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Smithers Rapra has provided a world leading portfolio of Rubber, Plastic and other
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Please visit our webside for more information:
www.polymerconferences.com 3rd INTERNATIONAL CONFERENCE
13-14 September 2011
The Radisson Blu Scandinavia Hotel, Düsseldorf
Conference Proceedings

Conference Proceedings
Organised by:

©iSmithers 2011

iSmithers
ISBN 978 1 84735 635 2
Nanopolymers 2011

Organised by

Düsseldorf, Germany
13-14 September 2011
 ISBN: 978-1-84735-635-2

© Smithers Rapra Technology Ltd, 2011

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 Nanopolymers 2011
Contents

SESSION 1: MARKET AND TRENDS

Paper 1 Market and trends - Introduction and background

Dr Alan Smith, AZ-Technology, UK

Paper 2 The market for nanotechnologies

Tim E Harper, Cientifica Ltd, UK

SESSION 2: NANO-COMPONENT DEVELOPMENTS & PROCESSING

Paper 3 New hybrid nanostructured organic-inorganic polymeric materials with silsesquioxane cores
H Harris & P J Lutz, Institut Charles Sadron CNRS/ University of Strasbourg, France

Paper 4 Nanofibrillar cellulose (NFC)- An emerging material for large-scale applications

Prof Tom Lindström, Mikael Ankerfors and Christian Aulin, Innventia AB, Sweden

SESSION 3: PROPERTY ENHANCEMENT WITH NANOMATERIALS

Paper 5 Poly (i-methylpyrrol-2-ylsquaraine): An absorbent carrier particle for additives in

thermoplastics
Dr Daniel Lynch, Exilica Ltd, UK

Paper 6 Nanocomposites – what we know and what is still unsolved

Dr Günter Beyer, Kabelwerk EUPEN AG, Belgium

Paper 7 Polymer-nanophosphor composites for some light relief

Prof Robert Withnall et al, Brunel University, UK

SESSION 4: REGULATORY, ENVIRONMENTAL & CHARACTERISATION IMPLICATIONS

Paper 8 Patents for nanotechnology inventions

Richard Michalitsch, European Patent Office, Germany

Paper 9 Regulatory challenges for nanomaterials in the EU

Dr Anna Gergely, Steptoe & Johnson, Belgium
SESSION 5: SPECIFIC APPLICATION AREAS FOR NANOPOLYMERS

Section 1: CLAYS

Paper 10 Montmorillonite – an effective additive to make “green” nanopolymers

Dr Tie Lan, Nanocor Inc, USA

Paper 11 Nanostructured polymer films: from brushes to colloidal templating

Prof Rigoberto Advincula, University of Houston, USA

Paper 12 Hybrid filler networks in hydrocarbon polymer compounds – the unexpected role of
organoclay building blocks
Luca Giannini, Pirelli Tyre SpA, Italy

Paper 13 Applications of nano-materials in new car design

Colin Chilles & Arunee Venables, Smithers Rapra, UK

Paper 14 Biocomposite materials for food packaging and high performance applications
Keith Dingwall, Institute of Nanotechnology, UK

Section 2: CARBON NANOTUBES

Paper 15 Inno.CNT – a novel cooperation model to conquer new markets for CNT based products
Dr Péter Krüger, Bayer MaterialsScience AG, Germany

Paper 16 An overview of the FP7 project “Contact – tailored supply chain development of the
mechanical and electrical properties of CNT-filled composites”
Dr Christof Hübner et al, Fraunhofer Institute for Chemical Technology (ICT), Germany

Paper 17 Carbon nanotubes – a review of their current applications and trends for the future
Cédric de Villepin, Dr Michaël Claes & Céline Dewaghe, Nanocyl SA, Belgium

Section 3: GRAPHENE

Paper 18 The potential of graphene in multifunctional composites

Dr Ian Kinloch et al, University of Manchester, UK

Paper 19 Polymer reinforcement with graphene – high performance at low cost

Prof Jonathan N Coleman, Trinity College, Dublin, Ireland
PAPER UNAVAILABLE AT TIME OF PRINT
Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

MARKET AND TRENDS - INTRODUCTION AND BACKGROUND

Dr Alan Smith
AZ-Technology
Hydowns Farm, Woodlands, Wimborne, Dorset, BH21 8LX, UK
Tel: 01202 825589 email: [email protected]

BIOGRAPHICAL NOTE

Dr Smith’s career began as a lecturer before moving into industry, and is now the
managing director of AZ-TECH. He is the author of numerous papers on
nanotechnology, and lectures worldwide on the topic to schoolchildren, the general
public, international experts, and Heads of State. He is also an advisor on
nanotechnology for several governments. He has facilitated over 50 technology
roadmaps in a variety of sectors, for establishments in many countries. His latest
publication is a book on roadmapping emergent technologies; and a free booklet on
nanotechnology for schools has been prepared for translation into a number of
languages.

ABSTRACT

Since the first Nanopolymers conference in 2007, there has been a large increased in the incorporation of
nanoscale ingredients into polymers to increase performance. Use of clays for transport and food packaging
applications are now commonplace, providing weight reduction and barrier properties. Carbon nanotube-
based materials are also being developed, not just for light-weighting, but for applications using their ability
to conduct a charge; hence fuel pumps and fuel lines for cars have appeared as an early application. There
is a great deal of work now being carried out on graphene-based nanopolymers which herald the next phase
in nanopolymer development. There is a lot of attention to the patent situation and societal aspects in this
field. Nanopolymers 2011 will give more information and detail about what applications and developments
we can expect over the few years.

MARKETS

Since the first Nanopolymers International Conference in 2007, there has been a huge increase in activity
incorporating nanotechnology-based components into polymeric materials. There are few industry sectors
where nanopolymers have not made a significant impact during the last four years, which is not surprising
when government spending throughout the world, even in 2005, was estimated to be $4.6 billion. At that
time it was estimated by one group that the value of goods incorporating nanotechnologies rose from $30
billion in 2005 to $147 billion in 2007.

The Emerging Technologies Project at the Woodrow Wilson International Center for Scholars, no longer
adds to its inventory of nanotechnology-based products, but in February 2010 over a thousand products from
25 countries were listed, coming from over 500 companies. Many groups have made market assessments
and optimistic ones have come up with a figure of $3 trillion by 2015, whereas more pessimistic ones
suggest the market will be $0.8 trillion (Figure 1).

Page 1 of 8 pages Paper 1 - Smith

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

Figure 1: World market forecasts for nanotechnology

Specifically for nanomaterials, world demand is projected to grow from $3.58 billion in 2013 to $34.3 billion in
2025.

Although particle size is most frequently talked about as being responsible for the property improvements
that can be achieved with nanoparticulate materials, it is more accurate to consider the morphology of the
small particles or agglomerates which give rise to property changes. The increase in surface area is the key
issue, and this is brought home when one considers a cubic centimetre of a material where around one in
ten million atoms are on the surface; if it was a one nanometre cube then 80% of the atoms would be on the
surface enabling more things to happen. If you imagine a cubic metre of a material and then break that
2
down into centimetre cubes, then there will be a million cubes and the surface area will be 600 m . If that
27
one metre cube is broken down into nanometre cubes, there would be 10 cubes with a surface area of
6,000 square kilometres, staggering when it is noted that Dusseldorf occupies just over 200 km2.

All the data being quoted about nanotechnologies has to be absorbed with caution, since nanotechnologies
are particularly diverse and even now an acceptable definition is hardly satisfactory. However,
nanotechnology components have been categorised according to their dimensions (Figure 2), thus
incorporating thin films, nanotubes and nanoparticles.

Figure 2: Types of nanotechnology-based components

Paper 1 - Smith Page 2 of 8 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

NANO-COMPONENTS

Clays

Smectite clays are made up of nanoscale platelets which measure around 500 nanometres across, and are
about 1 nm deep; in a small grain of clay there are over a million platelets. When incorporated into a
polymer, they act as reinforcement so that less polymer can be used while retaining acceptable strength.
However, the key point is that the platelets must be well dispersed in the polymer otherwise the property
enhancements do not occur. European plastics consumption, by end use, shows that it is dominated
primarily by the packaging sector and secondly by the construction sector (Figure 3).

Figure 3: European plastics consumption by end-use, 2009

For weight saving, the transport sector now uses clay-based materials as replacement for many metal
components on vehicles, but other property improvements are possible:

 Mass savings up to 25%

 Improved appearance
 Large processing window
 Reduced paint delamination
 Retains low temperature ductility
 Improved recyclability
 Lower flammability.

However, for packaging applications, the well dispersed clay platelets in polymer films provide a tortuous
route for gases and moisture to get at, or escape from, the product the film is protecting. These clay-based
films give excellent barrier properties to many different types of films, whether they are petroleum-based or
starch-based polymers. For example, in the food sector, the benefits on offer are that there is less food
wastage due to the increased shelf-life of foodstuffs protected by these films.

Also utilising barrier properties, Wilson Sports have used clay platelets in tennis balls. At Wimbledon, the cry
of “new balls please” echoes across the courts; nowadays the players strike the ball so hard forcing the air
out after only a few games. The new Wilson balls have clay platelets dispersed in the butyl rubber, and the
millions of tiny platelets provide a barrier for air trying to escape. The balls therefore hold their pressure and
retain the correct ‘bounce’ for far longer than conventional balls.

Fibres and nanotubes

A recent press release, has announced that the Audi R8 GT Spyder has reduced its weight and increased
performance, which Audi claim is partly due to carbon fibre body parts. Audi claim the reduction in weight
across the car, totalling 5.5 kg, has lead to increased speed. Fibres have been used for a number of years

Page 3 of 8 pages Paper 1 - Smith

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

in applications where weight saving is required, but carbon nanotubes offer the potential to give added
weight reduction benefits, certainly over the clay-based polymers (Figure 4).

Figure 4: Modulus versus filler type and concentration

However, the cost of carbon nanotubes will need to be dramatically reduced before commodity usage is
seen. By using small amounts of carbon nanotubes in polymers, data indicates that weight can be reduced
by about 60% over carbon fibre reinforced products.

Roger Federer and the Williams sisters use Wilson racquets which contain about 3% carbon nanotubes in
the plastic material used for the racquets, providing lighter and stronger equipment. Rafa Nadal now uses
Babolat racquets which have now also gone ‘nano’. Floyd Landis won the Tour de France a few years ago,
being the first to use a bike which had a carbon nanotube plastic frame.

Bayer Materials Science and California-based Velozzi have developed SOLO, a crossover alternative energy
vehicle which has carbon nanotubes for body panels, and achieves 100 miles per gallon. Other early
applications for polymers with carbon nanotubes have been in wind turbine blades, light-weight marine craft,
and military applications.

However, carbon nanotubes have an extra advantage over clay-based products; they conduct electricity.
Again Audi are in the lead with developments, working with BASF and Bosch to incorporate carbon
nanotube-based polymers for fuel pumps in the A4 and A5 models. In fact most fuel lines in new North
American cars have replaced metal fuel lines with plastic ones containing carbon nanotubes.

A European project, PolyCond, has developed a three-pin electrical plug which has replaced the brass parts
with carbon nanotube-based polymer. This gives 82% weight reduction compared to a brass pin, at one fifth
the cost of the brass pin, and the finished three-pin plug is 40% cheaper. Another European project,
CoNTact, has been looking at increasing the development of products using carbon nanotubes.

Graphene

Two researchers at the University of Manchester, received the Nobel Prize for physics last year for their work
on graphene, which they had originally isolated by using Scotch tape to separate the layers of graphite.
Although it is very early days there is a great deal of effort being put into research into graphene, with some
success.

Paper 1 - Smith Page 4 of 8 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

Companies are now beginning to manufacture and sell graphene for use in applications, and there is work
looking at including graphene ‘sheets’ into polymers.

Features and benefits of graphene are:

 Highest thermal conductivity known today, five times that of copper

 Electrical conductivity similar to copper
 Low density, four times lower than copper
 Many times stronger than steel
 Surface area twice that of carbon nanotubes
 Ultra-high Young’s modulus
 High intrinsic strength
 Outstanding resistance to gas permeation.

Thoughts are that graphene might overtake carbon nanotubes for new developemtns, since it has the
potential to give more benefits at a lower coat.

Nanoparticles

Silver has a long history of use as an antimicrobial. The Assyrians around 2,500 BC carried their water in
silver containers, and even today the Bedouins put a silver coin in their leather water carriers knowing that
the water will stay fresh for longer. Silver nanoparticles are being added to a variety of plastics for
refrigerators, food packaging and many other areas where they act as an antimicrobial agent.
FresherLonger™ food storage containers, also infused with silver nanoparticles, give clear examples of how
the storage time for foods can be extended, with 24 hour growth of bacteria being reduced by over 98%
compared with conventional containers.

There are many more examples where silver nanoparticles are being use in food contact areas such as
cleaning implements, gloves and contact surfaces. Other applications for silver nanoparticles are in fabrics
such as socks and underwear and these are available in high street shops today. Silver nanoparticles have
been introduced into fibres used for clothing for Koichi Wakata, a Japanese astronaut, who trialled garments
on a shuttle visit to the space station, with a view to developing clothing which could be used for a trip to
Mars. He wore the same underpants for 40 days! The new Boeing 787 Dreamliner has air filters containing
silver nanoparticles in order to maintain high air quality. It is claimed that they kill 99.7% of influenza viruses.

Marks and Spencer have been carrying out a trial in the UK with pyjamas impregnated with antimicrobial
silver, which are claimed to be clinically proven to reduce the risk of MRSA.

More recently, there has been interest in the antimicrobial properties of nanoparticulate copper as well,
comparing the effects on different strains of bacteria. The indication is that a mixture of silver and copper
nanoparticles would be most effective.

Nanoparticles of alumina and silica are used to provide coatings that achieve anti-scratch surfaces. Early
applications were for ten-pin bowling balls, but they are also now being used in the final lacquer on
Mercedes cars so that the surface remains brighter for longer, avoiding the minute scratches which result
from too many times through a car wash.

Surface modification

The colours of bird’s feathers, butterfly wings, etc. do not always contain pigments; they are the result of light
being diffracted from surfaces. The pearl colouration on shells has been copied onto the surface of Pure
Poison perfume bottles from Christian Dior where nanolayers of titania and silica on the inside of the glass
bottle have produced a product which looks like pearl. It is now possible, by modifying the surface of plastic
films to produce coloured films which do not have pigments in them. It is also possible to tailor the colour to
what a potential customer might require.

If a moth had not evolved with anti-reflective eyes, a bat or owl would be able to pick it off quite easily. The
Audi TT Roadster has copied the moths’ eyes anti-reflective nanoscale patterns for its instrument panel so
that it can be clearly seen in sunny conditions.

Page 5 of 8 pages Paper 1 - Smith

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

INTELLECTUAL PROPERTY

By 2010, patents granted under USPTO’s classification 977, which covers nanotechnologies, at the five year
end had reached over 700. With all the activity that is going on, the whole area is a mine field, and
professional help should be sought when considering activities relating to nanotechnogies.

REGULATION AND SOCIETAL ISSUES

Few technologies have attracted as much hype as nanotechnologies, and this has led to concerns on safety.
However, what is needed for the debate is a clear definition of what is meant by ‘manufactured
nanomaterials’. The Organisation for Economic Co-operation and Development (OECD) has been struggling
with this for quite a while now, and has come up with a definition:

Nanomaterials intentionally produced to have specific properties or specific composition, a size

range typically between 1 nm and 100 nm and material which is either a nano-object (i.e. that is
confined in one, two, or three dimensions at the nanoscale) or is nanostructured (i.e. having an
internal or surface structure at the nanoscale).

Recent changes to the regulations for cosmetics have introduced a definition of nanomaterials as:

‘Nanomaterial’ means an insoluble or biopersistent and intentionally manufactured material with

one or more external dimensions, or an internal structure, on the scale from 1 to 100 nm.

This is likely to be used as a framework for similar definitions for nanomaterials if regulation is introduced.
Currently it is considered by authorities that the existing legislation is sufficient for products made using
nanotechnologies.

It was recently pointed out that a boiled egg is a manufactured nanomaterial as it is well known that the act
of cooking eggs changes the nanostructure of the product. In addition, it has to be appreciated that milk
contains nanoparticulate casein, and that whiskey contains nanoparticles. As with beers the fine particles
are filtered off but the nanoparticles pass through the filters unseen. The miller in the middle ages was
grinding his corn so that it did not contain lumps which would inhibit the quality of his product. He would not
have known it, but he was also producing nanoparticulate flour. Just about any product which contains
ground down ingredients is going to contain a small proportion of nanoparticles. For interest, every time you
dry your hair, the hairdryer gives off nanoparticulate tungsten from the heating element; we have been living
with nanoparticles since creation and a report from Allianz and OECD gives some figures:

We live surrounded by nanoparticles. To provide an example: a normal room can contain 10,000 to 20,000
3 3
nanoparticles per cm , whilst these figures can reach 50,000 nanoparticles per cm in a forest and 100,000
3
nanoparticles per cm in urban streets.

This means that roughly every time you take a deep breath you are taking in several million nanoparticles!

The manufacture of carbon fibre and nanotubes may have risk implications and it needs to be monitored, but
their use in products is not deemed harmful.

Studies on consumer understanding of nanotechnologies and perception of risk have indicated that overall
there is little awareness of nanotechnology but in those who are informed there is a tendency to see benefit
rather than risk. Interestingly but perhaps not surprisingly, attitudes vary depending on the geographical
location of the study and cultural background. It is thought that consumers in the USA and Asia are more
likely to accept products incorporating nanotechnologies than those in Europe.

A recent report from Cientifica stated: “For policy makers who are not scientific experts (and few are)
speculative concerns are given equal weighting with scientific results”.

Some of the lobby groups are asking for a moratorium on anything ‘nano’. Toxicologists are also making hay
while the sun shines with a plethora of studies looking especially at what are being called engineered
nanoparticles. However, at an international conference (Nanotoxicology 2010) held in Edinburgh, the main
speaker, Prof. Gunter Oberdörster, University of Rochester, argued that most studies are of limited value to
a risk assessment as they have been performed at unrealistic exposure doses. Unlike chemists, lobby
groups and few toxicologists seem to have an understanding of risk assessment.

Paper 1 - Smith Page 6 of 8 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

What is needed is that we should do as previous government reports have suggested, and move forward
with caution, but at the same time we need to advance at a pace where we are not left behind in
nanotechnologies. There are considerable benefits to the consumer and society that can be obtained by
using the science from nanotechnologies.

At the Nanopolymers 2011 conference you will hear international experts present their research,
development and commercialisation for the exciting area of nanomaterials in more detail than has been
given here.

Page 7 of 8 pages Paper 1 - Smith

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

Paper 1 - Smith Page 8 of 8 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

THE MARKET FOR NANOTECHNOLOGIES

Dr Tim Harper
Cientifica Ltd
69 Brushfield Street, London, E1 6AA, UK
Tel: 07894 708989 email: [email protected];

BIOGRAPHICAL NOTE
Tim Harper is a serial technology entrepreneur, founding London based Cientifica Ltd, the world's leading
source of global business intelligence about nanotechnologies, co-founder of Salisbury based nanoparticle
visualisation and sizing company Nanosight Ltd., and is one of the worlds foremost experts on
commercialisation of technologies, with experience gained in both venture capital and the laboratory.

Tim has given over 100 invited talks and keynote lectures on nanotechnologies ranging from economic
implications to toxicology. He has been published in journals ranging from ‘Nanotechnology’ and 'Nature’ to
‘Microscopy and Analysis,’ in addition to being extensively quoted in media ranging from the Financial Times
and The Economist to Time and Business Week.

He is also the Founder and former Executive Director of European NanoBusiness Association and is an
advisor to many organizations around the globe including top tier Universities, the European Commission,
many of the world’s largest companies and national governments from Austria to Singapore. He is the co-
author of the Nanotechnology Opportunity Report™, described by NASA as "the defining report in the field of
nanotechnology."

ABSTRACT

After ten years of intense public funding and some equally intense public scrutiny, nanotechnologies are still
far from being a mature. Although great strides have been made in both our understanding of nanoscale
phenomena, and our ability to harness them in industrial processes, there are many other emerging
technologies competing for scarce public funding.

As other recent emerging technologies such as biotechnology, microelectronics and the Internet have
demonstrated, it can take twenty to thirty years for new technologies to have the impact that pundits often
initially predict will take two to three years.

Nanotechnology is now reaching the stage where market pull is beginning to be significant, and increasing
opportunities exist to deploy the technology is addressing major global risks such as insufficient water,
energy and food production.

Global Nanotechnology Funding 2011

Every year Cientifica undertakes one of the world’s most exhaustive searches into the global funding of
nanotechnologies in order to identify not only where the dollars, euros and yen are being spent, but also to
gain an unique insight into the trends shaping tomorrow’s applications.

Page 1 of 2 pages Paper 2 - Harper

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

For the 2011 report we have also integrated data from the World Economic Forum’s annual Global
Competitiveness Report in order to gain insights into how well various countries are able to capitalise on
their investment in research.

The white paper gives an overview of the key numbers, which we believe to be the most accurate available
anywhere.

Key Findings

 With US government funding of nanotechnology receding slightly in 2011, Purchasing Power Parity
(PPP) estimates indicate that for the first time, China will spend more than the US to fund
nanotechnology.

 In the last 11 years, governments around the world have invested more than US$67.5 billion in
nanotechnology funding. When corporate research and various other forms of private funding are
taken into account, nearly a quarter of a trillion dollars will have been invested in nanotechnology by
2015.

 Corporate research and private funding were thought to have surpassed government funding figures
as far back as 2004. But this year, according to Cientifica’s estimates, in PPP terms China will spend
US$2.25 billion in nanotechnology research while the US will spend US$2.18 billion. In real dollar
terms, adjusted for currency exchange rates, China is only spending about US$1.3 billion to the US’s
$2.18 billion.

 This appears to be a temporary hiccup in US dominance in public funding of nanotechnology with

the US again taking the lead next year even in PPP terms, spending $2.46 billion with China allotting
$2.2 billion.

 Cientifica’s index of countries’ ability to take advantage of emerging technologies indicates the US,
Germany, Taiwan and Japan have the combination of academic excellence, technology-hungry
companies, skilled workforces and the availability of early stage capital to ensure effective
technology transfer.

 When combined with levels of nanotechnology funding, the US is still the place to be, although China
and Russia are increasingly attractive. The UK and UK and India struggle at the bottom of the
league.

For more detailed information about specific technology funding, detailed analysis, country specific
information, further insights and strategy, please contact us.

Download Global Nanotechnology Funding 2011 here

Paper 2 - Harper Page 2 of 2 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

NEW HYBRID NANOSTRUCTURED ORGANIC-INORGANIC

POLYMERIC MATERIALS WITH SILSESQUIOXANE CORES
H. Harris & P.J. Lutz
Institute Charles Sadron CNRS / University of Strasbourg
23 rue du Loess F-67083 Strasbourg Cedex
Tel: +33(0)3 88 41 40 74, Fax: 33(0)3 88 41 40 e-mail: [email protected]

BIOGRAPHICAL NOTE

Pierre Lutz received his PhD in Macromolecular Engineering in 1981 from University
Louis Pasteur Strasbourg (France). He then spent one year as a post-doctoral
researcher with Professor H. J. Cantow at the Institute of Macromolecular Chemistry,
University of Freiburg (Germany). In 1988, he spent a sabbatical year in Freiburg with
Professor W. Burchard as Humboldt Visiting Scientist. His research activities at the
ICS-CNRS (Strasbourg) were centered on the synthesis of polymers of controlled
topologies via ionic polymerization and their characterization: functional polymers
including macromonomers, branched polymers, crosslinked and cyclic polymers. In
1996 he was nominated Directeur de Recherche at the ICS. His research interests
have been extended over the years to water soluble polymers or hydrogels designed
for biomedical applications and to the development of new transition metal catalysts
including water soluble ones for the co-polymerization of α-olefins. He is presently part time visiting scientist
at the University of Jena with Prof. U. S. Schubert where his working on water soluble biocompatible
polymers. He has authored more than 160 publications and is a member of the French Polymer Group, the
French Chemical Society and the American Chemical Society.

ABSTRACT

The present work discusses the synthesis and some properties of novel hybrid materials based on
H
macromonomers and octafunctional silsesquioxanes (Q8M8 ). α, ω- or ω-undecenyl macromonomers were
synthesized by anionic deactivation and characterized by Size Exclusion Chromatography (SEC) to
determine molecular weight, and by 1H NMR (and MALDI-TOF MS for selected samples) to check
composition, when the case, and functionality. They were reacted by hydrosilylation with Q8M8H, whereupon
chemical links are formed between the precursor chains and the spherosilsesquioxane compound to yield
novel hybrid macromolecular star-shaped structures constituted of poly(ethylene oxide) (PEO), polystyrene
(PS), polyisoprene (PI), poly(styrene-b-isoprene) (PS-b-PI) or poly(isoprene-b-styrene) (PI-b-PS) branches
and octafunctional silsesquioxane cores. Well defined octafunctional PS, PI or PS-b-PI star-shaped polymers
could be obtained. PS and PEO networks could also be synthesized by coupling well-defined α,ω-
diundecenyl PS macromonomers (or α,ω- diallyl PEO macromonomers) with octafunctional silsesquioxanes
via hydrosilylation. Some results on the behavior of the PEO or PS networks exhibiting octafunctional
silsesquioxane crosslinking points will also be presented.

Hybrid materials (organic/inorganic) have physical properties that are not obtained by mixture of their
components. Hybrid materials can be constituted by well-defined nanocomposite compounds. The most
important feature of such nanocomposites is their control of size of particular phase.1, 2 Octafunctional cubic
silsesquioxane compound are very versatile building blocks. They offer an efficient route in developing novel
hybrid nanocomposites. The main features of octafunctional cubic silsesquioxane are their well-defined
nanometer-sized structure, their high surface area or porosity control, and eight available functional points.
The silica structure of cubic silsesquioxane is very stable and has been used in the synthesis of hybrid
materials with improved thermomechanical properties3 Derivatives of octafunctionalized cubic silsesquioxane
compounds such as polybromophenyl-octasilsesquioxanes have been used as nano-sized building block for
the incorporation of a great number of functional groups. Under standard “Suzuki” coupling conditions, it is
possible to reach in the case of octaphenylsilsesquioxanes a complete conversion of all bromo substituents
to aryl and heteroaromatics substituents.4 Atom transfer radical polymerization (ATRP) initiated by octakis(2-
bromo-2-methyl propionoxypropyl dimethylsiloxy) octasilsesquioxane using CuCl as catalyst provide access
to octafunctional hybrid poly(methyl methacrylate). In this synthesis, coupling products are formed due to
reaction between two star-shaped polymers.5 The synthesis of organic/inorganic hybrid polyurethanes has
been performed in two steps. The first step involves the hydrosilylation reaction of the polyhedral
oligosilsesquioxane (POSS) with m-isopropenyl-α-α´-dimethyl benzyl isocyanate in the presence of a
Karstedt’s catalyst. On second step PEO was reacted using dibutyltin dilauretane as catalyst.6 The
Page 1 of 12 pages Paper 3 - Lutz
13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

versatility of octasilsesquioxane derivates to yield nanocomposites is also demonstrated in the synthesis of

octa(maleimido phenyl) silsesquioxane copolymers by reaction of octa(aminophenyl) silsesquioxanes with
maleic anhydride based on chemical imidization.7 Silsesquioxanes served as well-defined building blocks for
the synthesis of many other materials. These different aspects of POSS have been discussed recently by
Kuo et al. in a review article.8

The synthesis and some properties of monosubstituted cube-shaped spherosilsesquioxanes with amphiphilic
properties, combining the relatively hydrophobic spherosilsesquioxane core with hydrophilic oligo (ethylene
oxide) segments were reported around 10 years ago.9 The approach was extended to the synthesis of star-
shaped polymers constituted of octafunctional silesquioxane cores and poly(ethylene oxide) PEO chains.
However almost no work was made on the synthesis of star-shaped polymers with polystyrene (PS)
branches or poly(styrene-block-isoprene) PS-b-PI branches and silsesquioxane cores. The present work
discusses the synthesis and some properties of novel hybrid macromolecular architectures constituted of
PEO, PS or (PS-b-PI) chains and octafunctional spherosilsesquioxane (Q8M8H) cores or cross-linking points.
The synthesis and the characterization of a series of ω-allyl, ω-undecenyl PEO, PS or PS-b-PI
macromonomers by anionic deactivation reactions will be discussed first. The major part of the text will be
devoted to a systematic investigation of the reaction of these ω-allyl or ω-undecenyl macromonomers via
hydrosilylation with octafunctional silsesquioxanes to yield star-shaped polymers. The final section discusses
some preliminary results concerning the synthesis and some properties of networks obtained upon reaction
of α,ω- diundecenyl PEO or PS macromonomers with octafunctional silsesquioxanes.

1. Synthesis and characterization of the macromonomers

1.1 Poly(ethylene oxide) (PEO) macromonomers.

Poly(ethylene oxide) is a water soluble polymer, with outstanding biocompatibility, and its macromonomer is
the building block of a large number of structures suited for various applications. PEO macromonomers,
polymers of low molecular weights fitted at one or two chain-ends with polymerizable end-groups have
gained increasing interests. Several approaches have been developed over the years to design PEO
10
macromonomers by initiation or by deactivation (or by chain-end modification). Potassium p-vinyl or p-
isopropenyl benzylates belong to the first generation of heterofunctional initiators aimed to design well-
defined PEO macromonomers via anionic polymerization of ethylene oxide. Indeed, a wide range of
hydrophilic / hydrophobic balance is accessible by anionic polymerization by modifying the initiator type, the
length of the methylene spacer or the nature of the terminal polymerizable unit and their solution behaviour
was investigated systematically.11 In the present work PEO macromonomers were designed essentially by
chain-end modification of existing polymers.12 This latter way to prepare PEO macromonomers involves
deactivation of the alkoxide function of a monofunctional (or bifunctional) PEO by means of an unsaturated
electrophile such as p-chloro methyl styrene, allyl bromide or 11-bromo-1-undecene to yield the expected
PEO macromonomers. This strategy revealed very efficient for the synthesis of PEO macromonomers fitted
at one or at both chain-ends with styrenyl or allyl end groups: a quantitative functionalization could be
reached. This was confirmed by SEC, 1H NMR and by matrix-assisted laser-desorption/ionization time-of-
flight mass spectroscopy (MALDI-TOF MS) measurements. A typical MALDI-TOF MS spectrum of a PEO
macromonomer fitted at one chain-end with an allyl end group is presented in Figure 1 below (left). On the
same Figure, the MALDI-TOF MS spectrum of a PEO macromonomer obtained by deactivation of the PEO
alcoholate with 11-bromo-1-undecene, under conditions similar to those used in the case of allyl bromide, is
presented. This spectrum is characterized by at least three distributions. The functionalization of PEO with
11-bromo-1-undecene to yield PEO macromonomers is also less efficient.

8000
I I (a.u.)

6000

4000

2000

1600 1800 2000 2200 2600

m/z 3750 4000 4250 4500 4750 5000 5250 5000 5750 6000 6250
1400 2400 m/z

-1
Figure 1. MALDI-TOF MS spectra of PEO macromonomers (Mn=1 900 g.mol ):
left : ω-allyl PEO, right: ω-undecenyl PE0

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Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

1.2 Polystyrene (PS) macromonomers

Different polystyrene (PS) macromonomers have been prepared by quenching living anionic PS either
directly with allyl bromide or with 11-bromo-1-undecene as described earlier.13, 14 Some results are displayed
in Table 1.

Table 1. Some molecular characteristics of ω-undecenyl PS macromonomers.

Run Mn,th a) Mn,PS b) Mn,SEC c) Mw,SEC d) Mw,SEC DFf)

(g.mol-1) (g.mol-1) (g.mol-1) (g.mol-1) / Mn,SEC e) (%)
M-PS12000 2 000 1 900 2 100 2 200 1.05 98
5 000 5 900 1.08
M-PS25000 5 300 5 500 99
M-PS310000 10 000 11 000 11 100 12 000 1.08 97
M-PS425000 25 000 28 800 29 100 31 500 1.08 98
M-PSX refers to ω-functional PS macromonomers with undecenyl end-groups,
a)
Theoretical molecular weight calculated from the ratio [Monomer converted]/[initiator]
b)
PS precursor experimental number average molecular weight measured by SEC, (linear PS calibration)
c)
PS macromonomer number average molecular weight measured by SEC (linear PS calibration)
d)
PS macromonomer weight average molecular weight measured by SEC (linear PS calibration)
e)
Dispersity measured by SEC (Mw / Mn), (linear PS calibration)
f) 1
DF: Degree of functionalization measured by H NMR using an internal standard (C2H2Cl4)

Well-defined PS macromonomers with a narrow dispersity, free of coupling products (no shoulder detected
on the SEC diagram peak) have been obtained for PSs of molecular weights ranging from 2 000 to 50 000
g.mol-1. Polymerization yields are quantitative. Experimental and theoretical molecular weights (calculated
from the [monomer converted]/[initiator] ratio) are in good agreement. The degree of functionalization
measured by 1H NMR using an internal standard (C2H2Cl4) is close 100% for all the samples. One of the PS
macromonomer samples, has been analyzed by MALDI-TOF MS. Each peak of the spectrum corresponds to
a PS macromonomer of a given polymerization degree. The molecular weight of each macromonomer can
be easily calculated. The difference between the molecular weight determined for each peak (taking into
account the presence of the undecenyl group) and the calculated molecular weight assuming quantitative
functionalization of the macromonomer is never higher than +- 0.5 Dalton. Only traces of unfunctionalized
polymers are detected by MALDI-TOF MS. This strategy was extended to the synthesis of bifunctional
undecenyl PS macromonomers. The detailed synthesis of such macromonomers has been described
elsewhere.15

1.3. Poly(styrene-block-isoprene) (PS-b-PI) macromonomers

A similar strategy is used to access PS-b-PI macromonomers. Once the synthesis of the poly(styrene-block-
isoprene) copolymer by sequential anionic polymerization has been completed, the “living” anion was
reacted with the unsaturated deactivator 11-bromo-1-undecene (Scheme 1). To decrease the probability of
the unsaturation to get involved in side reactions, the deactivation had to be conducted in tetrahydrofuran
(THF) at –70°C.16-18
Sec-BuLi Li
n +
Toluene m
Toluene
at 40°C
n-1

(CH2)9 Li
+ THF 0 .1
0 .9
0 .1 at - 70°C
0 .9 m m-1

Br
n
CH2
n 9
Scheme 1. Schematic representation of the synthesis of -undecenyl poly(styrene-block-isoprene)
macromonomers (source ref.18)

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13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

As in the case of the PEO or the PS macromonomers, the resulting poly(styrene-block-isoprene) copolymers
have to be submitted to detailed characterization to assess molecular weight and to establish, whether or
not, every single macromolecule is fitted with an end-standing undecenyl double bond. The SEC curves of
the diblock copolymers displayed a low dispersity, which demonstrates the efficiency of the
(co)polymerization process. SEC measurements confirmed the absence of PS homopolymer and of coupling
products (no shoulders are present on the SEC curves). However, the weight or number average molecular
weights of the macromonomers determined by SEC are overestimated as a calibration based on standard
linear PS samples is used. The determination of the functionality of these diblock macromonomers was
made, as in the case of the PS or PEO macromonomers, by 1H NMR, and provides strong evidence for
quantitative end-capping (> 98%). SEC on line light scattering was used to access the real weight average
molecular weights of the PS-b-PI macromonomers.

Table 2. Some molecular characteristics of -undecenyl PS-b-PI macromonomers (Source ref.18)

ω-undecenyl Mn, SECa) wt.-% of

DF
Run macromonomer (g.mol-1) blocks b) (dn/dc)Cop.c) MW/ Mn,d)
(%)e)
PS Macro. PS PI
1 PS1000-b-PI1000 1 000 2 500 47 45 0.141 1.06 99
3 PS5000-b-PI1000 4 600 6 400 83 14 0.171 1.07 97
4 PS5000-b-PI5000 5 600 15 300 49 50 0.150 1.09 95
5 PS10000-b-PI1000 10 400 13 200 90 9 0.178 1.06 98
a)
Number average molecular weight determined by SEC, (linear PS calibration)
PS refers to homopolymer, Macro refers to PS-b-PI macromonomer.
b) 1
Calculated from H NMR signals of phenyls proton of the PS chain, olefin proton of the PI chain,
methyl proton of sec-Butyl group and olefin proton of the undecenyl end-group.
c)
Specific refractive index increment: (dn/dc)Cop = x (dn/dc)PS + (1-x) (dn/dc)PI, where x is weight
fraction of polystyrene, (dn/dc)PS = 0.186, and (dn/dc)PI = 0.118 determined in THF
d)
Dispersity measured by SEC (Mw / Mn) (linear PS calibration)
e) 1
DF: Degree of functionalization determined by H NMR spectroscopy with internal C2H2Cl4 standard

Besides chain-end determination, discussed above, 1H NMR analysis provided also access to the
composition of the macromonomer and the microstructure of the PI sequence. The results are given in Table
2 above and in Figure 2 below.

C2H2Cl4

CH2=CH~
Integral

8.1963

10.000

6.0 5.9 5.8

(ppm)
562.42

10.000

34.653

1097.8
8.1963

149.98
19.538

793.22

72.899

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
(ppm)

Figure 2. 1H NMR spectrum of an ω-undecenyl PS1000-block-PI1000 macromonomer

The copolymer composition is in good agreement with the respective amount of monomers used. From
these values, the specific refractive index increment (dn/dc)cop of the copolymers could be calculated (Table
2). As expected for a polymerization reaction carried out in non polar solvents, and with lithium as counter-
ion, the 1,4 content (cis and trans) is close to 90%. MALDI-TOF MS measurements of these macromonomes
are now under progress. The results will be published in a forth coming paper together with some data on
the solution properties of the PS-b-PI star-shaped polymers with silsesquioxane cores.19

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Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

2. Synthesis and characterization of octafunctional hybrid star-shaped polymers with silsesquioxane

cores.

2.1 Synthesis and characterization of hybrid octafunctional poly(ethylene oxide) star-shaped polymers with
silsesquioxane cores.

PEO (polyethylene oxide) star-shaped polymers are regarded as a particularly interesting class of materials,
since they represent variable building blocks for structured polymer networks, e.g., hydrogels or amphiphilic
network systems. They are also of great interest for biomedical and pharmaceutical application. In this
context, it was demonstrated that due to their high functionality PEO-stars attached to a surface permit size-
selective protein adsorption. Generally, PEO based star-shaped polymers can be prepared by two different
routes, the “arm-first“ strategy and the “core-first“ approach on the basis of a multifunctional core used as
initiator. In the latter case, the arm length can be tailored by the ratio of active sites to the amount of added
monomer. Well-defined PEO star polymers with 3 or 4 arms have been obtained in a “core-first” manner on
the basis of trimethylolpropane or pentaerythrol cores, respectively. For the synthesis of PEO multiarm stars
with considerably higher functionality the “core-first” method employing a polydivinylbenzene core (DVB) is
used. The main disadvantage of the materials obtained by this procedure is the relatively high dispersity both
20
concerning molecular weights as well as functionality. This can lead to undesired aggregation in aqueous
media or in methanol because of insufficient shielding of the apolar hydrocarbon cores by PEO chains, which
causes amphiphilic properties of the resulting stars. Hyperbranched polyglycerol as well as polyglycerol
modified with short apolar oligo(propylene oxide) segments (DPn = 23 - 52; Mw/Mn = 1.2-1.4), deprotonated
with diphenyl-methyl potassium, were also used successfully as polyfunctional initiators for the anionic
polymerization of ethylene oxide to prepare PEO multiarm star-shaped polymers.21 The different synthetic
approaches, properties and some applications of star-shaped polymers with arms constituted of homo- or
copolymers of poly(ethylene oxide) (PEO) are reviewed in recent article published by Lapienis et al.22

Some studies on the synthesis and the characterization of amphiphilic cubic silsesquioxane-poly(ethylene
oxide) prepared by hydrosilylation reactions using Karstedt’s catalyst under anhydrous conditions have been
published a few years ago.23, 24 However no systematic investigation of the grafting reaction of PEO
macromonomers onto octafunctional silsesquioxanes i.e on the synthesis, the purification, and the detailed
characterization of star-shaped PEO’s with silsesquioxane cores has been published until now. In the
present work, the synthesis and the characterization of new class of hybrid star-shaped polymer constituted
of water soluble PEO branches and octafunctional silsesquioxanes cores (Q8M8PEO) is discussed. If an ω-
allyl PEO macromonomer is reacted by hydrosilylation with octafunctional silsesquioxanes fitted with 8 SiH
functions (Q8M8H) chemical links are formed between the precursor chains and the spherosilsesquioxane
compound (Scheme 2).12 The former becomes the branch and the latter the core of the star-shaped polymer
named Q8M8PEO. Different grafting experiments of ω-ally PEO macromonomers were carried out by varying
the molecular weight of the PEO macromonomer from 1 900 to 10 000 g.mol-1, the concentration and the
nature of the catalysts. The influence of the reaction temperature and the type of hydrosilylation catalyst on
the yield of the grafting reaction was also examined.

H (CH3) 2Si O
OSi(CH 3) 2H
All
O O Si(CH 3) 2H
Si Si
O O
Si Si O O
H (CH3) 2Si O O
O Si Hydrosily
O
O Si
O Si O O Si(CH 3) 2H +
Si
H (CH3) 2Si O O
H (CH3) 2Si O O Si(CH 3) 2H
Undece

Scheme 2. Schematic representation of the synthesis of hybrid PEO star-shaped polymers with
PEO
silsesquioxane cores (Q8M8 )

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13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

The resulting products were characterized by SEC to evaluate the amount of grafted PEO and to determine
the apparent molecular weight. A typical SEC trace is given in Figure 3. Figure 3 reveals the presence of two
peaks: a major one attributed to the star-shaped PEO and a second one corresponding to unreacted PEO
macromonomer (Molecular weight close to 1 900 g.mol-1). Based on calibration with linear PEOs, an
apparent molecular weight of 10 000 g.mol-1 is obtained for the former. This value is lower than expected.
However, it is well established that star-shaped polymers, owing to their higher segment density, which
implies a smaller hydrodynamic volume, exhibit higher elution volumes than the linear equivalent.
100
before
beforepurification
fractionation
90
80
Série2
after fractionation
70
60

RD
50
40
30
20
10
0
17 19 21 23 25 27 29
elution volume

PEO1900
Figure 3. Typical SEC traces (RI detector) of Q8M8 .

Figure 3 depicts the SEC trace of the same sample purified by fractional precipitation. As it can be seen, this
sample is almost free of the precursor PEO macromonomer. Accurate characterization of the purified
Q8M8PEO1900 star by static light scattering in methanol demonstrates the efficiency of the method: the
molecular weight of the star-shaped PEO is very close to the expected value. Additional characterization by
1
H NMR confirmed to absence of the Si-H signal at 4.7 ppm. The number of PEO chains attached to Q8M8H
was also determined from the ratio between the integrals of peak for the methylene group at 0.12 ppm
(Si(CH3)2) and the methyl group at 0.56 ppm (Si-CH2-CH2), and its value is close to 8.

2.2. Synthesis and characterization of hybrid octafunctional polystyrene star-shaped polymers with
silsesquioxane cores.

Branched polymers based on polystyrene (PS) have been subject of interest since many years as they
exhibit strong differences in properties as compared to linear polymers in solution as well as in the bulk.
They allow to test existing theories without changing the basic nature of the polymer chain. The existence of
branched PS structures in polymers obtained by free radical polymerization processes is well established.
The real structures of such species are yet complex and their branch length, their functionality or type of
branching cannot be predetermined in advance. One exception may be the polymerization of
11
macromonomers leading to comb-shaped branched species where all the grafts are of identical length.
Star-shaped PSs are characterized as branched species where all the chains of one molecule are connected
to a central body which is called the core. The interest for star-shaped polymers arises from their
compactness and enhanced segment density as compared to their linear counterparts of the same molecular
weight. As described above, they are basically two different ways to access star-shaped polystyrenes. Either
the branches are made first, and reacted on a second step to build the core; or the core is formed first, and
used subsequently as plurifunctional initiator to grow the branches.25 The synthesis of these species is
essentially based on controlled polymerization methods because they allow a good control in advance of the
molecular weight of linear chains and correlatively of the branch of the star-shaped macromolecules. In “arm-
first“ methods control of the structural parameters in advance is well possible. The individual branch can be
characterized independently, and the number average of branches per star arises from the ratio of the
molecular weight of the star and of the individual branches. Hydrosilylation reaction should constitute an
interesting alternative to living anionic polymerization to access PS star-shaped polymers, by a “core-first”
method. Here again control in advance of the molecular weight of the branches and core-functionality
provided should be possible provided cores of controlled functionality are used. The present work proposes
to synthesize and characterize “arm-first“ star-shaped polymers based on the coupling via hydrosilylation of
ω-undecenyl polystyrene macromonomers, obtained by anionic deactivation reactions, with octafunctional
silsesquioxanes. As in the case of the synthesis of hybrid star-shaped PEOs, ω-undecenyl PS
-1
macromonomers covering a domain of molecular weights going from 2 000 to 30 000 g.mol are reacted via
H
hydrosilylation with Q8M8 . The resulting samples were characterized, by SEC in THF with refractive index
(RI) detection and by SEC online light scattering in THF and chloroform. Provided the coupling reaction
between the macromonomers and the silsesquioxane core is quantitative, the number of branches should be
equal to eight. The SEC diagram of the raw reaction product is characterized by the presence of two peaks:
a major one corresponding to the star-shaped polymer and a second one attributed to unreacted
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Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

macromonomer. Therefore the sample was submitted to fractional precipitation to isolate the star-shaped
polymer from unreacted macromonomer. Fractional precipitation proved very efficient to remove the residual
macromonomer. Detailed investigations on the solution properties of these PS / silsesquioxane star-shaped
polymers are now under progress and will be published in a forthcoming paper.26

2.3 Synthesis and characterization of hybrid octafunctional poly(styrene-block-isoprene) (PS-b-PI) star-

shaped copolymers with silsesquioxane cores.

It is well established since many years that, when block copolymers are dissolved in a selective solvent of
one of the sequences, supramolecular structures i.e. micellar structures are formed.27 This phenomenon has
been the subject of increasing interest and has been extensively studied for block copolymers covering a
large domain of molecular weights, chemical nature and composition.28. Most of these studies were devoted
to linear copolymers. In the 1998th, Hadjichistidis et al.29 have shown that the molecular architecture plays
also an important role in controlling the self-assembling of diblock copolymer based structures. These
authors examined the behavior of well-defined 16-miktoarm star-shaped copolymers of type (PS)8(PI)8 when
dissolved in a selective solvent of one of the sequences of the copolymer. The present work aims at the
synthesis and the solution properties in selective solvents of hybrid octafunctional star-shaped polymers with
PS-b-PI branches and a silsesquioxane core. These star-shaped octafunctional PS-b-PIs can be
synthesized starting from ω-undecenyl PS-b-PI, macromonomers using an hydrosilylation reaction under
conditions close to those used for the grafting of ω-undecenyl PS macromonomers.18 Provided the reaction
is quantitative, the number of branches is determined by the functionality of the silsesquioxane core, and the
number of arms in each star-shaped polymer should be equal to eight. The resulting products were
characterized by first by SEC in THF to determine the conversion and by online static light scattering (LS) to
assess molecular weight and functionality. In most cases a excess of 10 % of macromonomer with respect
the molar content of SiH functions of the silsesquioxane core was used to favor quantitative coupling.
Therefore it is not surprising to detect, even in the case of quantitative coupling, two peaks on the SEC
diagrams. The SEC diagram (refraction index detection, R.I) of the raw reaction product reveals, as
expected, the presence of two peaks, a major one corresponding to the star-shaped polymer and another
one attributed to unreacted macromonomer (Figure 4). This is the case for most of the samples. It has also
to be mentioned that the SEC diagrams of some samples reveals also the presence of a strong light
scattering associated to a low RI detector signal at the same elution volume. A possible explanation for the
presence of these species of molecular weights much higher than expected for the real star-shaped polymer,
may be the occurrence of some side reactions due to the presence of the pendant doubles bonds in the
polyisoprene sequence of the PS-b-PI macromonomers. These double bonds were probably also partially
involved in the hydrosilylation process. Therefore all the raw samples had to be systematically purified by
fractional precipitation. The star-shaped polymer could be isolated from the crude mixture by fractional
precipitation. The molecular weights determined by SEC online LS are significantly higher than those
obtained by SEC/RI detection as expected. This is due to the much smaller hydrodynamic volume of the
star-shaped polymer compared to the linear homologous. As in all star-shaped polymers, the functionality (f)
is obtained by dividing the real molecular weight of the star by the molecular weight of the branch. For the
PS-b-PI star-shaped polymers with the silsesquioxane core described above, a functionality value close to 8
was determined for most of the samples.

70

60

50

40
RD

30

20

10

0
20 25 30 35 40 45
volume d'élution (m L)

Elution
volume (mL)
Figure 4: Typical SEC trace of a PS-b-PI star-shaped polymer with an octafunctional silsesquioxane core

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Besides the characterization of the individual star-shaped PS-b-PI with octafunctional silsesquioxane cores
aimed to determine the molecular characteristics of the individual molecules, a systematic study of the
solution behavior of these star-shaped copolymers has been conducted by dynamic light scattering. The
studies were made in good solvents of both homopolymers and in selective solvents of one of the
sequences. The results of these studies have been partially published in reference 18 and will discussed
extensively in a forthcoming paper.19

3. Synthesis of “model” hybrid networks with octafunctional cross-linking points.

Numerous methods have been developed to synthesize cross-linked polymeric networks. These methods
can be classified into three groups: methods involving free radical (co) polymerization of two monomers,30 or
free-radical (co-) polymerization of macromonomers31, 32 (Figure 5 left), methods employing formation of
bridges between existing linear or branched chains by vulcanization, peroxidation, or irradiation,33 and those
based on chemical reactions involving difunctional polymers bearing living anionic or other functions at the
chain ends and multifunctional low molecular compounds.34-36 (Figure 5 right).

Figure 5. Schematic representation of cross-linking reactions: on the left free-radical cross-linking of

31
difunctional PEO macromonomers in water, , end-linking reaction of α-hydro,ω-hydroxy PEOs with
35
pluriisocynates.
I
In the last method, the average length of the precursor polymer can be chosen arbitrarily, and determined
precisely. The precursor chains become the elastic chains of the network, and the functionality of the core is
given by that of the interconnecting molecular compound. However, the real functionality of the cross-linking
point is, in most cases, not directly accessible. The synthesis and the physicochemical properties of these
“model” networks have been extensively studied during the last 40 years. In the present work, the synthesis
and some properties of a new type of complex hybrid “model” cross-linked architecture based on
poly(ethylene oxide) (PEO) or polystyrene (PS) macromonomers and octafunctional silsesquioxane will be
briefly presented. More details concerning these networks are given in a work recently published.37 Some
earlier attempts to access hybrid networks based on the isocyanate chemistry have also to be mentioned.38
As schematically presented below (Scheme 3) the synthesis of such networks is based on the reaction of
α,ω-allyl difunctional PEO macromonomers with octafunctional silsesquioxanes fitted with antagonist SiH
functions. A series of PEO networks could be obtained, as indicated just above starting from difunctional
PEO macromonomers of molecular weights extending from 3 300 to 10 600 g.mol-1, and at three different
concentrations (20, 30 and 40 wt.-%) The gel point was reached after a few minutes, and was dependent
upon the chain length of the macromonomer precursor and its concentration.

O
O
n

+ Hydrosilyl
ation

H
Scheme 3. Schematic representation of the reaction of α,ω-diallyl PEO macromonomers with Q8M8

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Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

The reaction was kept going for 24 hours in order to reach the highest possible conversion (i.e. to
incorporate as many chains as possible). Then the gels were placed in toluene, dioxane or water for
swelling. The different PEO hydrogels resulting from coupling via hydrosilylation of α,ω-diallyl PEO
macromonomers with Q8M8H were submitted to detailed physico-chemical characterization to access the
degree of equilibrium swelling and uniaxial compression modulus. It is well established that the volume
degree of equilibrium swelling is related to parameters, which are experimentally accessible: the volume
segment concentration upon cross-linking and the average molecular weight of the elastics chains. The
weight degree of equilibrium swelling in toluene and dioxane (Qw) increases with increasing molecular weight
of the macromonomer precursor chains. An increase in the length of the polymer chain, corresponds to a
decrease of the uniaxial compression modulus. However, the value of the modulus increases with increasing
macromonomer concentration. This demonstrates that the density of elastically effective chains is essentially
influenced by the macromonomer concentration. The mechanical properties of these networks were
compared to those of networks obtained via free-radical homopolymerization of difunctional PEO
macromonomers.

Conclusion.

The reaction of well-defined α- or α,ω-mono or difunctional macromonomers via hydrosilylation with

octa(dimethyl-siloxy)octasilsesquioxanes has been successfully used for the synthesis of octafunctional star-
shaped or cross-linking hybrid materials. The resulting star-shaped polymers were characterized by SEC
and by static light scattering, to assess molecular weight and functionality. In most cases the raw reaction
product contains both the star-shaped polymer and residual macromonomer (added in excess on purpose).
The non-grafted macromonomer could be easily removed by fractional precipitation. These well-defined
octafunctional PS, PS-b-PI and PEO star-shaped polymers with silesquioxane cores were submitted to
detailed characterization in dilute solution and in the solid state. Special interest was devoted to the star-
shaped polymers with PS-b-PI branches. Their solution behavior in good solvents of PS and PI or in a
selective solvent of one of the sequences was examined by dynamic light scattering. The formation of
supramolecular assemblies could be demonstrated unambiguously. The approach was extended to the
synthesis of Janus type architectures in which PS and PI homopolymeric chains are grafted to the same
octafunctional silsesquioxane core. The strategy has been extended to the synthesis by hydrosilylation of
PEO or PS networks characterized by well-defined elastic chains and octafunctional cross-linking points. The
resulting hydrogels were submitted to physico-chemical characterization to determine the influence of
structural parameters such as molecular weight of the difunctional macromonomer precursor or the
functionality of the core on the volume degree of equilibrium swelling (Qv) and the uniaxial compression
modulus (EG) in toluene and dioxane. Further studies are now under progress to evaluate the
biocompatibility of the PEO hydrogels containing silsesquioxanes as cross-linking points.

Acknowledgements

A great part of this work was financially supported by the CNRS, the French Ministry for Higher Education
and Research (MESR) and the ANR (ANR Watercat). The authors thank all their colleagues who have
contributed to the work. Special thanks are addressed to Prof. M. Schmidt and Dr. K. Fischer, University of
Mainz (Germany) for their help in the characterization of the PS-b-PI samples by dynamic light scattering.
The authors are also grateful to the characterization Departement of the ICS: A. Rameau, C.Foussat O.
Gavat, R. Meens, and J. Druz.

Page 9 of 12 pages Paper 3 - Lutz

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

References

[1] Laine, R. M., Zhang, C., Sellinger, A. and Viculis, L., Appl. Organometal. Chem. 1998, 12, 715

[2] Laine, R. M., Choi, J. and Lee, I., Adv. Mater. 2001, 13, 800

[3] Rikowski, E. and Marsmann, H. C., Polyhedron 1997, 16, 3357

[4] Brick, C. M., Ouchi, Y., Chujo, Y. and Laine, R. M., Macromolecules 2005, 38, 4661

[5] Costa, R. O. C., Vansconcelos, W. L. and Laine, R. M., Materials Research 2002, 5, 247

[6] Neumann, A., Fisher, M., Tran, L. and Matisons, J. G., J. Am. Chem. Soc 2002, 124, 13998

[7] Santhana, P., Krishnan, G. and He, C., J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 2483

[8] Kuo, S. W. and Chang, F. C., Prog. Polym. Sci. 2011, in press,

[9] Knischka, R., Dietsche, F., Hanselmann, R., Frey, H., Mulhaupt, R. and Lutz, P. J., Langmuir 1999,
15, 4752

[10] Boutevin, B., Boyer, C., David, G. and Lutz, P. J.,Synthesis of Macromonomers and Telechelic
Oligomers by Living Polymerizations, Wiley-VCH Verlag, K. Matyjaszewski, Y. Gnanou and L.
Leibler, Weinheim, 2007, 2, 775-808,

[11] Ito, K., Prog. Polym. Sci. 1998, 23, 581

[12] Harris, H., Lamy, J. and Lutz, P. J., Polym. Prep., Am. Chem. Soc. Div. Polym. Chem., San
Francisco, (USA) 2006, 47, 551

[13] Lahitte, J. F., Peruch, F., Plentz Meneghetti, S., Isel, F. and Lutz, P. J., Macromol. Chem. Phys.
2002, 203, 2583

[14] Harris, H., Catari, E. and Lutz, P. J., Polym. Prep., Am. Chem. Soc. Div. Polym. Chem., San
Francisco, (USA) 2006, 47, 714

[15] Lahitte, J. F., Plentz Meneghetti, S., Peruch, F., Isel, F., Muller, R. and Lutz, P. J., Polymer 2006, 47,
1063

[16] Lahitte, J. F., Peruch, F., Raeder, J. and Lutz, P. J., to be sent

[17] Catari, E., Peruch, F., Isel, F. and Lutz, P. J., Macromol. Symp 2006, 236, 177

[18] Harris, H., Fischer, K., Schmidt, M. and Lutz, P. J., Polym. Prep., Am. Chem. Soc. Div. Polym.
Chem., Boston (USA) 2010, 51 (2), 327

[19] Harris, H., Fischer, K., Schimdt, M. and Lutz, P. J., to be sent to Macromol. Chem. Phys.,

[20] Rein, D., Lamps, J. P., Rempp, P., Lutz, P. J., Papanagopoulos, D. and Tsitisilianis, C., Acta
Polymerica 1993, 44, 222

[21] Knischka, R., Lutz, P. J., Sunder, A., Mülhaupt, R. and Frey, H., Macromolecules 2000, 33, 315

[22] Lapienis, G., Prog. Polym. Sci. 2009, 34, 852

[23] Maitra, P. and Wunder, S., Chem. Mater. 2002, 14, 4494

[24] Mya, K. Y., Li, X., Chen, L., Ni, X., Li, J. and He, C., J. Phys. Chem. 2005, 109, 9455

Paper 3 - Lutz Page 10 of 12 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

[25] Plentz Meneghetti, S., Lutz, P. J. and Rein, D.,Star-shaped Polymers via Anionic Polymerization
Methods, Marcel Dekker, Inc, M. K. Mishra and S. Kobayashi, New-York, Basel, 1999,

[26] Harris, H., Guenet, J.M Lutz, P. J., to be sent to Macromolecules

[27] Tuzar, Z. and Kratochvil, P., Surf. Colloid. Sci. 1993, 15, 1

[28] Abetz, V. and Simon, P. F. W., Adv. Polym. Sci. 2005, 189, 125

[29] Pispas, S., Poulos, Y. and Hadjichristidis, N., Macromolecules 1998, 31, 4177

[30] Hild, G. and Okasha, R., Makromol Chem. 1985, 186, 389

[31] Schmitt, B., Alexandre, E., Boudjema, K. and Lutz, P. J., Macromol. Biosci. 2002, 2, 341

[32] Buathong, S., Isel, F., Peruch, F. and Lutz, P. J., Designed Monomers and Polymers 2004, 7, 583

[33] Bray, J. C. and Merrill, E. W., J. Appl. Polym. Sci. 1973, 17, 3779

[34] Lutz, P. J., Picot, C., Hild, G. and Rempp, P., The British Polymer Journal 1977, 9, 151

[35] Gnanou, Y., Hild, G. and Rempp, P., Macromolecules 1984, 17, 945

[36] Hild, G., Prog. Polym. Sci. 1998, 23, 1019

[37] Harris, H., Nohra, B., Gavat, O. and Lutz, P. J., Macromol. Symp. 2010, 291-292, 43

[38] Liu, H. and Zheng, S., Macromol. Rapid Commun. 2005, 26, 196

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13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

Paper 3 - Lutz Page 12 of 12 pages

Nanopolymers 2011 13-14 September, 2011 – Düsseldorf, Germany

NANOFIBRILLAR CELLULOSE (NFC)-AN EMERGING

MATERIAL FOR LARGE-SCALE APPLICATIONS
Tom Lindström, Mikael Ankerfors & Christian Aulin
Innventia AB
Drottning Kristinas väg 61, 114 86 Stockholm, Sweden
Tel: 0046 8 676 7261 Fax: 0046 8 21 42 35 email: [email protected] or [email protected];

BIOGRAPHICAL NOTE

Tom Lindström holds the position as the Director of the Biofibre Materials Research
Centre (BiMaC Innovation) at the Royal Institute of Technology (KTH) and is also a
Senior Research Scientist at Innventia AB in Stockholm.

His interests span from physical and surface science of cellulosic fibers including
nanocellulosics and bio-(nano)composite materials.

He is a fellow of Tappi and the International Academy of Wood Science, a George

Jayme medallist (ZellCheming), and an Ekman medallist (SPCI).

ABSTRACT

There has been extensive research and development activities in the field of nanocellululosic materials
during recent years, although microfibrillated cellulose was developed already during the late 70s at ITT-
Rayonnier in USA.

A major impediment for the large-scale use of NFC has been the high energy use (excess of 25000
kWh/tonne NFC) for its energy use. This problem has now been alleviated by a series of different pre-
treatment procedures of the fibres prior to the subsequent mechanical cell wall delamination.

Today, there are many companies in the process of commercializing NFC and several pilot plants are
available and some companies are in the planning phase for further up-scaling. A pilot plant for the nominal
production of 100 kg/day (dry based NFC) has also been taken into operation at Innventia AB.

The current contribution will highlight critical issues in the production of NFC and discuss various
applications and hurdles to overcome in order to make NFC production for various end-use applications
viable.

Background

Cellulose is a most important natural polymer and forms a key source of sustainable materials on an
industrial scale. It has been used by man in the form of wood and plant fibres as an energy source, for paper
and building applications, clothing etc. and as a chemical raw material for many years.

Today the isolation, characterization and search for novel applications of various nanocellulosic materials are
generating a lot of research and development activities.

Nanocellulosic materials constitute a new family of nature-based materials (Klemm, Kramer et al. 2011).
Basically, three different domains of nanocellulosic materials can be distinguished:

 MicroFibrillated Cellulose (MFC), also referred to as Nanofibrillar Cellulose (NFC) today, although
NFC usually refers to a more finely delaminated nanoscale cellulosic material. The nomenclature is
not entirely clear.
 NanoCrystalline Cellulose (NCC)
 Bacterial NanoCellulose (BNC)

Page 1 of 6 pages Paper 4 - Lindström

13-14 September 2011- Düsseldorf, Germany Nanopolymers 2011

These nanocelluloses are produced by top-down methods involving enzymatic/chemical/physical methods

for their isolation to the bottom –up production of cellulose nanofibrils from glucose by bacteria. All these
domains have been extensively reviewed by various authors, e.g. (Dufresne 1998; Berglund 2005; Klemm,
Schumann et al. 2006; Hubbe and Rojas 2008; Eichorn, Dufresne et al. 2010; Klemm, Kramer et al. 2011)
and it should be stressed that they seem to have widely different use in a multitude of application areas.
The current contribution deals primarily with the practical utility of nanofibrillar cellulose (NFC).

The manufacture of MFC was pioneered by ITT Rayonnier in the late 70s and early 80s (Herrick, Casebier et
al. 1983; Turbak, Snyder et al. 1983). MFC was simply produced by forcing wood-based fibres through
mechanical devices, such as high-pressure homogenizers, commonly employed in the food industry. Under
such conditions it is possible to delaminate the wood fibres so the microfibrils (around 20 nm wide) are
liberated. The liberated microfibrils have a high aspect ratio and exhibit gel-like characteristics in water with
thixotropic properties. The early developments at ITT Rayonnier also targeted the use of MFC as a gellant in
various food applications.

ITT Rayonnier and other research, however, abandoned further efforts during the mid 80s. The major
hurdles were the high-energy consumption (excess of 25000 kWh/tonne NFC) in the production of MFC as a
result of the required multiple passes through the homogenizers and the extensive clogging of the
homogenizers.

More recent activities in our (Pääkkö, Ankerfors et al. 2007; Wågberg, Decher et al. 2008) and other
laboratories (Saito, Nishiyama et al. 2006) have focused on various pre-treatments of fibres by means of
physical, chemical and enzymatic pre-treatments to decrease the energy consumption. These pre-
treatments focus on decreasing the cohesion of the cell wall, so the cell wall delamination will be easier to
accomplish. By charging the cell wall of fibres by carboxymethylation or other oxidative pre-treatment
methods (e.g. TEMPO-oxidation) or by enzymatic pre-treatments, the energy consumption can be decreased
to much lower energy levels, 500-2000 kWh/tonne. These developments have now opened up for large-
scale applications of MFC/NFC, some of which are discussed below.

Applications of MFC

Paper/board applications

The role of fibre fragments (“fines”) in enhancing the bond strength in paper/board materials is well known to
papermakers and NFC acts in a similar fashion as an efficient dry- and initial wet strength agent in
papermaking. Obvious large-scale applications are to reinforce paper/board, in order to decrease resource
use. Examples include z-strength in paperboard materials and the use of NFC in printing and writing papers,
so the filler content can be increased without strength losses.

Basically, these applications are straightforward, but there are many practical issues connected with up-
scaling, such as pumping, NFC mixing, dilution and homogenization in a robust and industrially suitable way,
when it comes to continuous processing in large scale applications.

Some tentative critical key characteristics for this and other sectors are given in the table overleaf.

Paper 4 - Lindström Page 2 of 6 pages

Exploring the Variety of Random
Documents with Different Content
 288 SCHUYLKILL COUNTY, PENNSYLVANIA wife of William
A. Super; Ida, deceased; Annie, deceased; Maggie, deceased; Alma,
storekeeper at Pottsville; and Charles J., of Port Carbon. David
Williams, father of Mrs. William J. Reese, came to America at the
same time as John Reese, and also settled at St. Clair. A miner by
occupation, he went to California about 1849, <^^ the time of the
gold excitement, and died there afterwards. Mrs. Reese had a sister
Catherine. John W. Reese was born June 23, 1861, at St. Clair,
Schuylkill county, and took the full course in the public schools there,
graduating in 1879. When a boy he began to work in the mines, and
when seventeen years old went to learn the machinist's trade at Port
Carbon, this county, in the Franklin shops. Following his trade until
September, 1892, he then became superintendent of the electric
light plant in St. Clair borough, holding that position until 1894. Then
he returned to his trade for a time, in 1896-97 serving as steward at
the almshouse. In 1900 he again became superintendent of the
electric light plant, continuing to act as such until he assumed the
duties of his present position, in 1909. In the fall of 1908 he was
elected prothonotary of Schuylkill county on the Republican ticket,
by a majority of over twenty-five hundred, and his work was heartily
indorsed at the next election, in 191 1, when he was re-elected by a
majority of over thirty-two hundred. His earlier experiences in public
office included two years' service as councilman of St. Clair, one year
as president of the board of councilmen, and six years as deputy
coroner of the county under Dr. A. L. Gillars. Mr. Reese's various
successes as a candidate are sufficient evidence of his worth. Mr.
Reese makes his home at St. Clair and has always had the keenest
interest in borough affairs. He has been president of the Alert Steam
Fire Company; is a member of the Independent Order of Americans,
and a prominent worker in the P. O. S. of A., holding membership in
Washington Camp No. 75, at St. Clair, in which he has filled all the
administrative offices, serving also as secretary and trustee; in 1910-
11 he was State president of the order, and for a number of years
has been a delegate to its national gatherings. He formerly belonged
to Camp No. 21, P. O. of T. A., an auxihary order of the P. O. S. of A.,
and has filled local and State offices in that body. On April 29, 1883,
Mr. Reese married Bertha Fielding, daughter of Thomas and Mary
Fielding, of St. Clair, and she died Sept. 29, 1889, at the age of
twenty-eight years. On March 10, 1892, he was united in marriage
(second) with Bertha Greenwood, daughter of Luke and Ann
Greenwood, of Locust Summit, Northumberland Co., Pa., and seven
children have been born to this union: Natalie B., Jay (deceased),
Lillian (deceased), Dorris, Annie, Stanley (deceased) and Bertha. Mr.
Reese affiliates with the M. E. Church, while his family are Baptists.
JOHN H. DAVIS, late of St. Clair, filled a conspicuous place in the
activities of that borough for so long a period that his death aflfected
all circles and classes. Well fitted by nature and training for
leadership, he took his responsibilities toward his fellow men
seriously, and that he regarded his opportunities to improve
conditions in his own community as a duty of privilege may be
judged by his earnest efforts in that direction and the enjoyment he
had in their success. In business he showed initiative and executive
ability. He could plan largely and follow his ambitions to prosperous
achievement. But he did not restrict those ambitions to the narrow
limits of personal benefit. All shared in his good fortune, and the
breadth of his sympathy
The text on this page is estimated to be only 0.00%
accurate

'^y/'S/vvl^/. ^^
 SCHUYLKILL COUNTY, PENNSYLVANIA 289 was well
indicated by the variety of his interests, business, social, religious
and benevolent organizations all having their due part in his well
rounded life. He owned the Ellsworth colliery and was a coal
ojjerator principally, but he had a hand in the organization and
management of other important undertakings, and he gave
considerable attention to public affairs and other interests not of a
business nature, but which he deemed vital to the general welfare.
Mr. Davis was born in 1849 ^^ Minersville, Schuylkill county, son of
John R. and Hannah (Rowe) Davis. He grew up in his native town
and received the principal part of his education in its public schools,
later attending the Crittenden commercial college. During practically
all of his business life he was engaged in the mining of coal, being
associated with his father until the hitter's death, in 1900, and the
large and varied operations of the firm afforded him rare
opportunities for valuable experience which he used in the most
intelligent manner. Moreover, he had plenty of occasion to employ
his executive faculties, at the Ellsworth colliery particularly, having a
hard struggle to make a success of its development for several years
prior to 1900. From that time until his death he w^as sole owner
there, but he also had coal interests at Gilberton, this county, having
joined Philadelphia capitalists under the name of the Brighton Coal
Company in the construction of the colliery there a number of years
ago, and he was treasurer of the company up to the time of his
death. He was an incorporator and one of the principal stockholders
of the Citizens' Bank of St. Clair, established in 1904, and its
president from that time until his death. He was a director of the
Schuylkill Pressed Brick Company. It was in the early nineties that he
came to St. Clair. Mr. Davis was interested in politics, but though a
Republican on national questions was non-partisan in local matters,
supporting the movements which in his judgment promised most to
the community. Indirectly he exerted a continuous influence in all
things afifecting the general good, but he also gave personal service,
being a member of the board of health and of the town council for
several terms ; his work in the latter body was especially
notevs'orthy, and he served as president of the council until within a
short time of his death. As an earnest member of the First Methodist
Episcopal Church of St. Clair he labored zealously in its interest,
acting as president of the board of trustees which rebuilt the church
several years ago and did so much to put the financial affairs of the
congregation on a sound basis. Mr. Davis was keenly interested in
conditions in the borough and endeavored to promote social and
living standards through every available channel. The Pottsville Daily
Republican of April 13, 1914, said: "His workmen particularly were
under his constant kindly supervision, and no employer ever had a
more loyal set of men. During the recent strike no watchmen were
necessary at his colliery, for the men took care of the plant
themselves. When coal became scarce his banks were the only ones
in the region that were freely turned over to the pickers. Churches
and charitable institutions of every denomination received frequent
contributions from him. In St. Clair he was a contributor to every
church and in other parts of the county he frequently sent
substantial aid to the needy religious bodies. He was a frequent
visitor to the Miners' hospital and took a keen interest in the patients
there. Although not a member of the Odd Fellows he took a big
interest in the Orphanage of that lodge at Sunbury, and the trustees
are witnesses to the fact that his contributions were always received
when most needed." Aside from all this he looked personally after
the wants of many needy ones, being beloved for his generosity Vol.
1—19
 290 SCHUYLKILL COUNTY, PENNSYLVANIA in many homes
which feh his kindly interest when their burden of want was reheved
by substantial gifts bestowed without ostentation. In fact there were
a number of families of small means in the borough who knew him
for a sympathetic friend, especially to widows and orphans, though
he did not discriminate against any unfortunates. His modesty never
allowed him to speak of any such services to his less favored fellows,
but their testimony shows how far his liberality reached. His sudden
death, on Saturday, April ii, 1914, was a shock such as St. Clair has
seldom experienced. Though Mr. Davis had been ailing for several
months his condition had improved so that he was apparently on the
road to recovery, and he was downtown with his wife early in the
evening -when stricken. The Pottsville Daily Republican, in a lengthy
obituary, said: "In John H. Davis, St. Clair has lost a citizen who will
be missed for years to come. As owner of the Ellsworth colliery he
reached a position of prominence in the town and was classed as
one of its wealthiest residents. * * * Ten years ago Air. Davis erected
the beautiful home at Second and Franklin streets, the handsomest
residence in St. Clair." He was buried from that home, the remains
being taken to the Charles Baber cemetery at Pottsville. Mr. Davis
was a thirty-second-degree Mason, a member of Williamsport
Consistory and of Rajah Temple, A. A. O. N. M. S., the latter of
Reading. Mr. Davis was first married to Mary E. Davis, daughter of
Rev. Daniel T. Davis, of Scranton, Pa. She died a year later, and he
was subsequently married to Mary E. Bomboy, daughter of Percival
and Sarah Bomboy, of New Castle township, this county. By this
union there were two children, William B. and Edith B. The daughter
died in infancy, and the son when twenty-six years old. Their mother
passed away in 1898, and Mr. Davis afterwards married Ida H.
Honsberger, daughter of Charles C. and Lucy (Rarig) Honsberger, of
Zion Grove, in North Union township, Schuylkill county, where they
still reside. Mr. Honsberger was postmaster at Zion Grove for many
years, and was also engaged in the timber business. Mrs. Davis
survives her husband with the only child of this marriage, June H.
DAVID V. RANDALL is directing the operation of one of the most
important collieries in Schuylkill county, the Lytle property in Cass
township. Affording employment to about nine hundred and support
to approximately as many families, it provides a living for a large
share of the local population directly, to say nothing of the incidental
business of the merchants and tradesmen who depend upon Ihe
patronage of these workers for their prosperity. The Lytle mines
constitute therefore a large asset in the estimated resources of the
county. Their judicious exploitation is a worthy problem for an
expert, a man possessing business and executive qualities as well as
the necessary scientific information. Mr. Randall is the son of a
prominent attorney of Wilkes-Barre, Pa., and he was bom in that city
April 2, 1874. There he obtained his edi]cation in the public schools,
and when a young man was given a place in the city engineer corps.
Later he was employed with H. S. Reets, mining engineer, for a time
and then took a position with the Delaware & Hudson Coal Company,
remaining in their employ until 1898. That year he changed to the
Susquehanna Coal Company, with whom he has since been
associated, the Lytle coUien,', at Primrose, Schuylkill county, being
one of the holdings of that concern. In February, 1909, Mr. Randall
was transferred to this colliery, of which he has since
 SCHUYLKILL COUNTY, PENNSYLVANIA 291 had charge. It
was founded in 1889 by John Hosie and others, who sold out to
Stickney & Conyngham, and in 1909 the property was taken over by
the Susquehanna Company, since when it has been known as the
Lytle colliery. At present the annual output is about 400,000 tons,
and employment is given to about nine hundred men. The
equipment has been modernized to suit the needs of the work, and
better facilities for mining have been devised, and at present the
colliery is one of the most up-to-date in this region. Mr. Randall is a
member of the Pottsville Club, and of the Mercantile Club of
Minersville, as well as the Alasons, in the latter connection belonging
to Lykcns Lodge, No. 570, F. & A. M.; Keystone Consistory, of the
Valley of Scranton, and Irem Temple, A. A. O. N. M. S., of Wilkes-
Barre. ]\Ir. Randall married Harriet Witt, of Wilkes-Barre, daughter of
Anthony Witt, who was born in Baden, Germany. Mrs. Randall is a
native of Williamsport, Pa. Mr. and Mrs. Randall have two sons,
Planadon Reets and David Anton. C. ARTHUR FISHER, proprietor of
the "Rising Sun Hotel" at Orwigsburg, and operator of a coal
washery at Landingville, in North jManheim township, Schuylkill Co.,
Pa., was born Jan. 20, 1877, ^^ historic Valley Forge, Chester Co.,
Pa., son of Gen. Benjamin F. Fisher, grandson of Rev. Peter S. Fisher,
and great-grandson of William Fisher (Fischer). William (or Wilhelm)
Fisher was of German birth, a farmer by occupation and he lived in
Lower Heidelberg township, Berks Co., Pa. He is buried at Plain's
Church, in that township. From him are descended many of the
name in that section of the State. He was an adherent of the
Reformed Church, as were most of his family. Rev. Peter S. Fisher,
son of William, was born near Hain's Church, where he attended the
services of the Reformed denomination. So strongly were the tenets
of that faith implanted in his youthful mind that he decided to follow
the profession of minister of the gospel. He was located soon after
graduation at Boalsburg, Centre Co., Pa., later going to Sellersville,
Bucks county, where he died. He was united in marriage to
A''eronicca Heckert, of Hummelstown, Dauphin county, by whom he
had the following children : Alfred ; Calvin; Benjamin F. ; Aaron;
Nevin ; Maggie, wife of Dr. Wireback; and Ada, wife of William
Cordy, of Oil City, Pennsylvania. Benjamin Franklin Fisher, father of C.
Arthur Fisher, was born at Boalsburg, Centre Co., Pa., and was
educated in the common schools, Boalsburg Academy, and Franklin
and Marshall College, Lancaster, Pa. Immediately after graduating, in
1859, he entered the law office of the late Judge Stokes L. Roberts,
of Doylestown, Pa., and was admitted to the bar in October, i860.
]\Ir. Fisher and Dr. Joseph H. Thomas organized Company H, of the
3d Pennsylvania Reserve Corps, and on the President's call for troops
in 1861 this company was mustered into the United States volunteer
service as Company "H" of the 32d Pennsylvania Volunteers, with Mr.
Fisher as first lieutenant. Immediately after entering the volunteer
service Lieutenant Fisher was detached for duty at the School of
Instruction for the Signal Corps, at George- ■ town, D. C, and in the
fall was assigned for duty in the field on the staff of General Hooker,
with the Anny of the Potomac. In the fall of 1862 he was promoted
to captain and chief signal officer in the field of the Army of the
Potomac, and sen'ed successively on the stafl^s of Generals
McClellan, Burnside and Hooker. In June, 1863, on the retirement
North of General Hooker's
 292 SCHUYLKILL COUNTY, PENNSYLVANL\ army from
Chancellorsville, which ended in the battle of Gettysburg, Captain
Fisher was captured by a detachment of Colonel Mosby's men, while
trying to locate the position of Lee's army. As a prisoner of war he
w,as confined in Libby prison, Richmond, Va., until February, 1864,
when he helped to dig and escaped through the famous Rose
tunnel. After reaching the Union lines at Williamsburg, Va., Captain
Fisher found that he had been promoted major for "meritorious and
gallant conduct," and returned to Washington, where he married
Alice Eliza, daughter of James H. Causton, a prominent Union
sympathizer of Georgetown. To them were born si.x children : Alice
E., married to F. K. Pennypacker, a cousin of e.x-Governor
Pennypacker ; Fannie H., who married A. M. Vanderslice; Benjamin
F., Jr., an electrical engineer of New York City, who married Louise B.
Reynolds ; Mary C, married to Benjamin R. Walker; C. Arthur,
mentioned below; and William P., who married Mary Alexander. In
the fall of 1864, Major Fisher was promoted lieutenant colonel for
"meritorious and conspicuous service," and in the spring of 1865 he
was promoted colonel, with the rank of brevet brigadier general of
volunteers, and appointed chief signal officer of the United States
army. In November, 1866, he resigned this office to return to the
practice of law and accept the position of registrar of bankruptcy for
the Eastern district of Pennsylvania. General Fisher practiced law for
forty years in the city of Philadelphia, enjoying a large clientage. He
was appointed receiver of the Spring Garden National Bank upon its
failure and for many years was trust officer of the German-American
Title & Trust Company. In 1907, upon the death of his wife, he
retired to his summer residence (Colonial Springs) at Valley Forge,
where he died Sept. 9, 191 5. C. Arthur Fisher was educated in the
public schools of Schuylkill township, Chester county, at the Quaker
School in Philadelphia, Franklin and Marshall Academy, and Franklin
and Marshall College, Lancaster, Pa. He began his business career as
a clerk in his father's law office in Philadelphia, where he remained
for several years. He studied law for two years, but finally gave it up
to become a farmer on the homestead of his father, the old Joseph
Anderson place. For seven years he was supervisor of Schuylkill
township, Chester county, and then he located at Pine Grove,
Schuylkill county, where he conducted a hotel for six years. In 1912
he became proprietor of the "Rising Sun Hotel" at Orwigsburg, Pa.,
the oldest licensed stand in Schuylkill county, and still conducts this
hotel with success. He is also engaged in the coal washing business
at Landingville, doing both a wholesale and retail business. On April
30, 1902, Mr. Fisher married Annie R. Hoy, a daughter of John L. and
Elizabeth (Coats) Hoy, of \^alley Forge, Pa., and to this union two
children have been born: Charles A., Jr., and B. Franklin. Mr. Fisher is
a member of the Knights of the Golden Eagle and of the Sons of
Veterans, at Orwigsburg. In politics he is a Republican. SAMUEL
REED, now living retired at Schuylkill Haven, is one of the best
known men in and around that borough. His earlier years were spent
as a boatman, and when the cessation of business on the canal
made a change desirable he engaged in railroad work, afterwards
carrying on a grocery store at SchuylkillHaven until his retirement.
The Reed family were early known in Schuylkill county. In 1771,
when
 SCHUYLKILL COUNTY, PENNSYLVANIA 293 Pine Grove
township, that county, was established, Phihp Rith (Reed) was a
taxable. He was a native of Berks county, however, a member of the
Tulpehocken family. In 1791 Jeremiah Reed, Michael Reed (both
married) and Thomas Reed (single) were taxables in Manheim
township, Schuylkill county. In 1802 Theodore Reed, John Reed,
John (Morris) Reed, Thomas Reed, Sr., and Isaac Reed were
taxpayers in Norwegian township, and John and Philip Reed in
Mahantango township, that county. Christopher (Stophel), George
and Conrad Reed, brothers, were born in Brunswick township,
Schuylkill county. Of these, Christopher passed all his life in his
native township, and there reared his four sons, Obediah, George,
Charles and Emanuel. Christopher Reed was the great-grandfather of
Samuel Reed. George Reed, the grandfather, was a pioneer resident
of Schuylkill Haven, and one of the successful business men of his
day. He learned the trade of butcher and followed it all his life. He
lived to the age of eightyfour years, and is buried in the family plot
in the Union cemetery, at Schuylkill Haven. By his first wife, whose
maiden name was Achey, he had five children: Samuel; Daniel, a
blacksmith, who died near Ringgold; Prank, a butcher at Weissport,
where he died ; Joseph, who served in the Civil war with his three
sons, and died at Pottsville, Pa. ; and Caroline, who married Lorry
Heebner and died at Schuylkill Haven. To his second marriage, with
a Miss East, were born three children : Tamsey, who married James
Palsgrove, of Schuylkill Haven; Missouri, who married Josiah Karcher,
and is now living at Philadelphia; and Elizabeth, who married Henry
Quinter and (second) William A. Yost (she and her first husband died
at Schuylkill Haven). Samuel Reed, son of George, was born May 26,
1805, in Schuylkill Haven, and during his boyhood was bound out to
a Mr. Faust, in Brunswick township, where he remained a few years.
His early life was spent in hard labor. Learning the butcher's trade
after leaving Mr. Faust, he followed it at Schuylkill Haven for many
years, and also worked as a cigarmaker, manufacturing the Lincoln
cigar, a well known brand in its day. He was able to retire before his
death, which occurred July 19, 1869, when he was sixty-four years
old. He is buried in the Union cemetery. His wife, Mary (Ellinger),
daughter of John Ellinger, was born in Dauphin county. Pa., Jan. 11,
181 1, and died in Schuylkill Haven July 6, 1866. They had a large
family, namely: Polly married Godfried Boyer; William died at
Harrisburg, Pa.; Thomas died at Schuylkill Haven ; John died young ;
Francis died young ; Charles E. died at Schuylkill Haven; Elizabeth,
widow of Charles Mengel, is living at Port Clinton, Pa. ; George S.,
who died at Philadelphia, Pa., was a soldier in the Civil war, serving
four years in Company C, 50th Pennsylvania Regiment ; Sarah Louisa
married Hiram Hahn and (second) Charles Jordan; Lucy married
Samuel Blackburn, who is deceased, and she lived at Schuylkill
Haven ; Samuel is mentioned below; Henry died at Wilmington, Del,
but is buried at Schuylkill Haven; Morris is living at Allentown, Lehigh
Co., Pennsylvania. Samuel Reed was born Jan. 3, 1849, at
Friedensburg, Schuylkill county, had such education as the common
schools of the day afiforded, and during his boyhood assisted his
father, stripping tobacco. In 1863 he went to work as a driver on the
Schuylkill canal, with the boat "P. D. Thomas," and he continued to
work on the canal until business there was discontinued, becoming a
captain when seventeen years old. Changing to railroad work, he
was in the employ of the Philadelphia & Reading Railway Company
for a period of about twenty-five years, as brakeman, conductor and
train dis 
 294 SCHUYLKILL COUNTY, PENNSYLVANL\ patcher, giving
up this occupation in 1898 to go into business. He was a green
grocer at Schuylkill Haven for the next twelve years, having an
excellent trade throughout that period, and retired in 1910 with an
excellent reputation for honorable dealing and ability to please his
patrons. The only public office Mr. Reed has held is that of ward
assessor. He is a Republican in politics, in religion a member of the
United Evangelical Church, at Schuylkill Haven, in which he has been
prominent, having served on the building committee which had
charge of the erection of the parsonage. For thirty-four years he was
a member of the Patriotic Order Sons of America, and he is
prominent in Jere Helms Post, No. 26, G. A. R., of which he was a
charter member ; he has been commander for the last six years.
Though only a boy when the Civil war was started Mr. Reed served
four months in the army during 1865. He enlisted from Dauphin
county. Pa., Feb. 15, 1865, to serve one year or during the war, and
was mustered into the United States service at Harrisburg, Pa., the
next day, as a private of Capt. Solomon Cover's new company, I, of
the 87th Regiment, Pennsylvania \'olunteer Infantry, Col. John M.
Schall commanding. The regiment was first organized in September,
1861, under Col. George Hay, and was employed in drilling, and on
guard and picket duty until the 26th of May, 1862, when it marched
to Baltimore, Md., thence to Martinsburg and New Creek, W. Va.
There it remained during the heat of the succeeding summer, taking
part in a number of expeditions, to Beverly, Philippi, and \A'ebster,
thence returning to New Creek. Later the regiment was assigned to
the ist Brigade, 3d Division, 6th Corps, Army of the Potomac, and
took part in the engagements at Bunker Hill, Strasburg, Caster's
Woods, Manassas Gap, Bealton, Kelly's Ford, Brady Station, Locust
Grove, Aline Run, Wilderness, Spottsylvania, Cold Harbor, siege and
assault of Petersburg, Weldon Railroad, all in Virginia ; Monocacy,
Md. ; Opequan or Winchester, Fisher's Hill, Strasburg, Cedar Creek
and Appomattox, ^'a., where Lee surrendered. It was also in a
number of minor engagements and skirmishes, and took part in the
grand review at Washington, D. C, May 24, 1865. Mr. Reed joined
this regiment in front of Petersburg, Va., participating in all its
movements and engagements thereafter, performing gallant and
meritorious service, in recognition of which he was promoted to
corporal. After leaving Petersburg, Va., two companies from the 7th
were allotted from the main army and sent to capture Clover Station,
Va., and hold it until relieved. On the first day of occupation he was
detached with two comrades to protect Walker's farm, near Clover
Station, from depredation. On the second day several Confederate
officers arrived at the farm, having been paroled. Among them was
General Walker, a son of the owner of the farm, and the next
morning, as Mr. Reed was eating his breakfast. General Walker
entered and took a seat at the opposite side of the table, wearing
his gray uniform, while the other wore the blue. This was the only
time Mr. Reed ever ate a meal with a Confederate general, and it
was devoured in utter silence, although the General's father
apologized for his son's silence 9ifterwards. He said that he was
forced to maintain sympathy for the Southern cause, being at that
time surrounded by a band of guerrillas, but he promised that in
case young Reed were captured by the guerrillas he would see that
he was liberated at once. After this incident the owner of the farm
furnished him with a horse to ride to Clover Station, and one of his
colored servants to accompanv him and take the horse back. Upon
his arrival at Clover Station the captain of his company inquired as to
where he had pro 
 SCHUYLKILL COUNTY, PENNSYLVANIA 295 cured the horse,
but when informed tliat it was a loan, and to be returned by the
servant, declined to allow it. The horse was accordingly packed for a
march to Danville, and the colored man taken along also. At Danville
the captain sold the horse, and the colored man remained *vith the
company until it arrived at Harrisburg, Pa., and was mustered out.
Mr. Reed was honorably discharged June 29, 1865, at Washington,
D. C, by reason of the close of the war. On Feb. 2, 1868, Mr. Reed
married Mary C. Kerkeslager, daughter of Noah and Caroline
(Emerich) Kerkeslager, who had a family of six children, bom as
follows : Charles W., Nov. 29, 1847 ; Mary C, Dec. 14, 1849 ; Alice v.,
Dec. 25, 1851 ; Carrie E., Dec. 9, 1854; Sallie L., April 12, i860;
Harry A., Dec. 26, 1862. Mr. Kerkeslager, born Oct. 22, 1820, died
Oct. 15, 1863; his wife died in 1879. Mr. and Mrs. Reed had the
following family : Carrie May, born June 2, 1869, died Feb. 19, 1S73;
Florence Ellinger, born Oct. 9, 1871, married John H. Emery, and is
living at Palo Alto ; Ellis William, born Nov. 19, 1873, u"" married and
living at home, is a veteran of the Spanish-American war, having
enlisted in 1899 in Company C, i6th Infantry-, and served three
years in the Philippine Islands (before the war was in the navy three
years, having enlisted at League Island) ; Samuel Noah, bom June
24, 1876, married Kate Weldon (he is in the grocery business at
Orwigsburg, Pa.) ; Maude Irene, born May I, 1880, married Jacob
Boltz, a box manufacturer, of Pottsville, Pa. ; Joseph Alfred, born
Feb. 28, 1885, died Dec. 14, 1894. HENRY A. DIRSCHEDL, M. D., of
Pottsville, has been making a creditable professional record during
his comparatively brief career as a practitioner. Though busy with
private practice he has entered heartily into the larger duties of the
medical profession, according to modern ideas, doing effective work
in establishing and promoting sanitary conditions and hygienic living
in a general way. His ability to put advanced ideas into practical
operation has gained the recognition of his brother physicians as
well as of the public. Dr. Dirschedl was born at Pottsville, June 12,
1874, son of Joseph and Theresa (Reichenberger) Dirschedl. The
parents were natives of the same place in Bavaria, Germany. They
came to America with one child and first settled in Philadelphia for a
time, Joseph Dirschedl following the bakery business. He then came
to Schuylkill Haven, Schuylkill county, and after a short stay there
moved to Pottsville, in 1864, where he was also engaged in the
bakery business. He continued it until forty years old, afterwards
living retired until his death, which occurred Jan. 30, 1883, when he
was forty-nine years old. He is buried at Pottsville. His widow died
April 24, 1905. Of their three children, two were bom in Pottsville,
Mary and Henry A., the latter being the only survivor of the family ;
]\Iary died Nov. 29, 1882 ; Max died July 3, 1878. Joseph Dirschedl
was one of the first members of the German Catholic Church o"f
Pottsville. then situated at Fourth street and Howard avenue, and
later assisted in erecting the present church, in 1872. Henry A.
Dirschedl obtained his preparatory education in the Pottsville
parochial schools. When Dives, Pomeroy & Stewart opened a store in
the borough in 1887 he was the first to enter 'their employ here, and
he remained with them uninterruptedly until he entered medical
college in 1905.^ Meantime he had gained steady promotion on
merit alone, becoming financial secre 
 296 SCHUYLKILL COUNTY, PENNSYLVAXL\ tary and
assistant manager of the Pottsville store. After entering college he
made a number of special trips for the company, with which he
maintained his connection until 1913. Dr. Dirschedl took the full
course at the MedicoChirurgical College, Philadelphia, graduating in
1910, and served as interne at St. Joseph's Hospital, Reading, Pa.,
returning to Pottsville for practice in 191 1. His office is at No. 613^
West Market street. Dr. Dirschedl is medical examiner for the
German Roman Catholic Knights of St. George, and several other
similar organizations, as well as for a number of insurance
companies ; is a member of the Pottsville city board of health; and a
lieutenant surgeon in the Pennsylvania National Guard, attached to
the 4th Regiment. He received his appointment to the latter office
from Colonel O'Neil in 1914 and began his services in that capacity
during the encampment of that year. Nothing could have shown
more plainly his standing among the members of his profession than
the fact that at least thirty of the leading physicians of the county
recommended him for the position. He is a district deputy of the
Knights of St. George in Schuylkill and Dauphin counties, and at the
1915 State convention was made State organizer. Politically Dr.
Dirschedl is a Republican, but he is guided by his own ideas in his
stand on local questions. Dr. Dirschedl married Laura W. Thomas,
daughter of Prof. William S. Thomas, of St. Clair, Schuylkill county,
whose family consisted of three children: Fannie married Harold
Schum, of Pittsburgh, Pa.; Lucy married Horace Priest, of Pottsville;
Laura W., Mrs. Dirschedl, received her education in the public
schools and at the Millersville State Normal School, from which she
was graduated in 1900. Dr. and Mrs. Dirschedl have two children,
William Thomas and Mary Louise. R. BRUCE CLAYTON has been
closely associated with the administration of municipal affairs in
Ashland for many years, his work in the various positions of trust to
which he has been chosen justifying the oft repeated honors he has
received at the hands of his fellow citizens. A native and lifelong
resident of the borough, his interest has been public-spirited and his
efforts have been thoroughly loyal, showing a sentiment highly
creditable to him. Mr. Clayton is a grandson of William Clayton, who
was a pioneer of Columbia county, Pennsylvania. Nelson Clayton, the
father of R. Bruce Clayton, was bom at Catawissa, Columbia county,
and lived at Ashland, Schuylkill Co., Pa., from 1853 to the end of his
life. By trade he was a carpenter, but after coming to Ashland he
was engaged in business for several years, establishing a flour and
feed store, which he carried on until 1859. Thereafter he was
employed at his trade until his death, which occurred in 1878. At one
time he served as assessor of Ashland. He married Mary Jane Zarr, a
native of Union county. Pa., daughter of Benjamin Zarr, who was a
pioneer of Union county; he was a hatter by trade. The Zarr family
eventually moved to Catawissa, Columbia Co., Pa., where Mrs.
Clayton's parents died. Mrs. Clayton, now (1914) eightythree years
of age, is living in Philadelphia with two of her daughters. She is the
mother of five children, of whom R. Bruce is the eldest; Winfield
Scott died about i860; Laura is the wife of E. P. Meiswinkle, of
Philadelphia; Cora B. is the wife of Brainerd Webb, of Philadelphia;
Harriet M. is the wife of Harry K. Buchanan, of Lanark, Pennsylvania.
R. Bruce Clayton was born at Ashland Dec. 13, 1854, the wmter of
deep snow. His education was acquired in the public schools there,
and when
 SCHUYLKILL COUNTY, rENXSYLVANL\ 297 a youth he
began to learn the trade of machinist in the machine shop of JVJ.
Garner. He followed the trade for twenty-hve years in all as
apprentice, journeyman and foreman, giving it up to assume the
duties of postmaster of Ashland, to which important position he was
appointed in 1897. He served nine years, being succeeded by IMrs.
Patterson. He has since been chosen to other positions in the public
service, having been inspector of the streets for some time, and for
the last four years he has been sealer of weights and measures.
Especially interested in promoting the public school efficiency of
Ashland, he has been a member of the school board for eleven
years, and for seven years secretary of that body. His work in this
connection has been valuable and worthy of the appreciation it has
received. In 1878 Mr. Clayton was united in marriage with Matilda A.
Kintzle, who was born in Bernville, Berks Co., Pa., daughter of John
L. and Rosanna (Sheets) Kintzle, and granddaughter of Henry and
Sarah (Boyer) Kintzle, who were early residents of Berks county. The
family is of German ancestry. Mrs. Clayton's grandparents removed
to Port Clinton, Schuylkill Co., Pa., and died there. Mrs. Clayton's
maternal grandfather was also an early resident of Berks county. Mr.
and Mrs. John L. Kintzle emigrated to the West and passed the
remainder of their lives there, his death occurring in 1897, hers in
191 1. Of their family of four children William, the eldest, is now a
resident of Freeport, 111. ; Naomi is deceased ; Matilda A. is the
wife of R. Bruce Clayton ; Anna is married to George Gheen, of
Kansas City, Missouri. Three children, all sons, have been born to Mr.
and Mrs. Clayton : Nelson lives at Pottsville and is at present
superintendent of the Pottsville Water Company ; he married Sarah
Evans, of Ashland, Pa., and they have three children, Bruce Samuel,
Sarah Dorothy and Nelson John. Robert Bruce, now living at
Sonman, Cambria .Co., Pa., married Gertrude Greshman, of Ashland
; they have no children. William R., who lives at Ashland, married
Mariam Faust, of Reading, Pa., and they have one child, Thelma. Mr.
Clayton and his wife and family are members of the Lutheran Church
at Ashland. He has made many friends in his various social
connections, being a member of Ashland Lodge, No. 294, F. & A. M.
(which he has served as secretary) ; of Griscom Chapter, No. 219, R.
A. M.; of Ashland Lodge, No. 384, B. P. O. Elks (he is serving as
trustee of same) ; of Prince of Peace Commandery, No. 39, K. T. ; of
Camp No. 84, P. O. S. of A. (in which his membership dates from
1871) ; and of the Royal Arcanum. ABRAHAM L. ECKERT is a
prosperous business man of Pottsville and a member of the present
city council. He was one of the most active workers in securing the
system of municipal government now in operation, and his public-
spirited efforts in that direction have given him a high place in the
gratitude of his fellow citizens. Mr. Eckert was born in Pottsville April
28, 1862, son of Josiah Eckert, who lived and died here. His death
occurred when he was forty-six years old, and he is buried at
Schuylkill Haven. His wife, whose maiden name was Sarah Bowman,
died when fifty-one years old. Abraham L. is the only surviving child
of their family. Abraham L. Eckert attended public school in Pottsville
and began work there as errand boy for Jacob Ulmer, the packer.
After four years in his employ he learned steam and pipe fitting,
following that work for about six years. At the end of that period he
went to Florida, where he started an orange grove, and after it was
destroyed by frost he spent two years assisting in the
 298 SCHUYLKILL COUNTY, PENNSYLVANIA construction of
the well known "Tampa Bay" hotel. After seven years in Florida he
returned to Pottsville, where he embarked in the tea and coffee
business, carrying it on for about six years. When the Spanish-
American war broke out he enlisted in Company H, Pennsylvania
Volunteers, serving for eleven months. Coming back to Pottsville
again, he was engaged as solicitor for the International
Correspondence Schools of Scranton, Pa., continuing this work for
four years. In 1902 he bought out the business of the Pottsville Ice
Company, owned by James Green, and is now conducting same
under his own name, dealing in coal and wood as well as ice. He has
built up a large trade, keeping three teams constantly employed, and
the satisfactory service which he has endeavored to render to all his
patrons has held old customers and attracted many new ones. Air.
Eckert has been very keenly interested in the welfare of his home
town, and of late has been particularly active as president of the City
Charter Association, to whose objects he has given a great deal of
his time, his reward being in the thorough success of the plans for
the improvement of local government. In November, 1913, he was
elected a councilman, and is also acting as superintendent of public
safety. Mr. Eckert is a prominent member of the Merchants'
Association, and has been appointed State organizer of same.
Politically he is independent of party ties, supporting the men and
ideas he considers best adapted to achieve the best results in
working for the general good. He is noted for absolute fearlessness
in the exposition and defense of his convictions, by which he will
stand regardless of cost. While in Florida he was one of five men
who organized the first and only Republican association ever formed
in Citrus county. Mr. Eckert is a member of the I. O. O. F. (both lodge
and encampment), the P. O. S. of A., the Order of Independent
Americans and the SpanishAmerican War Veterans, in the latter
connection belonging to Theodore F. Hofl'man Camp, of which he
was the first commander. He is a past commander of the United
Spanish-American War Veterans. Mr. Eckert was married to Ruth
Harrington, daughter of Caleb and Margaret Harrington, and the four
children born to this union are: Ruth, Nelson, Harrington and Iva. Mr.
Eckert and his family are members of the Methodist Church in
religious connection. PERRY W. FEGLEY, of Orwigsburg, has been a
member of the A. E. Brown Shoe Company throughout the period of
its existence. A man of notable ability, strength of character and with
no disposition to shirk the responsibilities of life, he has devoted
himself sincerely to the upbuilding of every undertaking with which
he has become associated, and the record of his useful service
stamps him as one of the most valuable citizens of the borough. His
often tried ability has made him a desirable coworker in movements
designed for the common benefit, and he has never failed his
associates m the numerous enterprises with which he has been
identified. The Fegley family has long been settled in Pennsylvania,
Bernhard Fegley, the first of the name in this country, coming from
Switzerland at an early date. He first located in Montgomery county,
Pa., near Greenville, but died in Longswamp township, Berks county,
in 1782. Little is known of his son, Peter Fegley, the progenitor of a
large family in Berks county, except that he was born in Montgomery
county and settled in Douglass township, that county, induced by the
fact that his uncle (a brother of Bernhard) had made a permanent
settlement there. Some members of the Fegley family write the ^
 ■ SCHUYLKILL COUNTY, PENXSYLVANLV 299 name "Bird,"
the English version of the original name, and others "Vogel" or
"Fogel." There are descendants of Peter Fegley living in New Jersey
who use the English form. Abraham I-'cgley, the grandfather of Perry
W. Fegley, was born in Longswamp township, IBerks county, and
was an early settler in the vicinity of Orwigsburg, Schuylkill county,
making his home on the farm later knownas the Martin Schaeffer
place. There he followed farming all his active life, spending his
closing years in retirement at Orwisburg, where he died in 1874. In
December. 1813, he married Sohna Berger. and three children were
born to them, two sons and one daughter, Charles, Nathan and
Amanda. By his second marriage Abraham Fegley had two children,
Reuben and Daniel. Charles Fegley, son of Abraham, was born Sept.
4, 1814, in Longswamp township, Berks county. Moving with his
father to the neighborhood of Orwigsburg, he passed his early life
there, being reared to farming, which he continued to follow until
the spring of 1839, cultivating the place in East Brunswick township.
At that time he traded his farm for a boat, the "Jenny Lind," which
he operated on the Philadelphia & Schuylkill canal until 1862. For the
ne.xt ten years he was engaged in mine contracting in the Schuylkill
coal region, and then located at Pottsville, where he was in the
employ of the Reading Company. After a short residence there he
settled at Orwigsburg, where he lived retired until his death, which
occurred in 1898 in his eightyfourth year. He was twice married, his
second wife being Lovenia Hoffman, whom he married Dec. 24,
1849. Two children were born to this union, Henry C. and Perry W. ;
the former, born Jan. 20, 1852, graduated from Jefferson Medical
College in March, 1877, and located at Ashland, where he had
acquired a large practice at the time of his death. May 28, 1888,
when he was thirty-six years old. The father was a member of the
Democratic party, and belonged to the Lutheran Church. Mrs. Fegley
died Aug. 3, 1902, at the age of eighty-four years. She was born
April 26, 1818, daughter of Jacob Hoffman, and a descendant of a
family of German lineage of Halle, Prussia, which has been
prominent in the medical profession since 1460. Its foremost
member, Frederick Hoffman (1660-1742), was one of the founders
of the Halle LTniversity in 1693, and its first professor of practice of
medicine, which position he held until the time of his death, with the
exception of four years (1708-1712) which he passed in Berlin as the
royal physician. His grandson, Cornelius, having taken up his
residence in Switzerland, emigrated to the Colonies in 1768, locating
on the Schuylkill below the present site of Pottstown, from which
place he entered the service of his adopted country as a captain in
Colonel Magraw's 6th Pennsylvania Regiment, 2d Brigade, in 1776,
and was with Washington on that memorable night when he crossed
the Delaware river and surprised and captured the Hessians at
Trenton. After the close of the war for independence, in 1783, he
was mustered out of the service, took up his residence in Brunswick
township, in what was then Berks county, at the present site of
Orwigsburg, Schuylkill county, and followed farming the remainder of
his days. His son, Jacob, retaining possession of the homestead,
married Kate Benninser, and was the father of Mrs. Fegley. Perry W.
Fegley was born Mav 8. 1855, at Orwigsburg, Schuylkill county, and
obtained his education in the public schools there. When a youth of
sixteen, in the spring of 1871, he began an apprenticeship to the
carpenter's trade, but as he did not care for the work he gave it up
in October, and went to learn tinsmithing. which he followed imtil
June, 1873. His next change was to
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