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 Smart Polymer Systems 2010
1 st International Conference

Smithers Rapra has provided a world leading portfolio of Rubber, Plastic and other
Polymer Information products and services for 85 years. To improve the delivery and
Smart
Polymer Systems
range of products a new business was formed in July 2008 called iSmithers.

iSmithers, working alongside Smithers Rapra and still part of the Smithers group, has
expanded its service offering to cover other business areas and industries harnessing
the expertise of the iSmithers management team and the knowledge from other

2010
companies within the group.
Please visit our webside for more information:
www.polymerconferences.com 5-6 May, Atlanta, USA

Conference Proceedings
Cover Image: A. Chilkoti and J.A. Hubbell, Guest Editors, "Biointerface Science" MRS Bulletin Vol. 30, No. 5 (2005)
Image reproduced by permission of the MRS Bulletin

Conference Proceedings
Organised by:

iSmithers
©iSmithers 2010
ISBN 978 1 84735 494 5
Organised by

Atlanta, USA
5-6 May 2010
 ISBN: 978-1-84735-494-5

© Smithers Rapra Technology Ltd, 2010

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted
in any form by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written
permission of the publisher, Smithers Rapra Technology Ltd, Shawbury, Shrewsbury, Shropshire, SY4 4NR,
UK.

The views expressed in this publication are those of the individual authors and do not necessarily correspond
to those of Smithers Rapra Technology Ltd. This publication is published on the basis that no responsibility or
liability of any nature shall attach to Smithers Rapra Technology Ltd. arising out of or in connection with any
utilization in any form any material contained in this publication.
About the pagination of this eBook

Due to the unique page numbering scheme of this book, the

electronic pagination of the eBook does not match the pagination
of the printed version. To navigate the text, please use the
electronic Table of Contents that appears alongside the eBook or
the Search function.

For citation purposes, use the page numbers that appear in the text.
 Contents

SESSION 1: RESPONSIVE COATINGS

Paper 1 Stimuli-responsive polyelectrolyte multilayers: from pH and temperature-sensitive

nanotube surface arrays to living cells with functional synthetic backpacks
Dr Michael Rubner, Department of Materials Science & Engineering, Massachusetts Institute
of Technology, US
Paper unavailable at time of print
Paper 2 Self-repairing polymeric films
Dr Marek W Urban, School of Polymers & High Performance Materials, University of
Southern Mississippi, US
Paper unavailable at time of print
Paper 3 Interactive polymer substrates via polymer grafting
Dr Igor Luzinov, School of Materials Science & Engineering, Clemson University, US

Paper 4 Hybrid materials for application in anti-reflective coatings

Dr Pascal Buskens, N Arfsten, R Habets, H Langermans, A Overbeek, B Plum, R de Rijk & J
Scheerder, DSM Research, The Netherlands

SESSION 2: SMART TEXTILES

Paper 5 Preparation and application of responsive coatings prepared on textile fibers

Prof Jan Genzer & Kiran K Goli, North Carolina State University, US
Paper unavailable at time of print
Paper 6 Responsive coating design on substrates/ particles
Dr Maxim Orlov, D Salloum, R Sheparovych, V Gartstein & F Sherman, The Procter &
Gamble Company, US & S Minko, M Motornov & R Lupitskyy, Clarkson University, US
Paper unavailable at time of print
SESSION 3: RESPONSIVE COMPOSITES

Paper 7 New microfluidic elastomer composites with switchable shape, stiffness and color
Prof Orlin D Velev, Department of Chemical & Biomolecular Engineering, North Carolina
State University, US

Paper 8 New smart plastic with reversible and tunable transparent to opaque transition
Dr Chris DeArmitt, Phantom Plastics, US

SESSION 4: BIOINTERFACES, CAPSULES, SENSORS AND SEPARATION DEVICES

Paper 9 “Smart” (bio) polymeric surfaces: fabrication and characterization

Prof Stefan Zauscher, Department of Mechanical Engineering & Materials Science, Duke
University, US

Paper 10 Emulsions-templated assembly of stimulus-responsive particles: smart colloidosomes

with tunable permeability and dissolution trigger
Dr Sven Holger Behrens, School of Chemical & Biomolecular Engineering, Georgia Institute
of Technology, US

Paper 11 Multifunctional layer-by-layer tailored capsules: delivery nanosystems with externally

triggered properties
Prof Gleb B Sukhorukov, Centre for Materials Research, Queen Mary University of London,
UK

Paper 12 Stimuli-responsive thin hydrogel films and membranes

Dr Sergiy Minko, Department of Chemistry & Biomolecular Science, Clarkson University, US
SESSION 5: SMART COLLOIDS AND HYDROGELS

Paper 13 Biopolymer based colloidal delivery systems

Dr Ashok Patel, Unilever R&D Vlaardingen, The Netherlands
Paper unavailable at time of print
Paper 14 Autonomic self-healing in hydrogel thin films
Prof Andrew Lyon & Antoinette B South, Georgia Institute of Technology, US

Paper 15 Developments in “smart” temperature-responsive chromatographic resins

Dr Brad Woonton, K De Silva, P Maharjan, CSIRO, Australia & M Hearn & W Jackson, ARC
Special Research Centre for Green Chemistry, Australia

SESSION 6: CELL INTERACTIONS WITH RESPONSIVE BIOMATERIALS

Paper 16 Cell-responsive biomaterials for regenerative medicine applications

Prof Sarah Heilshorn, Stanford University, US

Paper 17 Micropatterned poly (NIPAM) for engineering cell sheets with defined structural
organization
Prof Joyce Y Wong, B C Isenberg, C Williams, Y Tsuda, T Shimizu, M Yamato & T Okano,
Department of Biomedical Engineering, Boston University College of Engineering, US
Paper unavailable at time of print

SESSION 7: GENETICALLY ENGINEERED “SMART” POLYPEPTIDES

Paper 18 Bioengineering of elastim-mimetic smart materials

Prof Vincent P Conticello, M Patterson, S Payne, W Kim, A McMillan & E Wright,Department
of Chemistry, Emory University, US

Paper 19 Recombinamers and derived functional systems: from nano-objects to macro gels
Prof J Carlos Rodriguez-Cabello, GIR BIOFORGE, University of Valladolid, Spain

Paper 20 Thermally targeted delivery of therapeutic peptides

Prof Drazen Raucher & Gene L Bidwell III, Department of Biochemistry, University of
Mississippi Medical Center, US
Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

STIMULI-RESPONSIVE POLYELECTROLYTE MULTILAYERS:

FROM PH AND TEMPERATURE-SENSITIVE NANOTUBE
SURFACE ARRAYS TO LIVING CELLS WITH FUNCTIONAL
SYNTHETIC BACKPACKS
Dr Michael Rubner
Massachusetts Institute of Technology
Center for Materials Science and Engineering
Room 13-5106, 77 Massachusetts Ave, Cambridge, MA 02139, USA
Tel: +1 617-253-4477 fax: +1 617-258-7874 email: [email protected]

BIOGRAPHICAL NOTE

Michael F. Rubner is currently the TDK Professor of Polymer Materials Science and
Engineering within the Department of Materials Science and Engineering at MIT. He
has also been the Director of MIT’s Center for Materials Science and Engineering, one
of the largest NSF supported Materials Research Science and Engineering (MRSEC)
programs, for eight years.

Rubner received his B.S. in Chemistry from the University of Lowell (summa cum laude, 1982) and his Ph.D.
from the Department of Materials Science and Engineering at MIT (1986). While pursuing his undergraduate
and graduate degrees, he worked as a full-time staff member in GTE Laboratories. He accrued a total of
over twelve years industrial experience before accepting a faculty position at MIT in 1986.

Rubner has received all of the major teaching awards given at MIT and was named a MIT MacVicar
Teaching Fellow in 1996. He has given more than 200 invited lectures including the Robert Maddin Lecture
in Materials Science at the University of Pennsylvania (2010), the GE Distinguished Lecture at Rensselaer
Polytechnic Institute (2009), the Bayer Distinguished Lecture at the University of Pittsburgh (2005), and the
Dow Distinguished Lecture at Northwestern University (1995). He has published more than 200 technical
papers, including five book chapters and is holder of 15 U.S. patents. From 1995-1999, he was U. S. Editor
of Supramolecular Science, Elsevier Science Publishers. He currently serves on the Board of Directors for
the Materials Research Society, and the Advisory Boards of the Brookhaven National Lab and the ACS
Chemistry of Materials Journal.

In the research arena, he is considered one of the founding scientists of the rapidly expanding area of
polyelectrolyte multilayer (PEM) assemblies. His contributions have played a seminal role in defining and
shaping the fundamental and technological landscape of this area and have resulted in the development of
new PEM-based technologies. His current research interests include investigations of molecularly
assembled PEM thin films as multifunctional coatings that provide new capabilities in the areas of thin film
optics, extreme surface wetting behavior and biomaterial interface design.

ABSTRACT

In this work, we show that suitably designed polyelectrolyte multilayers can exhibit a range of interesting
stimuli-responsive properties. Through the use of weak polyelectrolytes and track-etched polycarbonate
membranes, for example, it is possible to fabricate a surface anchored array of hollow nanotubes that can be
rendered reversibly nanoporous with suitable pH changes. The size, shape and porosity of the nanotubes in
these arrays can be switched dramatically by simply exposing the surface to different aqueous solutions. In
addition, in specific multilayers containing triblock copolymers, temperature changes can be used to activate
dramatic swelling transitions of the nanotubes. This temperature driven effect occurs over a wide range of
solution pHs and ionic strengths, making it useful for manipulating surface interactions with biological
entities. When hydrophobic poly(acrylamides) are combined with weak polyelectrolytes, it is further possible
to create coatings that undergo a temperature induced release process; the films are stable at room
temperature in water but dissolve when the temperature is reduced to 5°C. This behavior, associated with
the lower critical solution temperature (LCST) of the poly(acrylamide), can be utilized to create on-demand
releasable layers. Using this approach, functionalized polymer multilayer “backpacks” have been attached to
only a portion of the surface of living immune system cells. As a result, the cells retain their native cell

Page 1 of 2 pages Paper 1

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

migration functions and can interact with local environments. The multilayer backpack provides the living
cell with additional functionality such as the ability to release beneficial drugs and to be manipulated spatially
with magnetic fields. This latter development opens the door to synthetically functionalized living cells with
novel cell tracking, drug delivery and imaging capabilities.

+++ Paper unavailable at time of print +++

Paper 1 Page 2 of 2 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

SELF-REPAIRING POLYMERIC FILMS

Prof Marek Urban
University of Southern Mississippi
School of Polymers and High Performance Materials
Polymer Science Building,Room 185, 118 College Drive #10076, Hattiesburg, MS 39406-0001, USA
Tel: +1 601-266-6454 Fax: +1 601-266-6178 email: [email protected]

BIOGRAPHICAL NOTE

UNAVAILABLE

ABSTRACT

Considerable challenges and significant inter-disciplinary scientific and technological interests stimulated the
development of new heterogeneous polymeric solids that maintain their useful functions and, at the same
time, are capable of stimuli-responsiveness. The presence of heterogeneous regions within polymeric
networks facilitates localized structural variations enabling favorable spatial and energetic conditions for
spontaneous macroscopic responses to minute external or internal stimuli. Although stimuli-responsiveness
can be easily obtained in polymeric solutions, significant spatial restrictions in solids, near surfaces, and at
interfacial regions impose various degrees of limitations. These generalized concepts formulated the
principles leading to the development of heterogeneous self-repairing solid polymeric films where a new
generation of thermosetting polymer networks containing energetically favorable substitutions and pending
groups was developed to provide self-repairing characteristics upon exposure to UV light. One example of
such networks are polyurethanes that contain crosslinkable oxetane-modified chitosan entities. While
maintaining useful polyurethane properties, these materials upon mechanical damage and subsequent
exposure of the damaged area to UV light self-repair the damage. Kinetics of the repair as well as the
degree of damage can be controlled and correlated with molecular level processes responsible for self-
repair. Different approaches were utilized to achieve self-repairing characteristics in thermoplastic polymers
where in-situ synthesis of superparamagnetic iron oxide nanoparticles facilitates dispersity and application of
oscillating magnetic fields results in polymer repair. When magnetic nanoparticles oscillate, interfacial
particle-polymer temperature increases, causing melting of the surrounding matrix and seamless repair.

+++ paper unavailable at time of print +++

Page 1 of 2 pages Paper 2

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Paper 2 Page 2 of 2 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

INTERACTIVE POLYMER SUBSTRATES VIA

POLYMER GRAFTING
Dr Igor Luzinov
Clemson University
School of Materials Science and Engineering
271C Sirrine Hall, Clemson University, Clemson. South Carolina 29634-0971, USA
Tel: +1 864-656-5958 Fax: +1 864-656-5973 email: [email protected]

BIOGRAPHICAL NOTE

Igor Luzinov is a Professor of Polymer Science at School of Materials Science and Engineering (Clemson
University, Clemson, SC, USA). He joined Clemson University in 2000. Dr. Luzinov received a M. S. degree
in Chemical Engineering and Technology in 1985 and a Ph.D. degree in Polymer Chemistry in 1990 from
Lviv Polytechnic National University (Ukraine). Prior to joining the faculty of Clemson University, he served
as a Senior Research Scientist at Physical Chemistry Institute (National Academy of Science of Ukraine),
NATO Research Fellow at Center Education and Research on Macromolecules (University of Liege,
Belgium) and Postdoctoral Research Associate at Iowa State and Western Michigan Universities. The
research program of Dr. Luzinov’s group is focused on fundamental and applied research problems in
nanofabrication of thin polymer films and their utilization for multi-component polymer systems. Igor Luzinov
has published over 100 articles. He holds 7 patents.

ABSTRACT

Further advances in modern materials science imposes requirements for the surface properties that
frequently are in conflict: a given material, depending on the conditions under which it is utilized, has to be
hydrophobic or hydrophilic, acidic or basic, conductive or nonconductive, adhesive or repellent, and be able
to release or adsorb some species. Modification of material’s boundary with ultrathin grafted polymer layer
can provide a powerful synthetic route to designing the surfaces with necessary performance. In this
presentation a reasonably universal approach for modification of a wide range of substrates with the grafted
layers is discussed. The polymer grafting technique developed can be readily applied to surface
modification of various objects leading to generation of hydrophobic, hydrophilic, switchable, optically active,
and sensing materials.

Slide 1

FUNCTIONAL FILMS VIA POLYMER GRAFTING

Grafted polymer layers affect:

adhesion
lubrication
wettability
friction
biocompatibility
colloidal stability

Page 1 of 16 pages Paper 3

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 2

Methods of the layer synthesis

“Grafting to”
Grafting polymer by reaction between polymer
and surface functional groups

Polymer with
functional group(s)

Inorganic or polymer
+ Surface functional
surface groups

Grafted
polymer

Slide 3

Methods of the layer synthesis

“Grafting from”
Polymerization initiated from the surface by attached
initiator
Inorganic or
polymer Attached
surface initiator

Grafted
Monomer Polymerization polymer

Paper 3 Page 2 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 4

Surface functional groups:

native or created
“Grafting to” “Grafting from”

Additional groups Additional groups

Initiator Initiator

Grafting Grafting Grafting Grafting

Slide 5

 Many methods for “grafting from”

and “grafting to” have been
developed;
 The methods for the brush
attachment are non-universal;
 The methods work well for specific
surface/polymer or surface/initiator
combinations.

Page 3 of 16 pages Paper 3

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 6

Macromolecular anchoring layer:

Reactive polymer adsorbed on surface
“Free” reactive groups
in “loops” and “tails”

Reactive groups in “trains”

attach polymer to the surface

If the groups are highly reactive, the approach become

reasonably universal towards both surface and grafting.
Iyer, K. S.; Zdyrko, B.; Malz, H.; Pionteck, J.; Luzinov, I., Macromolecules 200 3, 36 , 65 19.
Z dyrko, B.; Klep, V.; Luzinov, I., Langmuir 2003, 19 (24), 10179.
Luzinov, I.; Iyer, K. L. S.; Klep, V.; Z dyrko, B. US patent 7,026,014 B2, Ap r. 11, 2006.

Slide 7

Macromolecular layer versus low

molecular weight layer

Macromolecular Less requirements for surface uniformity

layer More functional groups can be deposited

Paper 3 Page 4 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 8

Macromolecular anchoring layer

Polymer containing epoxy groups Poly(glycidyl methacrylate)

( CH2-C( CH 3 ) )n
PGMA O
O

Adsorption
O
Dip-coating
Spin-coating

Unreacted epoxy groups offer a potential

for further attachment;
Epoxy group reacts with carboxy,
anhydride, amino, hydroxy groups;
Surface concentration of functional
groups can be readily varied.

Slide 9

“Grafting from”: ATRP

C( O)-CH2 -Br OH
O O
OH C(O)-CH 2- (CH 2 -CH) n-Br
C( O) -CH 2-Br C(O)-CH2- (CH2-CH)n-Br
Br -CH2 -C(O )OH O Styrene O
OH OH
ATRP
C( O) -CH 2-Br
O C(O)-CH2- (CH2-CH)n-Br
OH O
OH

4 nm PGMA 1 nm BrAc 70 nm PS

1x1 m 1x1 m 7x7 m

Liu, Y.; Klep, V.; Zdyrko, B.; Luzinov, I., Langmuir 2005, 21, 11806.
Liu, Y.; Klep , V.; Zdyrko, B.; Luzinov, I., Langm uir 2004, 20, 6710.

Page 5 of 16 pages Paper 3

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 10

Surfaces modified with the “grafting from”

Polyester (PET), polyvinylidenedifluoride (PVDF), silicon resin,
silicon, silica, and glass
PVDF membrane modified with grafted P2VP
magnification 1000X
Virgin membrane Modified membrane

Singh , N .; Husson, S. M.; Z dyrko, B.; Luzinov, I., Journal of Membrane Science 2005, 262, 81.

Slide 11

“Grafting to” from melt

Polymers grafted: polyacids, polyamines, PEG, Polystyrene, Poly(vinyl pyridine),
Poly(meth)acrylates.

Carb oxy, an h ydrid e,

ami no , or h ydro xy gro u p

Surfaces modified with the grafting to

POLYMERIC: polyester (PET), cotton, nylon, polyethylene,

polypropylene, polyvinylidenedifluoride (PVDF), silicon resin

INORGANIC: silicon, silica, glass, titanium, alumina, gold, silver

Paper 3 Page 6 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 12

Modification of PET surface

Hydrophobic PET surface. Hydrophilic PET surface.
Polystyrene was grafted. Poly(ethylene glycol) was grafted.

Burto vyy, O.; Klep, V.; Chen, H . C.; Hu, R. K.; Lin, C. C.; Luzinov, I., J. of M acromol. Sci. Part B-Physics 2007, 46 , 137.

Luzinov, I ., Nanofabrica tion of thin polymer films, in Nanofibers an d N anotechn ology in Textiles, Eds: Brown, P. J. ; Ste vens, K
Woodhea d, 2007; p 448.

Slide 13

Adopting/switchable coatings

Polym er A Polymer B
MIXED GRAFTED LAYER
At least two different
polymers are grafted

Favorable for A situation Neutral situation Favorable for B situation

Page 7 of 16 pages Paper 3

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 14

Adopting coatings:
wettability, adhesion, patterning…
PS PVP After toluene treatment After ethanol treatment
PS chains occupy surface PVP chains occupy surface

Drap er, J.; Luzinov, I.; Minko, S.; Tokarev, I.; Stamm, M., Langmuir 200 4, 2 0, 4 064.

Slide 15

Tunable bacteria adhesion with (mixed)

polymer brushes
PEG, P2VP, quaternized (55%) P2VP brushes
25

20
QP2VP
PEG-QP2VP
Thickness, nm

P2VP PEG-P2VP
15

10
PEG

Zdyrko, B.; Klep, V.; Xiao wei, L.; Qian, K.; Minko, S.; Xu ejun, W.; Luzinov, I., Materials Science & Engineering: C 2009, 680.

Paper 3 Page 8 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 16

Bacteria Adhesion: Staphylococcus aureus

3.000

2.500

2.000

1.500

1.000

0.500

0.000
Control PEG P2VP PEG-P2VP Q-P2VP PEG-QP2VP
1.307 0.005 0.689 0.511 2.109 1.069

Y‐axis is in relative fluorescence of the samples after S. aureus adsorption. Numbers below the
bars indicating relative amount of S. aureus adsorbed to different brushes.

Slide 17

Patterned surfaces approach

PDMS mold
PS thin film
PGMA/BPA Macroinitiator
substrate

Heating, T > Tg

Binary patterned grafted

Cooling and mold removal polymer layers
PS

SIP of Nipam from aqueous

Second SIP
environment
PNIPAM

PS removal

Page 9 of 16 pages Paper 3

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 18

“Grafting from”: binary patterned grafted

polymer layers (PNIPAM/PEGMA)
PNIPAM layer PNIPAM/PEGMA layer

Image size: 20x20 microns Image size: 10x10 microns

Liu, Y.; Klep, V.; Luzinov, I., JACS 2006, 128, 8106.

Slide 19

PDMS stamp Layer for directed nanoparticles adsorption

PS
PGMA
5x5 m
T>Tg(PS) substrate

PS

PVP

Solvent assisted
T<Tg(PS)
grafting

Ag ND
adsorption
PDMS Peeling off

Zdyrko, B.; Kinnan, M. K.; Chumanov, G.; Luzinov, I., Chem. Comm. 2008,1284.
Zdyrko, B.; Hoy, O.; Kinnan, M. K.; Chumanov, G.; Luzinov, I., Soft Matter 2008, 4, 2213.

Paper 3 Page 10 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 20

PDMS film with Ag nanoparticles arrays

First imprint Second imprint

0.16 a 0.08 b

- Polariz ation - Polariz ation

0.12 0.06
Extinction

0.08 0.04

- Polariz ation - Polariz ation

0.04 0.02

0 0
400 500 600 700 800 400 500 600 700 800
W avelength (nm) W avelength (nm)

Slide 21

Fibers decorated with hydrophobic

nanoparticles for ultrahydrophobic fabric

Page 11 of 16 pages Paper 3

5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 22

4
Synthesis of Rhodamine B Labeled PGMA

H 2C C C C n
H2
O AIBN O RhB
nn
O M EK O MEK

O O

C C C C
H2 a H2 bn
NE t 2 O O

O O
O

O
- +
C lE t 2N O OH
OO

OH
O

RhB:
+ -
Et 2N O N Et 2Cl

Tsyalkovsky, V.; Klep, V.; Ramaratnam , K.; Lupitskyy, R.; Minko, S.; Luzinov, I., Ch emistry of Materials 2008, 20, 317.

Slide 23

PET with fluorescent reactive nanoparticles 8

7
8.0x10
Fluorescent intensity, a.u.

7
6.0x10

FL signal confir med

4.0x107
the dep osition

7
2.0x10

NPs for m m onolayer 0.0

Wavelength, nm
550 600 650 700
homogeneously distributed

NP are r eactive
Superhydrophobic fabric after
FL micr oscope confirm ed grafting of a hydropho bic polym er
even cover ing

Ramaratnam, K.; Tsyalkovsky, V.; Klep, V.; Luzinov, I., Ch em. Comm. 2007, 43, 4510.

Paper 3 Page 12 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 24

SEBS Triblock Copolymer

Poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS)
functionalized with 2% maleic anhydride (MA)
Styrene: 29 wt%; Maleic Anhydride: 2% ; Mn = 41,000 g/mol; M w/Mn = 1.16

Maleic Anhydride
Polystyrene Polystyrene

Ethylene/butylene copolymer
CH 3
H2 C

C C C C C C C C
H2 H H2 H2 x H2 H y n H2 H n
n

O
2% maleic anhydride (MA)
O

Slide 25

Antibody applications

 Biosensors
 Separation
 Drug development and screening
 Improvement of biomedical systems

Drawbacks
 Difficult to purify and separate
 Very sensitive to the environment
 Limited storage
 Costly

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5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Slide 26

Concept of artificial antibody via grafting

(a) (b)

(c)

(a) Cavities complementary to the protein shape

(b) Polymer brush, modulating surface properties
(c) Chemistry at the cavities bottom can
selectively recognize imprinted protein

Zdyrko, B.; Hoy, O.; Luzinov, I., Biointerphases 2009, 4 (2) , FA17-FA21 .

Z dyrko , B.; Hoy, O.; Kinnan, M. K.; Chumanov, G.; Luzinov, I., Soft Matter 2008, 4, 2213.

Slide 27

Conclusions
 PGMA monolayer can serve as an effective
anchoring primary layer;
 Varioussurfaces can be modified with polymer
brushes using the anchoring layer;
 The layer can be used for synthesis of the
brushes by “grafting to” and “grafting from”
approaches;
 Functional polymer films can be synthesized
using the anchoring layer.

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Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Slide 28

Acknowledgements
Dr. Viktor Klep, Dr. K. Swaminathan Iyer, Dr. Bogdan Zdyrko, Mr. John Draper,
Dr. Yong Liu, Dr. Ramaratnam Karthik, Dr. Olexandr Burtovyy, Dr. Olga Hoy, Dr.
Ruslan Birtovyy, Dr. Suraj Sharma, Dr. Volodymyr Tsyalkovsky, Mr. Marius
Chyasnavyachus (Clemson Unievrsity)
Prof. G. Chumanov and his research group: Clemson University
Prof. K. Kornev and his research group: Clemson University
Prof. S. Husson and his research group: Clemson University
Prof. S. Minko and his research group : Clarkson University
Prof. M. Stamm and his research group : IPF Dresden
Prof. Y. Gowaed and his research group: Auburn
This work was supported by National Science Foundation, Department of
Energy, Department of Commerce via the National Textile Center, Homeland
Security Advanced Research Projects Agency, AFRL.

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Paper 3 Page 16 of 16 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

HYBRID MATERIALS FOR APPLICATION IN ANTI-REFLECTIVE

COATINGS
Dr Pascal Buskens, R&D Program Manager Functional Coatings, N Arfsten, R Habets,
H Langermans, A Overbeek, B Plum, R de Rijk & J Scheerder
DSM Research
P.O. Box 18, 6160 MD Geleen, The Netherlands
Tel: +31 (0)46 47 63108 Fax: +31 (0)46 47 63 949 email: [email protected]

BIOGRAPHICAL NOTE

Pascal Buskens studied chemistry at the Technical University of Aachen in Germany. In 2006, he completed
his Ph.D. study, entitled "Bifunctional Organocatalysis in the Asymmetric Aza-Baylis-Hillman Reaction", at
the same university. After recieving his Ph.D., he started working at DSM in the Functional Coatings R&D
group. Since 2008, he leads the Functional Coatings R&D group. Examples of coatings developed by
the group are anti-reflective, anti-fogging, anti-fouling and self cleaning coatings.

ABSTRACT

The possibility of combining properties of organic and inorganic components for materials design is an
interesting area of research which found its origin in the second half of the twentieth century. Traditionally,
such hybrid materials are prepared through hydrolysis and condensation of metal oxide precursors in the
presence of organic molecules, polymers or bio-components. The resulting hybrid materials are then
processed into micro-structured coatings. The micro-domains which are present in such coatings are
generally polydisperse in size and locally heterogeneous in composition.

Further tailoring of properties can only be achieved through a higher level of control over local and semi-local
structures. For this purpose, we designed structurally defined hybrid building blocks that keep their integrity
in the final coating. Examples of such building blocks are polymer-metal oxide core-shell particles. These are
currently produced by DSM on a multi-ton scale for use in single-layer anti-reflective coatings on glass. By
incorporation of polymer-silica core-shell particles into an inorganic matrix and subsequent removal of the
core material, a coating with a refractive index of about 1.23 is achieved. This coating combines a low level
of rest reflection (less than 1.5%) with excellent mechanical resistance and outdoor durability. Hence, the
technology is applicable to a wide variety of in- and outdoor applications like anti-reflective picture glass,
glass displays, lighting covers, solar cell covers and green house covers. The technology is currently in use
for DSM’s anti-reflective picture glass – ®claryl – and for solar cover glass and other (outdoor) applications
under the brandname KhepriCoatTM. The technology is available to glass or module producers via licensing.

Currently, we are developing a slot-die coating process for the single-side application of optical coatings at
speeds up to 20 meters per minute and evaluating our coating for other single-side applications (e.g. roller
coating, spray coating). Latter make it possible to use DSM’s anti-reflective coating technology in large-
volume applications of up to ten million square meters per year.

Keywords: anti-reflective coating, core-shell particles, solar cell cover glass, slot-die coating

Introduction

In this report, we discuss the preparation of anti-reflective coatings (ARCs) for glass substrates based on a
single layer system containing a coating film of a refractive index of about 1.23. There are, however, no low
index solid materials that display a refractive index lower than 1.37 [i] and the best method to achieve lower
values is to reduce the packing density. According to Moulton and co-workers, this can be achieved by the
application of nanoparticles to form a nanoporous film.[ii] However, these traditional Moulton type single layer
ARCs normally exhibit a sharp trade-off between optics and mechanics: a high level of porosity is required to
obtain a low rest reflection.[iii] This is usually accompanied by a high surface roughness which causes poor
abrasion resistance, a high degree of optical fouling and problems with cleaning. Furthermore, these
coatings are typically sensitive when exposed to outdoor conditions.
Page 1 of 8 pages Paper 4
5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

To improve the properties of traditional single layer ARCs, a high level of control over the balance of surface
roughness and internal porosity is required. In contrast to the Moulton approach, we use polymer
nanoparticles with a silica shell to form ARCs. During the curing or tempering step, the polymer template is
removed resulting in a coating with a high level of internal porosity (Figure 1). This enables us to use higher
amounts of binder than for traditional Moulton-type ARCs which lowers the surface roughness and increases
the scratch resistance, cleanability properties and outdoor durability of the coating.

Traditional AR coating DSM approach

(Moulton-type)

High surface roughness Low surface roughness

Figure 1. Schematic representation of a traditional Moulton-type ARC and DSM’s single layer ARC.

Results and discussion

For the synthesis of polymer nanoparticles with a silica shell, small silica nanoparticles were deposited on a
spherical cationic polymer template. For silicification, both commercially available silica nanoparticles like
MT-ST from Nissan Chemicals [iv] and in-situ produced silica nanoparticles were used.[v] As polymeric
template, both cationically stabilized micelles[vi] and cationic latexes were applied.[vii] A schematic
representation of the synthetic approach starting from tetramethyl orthosilicate (TMOS) as precursor is
depicted in Figure 2. For this example, a cationic polymer with a particle size of about 80 nm is used as
template.[viii] This aqueous polymer system was treated with TMOS to form core-shell particles. At the
desired shell-thickness, the reaction was stopped via dilution with alcohol and subsequent acidification with
nitric acid.

Silica precursor

cationic polymer
- particle
alcohol,
+ HNO3
+
+
+ +
+
+ +
+ + +

Figure 2. Schematic representation of the synthesis of polymer-silica core-shell particles.

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Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Parameters that influence the growth rate of the particles are the concentration of solids in the reaction
mixture, pH, temperature and the addition rate of TMOS. At optimized reaction conditions, the growth
process started after a specific induction period and was nearly linear. A TEM image of the resulting core-
shell particles is shown in Figure 3.

Figure 3. Core-shell particles.

The alcoholic particle dispersion was subsequently treated with a binder. A variety of inorganic silica binders
were tested. For the preparation of the coatings described in this article, the above mentioned particles were
combined with alcoholic dispersions of pre-oligomerised tetraethyl orthosilicate (TEOS).[6] Under ambient
conditions, the resulting coating formulations were stable for more than six months.

The coatings were applied on both sides of the substrate via dip-coating. The coating thickness can be
controlled via the dip speed. Typical coating speeds for dip-coating are in the range of 0.5 to 1 mmin-1.
Currently, a horizontal slot-die coating process is being developed to apply these coatings on one single side
of the substrate. Initial pilot-scale results show that coating speeds up to 20 mmin-1 can be achieved using
this process (Figure 4). The resulting coatings show an excellent optical homogeneity and are similar in
performance to dip-coated samples.

Figure 4. Slot-die coating process as developed by DSM.

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5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

Directly after application of the coating material, a xerogel is formed. This xerogel has an overall reflection of
about 6.6% in the visible (VIS) and is surprisingly robust. The film withstands polishing and edge working
treatments which are commonly applied before tempering. During the curing (450C) or tempering step
(675C), the cross-link density in the inorganic network is increased and the polymeric template is removed.
The resulting coatings display a low surface roughness and a high level of internal porosity (see Figure 5).
They are steel wool resistant, easy to clean and display broad-band anti-reflective properties.

Figure 5. ARCs based on core-shell particles (SEM and AFM).

The anti-reflective coating was optimized for picture and art glazing. For this purpose, low-iron glass of a
thickness of 2 mm was coated with the above mentioned formulation in a dip-coating process and cured at
450C for one hour. The reflection minimum directly correlates to the coating thickness, which can be varied
either by changing the viscosity of the formulation or the dip speed. The reflection spectrum is optimized for
the sensitivity of the human eye, which is most sensitive around 550 nm. The reflection spectrum VIS is
shown in Figure 6.

Reflection spectrum Claryl

3.5

3.0

2.5
Reflection in [%]

2.0

1.5

1.0

0.5

0.0
425 475 525 575 625 675
Wavelength in [nm]

Figure 6. Reflection spectrum of ®claryl (VIS).

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Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

The optical properties of the picture glass are outstanding: the rest reflection VIS is 1.2  0.1%, the
transmission is higher than 98%. Furthermore, the color fastness and the viewing angle performance are
excellent. The coating is mechanically robust (steel wool resistant) and easy to clean with conventional glass
cleaners. This picture glass is available in Europe and the US under the brand name ®claryl and is produced
by DSM in The Netherlands.[ix]

A second technology comprising core-shell particles is DSM’s anti-reflective coating for outdoor applications,
like solar cell cover glass. The ®claryl system was used as starting point for this development and optimized
to reach the desired performance and durability. After formation of the xerogel, the coating was tempered.
The xerogel coating is sufficiently robust to withstand edge work and polishing steps (grinding).[x] With
respect to the optical properties, the coating was optimized for m-crystalline silicon cells. The transmission
curve of a resulting two-side coated low-iron float glass sample is displayed in Figure 7 (0 angle).

100

98

96
Transmission in [%]

94

92

90

88

86
300 500 700 900 1100 1300 1500 1700 1900 2100 2300 2500
Wavelength in [nm]

Uncoated glass DSM's anti-reflective solar glass

Figure 7. Transmission spectrum of DSM’s solar cell cover glass.

As shown in Figure 7, the transmission increase per side is about 2.5% in the regime 400 - 1100 nm. The
increase with respect to normal glass rises up to about 5% at 60. Experiments on small size solar modules
as performed by the Photovoltaik Institut (PI) in Berlin show a performance increase between 2 and 3% at
0, which is in line with the transmission increase. The performance increase rises up to about 5% at 60.

The durability of the anti-reflective cover glass was evaluated using following set of tests: abrasion
resistance test (EN 1096-2), damp-heat test (IEC 61215), humidity-freeze test (IEC 61215), thermal cycling
test (IEC 61215). During these tests, only minor changes in transmission and scratch resistance were
observed (up to 0.5% decrease in transmission per side, 400 – 1100 nm). To verify this behavior, small size
modules with coated and uncoated cover glass were subjected to the damp-heat test for 1500 h. The results
of this test are shown in Figure 8.

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5-6 May 2010 – Atlanta, USA Smart Polymer Systems 2010

3.5

3
performance increase in [%]

2.5

1.5

0.5

0
0 500 1000 1500
time in [h]

Figure 8. Damp-heat test results on small size modules.

Figure 8 clearly shows that the performance increase caused by the anti-reflective coating is constant for the
total duration of the test, which is in-line with the test results on the glass itself. Durability tests on real-size
modules gave similar results.

DSM has introduced its AR-coating technology for solar cell cover glass and other (outdoor) applications
under the brandname KhepriCoatTM. This technology is available to glass or module producers via licensing.

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Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

Conclusions

In this report, we clearly demonstrate that DSM’s single-layer ARCs can be applied both for indoor and
outdoor applications. The application of polymer nanoparticles with a silica shell provides us with a high level
of control over the balance of surface roughness and internal porosity in such coatings. During the curing or
tempering step, the polymer template is removed resulting in a coating with a high level of internal porosity.
This enables us to use higher amounts of binder than for traditional single layer ARCs which lowers the
surface roughness and increases the scratch resistance, cleanability properties and hydrolytic stability of the
coating.

The coating system was optimized for picture glass and solar cell covers. ®Claryl, DSM’s picture glass, has
excellent optical properties, is robust and easy to clean. ®Claryl is produced since 2007 and currently
commercially available in Europe and the US. DSM’s solar AR-coating results in a performance increase of a
solar module between 2 and 5%. Durability studies were performed both on the glass and on the modules
and show that the performance of the coating in the commonly accepted accelerated ageing tests is
excellent. The coating can be applied to both sides of a glass sheet in a dip-coating step. For high-speed
single-side application, DSM is developing a horizontal slot-die process. DSM’s AR coating technology for
solar cover glass and other (outdoor) applications is marketed under the brandname KhepriCoatTM and is
available to glass or module producers via licensing. Currently, we are in the process of expanding our
product portfolio towards an anti-reflective coating system suitable for plastic substrates.

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Acknowledgements

The authors thank Dorina van Haeringen, Michaela Rusu and Sven Kreisig (DSM) for their support.

References

[i] Magnesium fluoride has a refractive index of 1.35.

[ii] H. R. Moulton, Composition for Reducing the Reflection of Light, 1947, US19470739544 19470405.

[iii] D. Chen, Solar Energy Material & Solar Cells, 2001, 68, 313-336.

[iv] http://www.nissanchem-usa.com/products.php

[v] For example: (a) K. Nozawa, H. Gailhanou, L. Raison, P. Panizza, H. Ushiki, E. Sellier, J. P. Delville,
M. H. Delville, Langmuir 2005, 21, 1516-1523; (b) G. H. Bogush, M. A. Tracy, C. F. Zukoski, Journal
of Non-Crystalline Solids, 1988, 104, 95-106.

[vi] For example: (a) J.-J. Yuan, O. O. Mykhaylyk, A. J. Ryan, S. P. Armes, J. Am. Chem. Soc. 2007, 129,
1717-1723; (b) A. Khanal, Y. Inoue, M. Yada, K. Nakashima, J. Am. Chem. Soc., 2007, 129 (6), pp
1534–1535

[vii] For example: (a) K. B. Thurmond II, K. Kowalewski, K. L. Wooley, J. Am. Chem. Soc. 1996, 116,
7239-7240; (b) K. B. Thurmond II, K. Kowalewski, K. L. Wooley, J. Am. Chem. Soc. 1997, 117, 6656-
6665; H. Huang, T. Kowalewski, E. E. Remsen, R. Gertzmann, K. L. Wooley, J. Am. Chem. Soc.
1997, 117, 11653-11659; (d) H. Huang, E. Remsen, T. Kowalewski, K. L. Wooley, J. Am. Chem. Soc.
1999, 121, 3805-3806.

[viii] Particle size determined by dynamic light scattering.

[ix] See www.claryl.com

[x] Xerogel undamaged after abrasion resistance test (EN 1096-2).

Paper 4 Page 8 of 8 pages

Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

PREPARATION AND APPLICATION OF RESPONSIVE

COATINGS PREPARED ON TEXTILE FIBERS
Prof Jan Genzer & Kiran K Goli
North Carolina State University
PO Box 7905, Raleigh, NC 27685-7905, USA
Tel: +919 515 2069 Fax: +919 515 3465 email: [email protected]

BIOGRAPHICAL NOTE
Jan Genzer received his "Diploma-engineer" degree (Dipl.-Ing.) in Chemical & Materials Engineering from
the Institute of Chemical Technology in Prague in 1989. In 1991 he moved to the U.S. to pursue graduate
studies at the University of Pennsylvania under the direction of Professor Russ Composto, receiving the
Ph.D. degree in Materials Science & Engineering in 1996. After 2 post-doctoral stints with Professor Ed
Kramer first at Cornell University (1996-1997) and later at University of California at Santa Barbara (1997-
1998) Genzer joined the faculty of chemical engineering at the North Carolina State University as an
assistant professor in fall 1998. He's currently the Celanese Professor of Chemical & Biomolecular
Engineering at North Carolina State University. His honors include: Camille Dreyfus Teacher-Scholar
Award, NSF CAREER award, John H. Dillon Award of the American Physical Society, NSF Award for
Special Creativity, NCSU's Outstanding Teacher award, NCSU Alumni Outstanding Research Award and
others. He’s a Fellow of the American Physical Society. Genzer published over 130 peer-reviewed journal
articles and delivered more than 140 invited lectures. His group at North Carolina State University is actively
involved in research related to the behavior of polymers at interfaces and in confined geometries, with
particular emphasis on self-assembly and forced assembly and combinatorial methods.

ABSTRACT
Recent application of technical textiles in new generation devices (i.e., smart filters) has motivated increased
interest in developing methods for tailoring surface characteristics of fiber-forming materials. We present two
methodologies leading to fibers with tailorable and responsive chemical coatings prepared by means of
surface-initiated atom transfer radical polymerization (ATRP). In the first technique electrospun
poly(ethylene terephthalate) (PET) fibers were reacted with aminopropyltriethoxysilane (APTES), which, after
hydrolysis, provided surface-grafted hydroxyls needed for subsequent attachment of an ATRP-based
initiator. In the second approach, we modified chemically inert polypropylene (PP) fiber mats with denatured
proteins, which, after cross-linking using glutaraldehyde, were used as a substrate for attaching ATRP
initiators. “Grafting from” ATRP polymerization was employed to form functional and responsive polymer
coatings both on PET- and PP-based substrates; these included arrays of poly(N-isopropyl acrylamide)
(PNIPAAm), poly(2-hydroxyethyl methacrylate) (PHEMA) as well as chemically-modified PHEMA layers. A
few applications of those functional fibers will be outlined briefly, including, capture of metals or other
contaminants from waters, prevention of protein adsorption and attachment of metallic nanoparticles.

+++ Paper unavailable at time of print +++

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Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

RESPONSIVE COATING DESIGN ON SUBSTRATES/

PARTICLES
Dr Maxim Orlov1, D Salloum1, R Sheparovych1, V Gartstein1, F Sherman1
S Minko2, M Motornov2 & R Lupitskyy2,
1
The Procter & Gamble Company
Corporate Research, Emerging Technologies
MVIC, 11810 East Miami River Road, Cincinnati, OH 45252, USA
Tel: +1 513-627-0121 email: [email protected]
2
Clarkson University
Department of Chemistry and Biomolecular Science, Potsdam, New York 13699, USA

BIOGRAPHICAL NOTE

UNAVAILABLE

ABSTRACT

The field of adaptive/responsive surfaces began several decades ago in an attempt to understand the
relationship between bulk and surface properties of polymeric materials. The focus has shifted recently into
the design of “smart” or “intelligent” surface behavior. The ability to deliver surfaces capable of switching
from hydrophilic to hydrophobic or vice versa has been an area of interest for over a decade now. This talk
will highlight our approach in designing a responsive coating on surfaces comprised of hydrophobic and
hydrophilic moieties. The responsive coating comprised of polydimethylsiloxane and polyethyleneimine
formed on flat substrates and nanoparticles will be discussed.

+++ Paper unavailable at time of print +++

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Smart Polymer Systems 2010 5-6 May 2010 – Atlanta, USA

NEW MICROFLUIDIC ELASTOMER COMPOSITES WITH

SWITCHABLE SHAPE, STIFFNESS AND COLOR
Prof Orlin D Velev, INVISTA Professor
North Carolina State University
Department of Chemical and Biomolecular Engineering
North Carolina State University, Raleigh, USA
Tel: +1 (919) 513-4318 Fax: +1 (919) 515-3465 Email: [email protected]

BIOGRAPHICAL NOTE

Dr. Orlin Velev received M.Sc. and Ph.D. degrees from the University of Sofia,
Bulgaria, while also spending one year as a researcher in Nagayama Protein Array
Project in Japan. After graduating in 1996, Velev accepted a postdoctoral position with
the Department of Chemical Engineering, University of Delaware. He initiated an
innovative program in colloidal assembly and nanomaterials and was promoted to
research faculty in 1998. In 2001 formed his new research group in the Department of
Chemical and Biomolecular Engineering, North Carolina State University, where he
was promoted to an Associate Professor with tenure in 2006, to full professor in 2008
and to Invista named professor in 2009. He has contributed more than 110
publications, which have been cited more than 5800 times, and has presented more
than 120 invited presentations at major conferences and at many universities and
companies. Recent awards include NSF Career, Camille Dreyfus Teacher-Scholar,
Sigma Xi, Ralph E. Powe, and others.

Velev has established a record of innovative research in the area of nanostructures with electrical and
photonic functionality, biosensors and microfluidic devices. He has been the first to synthesize "inverse
opals", one of the most widely studied types of photonic materials today. He also pioneered principles for
microscopic biosensors with direct electrical detection, discovered novel types of self-assembling
supraparticles, microwires and designed new microfluidic chips. The Velev group is presently performing
among other projects research on “microfluidic materials,” an area which holds promise to advance rapidly in
the near future. Velev et al. reported a new class of microfluidic materials in the form of flexible sheets that
can be solidified by light to “memorize” specific shapes (Adv. Mater. 21, 2803, 2009). These functional
materials are based on an elastomeric matrix with embedded microfluidic channel networks filled with liquid
photocurable polymer.

ABSTRACT

This talk will present a few new classes of “smart” microfluidic materials. Microfluidic systems have recently
found wide application in bioanalysis, drug and nanoparticle synthesis. The potential of microfluidics in
making materials with extraordinary properties has only begun to be realized and explored. The microfluidic
materials that we have developed are in the form of flexible sheets that can be solidified by light or that can
repeatedly change their color on demand. These materials are based on engineered microfluidic channel
networks embedded into a matrix of thin sheets of polydimethylsiloxane (PDMS). The macroscopic
properties of the elastomer are determined by the stiffness or color of the material in the microchannels. The
microfluidic networks in the shape-locking sheets are filled with liquid photocurable polymer. The materials
formed in this way possess the unique ability to "memorize" and retain user-defined shapes upon
illumination. When the microchannel networks are deformed and exposed by UV light, the photoresist inside
the channels is solidified and subsequently acts as endoskeleton within the PDMS layer, locking in the
programmed shape. The bending and stretching moduli of the materials with solidified endoskeleton
increase drastically. The permanent locking in of the shape of the microfluidic sheets could be used in
making instant containers, creating "exoskeletons" for delicate devices, rapid prototyping and multiple other
applications. We will also present new microfluidic materials that can switch controllably their color and
transmittance in the visible and infrared range. The optical characteristics of these materials change when
colored solutions with different compositions displace each other by virtue of the laminar flow in the
microchannel networks. Such "chameleon" microfluidic sheets can find applications in smart windows and
energy management. Finally, we will discuss the potential applications of such liquid-containing polymer
composites in novel biomimetic photovoltaic cells.

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 Another Random Document on
Scribd Without Any Related Topics
where yet discovered in the county on the moory heights of Carmylie; its
newer deposits may be found on the sea-shore, beside the limeworks of
Hedderwick, and in the central hollows of Strathmore.
The most ancient beds in the county yet known belong, as unequivocally
shown by their fossils, to but the middle formation of the system. They have
been quarried for many years in the parish of Carmylie; and the quarries, as
may be supposed, are very extensive, stretching along a moory hill-side for
considerably more than a mile, and furnishing employment to from sixty to a
hundred workmen. The eye is first caught, in approaching them, as we
surmount a long, flat ridge, which shuts them out from the view of the distant
sea, by what seems a line of miniature windmills, the sails flaring with red
lead, and revolving with the lightest breeze at more than double the rate of
the sails of ordinary mills. These are employed—a lesson probably borrowed
from the Dutch—in draining the quarries, and throw up a very considerable
body of water. The line of the excavations resembles a huge drain, with nearly
perpendicular sides—a consequence of the regular and well-determined
character of the joints with which the strata are bisected. The stone itself is a
gray, close-grained fissile sandstone, of unequal hardness, and so very tough
and coherent—qualities which it seems to owe in part to the vast abundance
of mica which it contains—that it is quite possible to strike a small hammer
through some of the larger flags, without shattering the edges of the
perforation. Hence its value for various purposes which common sandstone is
too brittle and incoherent to serve. It is extensively used in the neighborhood
as a roofing slate; it is employed, too, in the making of water cisterns,
grooved and jointed as if wrought out of wood, and for the tops of lobby and
billiard tables. I have even seen snuff-boxes fashioned out of it, as a sort of
mechanical feat by the workmen,—a purpose, however, which it seems to
serve only indifferently well,—and single slabs of it cut into tolerably neat
window frames for cottages. It is most extensively used, however, merely as a
paving-stone for lobbies and lower floors, and the footways of streets. When
first deposited, and when the creatures whose organic remains it still
preserves careered over its numerous platforms, it seems to have existed as a
fine, muddy sand, formed apparently of disintegrated grauwacke rocks,
analogous in their mineral character to the similarly colored grauwacke of the
Lammermuirs, or of primary slates ground down by attrition into mud, and
mixed up with the pulverized fragments of schistose gneiss and mica schist.
I was first struck, on descending among the workmen, by the comparative
abundance of the vegetable remains. In some parts of the quarries almost
every layer of the strata is covered by carbonaceous markings—irregularly
grooved stems, branching oat into boughs at acute angles, and that at the
first glance seem the miniature semblances of the trunks of gnarled oaks and
elms, blackened in a morass, and still retaining the rough bark, chapped into
furrows: oblong, leaf-like impressions, too, and impressions of more slender
form, that resemble the narrow, parallel edged leaves of the sea-grass weed. I
observed, in particular, one large bunch of riband-like leaflets converging into
a short stem, so that the whole resembled a scourge of cords; and I would
fain have detached it from the rock, but it lay on a mouldering film of clay,
and broke up with my first attempt to remove it. A stalk of sea-grass weed
plucked up by the roots, and compressed in a herbarium, would present a
somewhat similar appearance. Among the impressions there occur irregularly
shaped patches, reticulated into the semblance of polygonal meshes. They
remind one of pieces of ill-woven lace; for the meshes are unequal in size, and
the polygons irregular. (See Plate IX., fig. 2.) When first laid open, every mesh
is filled with a carbonaceous speck; and from their supposed resemblance to
the eggs of the frog, the workmen term them puddock spawn. They are
supposed by Mr. Lyell to form the remains of the eggs of some gasteropodous
mollusc of the period. I saw one flagstone, in particular, so covered with these
reticulated patches, and so abundant, besides, in vegetable impressions of
both the irregularly furrowed and grass-weed-looking class, that I could
compare it to only the bottom of a ditch beside a hedge, matted with withered
grass, strewed with blackened twigs of the hawthorn, and mottled with
detached masses of the eggs of the frog. All the larger vegetables are
resolved into as pure a coal as the plants of the Coal Measures themselves—
the kind of data, doubtless, on which unfortunate coal speculators have often
earned disappointment at large expense. None of the vegetables themselves,
however, in the least resemble those of the carboniferous period.
The animal remains, though less numerous, are more interesting. They are
identical with those of the Den of Balruddery. I saw, in the possession of the
superintendent of the quarries, a well-preserved head of the Cephalaspis
Lyellii. The crescent-shaped horns were wanting, and the outline a little
obscure; but the eyes were better marked than in almost any other specimen
I have yet seen, and the circular star-like tubercles which roughen the large
occipital buckler, to which the creature owes its name, were tolerably well
defined. I was shown the head of another individual of the same species in
the centre of a large slab, and nothing could be more entire than the outline.
The osseous plate still retained the original brownish-white hue of the bone,
and its radiated porous texture; and the sharp crescent-shaped horns were as
sharply defined as during the lifetime of the strangely organized creature
which they had defended. In both specimens the thin angular body was
wanting. Like almost all the other fish of the Old Red Sandstone, the bony
skeleton of the Cephalaspis was external—as much so as the shell of the crab
or lobster: it presented at all points an armor of bone, as complete as if it had
been carved by the ivory-turner out of a solid block; while the internal
skeleton, which in every instance has disappeared, seems to have been
composed of cartilage. I have compared its general appearance to a saddler's
cutting-knife;—I should, perhaps, have said a saddler's cutting-knife divested
of the wooden handle—the broad, bony head representing the blade, and the
thin angular body the iron stem usually fixed in the wood. No existence of the
present creation at all resembles the Cephalaspis. Were we introduced to the
living creatures which now inhabit the oceans and rivers of Mars and Venus,
we could find nothing among them more strange in appearance, or more
unlike our living acquaintances of the friths and streams, than the
Cephalaspides of Carmylie.
I observed, besides, in the quarry, remains of the huge crustacean of
Balruddery. The plates of the Cephalaspis retain the color of the original bone;
the plates of the crustacean, on the contrary, are of a deep red tint, which
contrasts strongly with the cold gray of the stone. They remind one, both in
shape and hue, of pieces of ancient iron armor, fretted into semi-elliptical
scales, and red with rust. I saw with one of the workmen what seemed to
have been the continuous tail-flap of an individual of very considerable size. It
seemed curiously puckered where it had joined to the body, much in the
manner that a gown or Highlander's kilt is puckered where it joins to the
waistband; and the outline of the whole plate was marked by what I may
venture to term architectural elegance. The mathematician could have
described it with his ruler and compasses. The superintendent pointed out to
me another plate in a slab dressed for a piece of common pavement. It was a
regularly formed parallelogram, and had obviously composed one of the
jointed plates which had covered the creature's body. I could not so easily
assign its place to yet a third plate in the possession of the Rev. Mr. Wilson, of
Carmylie. It is colored, like the others, and like them, too, fretted into minute
scales, but the form is exactly that of a heart—not such a heart as the
anatomist would draw, but such a heart, rather, as we see at times on
valentines of the humbler order, or on the ace of hearts in a pack of cards.
Possibly enough it may have been the breastplate of this antique crustacean
of the Cornstones. The spawn of our common blue lobster is composed of
spherical black grains, of nearly the size of mustard-seed. It struck me as not
very improbable that the reticulated markings of the flagstones of Carmylie
may have been produced by the minute eggs of this fossil crustacean, covered
up by some hastily deposited layer of mingled mud and sand, and forced into
the polygonal form by pressing against each other, and by the weight from
above.
The gray fissile bed in which these organisms occur was perforated to its
base on two several occasions, and in different parts of the quarries—in one
instance, merely to ascertain its depth; in the other, in the course of
excavating a tunnel. In the one case it was found to rest on a bed of trap,
which seemed to have insinuated itself among the strata with as little
disturbance, and which lay nearly as conformably to them as the greenstone
bed of Salisbury Crags does to the alternating sandstones and clays which
both underlie and overtop it. In the other instance the excavators arrived at a
red, aluminous sandstone, veined by a purplish-colored oxide of iron. The
upper strata of the quarry are overlaid by a thick bed of grayish-red
conglomerate.
Leaving behind us the quarries of Carmylie, we descend the hill-side, and
rise in the system as we lower our level and advance upon the sea. For a very
considerable distance we find the rock covered up by a deep-red diluvial clay,
largely charged with water-worn boulders, chiefly of the older primary rocks,
and of the sandstone underneath. The soil on the higher grounds is moory
and barren—a consequence, in great part, of a hard, ferruginous pan, which
interposes like a paved floor between the diluvium and the upper mould, and
which prevents the roots of the vegetation from striking downwards into the
tenacious subsoil. From its impervious character, too, it has the effect of
rendering the surface a bog for one half the year, and an arid, sun-baked
waste for the other. It seems not improbable that the heaths which must have
grown and decayed on these heights for many ages, may have been main
agents in the formation of this pavement of barrenness. Of all plants, they are
said to contain most iron. According to Fourcroy, a full twelfth part of the
weight of oak, when dried, is owing to the presence of this almost universally
diffused metal; and the proportion in our common heaths is still larger. It
seems easy to conceive how that, as generation after generation withered on
these heights, and were slowly resolved into a little mossy dust, the minute
metallic particles which they had contained would be carried downwards by
the rains through the lighter stratum of soil, till, reaching the impermeable
platform of tenacious clay beneath, they would gradually accumulate there,
and at length bind its upper layer, as is the nature of ferruginous oxide, into a
continuous stony crust. Bog iron, and the clay ironstone, so abundant in the
Coal Measures, and so extensively employed in our iron-works, seem to have
owed their accumulation in layers and nodules to a somewhat similar process,
through the agency of vegetation. But I digress.
 The rock appears in the course of the Elliot, a few hundred yards above
the pastoral village of Arbirlot. We find it uptilted on a mass of claystone
amygdaloid, that has here raised its broad back to the surface amid the
middle shales and sandstones of the system. The stream runs over the
intruded mass; and where the latter terminates, and the sandstones lean
against it, the waters leap from the harder to the softer rock, immediately
beside the quiet parish burying-ground, in a cascade of some eight or ten
feet. From this point, for a full mile downwards, we find an almost continuous
section of the sandstone—stratum leaning against stratum—in an angle of
about thirty. The portion of the system thus exhibited must amount to many
hundred yards in vertical extent; but as I could discover no data by which to
determine regarding the space which may intervene between its lowest
stratum and the still lower beds of Carmylie, I could form no guess respecting
the thickness of the whole. In a bed of shale, about a quarter of a mile below
the village, I detected several of the vegetable impressions of Carmylie,
especially those of the grass-weed looking class, and an imperfectly preserved
organism resembling the parallelogramical scale of a Cephalaspis. The same
plants and animals seem to have existed on this high platform as on the
Carmylie platform far beneath.
A little farther down the course of the stream, and in the immediate
neighborhood of the old weather-worn tower of the Ouchterlonies, there
occurs what seems a break in the strata. The newer sandstones seem to rest
unconformably on the older sandstones which they overlie. The evening on
which I explored the course of the Elliot was drizzly and unpleasant, and the
stream swollen by a day of continuous rain, and so I could not examine so
minutely as in other circumstances I would have done, or as was necessary to
establish the fact. In since turning over the Elements of Lyell, however, I find,
in his section of Forfarshire, that a newer deposit of nearly horizontal strata of
sandstone and conglomerate lies unconformably, in the neighborhood of the
sea, on the older sandstones of the district; and the appearances observed
near the old tower mark, it is probable, one of the points of junction—a point
of junction also, if I may be so bold as venture the suggestion, of the
formation of the Holoptychius nobilissimus with the formation of the
Cephalaspis—of the quartzose conglomerate with the Cornstones. In my
hurried survey, however, I could find none of the scales or plates of the newer
ichthyolite in this upper deposit, though the numerous spherical markings of
white, with their centrical points of darker color, show that at one time the
organisms of these upper beds must have been very abundant.
 We pass to the upper formation of the system. Over the belt of mingled
gray and red there occurs in the pyramid a second deep belt of red
conglomerate and variegated sandstone, with a band of lime a-top, and over
the band a thick belt of yellow sandstone, with which the system terminates.
[AN] Thus the second pyramid consists mineralogically, like the first, of three
great divisions, or bands; its two upper belts belonging, like the three belts of
the other, to but one formation—the formation known in England as the
Quartzose Conglomerate. It is largely developed in Scotland. We find it spread
over extensive areas in Moray, Fife, Roxburgh, and Berwick shires. In England,
it is comparatively barren in fossils; the only animal organic remains yet
detected in it being a single scale of the Holoptychius found by Mr. Murchison;
and though it contains vegetable organisms in more abundance, so
imperfectly are they preserved, that little else can be ascertained regarding
them than that they were land plants, but not identical with the plants of the
Coal Measures. In Scotland, the formation is richly fossiliferous, and the
remains belong chiefly to the animal kingdom. It is richly fossiliferous, too, in
Russia, where it was discovered by Mr. Murchison, during the summer of last
year, spread over areas many thousand square miles in extent. And there, as
in Scotland, the Holoptychius seems its most characteristic fossil.
[AN] There still exists some uncertainty regarding the order in which the upper beds occur.
Mr. Duff, of Elgin, places the limestone band above the yellow sandstone; Messrs. Sedgwick
and Murchison assign it an intermediate position between the red and yellow. The respective
places of the gray and red sandstones are also disputed, and by very high authorities; Dr.
Fleming holding that the gray sandstones overlie the red, (see Cheek's Edinburgh Journal for
February, 1831,) and Mr. Lyell, that the red sandstones overlie the gray, (see Elements of
Geology, first edit., pp. 99-100.) The order adopted above consorts best with the results of
the writer's observations, which have, however, been restricted chiefly to the north country.
He assigns to the limestone band the middle place assigned to it by Messrs. Sedgwick and
Murchison, and to the gray sandstone the inferior position assigned to it by Mr. Lyell; aware,
however, that the latter deposit has not only a coping, but also a basement, of red sandstone
—the basement forming the upper member of the lower formation.

The fact seems especially worthy of remark. The organisms of some of the
newer formations differ entirely, in widely separated localities, from their
contemporary organisms, just as, in the existing state of things, the plants
and animals of Great Britain differ from the plants and animals of Lapland or
of Sierra Leone. A geologist who has acquainted himself with the belemnites,
baculites, turrilites, and sea-urchins of the Cretaceous group in England and
the north of France, would discover that he had got into an entirely new field
among the hippurites, sphærulites, and nummulites of the same formations, in
Greece, Italy, and Spain; nor, in passing the tertiary deposits, would he find
less striking dissimilarities between the gigantic, mail-clad megatherium and
huge mastodon of the Ohio and the La Plate, and the monsters, their
contemporaries, the hairy mammoth of Siberia, and the hippopotamus and
rhinoceros of England and the Continent. In the more ancient geological
periods, ere the seasons began, the case is essentially different; the
contemporary formations, when widely separated, are often very unlike in
mineralogical character, but in their fossil contents they are almost always
identical. In these earlier ages, the atmospheric temperature seems to have
depended more on the internal heat of the earth, only partially cooled down
from its original state, than on the earth's configuration or the influence of the
sun. Hence a widely spread equality of climate—a greenhouse equalization of
heat, if I may so speak; and hence, too, it would seem, a widely spread Fauna
and Flora. The greenhouses of Scotland and Sweden produce the same plants
with the greenhouses of Spain and Italy; and when the world was one vast
greenhouse, heated from below, the same families of plants, and the same
tribes of animals, seem to have ranged over spaces immensely more extended
than those geographical circles in which, in the present time, the same plants
are found indigenous, and the same animals native. The fossil remains of the
true Coal Measures are the same to the westward of the Alleghany Mountains
as in New Holland, India, Southern Africa, the neighborhood of Newcastle,
and the vicinity of Edinburgh. And I entertain little doubt that, on a similar
principle, the still more ancient organisms of the Old Red Sandstone will be
found to bear the same character all over the world.
 CHAPTER IX.
Fossils of the Upper Old Red Sandstone much more imperfectly preserved than those of the
Lower.—The Causes obvious.—Difference between the two Groups, which first strikes the
Observer, a Difference in Size.—The Holoptychius a characteristic Ichthyolite of the
Formation.—Description of its huge Scales.—Of its Occipital Bones, Fins, Teeth, and
General Appearance.—Contemporaries of the Holoptychius.—Sponge-like Bodies.—Plates
resembling those of the Sturgeon.—Teeth of various Forms, but all evidently the Teeth of
Fishes.—Limestone Band, and its probable Origin.—Fossils of the Yellow Sandstone.—The
Pterichthys of Dura Den.—Member of a Family peculiarly characteristic of the System.—No
intervening Formation between the Old Red Sandstone and the Coal Measures.—The
Holoptychius contemporary for a time with the Megalichthys.—The Columns of Tubal Cain.

The different degrees of entireness in which the geologist finds his organic
remains, depend much less on their age than on the nature of the rock in
which they occur; and as the arenaceous matrices of the Upper and Middle
Old Red Sandstones have been less favorable to the preservation of their
peculiar fossils than the calcareous and aluminous matrices of the Lower, we
frequently find the older organisms of the system fresh and unbroken, and the
more modern existing as mere fragments. A fish thrown into a heap of salt
would be found entire after the lapse of many years; a fish thrown into a heap
of sand would disappear in a mass of putrefaction in a few weeks; and only
the less destructible parts, such as the teeth, the harder bones, and perhaps a
few of the scales, would survive. Now, limestone, if I may so speak, is the
preserving salt of the geological world; and the conservative qualities of the
shales and stratified clays of the Lower Old Red Sandstone are not much
inferior to those of lime itself; while, in the Upper Old Red, we have merely
beds of consolidated sand, and these, in most instances, rendered less
conservative of organic remains than even the common sand of our shores, by
a mixture of the red oxide of iron. The older fossils, therefore, like the
mummies of Egypt, can be described well nigh as minutely as the existences
of the present creation; the newer, like the comparatively modern remains of
our churchyards, exist, except in a few rare cases, as mere fragments, and
demand powers such as those of a Cuvier or an Agassiz to restore them to
their original combinations. But cases, though few and rare, do occur in which,
through some favorable accident connected with the death or sepulture of
some individual existence of the period, its remains have been preserved
almost entire; and one such specimen serves to throw light on whole heaps of
the broken remains of its contemporaries. The single elephant, preserved in
an iceberg beside the Arctic Ocean, illustrated the peculiarities of the
numerous extinct family to which it belonged, whose bones and huge tusks
whiten the wastes of Siberia. The human body found in an Irish bog, with the
ancient sandals of the country still attached to its feet by thongs, and clothed
in a garment of coarse hair, gave evidence that bore generally on the degree
of civilization attained by the inhabitants of an entire district in a remote age.
In all such instances, the character and appearance of the individual bear on
those of the tribe. In attempting to describe the organisms of the Lower Old
Red Sandstone, where the fossils lie as thickly in some localities as herrings on
our coasts in the fishing season, I felt as if I had whole tribes before me. In
describing the fossils of the Upper Old Red Sandstone, I shall have to draw
mostly from single specimens. But the evidence may be equally sound so far
as it goes.
The difference between the superior and inferior groups of the system
which first strikes an observer, is a difference in the size of the fossils of which
these groups are composed. The characteristic organisms of the Upper Old
Red Sandstone are of much greater bulk than those of the Lower, which seem
to have been characterized by a mediocrity of size throughout the entire
extent of the formation. The largest ichthyolites of the group do not seem to
have much exceeded two feet or two feet and a half in length; its smaller
average from an inch to three inches. A jaw in the possession of Dr. Traill—
that of an Orkney species of Platygnathus, and by much the largest in his
collection—does not exceed in bulk the jaw of a full-grown coal-fish or cod;
his largest Coccosteus must have been a considerably smaller fish than an
ordinary-sized turbot; the largest ichthyolite found by the writer was a
Diplopterus, of, however, smaller dimensions than the ichthyolite to which the
jaw in the possession of Dr. Traill must have belonged; the remains of another
Diplopterus from Gamrie, the most massy yet discovered in that locality, seem
to have composed the upper parts of an individual about two feet and a half
in length. The fish, in short, of the lower ocean of the Old Red Sandstone—
and I can speak of it throughout an area which comprises Orkney and
Inverness, Cromarty, and Gamrie, and which must have included about ten
thousand square miles—ranged in size between the stickleback and the cod;
whereas some of the fish of its upper ocean were covered by scales as large
as oyster-shells, and armed with teeth that rivalled in bulk those of the
crocodile. They must have been fish on an immensely larger scale than those
with which the system began. There have been scales of the Holoptychius
found in Clashbennie which measure three inches in length by two and a half
in breadth, and a full eighth part of an inch in thickness. There occur occipital
plates of fishes in the same formation in Moray, a full foot in length by half a
foot in breadth. The fragment of a tooth still attached to a piece of the jaw,
found in the sandstone cliffs that overhang the Findhorn, measures an inch in
diameter at the base. A second tooth of the same formation, of a still larger
size, disinterred by Mr. Patrick Duff from out the conglomerates of the Scat-
Craig, near Elgin, and now in his possession, measures two inches in length by
rather more than an inch in diameter. (See Plate X., fig. 4.) There occasionally
turn up in the sandstones of Perthshire ichthyodorulites that in bulk and
appearance resemble the teeth of a harrow rounded at the edges by a few
months' wear, and which must have been attached to fins not inferior in
general bulk to the dorsal fin of an ordinary-sized porpoise. In short, the
remains of a Patagonian burying-ground would scarcely contrast more
strongly with the remains of that battle-field described by Addison, in which
the pygmies were annihilated by the cranes, than the organisms of the upper
formation of the Old Red Sandstone contrast with those of the lower.[AO]
[AO] I have permitted this paragraph to remain as originally written, though the
comparatively recent discovery of a gigantic Holoptychius (?) in the Lower Old Red Sandstone
of Thurso, by Mr. Robert Dick of that place, (see introductory note,) bears shrewdly against its
general line of statement. But it will, at least, serve to show how large an amount of negative
evidence may be dissipated by a single positive fact, and to inculcate on the geologist the
necessity of cautious induction. An individual Holoptychius of Thurso must have been at least
thrice the size of the Holoptychius of the Upper Old Red formation, as exhibited in the
specimen of Mr. Noble, of St. Madoes.

PLATE X.
 Of this upper formation the most characteristic and most abundant
ichthyolite, as has been already said, is the Holoptychius. The large scales and
plates, and the huge teeth, belong to this genus. It was first introduced to the
notice of geologists in a paper read before the Wernerian Society in May,
1830, by Professor Fleming, and published by him in the February of the
following year, in Cheek's Edinburgh Journal. Only detached scales and the
fragment of a tooth had as yet been found; and these he minutely described
as such, without venturing to hazard a conjecture regarding the character or
family of the animal to which they had belonged. They were submitted some
years after to Agassiz, by whom they were referred, though not without
considerable hesitation, to the genus Gyrolepis; and the doubts of both
naturalists serve to show how very uncertain a guide mere analogy proves to
even men of the first order, when brought to bear on organisms of so strange
a type as the ichthyolites of the Old Red Sandstone. At this stage, however, an
almost entire specimen of the creature was discovered in the sandstones of
Clashbennie, by the Rev. James Noble, of St. Madoes, a gentleman who, by
devoting his leisure hours to Geology, has extended the knowledge of this
upper formation, and whose name has been attached by Agassiz to its
characteristic fossil, now designated the Holoptychius nobilissimus. His
specimen at once decided that the creature had been no Gyrolepis, but the
representative of a new genus not less strangely organized, and quite as
unlike the existences of the present times as any existence of all the past. So
marked are the peculiarities of the Holoptychius, that they strike the
commonest observer.
The scales are very characteristic. They are massy elliptical plates, scarcely
less bulky in proportion to their extent of surface than our smaller copper
coin, composed internally of bone, and externally of enamel, and presenting
on the one side a porous structure, and on the other, when well preserved, a
bright, glossy surface. The upper, or glossy side, is the more characteristic of
the two. I have placed one of them before me. Imagine an elliptical ivory
counter, an inch and a half in length by an inch in breadth, and nearly an
eighth part of an inch in thickness, the larger diameter forming a line which, if
extended, would pass longitudinally from head to tail through the animal
which the scale covered. On the upper or anterior margin of this elliptical
counter, imagine a smooth selvedge or border three eighth parts of an inch in
breadth. Beneath this border there is an inner border of detached tubercles,
and beneath the tubercles large undulating furrows, which stretch
longitudinally towards the lower end of the ellipsis. Some of these waved
furrows run unbroken and separate to the bottom, some merge into their
neighboring furrows at acute angles, some branch out and again unite, like
streams which enclose islands, and some break into chains of detached
tubercles. (See Plate X., fig. 3.) No two scales exactly resemble one another in
the minuter peculiarities of their sculpture, if I may so speak, just as no two
pieces of lake or sea may be roughened after exactly the same pattern during
a gale; and yet in general appearance they are all wonderfully alike. Their
style of sculpture is the same—a style which has sometimes reminded me of
the Runic knots of our ancient north country obelisks. Such was the scale of
the creature. The head, which was small, compared with the size of the body,
was covered with bony plates, roughened after a pattern somewhat different
from that of the scales, being tubercled rather than ridged; but the tubercles
present a confluent appearance, just as chains of hills may be described as
confluent, the base of one hill running into the base of another. The
operculum seems to have been covered by one entire plate—a peculiarity
observable, as has been remarked, among some of the ichthyolites of the
Lower Old Red Sandstone, such as the Diplopterus, Dipterus, and Osteolepis.
And it, too, has its fields of tubercles, and its smooth marginal selvedge, or
border, on which the lower edges of the upper occipital plates seem to have
rested, just as, in the roof of a slated building, part of the lower tier of slates
is overtopped and covered by the tier above. The scales towards the tail
suddenly diminish at the ventral fins to about one fourth the size of those on
the upper part of the body; the fins themselves are covered at their bases,
which seem to have been thick and fleshy like the base of the pectoral fin in
the cod or haddock, with scales still more minute; and from the scaly base the
rays diverge like the radii of a circle, and terminate in a semicircular outline.
The ventrals are placed nearer the tail, says Agassiz, than in any other ganoid
fish. (See Plate X., fig. 2.)
But no such description can communicate an adequate conception to the
reader of the strikingly picturesque appearance of the Holoptychius, as shown
in Mr. Noble's splendid specimen. There is a general massiveness about the
separate portions of the creature, that imparts ideas of the gigantic,
independently of its bulk as a whole; just as a building of moderate size, when
composed of very ponderous stones, has a more imposing effect than much
larger buildings in which the stones are smaller. The body measures a foot
across, by two feet and a half in length, exclusive of the tail, which is wanting;
but the armor in which it is cased might have served a crocodile or alligator of
five times the size. It lies on its back, on a mass of red sandstone; and the
scales and plates still retain their bony color, slightly tinged with red, like the
skeleton of some animal that had lain for years in a bed of ferruginous marl or
clay. The outline of the occipital portion of the specimen forms a low Gothic
arch, of an intermediate style between the round Saxon and the pointed
Norman. This arch is filled by two angular, pane-like plates, separated by a
vertical line, that represents, if I may use the figure, the-dividing astragal of
the window; and the under jaw, with its two sweeping arcs, or branches,
constitutes the frame. All of the head which appears is that under portion of it
which extends from the upper part of the belly to the snout. The belly itself is
thickly covered by huge carved scales, that, from their massiveness and
regular arrangement, remind one of the flags of an ancient stone roof. The
carving varies, as they descend towards the tail, being more in the ridged
style below, and more in the tubercled style above. So fairly does the creature
lie on its back, that the ventral fins have fallen equally, one on each side, and,
from their semicircular form, remind one of the two pouch holes in a lady's
apron, with their laced flaps. The entire outline of the fossil is that of an
elongated ellipsis, or rather spindle, a little drawn out towards the caudal
extremity. The places of all the fins are not indicated, but, as shown by other
specimens, they seem to have been crowded together towards the lower
extremity, like those of the Glyptolepis, an ichthyolite which, in more than one
respect, the Holoptychius must have resembled, and which, from this
peculiarity, presents a brush-like appearance—the head and shoulders
representing the handle, and the large and thickly clustered fins the spreading
bristles.[AP]
[AP] There are now six species of Holoptychius enumerated—H. Andersoni, H. Flemingii,
H. giganteus, H. Murchisoni, H. nobilissimus, and H. Omaliusii.

Some of the occipital bones of the Holoptychius are very curious and very
puzzling. There are pieces rounded at one of the ends, somewhat in the
manner of the neck joints of our better known quadrupeds, and which have
been mistaken for vertebræ; but which present evidently, at the apparent
joint, the enamel peculiar to the outer surface of all the plates and scales of
the creature, and which belonged, it is probable, to the snout. There are
saddle-shaped bones, too, which have been regarded as the central occipital
plates of a new species of Coccosteus, but whose style of confluent tubercle
belongs evidently to the Holoptychius. The jaws are exceedingly curious. They
are composed of as solid bone as we usually find in the jaws of mammalia;
and the outer surface, which is covered in animals of commoner structure with
portions of the facial integuments, we find polished and japanned, and fretted
into tubercles. The jaws of the creature, like those of the Osteolepis of the
lower formation, were naked jaws; it is, indeed, more than probable that all its
real bones were so, and that the internal skeleton was cartilaginous. A row of
thickly-set, pointed teeth ran along the japanned edges of the mouth—what,
in fish of the ordinary construction, would be the lips; and inside this row
there was a second and widely-set row of at least twenty times the bulk of the
other, and which stood up over and beyond it, like spires in a city over the
rows of lower buildings in front. A nearly similar disposition of teeth seems
also to have characterized the Holoptychius of the Coal Measures, but the
contrast in size was somewhat less marked. One of the most singularly-formed
bones of the formation will be found, I doubt not, when perfect specimens of
the upper part of the creature shall be procured, to have belonged to the
Holoptychius. It is a huge ichthyodorulite, formed, box-like, of four nearly
rectangular planes, terminating in a point, and ornamented on two of the
sides by what, in a work of art, the reader would at once term a species of
Chinese fretwork. Along the centre there runs a line of lozenges, slightly
truncated where they unite, just as, in plants that exhibit the cellular texture,
the lozenge-shaped cells may be said to be truncated. At the sides of the
central line, there run lines of half lozenges, which occupy the space to the
edges. Each lozenge is marked by lines parallel to the lines which describe it,
somewhat in the manner of the plates of the tortoise. The centre of each is
thickly tubercled; and what seems to have been the anterior plane of the
ichthyodorulite is thickly tubercled also, both in the style of the occipital plates
and jaws of the Holoptychius. This curious bone, which seems to have been
either hollow inside, or, what is more probable, filled with cartilage, measures,
in some of the larger specimens, an inch and a half across at the base on its
broader planes, and rather more than half an inch on its two narrower ones.
[AQ]

[AQ] This bone has been since assigned by Agassiz to a new genus, of which no other
fragments have yet been found, but which has been named provisionally Placothorax
paradoxus.

Geologists have still a great deal to learn regarding the contemporaries of

the Holoptychius nobilissimus. The lower portion of that upper formation to
which it more especially belongs—the portion represented in our second
pyramid by the conglomerate and sandstone bar—though unfavorable to the
preservation of animal remains, represents assuredly no barren period. It has
been found to contain bodies apparently organic, that vary in shape like the
sponges of our existing seas, which in general appearance they somewhat
resemble, but whose class, and even kingdom, are yet to fix.[AR]
[AR] These organisms, if in reality such, are at once very curious and very puzzling. They
occur in some localities in great abundance. A piece of Clashbennie flagstone, somewhat more
than two feet in length, by fifteen inches in breadth, kindly sent me for examination by the
Rev. Mr. Noble, of St. Madoes, bears no fewer than twelve of them on its upper surface, and
presents the appearance of a piece of rude sculpture, not very unlike those we sometimes see
in country churchyards, on the tombstones of the times of the Revolution. All the twelve vary
in appearance. Some of them are of a pear shape—some are irregularly oval—some resemble
short cuts of the bole of a tree—some are spread out like ancient manuscripts, partially
unrolled—one of the number seems a huge, though not over neatly formed acorn, an
apprentice mason's first attempt—the others are of a shape so irregular as to set comparison
and description at defiance. They almost all agree, however, when cut transversely, in
presenting flat, elliptical arcs as their sectional lines—in having an upper surface
comparatively smooth, and an under surface nearly parallel to it, thickly corrugated—and in
being all coated with a greasy, shining clay, of a deeper red than the surrounding stone. I was
perhaps rather more confident of their organic character after I had examined a few merely
detached specimens, than now that I have seen a dozen of them together. It seems at least a
circumstance to awaken doubt, that though they occur in various positions on the slab—some
extending across it, some lying diagonally, some running lengthwise—the corrugations of their
under surfaces should run lengthwise in all—furrowing them in every possible angle, and
giving evidence, not apparently to the influences of an organic law, internal to each, but of
the operation of some external cause, acting on the whole in one direction.

It contains, besides, in considerable abundance, though in a state of very

imperfect preservation, scales that differ from those of the Holoptychius, and
from one another. One of these, figured and described by Professor Fleming in
Cheek's Edinburgh Journal, bearing on its upper surface a mark like a St.
Andrew's cross, surrounded by tubercled dottings, and closely resembling in
external appearance some of the scales of the common sturgeon, "may be
referred with some probability," says the Professor, "to an extinct species of
the genus Accipenser."[AS]
[AS] May I crave the attention of the reader to a brief statement of fact? I have said that
Professor Fleming, when he minutely described the scales of the Holoptychius, hazarded no
conjecture regarding the generic character of the creature to which they had belonged; he
merely introduced them to the notice of the public as the scales of some "vertebrated animal,
probably those of a fish." I now state that he described the scales of a contemporary
ichthyolite as bearing, in external appearance, a "close resemblance to some of the scales of
the common sturgeon." It has been asserted, that it was the scales of the Holoptychius which
he thus described, "referring them to an extinct species of the genus Accipenser;" and the
assertion has been extensively credited, and by some of our highest geological authorities.
Agassiz himself, evidently in the belief that the professor had fallen into a palpable error,
deems it necessary to prove that the Holoptychius could have borne "no relation to the
Accipenser or sturgeon." Mr. Murchison, in his Silurian System, refers also to the supposed
mistake. The person with whom the misunderstanding seems to have originated is the Rev.
Dr. Anderson, of Newburgh. About a twelvemonth after the discovery of Professor Fleming in
the sandstones of Drumdryan, a similar discovery was made in the sandstones of Clashbennie
by a geologist of Perth, who, on submitting his new found scales to Dr. Anderson, concluded,
with the Doctor, that they could be no other than oyster shells; though eventually, on
becoming acquainted with the decision of Professor Fleming regarding them, both gentlemen
were content to alter their opinion, and to regard them as scales. The Professor, in his paper
on the Old Red Sandstone in Cheek's Journal, referred incidentally to the oyster shells of
Clashbennie—a somewhat delicate subject of allusion; and in Dr. Anderson's paper on the
same formation, which appeared about seven years after, in the New Journal of Professor
Jameson, the geological world was told, for the first time, that Professor Fleming had
described a scale of Clashbennie similar to those of Drumdryan, (i. e., those of the
Holoptychius,) as bearing a "close resemblance to some of the scales on the common
sturgeon," and as probably referable to some "extinct species of the genus Accipenser." Now,
Professor Fleming, instead of stating that the scales were at all similar, had stated very
pointedly that they were entirely different; and not only had he described them as different,
but he had also figured them as different, and had placed the figures side by side, that the
difference might be the better seen. To the paper of the Professor, which contained this
statement, and to which these figures were attached, Dr. Anderson referred, as "read before
the Wernerian Society;"—he quoted from it in the Professor's words—he drew some of the
more important facts of his own paper from it—in his late Essay on the Geology of Fife he has
availed himself of it still more largely, though with no acknowledgment; it has constituted, in
short, by far the most valuable of all his discoveries in connection with the Old Red
Sandstone, and apparently the most minutely examined; and yet, so completely did he fail to
detect Professor Fleming's carefully drawn distinction between the scales of the Holoptychius
and those of its contemporary, that when Agassiz, misled apparently by the Doctor's own
statement, had set himself to show that the scaly giant of the formation could have been no
sturgeon, the Doctor had the passage in which the naturalist established the fact transferred
into a Fife newspaper, with, of course, the laudable intention of preventing the Fife public
from falling into the absurd mistake of Professor Fleming. There seems to be something rather
inexplicable in all this; but there can be little doubt Dr. Anderson could satisfactorily explain
the whole matter without once referring to the oyster shells of Clashbennie. It is improbable
that he could have wished or intended to injure the reputation of a gentleman to whose
freely-imparted instructions he is indebted for much the greater portion of his geological skill
—whose remarks, written and spoken, he has so extensively appropriated in his several
papers and essays—and whose character is known far beyond the limits of his country, for
untiring research, philosophic discrimination, and all the qualities which constitute a naturalist
of the highest order. Dr. Johnston, of Berwick, in his History of British Zoöphytes, (a work of
an eminently scientific character,) justly "ascribes to the labors and writings" of Professor
Fleming "no small share in diffusing that taste for Natural History which is now abroad." And
as an interesting corroboration of the fact, I may state, that Dr. Malcolmson, of Madras, lately
found an elegant Italian translation of Fleming's Philosophy of Zoölogy, high in repute among
the elite of Rome. Lest it should be supposed I do Dr. Anderson injustice in these remarks, I
subjoin the grounds of them in the following extracts from professor Fleming's paper in
Cheek's Journal, and from the paper in Jameson's New Edinburgh Journal, in which the Doctor
purports to give a digest of the former, without once referring, however, to the periodical in
which it is to be found:—
"In the summer of 1827," says Dr. Fleming, "I obtained from Drumdryan quarry, to the
south of Cupar, situate in the higher strata of yellow sandstone, certain organisms, which I
readily referred to the scales of vertebrated animals, probably those of a fish. The largest (see
Plate II., fig. 1, 'figure of a scale of the Holoptychius') was one inch and one tenth in length,
about one inch and two tenths in breadth, and not exceeding the fiftieth of an inch in
thickness. The part which, when in its natural position, had been imbedded in the cuticle, is
comparatively smooth, exhibiting, however, in a very distinct manner, the semicircularly
parallel layers of growth with obsolete diverging striæ, giving to the surface, when under a
lens, a reticulated aspect. The part naturally exposed is marked with longitudinal, waved,
rounded, anastomosing ridges, which are smooth and glossy. The whole of the inside of the
scale is smooth, though exhibiting with tolerable distinctness the layers of growth. The form
and structure of the object indicated plainly enough that it had been a scale, a conclusion
confirmed by the detection of the phosphate of lime in its composition. At this period I
inserted a short notice of the occurrence of these scales in our provincial newspaper, the Fife
Herald, for the purpose of attracting the attention of the workmen and others in the
neighborhood, in order to secure the preservation of any other specimens which might occur.
"Nearly a year after these scales had been discovered, not only in the upper, but even in
some of the lower beds of the Yellow Sandstone, I was informed that oyster shells had been
found in a quarry in the Old Red Sandstone at Clashbennie, near Errol, in Perthshire, and that
specimens were in the possession of a gentleman in Perth. Interested in the intelligence, I lost
no time in visiting Perth, and was gratified to find that the supposed oyster shells were, in
fact, similar to those which I had ascertained to occur in a higher part of the series. The
scales were, however, of a larger size, some of them exceeding three inches in length, and
one eighth of an inch in thickness. Upon my visit to the quarry, I found the scales, as in the
Yellow Sandstone, most abundant in those parts of the rock which exhibited a brecciated
aspect. Many patches a foot in length, full of scales, have occurred; but as yet no entire
impression of a fish has been obtained.
"Another scale, differing from those already noticed, (see Plate II., fig. 3, 'figure of an
oblong tubercle plate traversed diagonally by lines, which, bisecting one another a little above
the centre, resembles a St. Andrew's cross, and marked on the edges by faintly radiating
lines,') is about an inch and a quarter in length, and an inch in breadth. In external
appearance it bears a very close resemblance to some of the scales on the common sturgeon,
and may, with some probability, be referred to an extinct species of the genus Accipenser."—
(Cheek's Edinburgh Journal, Feb. 1831, p. 85.)
"Dr. Fleming, in 1830," says Dr. Anderson, "read before the Wernerian Society a notice 'on
the occurrence of scales of vertebrated animals in the Old Red Sandstone of Fifeshire.' These
organisms, as described by him, occurred in the Yellow Sandstone of Drumdryan and the Gray
Sandstone of Parkhill. From the former locality scales of a fish were obtained.... The same
paper (Professor Fleming's) contains a notice of similar scales in the Old Red Sandstone of
Clashbennie, near Errol, in Perthshire, one of which is described as bearing 'a very close
resemblance to some of the scales on the common sturgeon, and may with some probability
be referred to an extinct species of the genus Accipenser.'"—(Professor Jameson's Edin. New
Phil. Journal, Oct. 1837, p. 138.)

The deposit, too, abounds in teeth, various enough in their forms to

indicate a corresponding variety of families and genera among the ichthyolites
to which they belonged. Some are nearly straight, like those of the
Holoptychius of the Coal Measures; some are bent, like the beak of a hawk or
eagle, into a hook-form; some incline first in one direction, and then in the
opposite one, like nails that have been drawn out of a board by the carpenter
at two several wrenches, and bent in opposite angles at each wrench; some
are bulky and squat, some long and slender; and in almost all the varieties,
whether curved or straight, squat or slim, the base is elegantly striated like
the flutings of the column. In the splendid specimen found in the sandstones
of the Findhorn, the tooth is still attached to a portion of the jaw, and shows,
from the nature of the attachment, that the creature to which it belonged
must have been a true fish, not a reptile. The same peculiarity is observable in
two other very fine specimens in the collection of Mr. Patrick Duff, of Elgin.
Both in saurians and in toothed cetaceæ, such as the porpoise, the teeth are
inserted in sockets. In the ichthyolites of this formation, so far as these are
illustrated by its better specimens, the teeth, as in existing fish, are merely
placed flat upon the jaw, or in shallow pits, which seem almost to indicate that
the contrivance of sockets might be afterwards resorted to. Immediately over
the sandstone and conglomerate belt in which these organisms occur, there
rests, as has been said, a band of limestone, and over the limestone a thick
bed of yellow sandstone, in which the system terminates, and which is
overlaid in turn by the lower beds of the carboniferous group.
The limestone band is unfossiliferous, and resembling, in mineralogical
character, the Cornstones of England and Wales, it has been described as the
Cornstone of Scotland; but the fact merely furnishes one illustration of many,
of the inadequacy of a mineralogical nomenclature for the purposes of the
geologist. In the neighborhood of Cromarty the lower formation abounds in
beds of nodular limestone, identical in appearance with the Cornstone;—in
England similar beds occur so abundantly in the middle formation, that it
derives its name from them;—in Fife they occur in the upper formation
exclusively. Thus the formation of the Coccosteus and Dipterus is a cornstone
formation in the first locality; that of the Cephalaspis and the gigantic lobster
in the second; that of the Holoptychius nobilissimus in the third. We have but
to vary our field of observation to find all the formations of the system
Cornstone formations in turn. The limestone band of the upper member
presents exactly similar appearances in Moray as in Fife. It is in both of a
yellowish green or gray color, and a concretionary structure, consisting of
softer and harder portions, that yield so unequally to the weather, as to
exhibit in exposed cliffs and boulders a brecciated aspect, as if it had been a
mechanical, not a chemical deposit; though its origin must unquestionably
have been chemical. It contains minute crystals of galena, and abounds in
masses of a cherty, siliceous substance that strikes fire with steel, and which,
from the manner in which they are incorporated with the rock, show that they
must have been formed along with it. From this circumstance, and from the
general resemblance it bears to the deposits of the thermal waters of volcanic
districts which precipitate siliceous mixed with calcareous matter, it has been
suggested, and by no mean authority, that it must have derived its origin from
hot springs. The bed is several yards in thickness; and as it appears both in
Moray and in Fife, in localities at least a hundred and twenty miles apart, it
must have been formed, if formed at all, in this manner, at a period when the
volcanic agencies were in a state of activity at no great distance from the
surface.
The upper belt of yellow stone, the terminal layer of the pyramid, is
fossiliferous both in Moray and Fife—more richly so in the latter county than
even the conglomerate belt that underlies it, and its organisms are better
preserved. It was in this upper layer, in Drumdryan quarry, to the south of
Cupar, that Professor Fleming found the first-discovered scales of the
Holoptychius. At Dura Den, in the same neighborhood, a singularly rich
deposit of animal remains was laid open a few years ago, by some workmen,
when employed in excavating a water-course for a mill. The organisms lay
crowded together, a single slab containing no fewer than thirty specimens,
and all in a singularly perfect state of preservation. The whole space
excavated did not exceed forty square yards in extent, and yet in these forty
yards there were found several genera of fishes new to Geology, and not yet
figured nor described—a conclusive proof in itself that we have still very much
to learn regarding the fossils of the Old Red Sandstone. By much the greater
portion of the remains disinterred on this occasion were preserved by a lady in
the neighborhood; and the news of the discovery spreading over the district,
the Rev. Dr. Anderson, of Newburgh, was fortunately led to discover them
anew in her possession. The most abundant organism of the group was a
variety of Pterichthys—the sixth species of this very curious genus now
discovered in the Old Red Sandstones of Scotland; and as the Doctor had
been lucky enough to find out for himself, some years before, that the scales
of the Holoptychius were oyster shells, he now ascertained, with quite as little
assistance from without, that the Pterichthys must have been surely a huge
beetle. As a beetle, therefore, he figured and described it in the pages of a
Glasgow topographical publication—Fife Illustrated. True, the characteristic
elytra were wanting, and some six or seven tubercle plates substituted in their
room; nor could the artist, with all his skill, supply the creature with more than
two legs; but ingenuity did much for it, notwithstanding; and by lengthening
the snout, insect-like, into a point—by projecting an eye, insect-like, on what
had mysteriously grown into a head—by rounding the body, insect-like, until it
exactly resembled that of the large "twilight shard"—by exaggerating the
tubercles seen in profile on the paddles until they stretched out, insect-like,
into bristles—and by carefully sinking the tail, which was not insect-like, and
for which no possible use could be discovered at the time—the Doctor
succeeded in making the Pterichthys of Dura Den a very respectable beetle
indeed. In a later publication, an Essay on the Geology of Fifeshire, which
appeared in September last in the Quarterly Journal of Agriculture, he states,
after referring to his former description, that among the higher geological
authorities some were disposed to regard the creature as an extinct
crustaceous animal, and some as belonging to a tribe closely allied to the
Chelonia. Agassiz, as the writer of these chapters ventured some months ago
to predict, has since pronounced it a fish—a Pterichthys specifically different
from the five varieties of this ichthyolite which occur in the lower formation of
the system, but generically the same. I very lately enjoyed the pleasure of
examining the bona fide ichthyolite itself—one of the specimens of Dura Den,
and apparently one of the more entire—in the collection of Professor Fleming.
Its character as a Pterichthys I found very obvious; but neither the Professor
nor myself was ingenious enough to discover in it any trace of the beetle of
Dr. Anderson.[AT]
[AT] This interesting ichthyolite has since been regarded by Agassiz as the representative
of a distinct genus, to which he gives the name Pamphractus. As exhibited in his restoration,
however, it seems to differ little, if at all, (if I may venture the suggestion,) from a Pterichthys
viewed on the upper side. In Agassiz's beautiful restoration of Pterichthys, and his
accompanying prints of the fossils illustrative of that genus, it is, with but one doubtful
exception, the under side of the animal that is presented; and hence a striking difference
apparent between his representations of the two genera, which would scarce obtain had the
upper, not the under side of Pterichthys been exhibited. In verification of this remark, let the
reader who has access to the Monographic Poissons Fossiles compare the restoration of
Pamphractus (Old Red, Tab. VI., fig. 2) with the upper side of Pterichthys, as figured in this
volume, Plate I., fig. 1, making, of course, the due allowance for a difference of species.

Is it not interesting to find this very curious genus in both the lowest and
highest fossiliferous beds of the system, and constituting, like the Trilobite
genus of the Silurian group, its most characteristic organism? The Trilobite has
a wide geological range, extending from the upper Cambrian rocks to the
upper Coal Measures. But though the range of the genus is wide, that of every
individual species of which it consists is very limited. The Trilobites of the
upper Coal Measures differ from those of the Mountain Limestone; these
again, with but one exception, from the Trilobites of the upper Silurian strata;
these yet again from the Trilobites of the underlying middle beds; and these
from the Trilobites that occur in the base of the system. Like the coins and
medals of the antiquary, each represents its own limited period; and the whole
taken together yield a consecutive record. But while we find them merely
scattered over the later formations in which they occur, and that very
sparingly, in the Silurian System we find them congregated in such vast
crowds, that their remains enter largely into the composition of many of the
rocks which compose it. The Trilobite is the distinguishing organism of the
group, marrying, if I may so express myself, its upper and lower beds; and
what the Trilobite is to the Silurian formations, the Pterichthys seems to be to
the formations of the Old Red Sandstone; with this difference, that, so far as
is yet known, it is restricted to this system alone, occurring in neither the
Silurian System below, nor in the Coal Measures above.
I am but imperfectly acquainted with the localities in which the upper beds
of the Old Red Sandstone underlie the lower beds of the Coal Measures, or
where any gradation of character appears. The upper yellow sandstone belt is
extensively developed in Moray, but it contains no trace of carbonaceous
matter in even its higher strata, and no other remains than those of the
Holoptychius and its contemporaries. The system in the north of Scotland
differs as much from the carboniferous group in its upper as in its lower rocks;
and a similar difference has been remarked in Fife, where the groups appear
in contact a few miles to the west of St. Andrew's. In England, in repeated
instances, the junction, as shown by Mr. Murchison, in singularly instructive
sections, is well marked, the carboniferous limestones resting conformably on
the Upper Old Red Sandstone. No other system interposed between them.
There is a Rabbinical tradition that the sons of Tubal-Cain, taught by a
prophet of the coming deluge, and unwilling that their father's arts should be
lost in it to posterity, erected two obelisks of brass, on which they inscribed a
record of his discoveries, and that thus the learning of the family survived the
cataclysm. The flood subsided, and the obelisks, sculptured from pinnacle to
base, were found fast fixed in the rock. Now, the twin pyramids of the Old Red
Sandstone, with their party-colored bars, and their thickly crowded
inscriptions, belong to a period immensely more remote than that of the
columns of the antediluvians, and they bear a more certain record. I have,
perhaps, dwelt too long on their various compartments; but the Artist by
whom they have been erected, and who has preserved in them so wonderful a
chronicle of his earlier works, has willed surely that they should be read, and I
have perused but a small portion of the whole. Years must pass ere the entire
record can be deciphered; but, of all its curiously inscribed sentences, the
result will prove the same—they will all be found to testify of the Infinite Mind.
 CHAPTER X.
Speculations in the Old Red Sandstone, and their Character.—George, first Earl of Cromarty.—
His Sagacity as a Naturalist at fault in one Instance.—Sets himself to dig for Coal in the
Lower Old lied Sandstone.—Discovers a fine Artesian Well.—Value of Geological Knowledge
in an economic View.—Scarce a Secondary Formation in the Kingdom in which Coal has
not been sought for.—Mineral Springs of the Lower Old Red Sandstone.—Strathpeffer.—Its
Peculiarities whence derived.—Chalybeate Springs of Easter Ross and the Black Isle.—
Petrifying Springs.—Building-Stone and Lime of the Old Red Sandstone.—Its various Soils.

There has been much money lost, and a good deal won, in speculations
connected with the Old Red Sandstone. The speculations in which money has
been won have consorted, if I may so speak, with the character of the system,
and those in which money has been lost have not. Instead, however, of
producing a formal chapter on the economic uses to which its various deposits
have been applied, or the unfortunate undertakings which an acquaintance
with its geology would have prevented, I shall throw together, as they occur to
me, a few simple facts illustrative of both.
George, first Earl of Cromarty, seems, like his namesake and contemporary,
the too celebrated Sir George M'Kenzie, of Roseavoch, to have been a man of
an eminently active and inquiring mind. He found leisure, in the course of a
very busy life, to write several historical dissertations of great research, and a
very elaborate Synopsis Apocalyptica. He is the author, too, of an exceedingly
curious letter on the "Second Sight," addressed to the philosophic Boyle,
which contains a large amount of amusing and extraordinary fact; and his
description of the formation of a peat-moss in the central Highlands of Ross-
shire has been quoted by almost every naturalist who, since the days of the
sagacious, nobleman, has written on the formation of peat. His life was
extended to extreme old age; and as his literary ardor remained undiminished
till the last, some of his writings were produced at a period when most other
men are sunk in the incurious indifferency and languor of old age. And among
these later productions are his remarks on peat. He relates that, when a very
young man, he had marked, in passing on a journey through the central
Highlands of Ross-shire, a wood of very ancient trees, doddered and moss-
grown, and evidently passing into a state of death through the last stages of
decay. He had been led by business into the same district many years after,
when in middle life, and found that the wood had entirely disappeared, and
that the heathy hollow which it had covered was now occupied by a green,
stagnant morass, unvaried in its tame and level extent by either bush or tree.
In his old age he again visited the locality, and saw the green surface
roughened with dingy-colored hollows, and several Highlanders engaged in it
in cutting peat in a stratum several feet in depth. What he had once seen an
aged forest had now become an extensive peat-moss.
Some time towards the close of the seventeenth century he purchased the
lands of Cromarty, where his turn for minute observation seems to have
anticipated—little, however, to his own profit—some of the later geological
discoveries. There is a deep, wooded ravine in the neighborhood of the town,
traversed by a small stream, which has laid bare, for the space of about forty
yards in the opening of the hollow, the gray sandstone and stratified clays of
the inferior fish bed. The locality is rather poor in ichthyolites, though I have
found in it, after minute search, a few scales of the Osteolepis, and on one
occasion one of the better marked plates of the Coccosteus; but in the
vegetable impressions peculiar to the formation it is very abundant. These are
invariably carbonaceous, and are not unfrequently associated with minute
patches of bitumen, which, in the harder specimens, present a coal-like
appearance; and the vegetable impressions and the bitumen seem to have
misled the sagacious nobleman into the belief that coal might be found on his
new property. He accordingly brought miners from the south, and set them to
bore for coal in the gorge of the ravine. Though there was probably a register
kept of the various strata through which they passed, it must have long since
been lost; but from my acquaintance with this portion of the formation, as
shown in the neighboring sections, where it lies uplifted against the granitic
gneiss of the Sutors, I think I could pretty nearly restore it. They would first
have had to pass for about thirty feet through the stratified clays and shales of
the ichthyolite bed, with here and there a thin band of gray sandstone, and
here and there a stratum of lime; they would next have had to penetrate
through from eighty to a hundred feet of coarse red and yellow sandstone, the
red greatly predominating. They would then have entered the great
conglomerate, the lowest member of the formation; and in time, if they
continued to urge their fruitless labors, they would arrive at the primary rock,
with its belts of granite, and its veins and huge masses of hornblende. In
short, there might be some possibility of their penetrating to the central fire,
but none whatever of their ever reaching a vein of coal. From a curious
circumstance, however, they were prevented from ascertaining, by actual
experience, the utter barrenness of the formation.
Directly in the gorge of the ravine, where we may see the partially wooded
banks receding as they ascend from the base to the centre, and then bellying
over from the centre to the summit, there is a fine chalybeate spring,
surmounted by a dome of hewn stone. It was discovered by the miners when
in quest of the mineral which they did not and could not discover, and forms
one of the finest specimens of a true Artesian well which I have any where
seen. They had bored to a considerable depth, when, on withdrawing the kind
of auger used for the purpose, a bolt of water, which occupied the whole
diameter of the bore, came rushing after, like the jet of a fountain, and the
work was prosecuted no further; for, as steam-engines were not yet invented,
no pit could have been wrought with so large a stream issuing into it; and as
the volume was evidently restricted by the size of the bore, it was impossible
to say how much greater a stream the source might have supplied. The spring
still continues to flow towards the sea, between its double row of cresses, at
the rate of about a hogshead per minute—a rate considerably diminished, it is
said, from its earlier volume, by some obstruction in the bore. The waters are
not strongly tinctured—a consequence, perhaps, of their great abundance; but
we may see every pebble and stock in their course enveloped by a ferruginous
coagulum, resembling burnt sienna, that has probably been disengaged from
the dark red sandstone below, which is known to owe its color to the oxide of
iron. A Greek poet would probably have described the incident as the birth of
the Naiad; in the north, however, which, in an earlier age, had also its Naiads,
though, like the fish of the Old Red Sandstone, they have long since become
extinct, the recollection of it is merely preserved by tradition, as a curious,
though by no means poetical fact, and by the name of the well, which is still
known as the well of the coal-heugh—the old Scotch name for a coal-pit.
Calderwood tells us, in his description of a violent tempest which burst out
immediately as his persecutor, James VI., breathed his last, that in Scotland
the sea rose high upon the land, and that many "coal-heughs were drowned."
There is no science whose value can be adequately estimated by
economists and utilitarians of the lower order. Its true quantities cannot be
represented by arithmetical figures or monetary tables; for its effects on mind
must be as surely taken into account as its operations on matter, and what it
has accomplished for the human intellect as certainly as what it has done for
the comforts of society or the interests of commerce. Who can attach a
marketable value to the discoveries of Newton? I need hardly refer to the
often-quoted remark of Johnson; the beauty of the language in which it is
couched has rendered patent to all the truth which it conveys. "Whatever
withdraws us from the power of the senses," says the moralist—"whatever
makes the past, the distant, or the future, predominate over the present,
advances us in the dignity of thinking beings." And Geology, in a peculiar
manner, supplies to the intellect an exercise of this ennobling character. But it
has, also, its cash value. The time and money squandered in Great Britain
alone in searching for coal in districts where the well-informed geologist could
have at once pronounced the search hopeless, would much more than cover
the expense at which geological research has been prosecuted throughout the
world. There are few districts in Britain occupied by the secondary deposits, in
which, at one time or another, the attempt has not been made. It has been
the occasion of enormous expenditure in the south of England among the
newer formations, where the coal, if it at all occurs, (for we occasionally meet
with wide gaps in the scale,) must be buried at an unapproachable depth. It
led in Scotland—in the northern county of Sutherland—to an unprofitable
working for many years of a sulphureous lignite of the inferior Oolite, far
above the true Coal Measures. The attempt I have just been describing was
made in a locality as far beneath them. There is the scene of another and
more modern attempt in the same district, on the shores of the Moray Frith, in
a detached patch of Lias, where a fossilized wood would no doubt be found in
considerable abundance, but no continuous vein even of lignite. And it is
related by Dr. Anderson, of Newburgh, that a fruitless and expensive search
after coal has lately been instituted in the Old Red Sandstone beds which
traverse Strathearn and the Carse of Gowrie, in the belief that they belong not
to the Old, but to the New Red Sandstone—a formation which has been
successfully perforated in prosecuting a similar search in various parts of
England. All these instances—and there are hundreds such—show the
economic importance of the study of fossils. The Oolite has its veins of
apparent coal on the coast of Yorkshire, and its still more amply developed
veins—one of them nearly four feet in thickness—on the eastern coast of
Sutherlandshire; the Lias has its coniferous fossils in great abundance, some
of them converted into a lignite which can scarce be distinguished from a true
coal; and the bituminous masses of the Lower Old Red, and its carbonaceous
markings, appear identical, to an unpractised eye, with the impressions on the
carboniferous sandstones, and the bituminous masses which they, too, are
occasionally found to enclose. Nor does the mineralogical character of its
middle beds differ in many cases from that of the lower members of the New
Red Sandstone. I have seen the older rock in the north of Scotland as strongly
saliferous as any of the newer sandstones, of well nigh as bright a brick-red
tint, of as friable and mouldering a texture, and variegated as thickly with its
specks and streaks of green and buff-color. But in all these instances there are
strongly characterized groups of fossils, which, like the landmarks of the
navigator, or the findings of his quadrant, establish the true place of the
formations to which they belong. Like the patches of leather, of scarlet, and of
blue, which mark the line attached to the deep-sea lead, they show the
various depths at which we arrive. The Earls of Sutherland set themselves to
establish a coal-work among the chambered univalves of the Oolite, and a
vast abundance of its peculiar bivalves. The coal-borers who perforated the
Lias near Cromarty passed every day to and from their work over one of the
richest deposits of animal remains in the kingdom—a deposit full of the most
characteristic fossils; and drove their auger through a thousand belemnites
and ammonites of the upper and inferior Lias, and through gryphites and
ichthyodorulites innumerable. The sandstones of Strathearn and the Carse of
Gowrie yield their plates and scales of the Holoptychius, the most abundant
fossil of the Upper Old Red; and the shale of the little dell in which the first
Earl of Cromarty set his miners to work, contains, as I have said, plates of the
Coccosteus and scales of the Osteolepis—fossils found only in the Lower Old
Red. Nature, in all these localities, furnished the index, but men lacked the
skill necessary to decipher it.[AU] I may mention that, independently of their
well-marked organisms, there is a simple test through which the lignites of the
newer formations may be distinguished from the true coal of the
carboniferous system. Coal, though ground into an impalpable powder, retains
its deep black color, and may be used as a black pigment; lignite, on the
contrary, when fully levigated, assumes a reddish, or, rather, umbry hue.
[AU] There occurs in Mr. Murchison's Silurian System a singularly amusing account of one
of the most unfortunate of all coal-boring enterprises; the unlucky projector, a Welsh farmer,
having set himself to dig for coal in the lowest member of the system, at least six formations
beneath the only one at which the object of his search could have been found. Mr. Murchison
thus relates the story:—
"At Tin-y-coed I found a credulous farmer ruining himself in excavating a horizontal gallery
in search of coal, an ignorant miner being his engineer. The case may serve as a striking
example of the coal-boring mania in districts which cannot by possibility contain that mineral;
and a few words concerning it may, therefore, prove a salutary warning to those who
speculate for coal in the Silurian Rocks. The farmhouse of Tin-y-coed is situated on the
sloping sides of a hill of trap, which throw off, upon its north-western flank, thin beds of black
grauwacke shale, dipping to the west-north-west at a high angle. The color of the shale, and
of the water that flowed down its sides, the pyritous veins, and other vulgar symptoms of
coal-bearing strata, had long convinced the farmer that he possessed a large hidden mass of
coal, and, unfortunately, a small fragment of real anthracite was discovered, which burnt like
the best coal. Miners were sent for, and operations commenced. To sink a shaft was
impracticable, both from the want of means, and the large volume of water. A slightly inclined
gallery was therefore commenced, the mouth of which was opened at the bottom of the hill,
on the side of the little brook which waters the dell. I have already stated that, in many cases,
where the intrusive trap throws off the shale, the latter preserves its natural and unaltered
condition to within a certain distance of the trap; and so it was at Tin-y-coed, for the level
proceeded for 155 feet with little or no obstacle. Mounds of soft black shale attested the rapid
progress of the adventurers, when suddenly they came to a 'change of metal.' They were now
approaching the nucleus of the little ridge; and the rock they encountered was, as the men
informed me, 'as hard as iron,' viz., of lydianized schist, precisely analogous to that which is
exposed naturally in ravines where all the phenomena are laid bare. The deluded people,
however, endeavored to penetrate the hardened mass, but the vast expense of blasting it put
a stop to the undertaking, not, however, without a thorough conviction on the part of the
farmer, that, could he but have got through that hard stuff, he would most surely have been
well recompensed, for it was just thereabouts that they began to find 'small veins of coal.' It
has been before shown, that portions of anthracite are not unfrequent in the altered shale,
where it is in contact with the intrusive rock. And the occurrence of the smallest portion of
anthracite is always sufficient to lead the Radnorshire farmer to suppose that he is very near
'El Dorado.' Amid all their failures, I never met with an individual who was really disheartened;
a frequent exclamation being, 'O, if our squires were only men of spirit, we should have as
fine coal as any in the world!'"—(Silurian System, Part I., p. 328.)

I have said that the waters of the well of the coal-heugh are chalybeate—a
probable consequence of their infiltration through the iron oxides of the
superior beds of the formation, and their subsequent passage through the
deep red strata of the inferior bed. There could be very curious chapters
written on mineral springs, in their connection with the formations through
which they pass. Smollett's masterpiece, honest old Matthew Bramble,
became thoroughly disgusted with the Bath waters on discovering that they
filtered through an ancient burying-ground belonging to the Abbey, and that
much of their peculiar taste and odor might probably be owing to the "rotten
bones and mouldering carcasses" through which they were strained. Some of
the springs of the Old Red Sandstone have also the churchyard taste, but the
bones and carcasses through which they strain are much older than those of
the Abbey burying-ground at Bath. The bitumen of the strongly impregnated
rocks and clay-beds of this formation, like the bitumen of the still more
strongly impregnated limestones and shales of the Lias, seems to have had
rather an animal than vegetable origin. The shales of the Eathie Lias burn like
turf soaked in oil, and yet they hardly contain one per cent, of vegetable
matter. In a single cubic inch, however, I have counted about eighty
molluscous organisms, mostly ammonites, and minute striated scallops; and
the mass, when struck with the hammer, still yields the heavy odor of animal
matter in a state of decay. The lower fish-beds of the Old Red are, in some
localities, scarcely less bituminous. The fossil scales and plates, which they
enclose, burn at the candle; they contain small cavities filled with a strongly
scented, semi-fluid bitumen, as adhesive as tar, and as inflammable; and for
many square miles together the bed is composed almost exclusively of a dark-
colored, semi-calcareous, semi-aluminous schist, scarcely less fetid, from the
great quantity of this substance which it contains, than the swine-stones of
England. Its vegetable remains bear but a small proportion to its animal
organisms; and from huge accumulations of these last decomposing amid the
mud of a still sea, little disturbed by tempests or currents, and then suddenly
interred by some widely spread catastrophe, to ferment and consolidate under
vast beds of sand and conglomerate, the bitumen[AV] seems to have been
elaborated. These bituminous schists, largely charged with sulphuret of iron,
run far into the interior, along the flanks of the gigantic Ben Nevis, and
through the exquisitely pastoral valley of Strathpeffer. The higher hills which
rise over the valley are formed mostly of the great conglomerate—Knockferril,
with its vitrified fort—the wooded and precipitous ridge over Brahan—and the
middle eminences of the gigantic mountain on the north; but the bottom and
the lower slopes of the valley are occupied by the bituminous and sulphureous
schists of the fish-bed, and in these, largely impregnated with the peculiar
ingredients of the formation, the famous medicinal springs of the Strath have
their rise. They contain, as shown by chemical analysis, the sulphates of soda,
of lime, of magnesia, common salt, and, above all, sulphuretted hydrogen gas
—elements which masses of sea-mud, charged with animal matter, would
yield as readily to the chemist as the medicinal springs of Strathpeffer. Is it not
a curious reflection, that the commercial greatness of Britain, in the present
day, should be closely connected with the towering and thickly spread forests
of arboraceous ferns and gigantic reeds—vegetables of strange form and
uncouth names—which flourished and decayed on its surface, age after age,
during the vastly extended term of the carboniferous period, ere the
mountains were yet upheaved, and when there was as yet no man to till the
ground? Is it not a reflection equally curious, that the invalids of the present
summer should be drinking health, amid the recesses of Strathpeffer, from the
still more ancient mineral and animal debris of the lower ocean of the Old Red
Sandstone, strangely elaborated for vast but unreckoned periods in the bowels
of the earth? The fact may remind us of one of the specifics of a now obsolete
school of medicine, which flourished in this country about two centuries ago,
and which included in its materia medica portions of the human frame. Among
these was the flesh of Egyptian mummies, impregnated with the embalming
drugs—the dried muscles and sinews of human creatures who had walked in
the streets of Thebes or of Luxor three thousand years ago.
[AV] "In the slaty schists of Seefeld, in the Tyrol," say Messrs. Sedgwick and Murchison,
"there is such an abundance of a similar bitumen, that it is largely extracted for medicinal
purposes."—(Geol. Trans. for 1829, p. 134.)

The commoner mineral springs of the formation, as might be anticipated,

from the very general diffusion of the oxide to which it owes its color, are
chalybeate. There are districts in Easter-Ross and the Black Isle in which the
traveller scarcely sees a runnel by the way-side that is not half choked up by
its fox-colored coagulum of oxide. Two of the most strongly impregnated
chalybeates with which I am acquainted gush out of a sandstone bed, a few
yards apart, among the woods of Tarbat House, on the northern shore of the
Frith of Cromarty. They splash among the pebbles with a half-gurgling, half-
tinkling sound, in a solitary but not unpleasing recess, darkened by alders and
willows; and their waters, after uniting in the same runnel, form a little,
melancholy looking lochan, matted over with weeds, and edged with flags and
rushes, and which swarms in early summer with the young of the frog in its
tadpole state, and in the after months with the black water-beetle and the
newt. The circumstance is a somewhat curious one, as the presence of iron as
an oxide has been held so unfavorable to both animal and vegetable life, that
the supposed poverty of the Old Red Sandstone in fossil remains has been
attributed to its almost universal diffusion at the period the deposition was
taking place. Were the system as poor as has been alleged, however, it might
be questioned, on the strength of a fact such as this, whether the iron
militated so much against the living existences of the formation, as against the
preservation of their remains when dead.
Some of the springs which issue from the ichthyolite beds along the shores
of the Moray Frith are largely charged, not with iron, like the well of the coal-
heugh, or the springs of Tarbat House, nor yet with hydrogen and soda, like
the spa of Strathpeffer, but with carbonate of lime. When employed for
domestic purposes, they choke up, in a few years, with a stony deposition, the
spouts of tea-kettles. On a similar principle, they plug up their older channels,
and then burst out in new ones; nor is it uncommon to find among the cliffs
little hollow recesses, long since divested of their waters by this process, that
are still thickly surrounded by coral-like incrustations of moss and lichens,
grass and nettle-stalks, and roofed with marble-like stalactites. I am
acquainted with at least one of these springs of very considerable volume, and
dedicated of old to an obscure Roman Catholic saint, whose name it still
bears, (St. Bennet,) which presents phenomena not unworthy the attention of
the young geologist. It comes gushing from out the ichthyolite bed, where the
latter extends, in the neighborhood of Cromarty, along the shores of the
Moray Frith; and after depositing in a stagnant morass an accumulation of a
grayish-colored and partially consolidated travertin, escapes by two openings
to the shore, where it is absorbed among the sand and gravel. A storm about
three years ago swept the beach several feet beneath its ordinary level, and
two little moles of conglomerate and sandstone, the work of the spring, were
found to occupy the two openings. Each had its fossils—comminuted sea-
shells, and stalks of hardened moss; and in one of the moles I found
imbedded a few of the vertebral joints of a sheep. It was a recent formation
on a small scale, bound together by a calcareous cement furnished by the
fish-beds of the inferior Old Red Sandstone, and composed of sand and
pebbles, mostly from the granitic gneiss of the neighboring hill, and
organisms, vegetable and animal, from both the land and the sea.
The Old Red Sandstone of Scotland has been extensively employed for the
purposes of the architect, and its limestones occasionally applied to those of
the agriculturist. As might be anticipated in reference to a deposit so widely
spread, the quality of both its sandstones and its lime is found to vary
exceedingly in even the same beds when examined in different localities. Its
inferior conglomerate, for instance, in the neighborhood of Cromarty, weathers
so rapidly, that a fence built of stones furnished by it little more than half a
century ago, has mouldered in some places into a mere grass-covered mound.
The same bed in the neighborhood of Inverness is composed of a stone nearly
as hard and quite as durable as granite, and which has been employed in
paving the streets of the place—a purpose which it serves as well as any of
the igneous or primary rocks could have done. At Redcastle, on the northern
shore of the Frith of Beauly, the same conglomerate assumes an intermediate
character, and forms, though coarse, an excellent building stone, which, in
some of the older ruins of the district, presents the marks of the tool as
sharply indented as when under the hands of the workman. Some of the
sandstone beds of the system are strongly saliferous; and these, however
coherent they may appear, never resist the weather until first divested of their
salt. The main ichthyolite bed on the northern shore of the Moray Frith is
overlaid by a thick deposit of a finely-tinted yellow sandstone of this character,
which, unlike most sandstones of a mouldering quality, resists the frosts and
storms of winter, and wastes only when the weather becomes warm and dry.
A few days of sunshine affect it more than whole months of high winds and
showers. The heat crystallizes at the surface the salt which it contains; the
crystals, acting as wedges, throw off minute particles of the stone; and thus,
mechanically at least, the degrading process is the same as that to which
sandstones of a different but equally inferior quality are exposed during
severe frosts. In the course of years, however, this sandstone, when employed
in building, loses its salt; crust after crust is formed on the surface, and either
forced off by the crystals underneath, or washed away by the rains; and then
the stone ceases to waste, and gathers on its weathered inequalities a
protecting mantle of lichens.[AW] The most valuable quarries in the Old Red
System of Scotland yet discovered, are the flagstone quarries of Caithness and
Carmylie. The former have been opened in the middle schists of the lower, or
Tilestone formation of the system; the latter, as I have had occasion to remark
oftener than once, in the Cornstone, or middle formation. The quarries of both
Carmylie and Caithness employ hundreds of workmen, and their flagstones
form an article of commerce. The best building-stone of the north of Scotland
—best both for beauty and durability—is a pure Quartzose Sandstone
furnished by the upper beds of the system. These are extensively quarried in
Moray, near the village of Burghead, and exported to all parts of the kingdom.
The famous obelisk of Forres, so interesting to the antiquary—which has been
described by some writers as formed of a species of stone unknown in the
district, and which, according to a popular tradition, was transported from the
Continent—is evidently composed of this Quartzose Sandstone, and must have
been dug out of one of the neighboring quarries. And so coherent is its
texture, that the storms of, perhaps, ten centuries have failed to obliterate its
rude but impressive sculptures.
[AW] When left to time the process is a tedious one, and, ere its accomplishment, the
beauty of the masonry is always in some degree destroyed. The following passage, from a
popular work, points out a mode by which it might possibly be anticipated, and the waste of
surface prevented:—"A hall of which the walls were constantly damp, though every means
were employed to keep them dry, was about to be pulled down, when M. Schmithall
recommended, as a last resource, that the walls should be washed with sulphuric acid,
(vitriol.) It w T as done, and the deliquescent salts being decomposed by acid, the walls dried,
and the hall was afterwards free from dampness."—(Recreations in Science.)

The limestones of both the upper and lower formations of the system have
been wrought in Moray with tolerable success. In both, however, they contain
a considerable per centage of siliceous and argillaceous earth. The system,
though occupying an intermediate place between two metalliferous deposits,
—the grauwacke and the carboniferous limestone,—has not been found to
contain workable veins any where in Britain, and in Scotland no metallic veins
of any kind, with the exception of here and there a few slender threads of
ironstone, and here and there a few detached crystals of galena. Its wealth
consists exclusively in building and paving stone, and in lime. Some of the
richest tracts of corn land in the kingdom rest on the Old Red Sandstone—the
agricultural valley of Strathmore, for instance, and the fertile plains of Easter-
Ross: Caithness has also its deep, corn-bearing soils, and Moray has been well
known for centuries as the granary of Scotland. But in all these localities the
fertility seems derived rather from an intervening subsoil of tenacious diluvial
clay, than from the rocks of the system. Wherever the clay is wanting, the soil
is barren. In the moor of the Milbuy,—a tract about fifty square miles in
extent, and lying within an hour's walk of the Friths of Cromarty and Beauly,—
a thin covering of soil rests on the sandstones of the lower formation. And so
extreme is the barrenness of this moor, that notwithstanding the advantages
of its semi-insular situation, it was suffered to lie as an unclaimed common
until about twenty-five years ago, when it was parcelled out among the
neighboring proprietors.
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