lxxxiii.
Bishop of Caithness, lxxxvi.
Nidaros (Drontheim), 25, 57.
Njal’s burning, xxviii.
Njörfasund (Straits of Gibraltar), 141, 142.
Norfolk, round-towered churches of, xciii.
Normandy, lxxxix, 203.
Northumberland (Nordymbraland), 134.
Norway, 2, 3, 8, 12, 16, 26, 32, 35, 42, 47-49, 52, 54, 58, 75, 85,
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Novgorod (Hólmgard), 24, 25.
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Ochtha, x.
Oddi Litli, 130, 131, 147.
Odin, xiii, cxiv, cxvii, 206.
Offa, King, 21.
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" Thorfinn’s son, 151.
Olaf Bitling, King of Sudreyar, 181.
" Haraldson, King (the Holy), xxx, 8, 11, 14-16, 26, 38.
" Kyrri, King, 48, 49, 93.
" Magnusson, King, 58.
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" Rolf’s son, 74, 88, 89, 91, 92, 94.
" Swein’s son, 177, 192.
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" the White, xxi, xxiii, 203.
Olvir Rosta, 69, 72, 85, 86, 87, 88, 89, 92, 110, 114-116.
Onund, King, 23.
Ord of Caithness, 115, 165.
Orfjara (Orphir), 71, 92, 95, 159, 167, 168.
Orkahaug, ci, cv, 159.
Orkhill, 159.
Orkneys (Orkneyar), 1, 2, 4, 6, 7, 11, 14-16, 23, 26, 28, 29, 32, 36,
42, 47, 48, 52, 56, 58, 62, 64, 66, 68, 69, 72, 75, 85, 86, 98-100,
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Orkneymen (Orkneyingar), 2, 69, 112, 124, 132, 133, 134, 139, 191,
207.
Orm, 170.
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" Svarti, 16.
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Meiri (Papa Westray), 38, 39.
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Pentland Firth (Petlandsfiord), 18, 33, 34, 74, 86, 88, 92, 106, 113,
152, 155, 165, 193, 194, 196.
" Skerries (Petlandsker), lv.
Peter, Bishop of Orkney, lxxvi.
Pictish Towers, cix, cxxii, cxxiii, 33, 113, 161.
Pierowall (Hofn), in Westray, cxxii, 102.
Pull, Puglia (Apulia), 150.
Rafn, Lawman, 196, 200, 201.
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" Hrólf’s daughter, 203.
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Ralph, Bishop of Orkney, lxxii.
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Rattar Brough (Raudabiorg), 33.
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Ravensere (Hrafnseyri), 48.
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" of the Isles, xlii, xliv.
Reindeer in Scotland, 182.
Scalpeid, 69.
Renfrew, 181.
Rendale (Rennadal), 170, 171.
Reppisness, 74.
Restalrig, 197.
Richard I., King, 142.
Rikgard of Brekkur, 74, 105.
" priest, 78.
" Thorleif’s son, 120.
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119, 152, 165.
Rinar’s Hill, 206.
Robert, Bishop of Caithness, lxxxvii.
Roger, Bishop of St. Andrews, xliii.
" Bishop of Orkney, lxxiii.
Rögnvald Brúsi’s son, Earl, xxxi, lxxiv, 7, 11, 15, 23, 24-26, 28, 30,
31-39, 44.
" Eirikson, 183.
" (Kali) Kol’s son, Earl, xxxv-xxxvii, lxxxviii, xc, 58, 75-79, 83-91,
96, 97, 100, 102, 104, 105, 108-114, 118-154, 158, 163, 165-
172, 175-184, 188, 192, 193, 199.
" Earl of Moeri, xxiv, 1, 203, 204, 210.
" (Reginald) of the Isles, xlii, xliv, lxxx, 181, 195.
Rögnvaldsey (S. Ronaldsay), 89, 91, 165, 166, 175, 176, 194.
Ronaldsay, North; see Rinansey.
Rögnvaldsvoe, xlvii.
Rome (Rómaborg), xxxii, xxxv, xxxvii, lxxi, 43, 63, 68, 150.
Rorvag, 3.
Ross, 18, 21, 199.
" Hugh de, lxi.
" Hugh, Earl of, lvi, lxi.
" John of, lxx.
" William, Earl of, lvi, lxi.
Rouen (Ruda), 203.
Rousay (Hrólfsey), 73, 88, 91, 105, 106, 107, 171, 177.
Roxburgh Castle, xliv, 192.
Runic inscriptions, ciii, cxv, cxvi.
Rurik, King, 24.
Russia (Gardariki), 24.
St. Adamnan, xx.
St. Anschar, lxxiii.
St. Brigid, xiv.
St. Columba, x, xiii, xiv, 82.
St. Clair, Alexander, lxi.
" David, lxvii.
" Elisabeth, lxvii.
" Henry, ballivus of King Robert Bruce, lv, lxi.
" Henry, Earl, xl, lx.
" Isabella, lxii, lxvii.
" John, lxviii.
" Lucia, lxi.
" Thomas, lxi.
" William, Earl, lxi, lxix.
St. Kilda, cxxi.
St. Lawrence, xv.
St. Magnus, xv, lxxii, lxxxix, xc, xciii, xcv, cxv, 99.
" church of, xxxv, lxxiv, lxxxviii, 112, 173, 178, 188.
St. Mary’s, in the Scilly Isles, 179.
St. Ninian, xiv, xx.
St. Olaf, xv.
" church of, Kirkwall, lxxxix.
St. Oran’s chapel, Iona, xxxiv.
St. Patrick’s church, Down, xxxiv.
St. Peter, xv.
St. Peter’s church, S. Ronaldsay, xviii.
" Brough of Birsay, xcviii.
" Weir, xcvii.
St. Regulus, 197.
St. Sunniva, lxxvii.
St. Triduana (Tredwell), xiv, 197.
St. Vigeans, xx.
Sanday, 5, 104, 174.
Sandwick (Sandvik), in Deerness, Orkney, xxx, 5, 9, 169.
Saracens, 144.
Sardinia, 142.
Satiri (Kintyre), 21, 56, 195.
Saxi, 81.
Saxland, 43.
Saverough, xiv.
Savigny, 192.
Scapa (Scalpeid), xlviii, 74, 92, 110, 155, 166, 180.
Scarborough (Skardaborg), 47.
Scrabster (Skarabolstadr), xliii, lxxxiii, 196.
Scilly Islands (Syllingar), 117, 179.
Scone, lxxii, 108, 192.
Scotland (Skotland), 2, 17, 21-23, 28-31, 53, 60, 64, 70, 72, 75, 86,
105, 109, 114, 118, 152, 161, 210.
Scotland’s Firth (Skotlandsfiord), 27, 56, 115, 180.
Sculptured stones of Scotland, symbols of, xix.
Scytheboll (Skibo), 107.
Sekkr, 151.
Seley, 40.
Sepulchre, church of the Holy, xciii.
Serk, 54, 76.
Serkland, 142, 146.
Serlo, monk of Newbottle, xliv, lxxxi.
Setr, 76.
Shetland (Hjaltland), 14, 16, 22, 32, 35, 36, 47, 60, 67, 86-89, 91,
97, 99, 102, 130, 133, 155, 161, 164, 176, 178, 203, 205, 210.
Shurrery, in Caithness, 187.
Siddera, Sutherlandshire, 107.
Sigæum, promontory of, 149.
Sigmund Brestisson, 88, 89.
" Ongul, 139, 147, 148.
Sigtrygg, King, xxvii.
Sigurd, Andrew’s son, 116.
" Archbishop of Drontheim, lxxvi.
" Arnkell’s son, 92.
" Eystein’s son, Earl, xxiii, cxvii, 1, 107, 199, 204.
" Harald Gilli’s son, 151.
" Havard Hold’s son, 151.
" Hlödver’s son, Earl, xxv, xxvi, 3, 4, 11, 112, 209, 210, 211, 212.
" Hrani’s son, 54.
" Klaufi, 155.
" Magnusson (the Jorsala-farer), King, xxxiv, lxxiii,
Sigurd Murt, xli, 193, 194.
" Slembir, 70, 71.
" Sneis, 57, 75.
" Syr, King, 5.
" of Gloucester, 127.
" of Papuli, 59, 73.
" of Westness, 46, 70, 87, 91, 109, 110, 111.
Sigurdhaug (Siwardhoch), cxvii, 107.
Sinclair; see St. Clair.
Skaill, 33.
Skálpeid (Scapa), xlviii, 74, 92, 110, 155, 166, 180.
Skaney, 42.
Skapti, 54.
Skarabolstadr (Scrabster), near Thurso, xliii, lxxxiii, 196.
Skebro Head, 156.
Skeggbjarnarhöfdi, 156.
Skeggbjarnarstadir, 156.
Skida Myre (Skitten), in Caithness, xxvi, 112, 209, 210.
Skinnet, church, of, in Caithness, lxxxii.
Skuli, Earl, xxv, 2, 209, 211.
Skye (Skidh), xxxiv, 27, 28, 192.
Snæfrida, 205.
Snækoll Gunnason, xlvi, 126.
Snorri Sturluson, 58.
Sogn, 54, 76, 80.
Sölmund, 75, 77-82, 84, 86, 98, 105, 140.
Spain (Spánland), 140, 141.
Stamford Bridge, xxxiii, 40.
Staur (Ru Stœr), 167.
Stefán Radgafi, 180.
Steigar Thórir, 98.
Steinsnes (Stennis), in Orkney, xxv, cvii, cviii, 61, 157, 159, 208.
Steinvor the Stout, 69, 72.
Stewart, Alan, lxi.
" David, lx.
" Walter, lxi.
Stiklestadir, 23, 38, 118.
Stratherne, Elizabeth de, lxiii.
Stratherne, Euphemia de, lxi.
" Malise, Earl of, lv-lx.
" Marjory de, lviii.
" Matilda de, lviii.
Strickathro, 192.
Stroma (Straumsey), 91, 96, 176.
Stromness, 157.
Stronsay (Stiórnsey), 156.
Studla, 80, 81.
Sudreyar (Hebrides), xxii, 26, 27, 29, 31, 32, 35, 37, 44, 53, 56, 64,
75, 86, 95, 97, 105, 115, 120, 121, 153, 166, 177, 179, 189, 190,
195, 196, 203, 210.
Sudreyarmen, 116, 118.
Sumarlidi Hold, 176, 180, 181, 192.
" Kolbein Hruga’s son, 126.
" Thorfinn’s son, Earl, xxix, 3, 4.
Sumburgh, 74.
" Head, 164.
" Roost (Dynröst), 164.
Sutherland (Sudrland), 4, 17, 18, 21, 70, 115, 116, 123, 164.
Svelgr; see Swelkie.
Sverrir, King, xxxix, xli, 199.
Svöldr, 4.
Swefney; see Swona.
Swein Asleifson, xxxvi, xc, 5, 73, 91-95, 97, 105, 106, 108-110, 113-
125, 133, 151, 155, 156, 158, 164-166, 168-181, 188-190.
" Blakari’s son, 172.
" Brióstreip, 87, 89, 93-95, 97, 111.
 " Harald’s son, 119.
" Hróald’s son, 131, 134, 186.
" Ulf’s son, King, xxxii, 39, 42, 43.
Swelkie of Stroma (Svelgr), xlviii, 107.
Sweden, 23, 49.
Swona (Swefney, Swiney), 74, 91, 92.
Swynbrocht, 74.
Syllingar (Scilly Isles), 117, 179.
Sytheraw, 107.
Tankerness (Tannskarunes), 88.
Tarbatness (Torfnes), 21.
Thiálbi, King, 57.
Thing, 6, 61, 73, 83, 110, 112, 135, 158.
Thingstead, Thingavöll, 61, 171.
Thiostolf, Ali’s son, 83, 84, 85.
Thomas, Archbishop of York, lxxiii.
" de Fingask, Bishop of Caithness, lxxxvi.
" Tulloch, Bishop of Orkney, xlvi, lxviii, lxxviii.
Thony, Robert de, lviii.
Thora, Paul’s daughter, 46.
" Sumarlidi’s daughter, 47, 73.
Thórarinn Breidmagi, 119.
" Killinef, 179.
Thorberg Svarti, 131.
Thorbiörn of Borgarfiord, 60.
" Hornklofi, 2.
" Klerk, xxxviii, 69, 72, 114, 118, 119, 120-123, 125, 156, 159,
165, 167-180, 183-185.
 " Svarti, 147.
Thordis, Hall’s daughter, 47.
Thore Hakonson, li, liii.
Thórir Thegiandi (the Silent), 203, 206.
" Tréskegg, 204, 205.
Thorfinn Bessason, 156, 157.
" Harald’s son, xliv, 192, 198.
" Hausakliuf, Earl, xxiv, xxv, 2, 3, 207, 208.
" Sigurd’s son, Earl, xxix-xxxiii, lxxii, xciii, xcv, 4-9, 12, 14, 15, 18,
19, 26, 28, 29-45, 67, 179, 212.
Thorgeir Skotakoll, 131.
Thórhall, Asgrim’s son, 152.
Thorkel Flettir, 74, 88, 96, 120.
" Fóstri, Amundi’s son, xxx, 5-9, 13, 18, 19, 20, 22, 38.
" Sumarlidi’s son, 71.
Thorleif; see Frákork.
" Spaki, 54.
Thorliót, 69.
Thorolf, Bishop, lxxii.
Thorsa, Thórsey; see Thurso.
Thorsdal, 182.
Thorstein of Fluguness, 74, 92.
" Havard’s son, 47, 73, 91, 104, 186.
" Hold, 69, 72, 114, 118, 126.
" Krokauga, 74, 131.
" Ragna’s son, 73, 100, 101, 104, 119, 160.
" son of Hall of Sida, xxix.
" the Red, xxiii, 2, 203.
Thorvald Thoresson, 60.
Thrasness, 136.
Thraswick (Freswick), in Caithness, 154.
Thule, xi.
Thurso (Thorsa), 20, 73, 106, 152, 153, 159, 164, 165, 183, 194.
Thussasker, 44.
Tingwall, in Rendal, 61.
Tiree (Tyrvist), xxxiv, 95.
Torf Einar, Earl, xxiv, cxvii, 1, 2, 112, 203, 205, 207, 211.
Torfness, 21, 22, 152, 205.
Tröllhæna, 197.
Tunsberg, 75, 83, 84.
Turgot, Bishop of St. Andrews, lxxiii.
Tyrvist; see Tiree.
Uist (Ivist), xxxiv.
Uladstir; see Ulster.
Ulfreksfiord, xxx, 7.
Ulli, Strath, 115.
Ulbster, in Caithness, xx.
Ulster (Uladstir), xxxiv, 58.
Uni, 80, 81, 99-102.
Unn, 76, 77.
Uppland, in Hoy, 74, 105.
Upsala, 120.
Værings, 127, 150.
Vagaland (Walls), in Hoy, 167, 169, 176.
Valdimar, King, 151.
Valland, 135.
Valkyriar, xxvii.
Valthióf, Earl, 47, 125, 126.
" Olafson, 73, 91, 93, 96, 114.
Varangians, 127, 150.
Veradal, 25.
Verbon (Nerbon), 135, 145.
Vidivag (Widewall), 166.
Vidkunn Jonsson, 54.
Vigr (Weir), island of, 126.
Vik, in Norway, 40, 78, 85, 151.
in Caithness (Wick), 118, 122, 154, 155.
Vikings, xxii, xxiv, xxxvi, cxxi, 1, 25, 29, 33, 35, 59, 113.
Volga, cxviii, cxxiii.
Völuness, 174.
Walls (Vagaland), in Hoy, 167, 169, 176.
Walter, Bishop of Caithness, lxxxiii.
Wales (Bretland), xv, 7, 54, 56, 117.
Warrenne, John de, Earl of Surrey, lvi.
Wear (Hvera), river, 134.
Weir (Vigr), island of, 126.
Weir, church of, xcvi.
" castle of, cxxiii, 126.
Westness, in Rousay, 46, 70, 73, 91, 101, 109.
Westray, cxvii, cxxii, 74, 91, 96, 102, 177.
Wick (Vik), in Caithness, 118, 122, 154, 155.
William the Old, Bishop of Orkney, xxxvi, lxxii, lxxiv, lxxxix, xcv, 68,
95-97, 105, 109, 111, 113, 131, 134, 137, 143, 144, 150.
" II., Bishop of Orkney, lxxv, 193.
" III., Bishop of Orkney, lxxvi.
" IV., Bishop of Orkney, lxxvii.
" V., Bishop of Orkney, lxxviii.
" Tulloch, lxxix.
" Bishop of Caithness, lxxxiii.
" Earl of Ross, lvi.
" Fitz Duncan, 46.
" Freskyn, xlvi.
" of Egremont, xxxviii, 46, 181.
" the Lion, King of Scots, xxxix, xl, lxxx, 193, 195.
Wimund, Bishop, xxxvii, 181, 192.
Wulstan, Bishop, lxxii.
York (Yorvik), 47.
Yell (Jala), 86.
Yell Sound (Alasund), 86.
 Footnotes

1. Writing of the barrows and cairns of Orkney, Captain Thomas states that at
least 2000 might still be numbered. We have no estimate of the number in
Shetland, but there also they are very numerous. Not less remarkable is the
number of the early “dwellings of strength,” of which Mousa is the type—
huge edifices, constructed with amazing labour and wonderful skill. (See
under Maeshow and Mousa.)

2. The Frisic Sea is supposed to mean the Firth of Forth.

3. The “Historia Britonum” of Nennius (whoever he may have been) is believed,

on what seems reliable evidence, to have been written about A.D. 858. (See
the Irish Nennius, Irish Archæological Society, p. 18.)

4. Ireland was then called Scotia.

5. St. Ninian was commemorated at Dunrossness in Shetland (Sibbald’s

Description, 1711, p. 15); at Stove in South Ronaldsay, Orkney (Peterkin’s
Rentals, No. III.); at the north head of the bay of Wick in Caithness; and at
Navidale in Sutherland. St. Columba’s three chapels in South Ronaldsay were
at Grymness, Hopay, and Loch of Burwick (Peterkin’s Rentals, No. III. p. 86).
There were also dedications to St. Columba in the islands of Sanday and Hoy
in Orkney, at Olrig and Dirlet in Caithness, on Island Comb, at Tongue, and
at Kilcalmkill in Sutherlandshire (Bishop Forbes’s Calendar of Scottish Saints).
St. Triduana, whose name has been corrupted into St. Tredwell and St.
Trudlin (the Tröllhæna of the Saga), had dedications in Papa Westray in
Orkney (Martin’s and Brand’s Descriptions), and at Kintradwell in
Sutherlandshire. It seems also, from the narrative of Bishop John’s mutilation
in the Saga, that there was a dedication to her near Thurso. St. Brigid had
chapels in Stronsay and Papa Stronsay in Orkney. But it is impossible to tell
how many of these early religious sites had similar dedications, as scarcely a
tithe of those that are known have preserved their names. Brand and Sibbald
both mention the fact that in their time there were still recognisable the sites
 of 24 chapels in the island of Unst, 21 in the island of Yell, 10 or 11 in the
island of Fetlar: 55 religious foundations in the three most northerly islands
of the Shetland group. The Christian period of the Norse occupation is
marked by dedications showing the influence of the Crusades or of the
national religious feeling. The dedications to the Holy Cross, St. Mary, St.
Peter, St. Lawrence, St. Olaf, and St. Magnus, are probably all of this period.

6. Unfortunately, the readings of these inscriptions which have been attempted

are far from satisfactory. The Shetland and Orkney specimens are in different
styles of the Ogham writing, and the whole subject of the reading and
interpretation of the inscriptions in this character is beset with difficulties of
no ordinary kind. One rendering of the Bressay inscription makes it “the
cross of Natdod’s daughter here,” and on the other edge of the stone,
“Benres of the sons of the Druids here;” while the language is supposed to
be a mixture of Celtic and Icelandic. (Sculptured Stones of Scotland, vol. i. p.
30.)

7. Sculptured Stones of Scotland (Spalding Club), by John Stuart, LL.D., passim.

8. Sir James Simpson’s reading of the inscription, given in the Sculptured

Stones of Scotland, vol. ii. p. 71.

9. In Orkney we have the islands of Papa Westray and Papa Stronsay (the
Papey meiri and Papey minni, or greater and lesser Papa of the Saga),
Paplay in South Ronaldsay, Paplay in the parish of Holm, and Papdale, near
Kirkwall, in the Mainland. In Shetland we have the isles of Papa—Papa Stour
(Papey stora) and Papa Little (Papey litla), and Papill in the islands of Unst
and Yell. Papa Stronsay, Papa Westray, and Paplay, in the Mainland of
Orkney, are mentioned in the Saga. Papa Stour occurs in a deed of A.D. 1229
(Diplom. Norveg. i. 89), Papill in Unst in a deed of A.D. 1360 (Ibid. iii. 310),
and a “Sigurdr of Pappley” is mentioned in the agreement between Bishop
William of Orkney and Hakon Jonson, May 25, 1369 (Ibid. i. 404).

10. There is a cairn in Sanday called Ivar’s Knowe, which may be his burial
mound.

11. Olaf Tryggvason’s Saga, Flateyjarbók, chap. 180, in the Appendix; and
Ynglinga Saga, Heimskringla, chap. 22. Earl Sigurd’s grave-mound, on the
estuary of the Oykel (Ekkialsbakki), was known in the 12th century as
Siwardhoch, or Sigurd’s How, and is still identifiable in the modern Cyderhall.
(See the note on Ekkialsbakki, p. 107 of the Saga.)

12. Landnamabók, chap. ii.

13. Laxdæla Saga, chap. iv.

14. Olaf Tryggvason’s Saga, Flateyjarbók, chap. 180, in Appendix.

15. This was done by hewing the ribs from the backbone, and tearing out the
heart and lungs.

16. Bœndr, the odal landholders. (See note on this word, chap. i. of the Saga.)

17. Olaf Tryggvason’s Saga, Flateyjarbók, chap. 183, in Appendix.

18. Finnleik has been conjectured to be Finlay, the father of Macbeth.

19. Olaf Tryggvason’s Saga, Flateyjarbók, chap. 184, in Appendix.

20. Ibid. chap. 185.

21. This is probably the Celtic name Maelbrigd. Though it is suggestive of

Macbeth, the date is too early for Macbeth MacFinlay.

22. The locality of Skida Myre has been identified by Munch with the Loch of
Scister, in the parish of Canisbay. It seems rather to be indicated by the
modern Skitten, as the name formerly applied to the great tract of moorland
in the north-west corner of the parish of Wick, now generally known as the
Moss of Kilmster.

23. Olaf Tryggvason’s Saga, Flateyjarbók, chap. 186, in Appendix.

24. “He kept Caithness by main force from the Scots.” (See Appendix, p. 209.)

25. Njal Saga, chap. lxxxvii.

26. Njal Saga, loc. cit. This Hundi should be the father of the Kali Hundason of
the subsequent narrative.

27. Njal Saga, chap. clvi.

28. War of the Gaedhil with the Gaill, p. 191.

29. Hrafn the Red, whose denunciation of the raven-banner as the earl’s devil
may not altogether be accounted for by the fervour of his Christianity, was
chased into the river, where he was in danger of being drowned by the rising
tide. In this emergency he made a vow as follows:—“Thy dog, Apostle Peter,
hath run twice to Rome, and he would run the third time if thou gavest him
leave.” The Irish Chronicle states that the full tide in Dublin Bay on the day
 of the battle coincided with sunrise, and that the returning tide in the
evening aided in the destruction of the defeated foreigners. The date
assigned by the Chronicle for the battle is Good Friday, 23d April 1014. It has
been found by astronomical calculation that the full tide that morning did
coincide with sunrise—a remarkable attestation of the authenticity of the
narrative.

30. See the account of him in the Saga, chap. v. and note.

31. Rattar Brough, a little to the east of Dunnet Head, seems to be the modern
form of Rauda Biorg.

32. See the Saga account, chap. xxiii. and note. The dates do not bear out the
statement that Thorfinn was Earl for seventy years.

33. Fordun, v. 24.

34. Saga Magnus Berfoetts, Heimskringla, chap. xxv.

35. Chron. Manniæ, Munch’s edition, p. 59.

36. See the account of his death in the Saga, chap. xxxix. His feast days were
16th April and 13th December, the former commemorating his death, and
the latter the removal of his relics from Birsay by Bishop William. (Den
Norske Kirkes Historie af R. Keyser: Christiania, 1856, p. 162.)

37. The Earls of Athole seem at this time to have occupied the rath or fortress at
Logierait. It is mentioned in one of the Scone charters as the capital of the
earldom in the 12th century. (Lib. Eccles. de Scon, p. 35.)

38. This was the occasion in which he and his men spent the Yule-feast day in
the Orkahaug, which seems to be Maeshow. See the Saga, chap. xci.

39. See the notice from the Saga of Egill Skalagrimson, in the chapter on Mousa.

40. Some years after his death Earl Rögnvald was canonised, but his name is not
commemorated in any of the dedications now remaining in the Islands.

41. Munch, Chron. Manniæ, p. 84.

42. Fordun’s Annals, xvi.

43. From this time till 1379 Shetland passed into the immediate possession of
the crown of Norway. So we find in 1312-1319, that King Hakon Magnusson
grants to the Mary-Kirk in Oslo (Christiania), for the completion of the fabric
 of the kirk, “all our incomes of Hjaltland and the Faroes, so that those who
have charge of the kirk’s building and fabric every year shall render account
thereof to our heirs, and when the fabric is altogether completed, then shall
the foresaid revenues of Hjaltland and the Faroes revert to the crown.”
(Nicolaysen, Norske Fornlevninger, p. 426.)

44. Chronica Rogeri de Hoveden (Rolls Ed.), iv. pp, 10, 12.

45. In the Chronicle of Melrose, under the date 1175, it is stated that
“Laurentius, Abbot in Orkney, was made Abbot of Melrose.” But as his death
is recorded in the year 1178, the priest here mentioned by Hoveden must
have been a different person, though of the same name. At the same time,
as this passage shows that Earl Harald had a hird-priest named Laurentius, it
is not improbable that the so-called Orkney abbot, who was made abbot of
Melrose, may also have been Harald’s family or court priest. Being himself
the son of a Scottish earl, and allied by marriage first with the family of the
Earl of Fife, and subsequently with the MacHeths, and having, moreover,
such close relations with the abbey of Scone, it is not unlikely that he may
have had Scottish priests about his family in preference to those of
Norwegian extraction.

46. So says the Saga. Fordun says that the use of his tongue and of one eye was
in some measure left him. The letter of Pope Innocent, addressed to the
Bishop of Orkney, prescribing the penance to be performed by the man who
mutilated the bishop, only mentions the cutting out of the tongue. It is as
follows:—
“We have learnt by your letters that Lomberd, a layman, the bearer of these
presents, accompanied his earl on an expedition into Caithness; that there
the Earl’s army stormed a castle, killed almost all who were in it, and took
prisoner the Bishop of Caithness; and that this Lomberd, as he says, was
compelled by some of the earl’s soldiery to cut out the bishop’s tongue. Now
because the sin is great and grievous, in absolving him, according to the
form of the church, we have prescribed this penance for satisfaction of his
offence, and to the terror of others:—That he shall hasten home, and bare-
footed, and naked, except breeches, and a short woollen vest without
sleeves, having his tongue tied by a string, and drawn out so as to project
beyond his lips, and the ends of the string bound round his neck, with rods
in his hand, in sight of all men, walk for fifteen days successively through his
own native district, the district of the mutilated bishop, and the neighbouring
country; he shall go to the door of the church without entering, and there,
prostrate on the earth, undergo discipline with the rods he is to carry; he is
thus to spend each day in silence and fasting until evening, when he shall
support nature with bread and water only; after these fifteen days are
 passed he shall prepare within a month to set out for Jerusalem, and there
labour in the service of the Cross for three years; he shall never more bear
arms against Christians; for two years he shall fast every Friday on bread
and water, unless by the indulgence of some discreet bishop, or on account
of bodily infirmity, this abstinence be mitigated. Do you then receive him
returning in this manner, and see that he observe the penance enjoined
him.” (Epist. Innoc. III. Lib. iii. No. 77; Diplom. Norvegicum, vii. 3.)

47. Chron. de Mailros, p. 114; see also p. lxxxi. infra.

48. Magnus, son of the Earl of Angus, appears among those present at the
perambulation of the boundaries of the lands of the Abbey of Aberbrothock
on 16th January 1222 (Regist. Vet. de Aberbrothock, p. 163); but he seems
to have been Earl of Angus as well as of Caithness at the date after
mentioned. A charter of King Alexander II. to the chapel of St. Nicholas at
Spey, dated 2d October 1232, is witnessed by M. Earl of Angus and Kataness
(Regist. Moraviense, p. 123).

49. The title prefixed to the translation of this document by Dean Gule, made for
William Sinclair of Roslin, in 1554, calls it:—“A Diploma or Deduction
concerning the Genealogies of the ancient Earls of Orkney, drawn up from
the most authentic records, by Thomas, Bishop of Orkney, with the
assistance of his clergy and others, in consequence of an order from King
Eirik of Denmark, Sweden, and Norway, to investigate the rights of William
Sinclair to the earldom.” But in the document itself King Eirik is spoken of as
“our former lord of illustrious memory,” and the date is evidently erroneous.
It is probably to be assigned to about 1443. It was first printed by Wallace in
1699, and subsequently by Jonæus in the appendix to the Orkneyinga Saga
in 1780; by Barry in his History of the Orkneys in 1805; in the Bannatyne
Miscellany, 1848; and by Munch in his Symbolæ, Christiania, 1850.

50. Among the documents found in the King’s Treasury at Edinburgh in 1282,
were the letters addressed by the King of Norway (presumably Hakon) to the
inhabitants of Caithness. The inhabitants of Caithness seem to have been
also obliged by the Scottish King to give hostages for their fealty to him. In
the accounts of Laurence Grant, Sheriff of Inverness, for the year 1263,
there is a charge of £15:6:3 for the expenses of twenty-one hostages from
Caithness, at the rate of one denarius (penny) for each per day for twenty-
five weeks, “and then they were set at liberty.” (Compota Camerarium
Scotiæ, i. p. 31.)

51. Acta Parl. Scot., vol. i. p. 82.

52. Iceland Annals, sub anno.

53. The Scala Cronica says off the coast of Buchan. “One Master Weland, a
clerke of Scotlande, sent yn to Norway for Margaret, dyed with her by
tempeste on the se cumming oute of Norway to Scotland yn costes of
Boghan.” (Scala Cronica, Mait. Club, pp. 110, 282.) Wyntoun says she was
“put to dede by martyry,” and assigns as the reason that the Norwegians
would not have one who was of another nation and a female to be heir to
the throne of Norway, though their laws allowed it. He had probably heard
the story of the “false Margaret.” (See p. lii.)

54. In the Wardrobe Rolls of King Edward I. (1290) the following payments
occur:—“Sept. 1.—To Lord Eli de Hamville going by the king’s orders with the
Lord Bishop of Durham towards Scotland to meet the messengers of the
King of Norway and the princess, and was to return with the news to the
king. To John Tyndale, the messenger from the Bishop of St. Andrews, who
brought letters from his master to the king concerning the rumours of the
arrival of the Princess of Scotland in Orkney—by gift of the king, xxsh. To
William Playfair, messenger of the Earl of Orkney, who brought letters to our
Lord the King, on the part of Lord John Comyn, concerning the reported
arrival of the Scottish Princess in Orkney—by gift of the king, xiiish. 4d.”
There is also a detailed account of the expenses of two messengers who left
Newcastle on the 15th September, were at Haberdene on the 23d, at the
Meikle Ferry in Sutherland on the 30th, where they met the messengers from
Scotland, then proceeded by Helmsdale and Spittal to Wick, which they
reached on the 4th October. They left Wick on the 6th October, and arrived
at Norham on the 21st November. On the 13th May of the following year
(1291) Earl John of Orkney had a safe conduct to come to King Edward till
the 24th June, when the earl would doubtless communicate to the king all
that he knew of the princess’s death.

55. This letter was dated 1st February 1320, and the substance of it is given by
Suhm, vol. xii. p. 29. It does not seem to be known from the original
document however, but from a later “paraphrase,” as Munch calls it,
preserved in the Royal Library at Stockholm. (Det Norske Folks Historie, vol.
iv. part 2, p. 348.)

56. Under the date 1293 the following entry occurs in the Chronicle of Lanercost:
—“Dominica etiam post festum Sancti Martini (Nov. 15) desponsata est filia
Roberti de Carrick regi Norwagiae Magno.” (Chron. de Lanercost, p. 155.)
Magnus is plainly a mistake for Eirik, the son of Magnus, who reigned from
1280 to 1299.

57. Rymer’s Fœdera, Syllabus I. p. 114.

58. Det Norske Folks Historie, vol. iv. part 2, p. 202.

59. Munch, Det Norske Folks Historie, vol. iv. part 2, pp. 195, 344.

60. Haflidi Steinson died nearly nineteen years after this as priest of
Breidabolstad in Iceland. The Iceland Annals, recording his death in 1319,
recount the story as if this were the real Margaret (whose death they record
in 1290), and add that “to this Haflidi himself bore witness when he heard
that this same Margaret had been burnt at Nordness.” (See Wyntoun’s
Statement, p. 1, note 1.)

61. On the 2d April 1320 Bishop Audfinn writes to the Archbishop that on the 1st
February he had issued a prohibition against the bad custom of making
pilgrimages to Nordness, and offering invocations to the woman who had
been burnt many years ago for giving herself out as King Eirik’s daughter. He
also complains to the archbishop that opposition had been offered to the
reading out of the prohibition in the Church of the Apostles of Bergen.
(Munch, Det Norske Folks Historie, iv. part 2, p. 348.)

62. This noble document was signed by eight earls and thirty-one barons of
Scotland, at the abbey of Aberbrothock on the 6th April 1320. After asserting
the legitimate claims of King Robert the Bruce, and narrating his struggles in
the cause of Scottish independence, it goes on to say that “If he were to
desist from what he has begun, wishing to subject us or our kingdom to the
King of England or the English, we would immediately endeavour to expel
him as our enemy, and the subverter of his own rights and ours, and make
another king who should be able to defend us. For so long as a hundred
remain alive, we never will in any degree be subject to the dominion of the
English. Since not for glory, riches, nor honour, we fight, but for liberty alone,
which no good man loses but with his life.” The duplicate, preserved in the
General Register House, is printed in facsimile in the National Manuscripts of
Scotland, published under the superintendence of the Lord Clerk Register.

63. The lands are those of Stufum, Kuikobba, Klaet, Thordar, Borgh, Leika, Lidh,
Haughs-æth and Petland-Sker. (Diplom. Norvegicum, ii. 146.)

64. Munch, in his Genealogical Table of the Earls of Orkney, makes Katharina to
be the daughter of Earl John (following Douglas’ Peerage of Scotland), and
Magnus to be a son of Malcolm of Caithness, whom he conjectures to have
been a son of the first Magnus. But in a note on this subject in the second
series of his History, he acknowledges the mistake, referring to this
document in proof of Magnus’ descent from Earl John. (Det Norske Folks
Historie, Anden Afdeling, vol. i. p. 317.)

65. An entry in the Chamberlain Rolls for that year mentions the dues of the
fourth part of Caithness, which the Earl of Stratherne had. (Comp. Camer.
 Scot. i. p. 235.)

66. This document is not now to be found, but Mr. Cosmo Innes says (Lib. Insule
Missarum, p. xliii) that he made a note of its purport as given above in the
Dunrobin charter-room. Sir Robert Gordon, in his Genealogy of the Earls of
Sutherland (p. 49), gives the purport of the document in precisely similar
terms, but says that it is dated 28th May 1344. Sir James Balfour, in his
Catalogue of the Scottish Nobility, also gives 1344. The confirmation of this
contract by David II. is recorded as a “confirmation of a contract of marriage
betwixt Malisius, Earl of Stratherne, Caithness, and Orkney, and William, Earl
of Ross.” (Robertson’s Index of Missing Charters, p. 51.)

67. There is also on record a confirmation by Robert I. of a charter of the lands

of Kingkell, Brechin, to Maria (Marjorie?) de Stratherne, spouse of Malise of
Stratherne. (Robertson’s Index, p. 19.)

68. Chronicle of the Earls of Ross, Mis. Scot., vol. iv. p. 128.

69. There is an entry in the Chamberlain Rolls, in 1340, in regard to a payment

by Johannes More, “pro terris de Beridale in Cattania, de quibus dicit se
hereditarium infeodari per comitem de Strathern et per Regem confirmari.”
(Comp. Camerar. Scot. i. p. 265.)

70. Sir James Balfour (Catalogue of the Scottish Nobility) says:—“This Earl
Malisius was forfaulted by King David II. for alienating the earldom of
Stratherne to the Earl of Warrenne, an Englishman, the king’s enemy, and all
his possessions annexed to the crown.” Sir Robert Gordon says that the
charter by King David granting the earldom of Stratherne to Maurice Moray is
dated the last day of October 1345.

71. A dispensation granted by Pope Benedict XII. in July 1339 for the marriage
of Maurice de Moravia with Johanna, widow of John, Earl of Athole, styles
her Countess of Stratherne. (Theiner’s Monumenta, p. 275.) Maurice fell at
the battle of Durham in 1346. Johanna, Countess of Stratherne, in her
widowhood executed a charter in favour of Robert of Erskine and his wife,
Christian of Keith, her cousin, which is confirmed by Robert, Steward of
Scotland and Earl of Stratherne in 1361. (Chartulary of Cambuskenneth,
Grampian Club, p. 255.)

72. Third Report of Com. on Hist. MSS. p. 416.

73. Rymer’s Fœdera, Syllabus i. p. 272.

74. Robertson’s Index of Charters, pp. 18, 34.

75. Hist. Doc. Scot. i. p. 394.

76. Balnagown Charters, Orig. Paroch. ii. 487.

77. Robert Stewart, Seneschal of Scotland and Earl of Stratherne, certifies that,
in his court held at Crieff, 8th May 1358, he had seen read and confirmed the
charters granted to the abbot and convent of Inchaffray of the annual of 42
marcs of the thanage of Dunyne, given by the former earls of good memory
—Malise the first and Malise the second, his predecessors. (Liber Insula
Missarum, p. 55.) Et nihil hic de terris quondam Malesii infra comitatu
Cathanie quia comes de Ross se intromittit de eisdem. (Conqu. Camerar.
Scot., an. 1357, i. p. 320.) That the second Malise of Robert Stewart’s deed is
the last Malise who was Earl of Stratherne seems to be shown by another
deed of Robert Stewart, dated in 1361, in which, as Seneschal of Scotland
and Earl of Stratherne, he grants to James Douglas the lands of Kellor in
Stratherne, “which the late Malise gave.” In the confirmation of this grant by
Eufamia, Countess of Moray and Stratherne, he is styled “the late Malise of
good memory.” (Regist. Honoris de Morton, ii. pp. 60, 86.)

78. See p. lvi.

79. Called in the Diploma “Here Ginsill de Swethrik,” for “Erengisle de Suecia.” He
was lawman of Tisherad in Sweden in 1337.

80. In the Diploma he is called “quodam Gothredo, nomine Gothormo le

Spere”—Gothredo being a misreading for Gothricio, “a native of Gothland.”
(Munch, Symbolæ, p. 55.)

81. Munch, Norske Folks Historie, 2d series, i. p. 595.

82. In 1360 he grants certain lands to the monastery of Calmar for the souls of
his deceased wives, Meretta and Annot or Agneta, the latter being probably
Malise’s daughter, as the name is not a common one in Sweden.

83. He styles himself “Comes Orchadensis” in a deed of 4th March 1388.

(Diplom. Norvegicum, v. 246.)

84. Diplom. Norvegicum, ii. 337-339.

85. See the document dated at Cullen, 4th August 1321, quoted on p. lv, supra.

86. In a deed executed at Kirkwall, 20th January 1364, by which Bernard de

Rowle resigns to Hugh de Ross (brother of William, Earl of Ross) the whole
lands of Fouleroule in Aberdeenshire, the witnesses are John de Gamery and
Symon de Othyrles, canons of Caithness; Euphemia de Stratherne, one of
 the heirs of the late Malise, Earl of Caithness; Thomas de St. Clair, “ballivus
regis Norvagie;” and Alexander St. Clair. (Regist. Aberdonense, i. 106.)

87. Sir James Balfour calls her Lucia. She is also called Lucia by William
Drummond, author of the “Genealogie of the House of Drummond, 1681,”
but in neither case is any documentary authority cited. Camden says the
eldest daughter.

88. Barbour’s Bruce (Spald. Club), p. 482.

89. Munch’s Norske Folks Historie, 2d series, vol. ii. p. 96. See also the deed of
investiture, which is printed at length in the Diplomatarium Norvegicum, vol.
ii. pp. 353-358.

90. Balfour, Oppressions of Orkney (Maitland Club), p. xxvi. Such was not the
opinion of Father Hay, the panegyrist of the St. Clairs of Roslyn. He says that
“Henry, prince of Orknay, was more honoured than any of his ancestres, for
he had power to cause stamp coine within his dominions, to make laws, to
remitt crimes;—he had his sword of honour carried before him wheresoever
he went; he had a crowne in his armes, bore a crowne on his head when he
constituted laws; and, in a word, was subject to none, save only he held his
lands of the King of Danemark, Sweden, and Noraway, and entred with
them, to whom also it did belong to crowne any of those three kings, so that
in all those parts he was esteemed a second person to the king.” (Genealogie
of the St. Clairs, p. 17.) Father Hay’s romances receive no countenance
whatever from the deed of investiture.

91. About £333 sterling.

92. Father Hay states (Genealogie of the St. Clairs, p. 17) that Henry St. Clair
“married Elisabeth Sparres, daughter of Malesius Sparres, Prince of Orkney,
Earl of Caithness and Stratherne, through which marriage he became Prince
of Orkney.” But Malise Sperra never had any connection with the earldoms of
Caithness or Stratherne. In another place, p. 33, he says that Sir William
Sinclair (who fell fighting with the Saracens in Spain in 1330) “was married
to Elizabeth Sparre, daughter to the Earle of Orkney, and so by her became
the first Earl of Orkney of the Saintclairs. His name was Julius Sparre. He is
also reputed Earl of Stratherne and Caithness.” But this is manifestly a tissue
of impossibilities. He seems to have copied the last statement from the
Drummond MS. (1681), where the additional statement is made that
Elizabeth’s mother was Lucia, daughter of the Earl of Ross. (Genealogie of
the House of Drummond: Edinburgh, 1831, p. 237.) Both writers seem to
have confounded Malise, Earl of Stratherne, with his daughter’s son, Malise
Sperra.
93. Iceland Annals, sub anno. Munch, Det Norske Folks Historie, 2d series, vol. ii.
p. 106.

94. He seems to have held lands in Banffshire. In the Chamberlain Rolls, 1438,
there is an entry of a receipt of £9 from James M’fersane for the land
formerly belonging to Malis Speir, knight in the Sheriffdom of Banff,
remaining in the king’s hands. (Diplom. Norvegicum, i. 366.)

95. The Iceland Annals, under the date 1389, have the following entry:—“Malise
Sperra slain in Hjaltland, with seven others, by the Earl of Orkney. He had
previously been taken captive by him. From that conflict there escaped a
man-servant who with six men in a six-oared boat got away safely to
Norway.”

96. Diplom. Norvegicum, ii. 401. Regist. Mag. Sigill. 196.

97. This deed is said by Robert Riddell to be in the Perth Charter-chest. A copy
of it is in one of his MS. note-books in the Advocates’ Library. See also
Robertson’s Index of Charters, p. 128. The “double” of this deed is said by
William Drummond (1681) to have been given to him by a friend, and the
substance of it is given by him as follows:—“Sir John Drummond and his lady
Elisabeth Sinclair oblige themselves to a noble and potent Lord, Henry, Earle
of Orkney, Lord Roslin, their father, that they nor their aires shall never
claime any interest or right of propertie to any lands or possessions
belonging to the said earle or his aires lying within the kingdome of
Norroway, so long as he or any air-male of his shall be on lyfe to inherit the
same; bot if it happen (which God forbid) the said earle to die without any
air-male to succeed to him, then it shall be lawful for them to claim such a
portion of the aforesaid lands as is known by the Norwegian laws to
appertain to a sister of the family. Sealled at Rosline 13th May 1396.”
(Genealogie of the House of Drummond, p. 91.)

98. Henry himself had married a daughter of Malise. See p. lxiii.

99. Father Hay says that he escaped through the instrumentality of one John
Robinsone, indweller at Pentland, one of his tenants, who went to the place
where his master was confined and played the fool so cunningly that he was
allowed access to the prison, and so found means to convey the earl out in
disguise. (Genealogie of the St. Clairs, p. 81.)

100.
Balfour’s Annals, i. 148.
101.
Diplom. Norvegicum, ii. 482.

102.
Fordun, Scotichron. xv. chap. 32.

103.
Douglas’ Peerage. The Diploma says nothing of his wife, but he is said to
have married Egidia Douglas, daughter of Lord William Douglas, and Egidia,
daughter of Robert II. (Extracta ex Cronicis Scocie, p. 200.)

104.
Diplom. Norvegicum, ii. 489. This document is endorsed—“Biscop Thomes
breff af Orknoy, at han skal halde Orknoy til myn herres konnungens hand,
oc hans effterkommende, oc lade him with Noren lagh.”

105.
Diplom. Norvegicum, ii. 498. This document is endorsed—“Item biscop
Thomes aff Orknoy bref um Kirkwaw slot i Orknoy, oc um landet oc
greveschapet ther samestads.”

106.
This document is printed at length in Torfæus, pp. 179-182; in Balfour’s
Oppressions of Orkney (Maitland Club), pp. 105-110; and also in the Norse
language of the time in the Diplomatarium Norvegicum, ii. 514.

107. Torfæus, Hist. Orc. 182. The document of which Torfæus here gives a copy,
however, is that of the 31st year of the reign of King Eirik (1420), previously
noticed, and refers not to the bishop’s second appointment but to his first.

108.
Torfæus, p. 183.

109.
Balfour’s Annals, i. 155.

110.
Diplom. Norveg. vii. 430.

111.
He had received a grant of the earldom of Caithness from King James II.
28th August 1455, as formerly mentioned, p. lxi.

112.
Diplom. Norvegicum, v. 599.