Richard Palmer --- D3O Energy Absorber -- articles & 2 US
Patent Applications

**[rexresearch.com](../index.htm)**

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**Richard PALMER, *et al*.**

**D3O Energy Absorber**

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![](palmer.jpg)

**Richard Palmer**

[**http://www.d3o.com**](http://www.d3o.com)

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**<http://www.sundayherald.com/news/heraldnews/display.var.1528394.0.holy_batcapes_the_age_of_the_superhero_suit_is_upon_us.php>**

**Richard Palmer, d3o Inventor, O2 X
Entrepreneur of the Year**

When Richard Palmer created d3o, a very cool advanced polymer
with shear thickening properties, nobody thought it would work -
and what good is it?

Here's what you can do with d3o - you can make a supersuit, a
flexible outfit that turns instantly as rigid as a tough
fiberglass helmet. See Skiers Get d3o-based 'Impact Suits' for
more information.

What kind of guy would sell his house and car, and move into a
friend's spare bedroom, and work until he made his dream a
reality? Listen up:

"It has been a battle against the odds to get this far. I've
had to struggle against ignorance of the major players, work out
of a back bedroom and beg, borrow and steal to keep development
going, but I never doubted that it could be done," said Palmer.

"What we've developed is already being incorporated into
everything from police body armour to protective sportswear, and
the number of applications is almost infinite.

"At the moment a complete superhero suit made of our material
would be a bit too heavy and far too expensive, but those
challenges should be overcome within the next few years."

Palmer was named the O2 X Entrepreneur of the Year award for
2007 in a ceremony in London last week. A former DuPont
scientist, he approached the world's largest polymer companies
with his invention - and they said it was impossible. See
Flexible-Rigid Beanie-Helmet For Snowsports for examples of
consumer goods now possible.

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**<http://www.reuters.com/news/video/videoStory?videoId=66435>**  
Sept 14 , 2007

**A Scientific Leap of Faith**

**by Matt Cowan**

The Brighton-based d3o Lab in the UK is winning recognition for
its shock-absorbent material that protects athletes without
restricting movement.

O2 and Arena magazine recently recognized d3o founder Richard
Palmer as the 2007 Entrepreneur of the Year.

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[**http://news.sky.com/skynews/article/0%2C%2C91221-1286736%2C00.html**](http://news.sky.com/skynews/article/0%2C%2C91221-1286736%2C00.html)  
**( October 4, 2007 )**

**Super Foam Fends Off Swinging Shovel**

**By Derek Tedder**

*A revolutionary new foam has been developed which its makers
claim can protect people from pain and injury when they hit
something at speed - or when something hits them.*

No pain, big gain

Bikers, cyclists, snowboarders and skiers could benefit from
wearing suits and helmets containing D3O, and riot police in the
US are putting it through its paces.

When I went to see its inventor, Richard Palmer, he said he was
so confident of its miraculous properties that he would put some
of it into his beanie hat and let me smash him over the head
with a shovel.

He assured me it would not hurt, no matter how hard I whacked
him.

When I hit him the first time, I was reluctant to put much
effort into it fearing he would collapse and pass out. No
reaction.

I swung the shovel over my head and hit him harder. Still no
reaction!

I at least expected his eyes to spin like Catherine wheels ---
but they did not. He admitted he could feel the impact, but
exper--ienced no pain.

The secret formula inside D3O means the greater the impact the
more resilient it becomes. In its raw state, the substance looks
like translucent orange putty which you can squeeze and mould
without effort.

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**US20050037189**

**Energy Absorbing Material**

**Abstract**

There is provided a self-supporting energy absorbing composite
comprising: i) a solid foamed synthetic polymer matrix; ii) a
polymer-based dilatant, different from i) distributed through
the matrix and incorporated therein during manufacture of i);
and iii) a fluid distributed through the matrix, the combination
of matrix, dilatant and fluid being Such that the composite is
resiliently compressible. There is also provided a
self-supporting energy absorbing composite comprising: iv) a
solid, closed cell foam matrix; v) a polymer-based dilatant,
different from i), distributed through the matrix; and vi) a
fluid distributed through the matrix, the combination of matrix,
dilatant and fluid being such that the composite is resiliently
compressible.

Inventors:  Palmer, Richard Martin; (Herts, GB) ; Green,
Philip Charles; (Herts, GB)

**Description**

[0001] This invention relates to energy absorbing materials
e.g. of the kind employed in systems designed for the protection
of humans, animals or objects from damage by impact; referred to
hereinafter as impact protection systems.

[0002] Conventionally, impact protection systems have employed,
as the energy absorbing material, elastomer foams or similar
relatively soft resiliently compressible materials. However only
limited protection is achieved. In some systems, this energy
absorbing material is employed in combination with a rigid
member the purpose of which is to spread the impact force over a
greater area and therefore reduce its effect. However, such
systems tend to be inflexible and uncomfortable if in contact
with a human body. Most vulnerable areas of the body which
require protection, e.g. elbows and knees, undergo significant
changes in geometry and thus any attempt to match a rigid
load-spreading shape will usually fail. One solution is to
introduce articulation into the rigid element but this can
compromise performance and increases cost.

[0003] More recently, proposals have been made for the use of
shear thickening silicone putty materials, known as silicone
dilatants, in or as energy absorbing materials in impact
absorption systems. By a shear thickening material or dilatant,
we mean a material which viscously flows at low rates of
deformation but, at an elevated rate of deformation, undergoes a
substantial increase in viscosity with rate of change
deformation. At significantly higher deformation rates, such as
those induced by impact, the material becomes substantially
stiff or rigid. For example, U.S. Pat. No. 5,599,290 describes a
bone fracture prevention garment which employs, as the dilatant
or shear-thickening material, a dispersion of solid particles in
a viscous fluid. GB-A-2349798 describes an energy absorbing pad
including a putty-like dilatant. However, in both cases, the
dilatant has to be contained in an envelope because of its non
self-supporting nature. The resulting products therefore tend to
lack flexibility and will require relatively complex and
expensive manufacturing processes.

[0004] JP 6-220242 discloses a shock absorbing material which
consists of a flexible, three-dimensional mesh or foam body
which has interconnected hollow spaces in its interior, and
whose surface is coated with silicone bouncing putty.

[0005] The present invention provides an energy absorbing
material suitable for use in or as an impact absorption system
and which is self-supporting.

[0006] According to one aspect of the present invention, there
is provided a self-supporting energy absorbing composite
comprising:

[0007] i) a solid foamed synthetic polymer, suitably an
elastic, preferably an elastomeric matrix;

[0008] ii) a polymer-based dilatant, different from i),
distributed through the matrix and incorporated therein during
manufacture of i); and

[0009] iii) a fluid distributed through the matrix, the
combination of matrix, dilatant and fluid being such that the
composite is resiliently compressible, and preferably also
flexible.

[0010] By resiliently compressible we mean a resistance to
compressive set.

[0011] By a solid matrix, we mean a matrix material which
retains its own boundaries without need of a container. Usually,
the matrix will be elastic.

[0012] According to a second aspect of this invention, there is
provided a self-supporting energy absorbing composite
comprising:

[0013] i) a solid, closed cell foam matrix;

[0014] ii) a polymer-based dilatant, different from i),
distributed through the matrix; and

[0015] iii) a fluid distributed through the matrix, the
combination of matrix, dilatant and fluid being such that the
composite is resiliently compressible.

[0016] In addition to being self-supporting, the composite of
the invention offers a degree of impact protection which can
potentially exceed that of current rigid systems and moreover,
in the preferred embodiment wherein it is both flexible and
resiliently compressible, it has the ability to conform to the
geometry of what it is designed to protect by maintaining
intimate contact through relatively large changes in geometry.
This is a key feature for the design of protective components
because induced damage is a function of the maximum force
resulting from the impact divided by the area over which this
force is distributed. The composite of the invention enables
both a reduction in the force and an increase in the area on
which the force acts or is reacted, thereby significantly
reducing the resulting pressure or stress transmitted for a
given impact energy. It also offers the ability to exhibit some
conformity to the impactor and thus produce additional force
absorption as well as favourable geometry in terms of abrasion
resistance. By means of the invention, it is also possible to
achieve improved performance compared to the use of an
equivalent mass of dilatant when used on its own.

[0017] While it is to be understood that other solid materials
may be suitable for use as the matrix, in one, preferred
embodiment of the invention, the matrix is selected from
elastomers. While natural elastomers, e.g. latex rubbers, may
also be used, our preference is for synthetic elastomers,
including synthetic thermoplastic elastomers. One preferred
class of synthetic elastomers is elastomeric polyurethanes but
it is expected that others such as silicone rubbers and EP
rubbers, e.g. EPDM rubbers may also be suitable.

[0018] In general, the resilient compressibility of the
composite will be provided by the fluid which is dispersed
throughout the matrix. Usually, the fluid will be substantially
uniformly dispersed throughout the matrix but non-uniform
dispersion may be desirable in certain cases. The resilient
compressibility may be due to redistribution of fluid within the
matrix and/or (in the preferred case wherein the fluid comprises
gas) compression of the fluid. Thus, for example, the
combination of matrix and fluid may advantageously be a foamed
elastomer, e.g., a foamed polyurethane elastomer, the foam may
be open-cell, closed-cell or part open, part closed. An
important property of the foam is the rate at which it recovers
after being subjected to compression. Preferably, recovery is
complete or substantially complete within a few seconds, e.g. 5
seconds or less, more preferably 2 seconds or less. However, a
slower rate of return may actually be preferably for some
applications.

[0019] Any polymer-based dilatant that can be incorporated into
the chosen matrix may be used. By a "polymer-based dilatant"it
is meant a material in which the dilatancy is provided by
polymer alone or by a combination of polymer together with one
or more other components, e.g. finely divided particulate
material, viscous fluid, plasticiser, extender or mixtures
thereof, and wherein the polymer is the principal component. In
one preferred embodiment, the dilatant is selected from silicone
polymer-based materials exhibiting dilatant characteristics. The
silicone polymer is preferably selected from borated silicone
polymers. The dilatant may be combined with other components in
addition to the components providing the dilatancy, e.g.
fillers, plasticisers, colorants, lubricants and thinners. The
fillers may be particulate (including microspheres) or fibrous
or a mixture of particulate and fibrous. One class of
particularly preferred dilatants comprises the borated
siloxane-based material marketed by Dow Corning under catalogue
no. 3179 where polyborondimethylsiloxane (PBDMS) constitutes the
base polymer.

[0020] Other polymer-based dilatant materials having similar
dilatancy characteristics, e.g. a similar modulus at low rates
of strain and a similar plot of modulus against strain rate are
also included.

[0021] The composite of the invention may be formed by
combining a solid matrix, a polymer-based dilatant and a fluid
whereby the dilatant and fluid are distributed, generally
substantially uniformly, throughout the matrix to produce a
resiliently compressible material. Where the matrix is chosen
from synthetic elastomers, one suitable method comprises
incorporating a polymer-based dilatant into a foamed synthetic
elastomer. The dilatant may be incorporated during the formation
of the foam. For example, the foam-forming ingredients may be
reacted to form the foam in the presence of a solution or
dispersion of the dilatant. Whatever method is used, however,
while the dilatant may be incorporated into the pores of the
foam, it is important that it does not completely displace the
fluid from the pores.

[0022] The composite of the invention may include components
other than the dilatant and fluid, e.g., fibrous and/or
particular fillers, plasticisers, lubricants, extenders,
pigments, dyes, etc. If desired, the composite of the invention
may be incorporated within an envelope which may be rigid or
flexible, but this is not essential. Likewise, it may be
associated with a rigid component but this is not essential for
the use of the composite and may even compromise some of its
properties.

[0023] A coating may be applied to the composite, if desired.

[0024] The actual constitution of the composite will be
influenced by the intended application. Applications cover a
wide range of uses and include impact protection for objects,
animals and humans. Potential applications extend to any dynamic
situation where the object may already be in contact with a
surface and the combination of object and surface may undergo
severe acceleration and/or deceleration, e.g. as in packaging
for delicate equipment or a human body in a vehicle seat. Thus,
the nature of resiliently compressible mass, the amount of fluid
in the mass, e.g. as indicated by the density of the mass, and
the choice and level of loading of the dilatant in the mass,
will be determined by the requirements of the protective system
in which the composite is to be employed. In general, the
dilatant will form from 5 to 80%, preferably 10 to 50%, more
preferably 20 to 40% (such as 15 to 35%) by volume of the
composite, and the amount of fluid (in the preferred case where
it is gas) will be such that the fluid content of the composite
is preferably about 30 to 90% (such as 20 to 90%) more
preferably about 45 to 90% (such as 30 to 80%) still more
preferably about 55 to 85% (such as 40 to 70%) by volume. It
should be noted that these proportions are excluding the use of
any fillers or additional components.

[0025] The energy absorbing composite of the invention may be
employed in a wide variety of applications; for example in
protective pads or clothing for humans and animals, in or as
energy absorbing zones in vehicles and other objects with which
humans or animals may come into violent contact, and in or as
packaging for delicate objects or machinery. Specific examples
of applications are in headwear and helmets; protective clothing
or padding for elbows, knees, hips and shins; general body
protection, for example for use in environments where flying or
falling objects are a hazard, vehicle dashboards, suspension
bushes, upholstery and seating. Other potential uses are in
garments or padding to protect parts of the body used to strike
an object e.g. in a sport or pastime; for example in running
shoe soles, football boots, boxing gloves and gloves used in the
playing of fives. This list is not intended to be exclusive and
other potential uses will occur to the reader.

[0026] The following Examples illustrate the invention in which
dilatant materials were incorporated into a solid foamed
synthetic polymer matrix during its manufacture.

**EXAMPLE 1**

[0027] This example details the inclusion of the pure
polyborondimethylsiloxane (PBDMS) dilatant during the
manufacture of polyurethane (PU) foam.

[0028] The base PU system is marketed by Jacobson Chemicals
Ltd., Farnham, Surrey. The product is a modelling foam reference
J-Foam 7087. This is a two part system which requires the mixing
of two components, part A and part B in the ratio of 3 to 1
respectively. This mix can then be cast into open or closed
moulds to produce a shaped foam component. During the reaction
of parts A and B a gas (believed to include carbon dioxide) is
evolved to produce a closed cell structure in a PU soft foam.

[0029] The PBDMS supplied by the Chemical Institute, Warsaw,
Poland was pre-mixed with the J-Foam part A at room temperature
in a polyethylene beaker by hand with the aid of a wooded
spatula for approximately 15 minutes until the mix appear
homogenous. Various ratios of PBDMS to part A were trialed and
are detailed as follows:

[0030] Trial 1-15 g PBDMS+40 g part A

[0031] Trial 2-15 g PBDMS+30 g part A

[0032] Trial 3-39 g PBDMS+50 g part A

[0033] Each of the above pre-mixes was then mixed with part B
using the same mixing method and maintaining the 3 to 1 ratio of
part A to part B irrespective of the amount of PBDMS. This
mixing time was typically around 10 seconds. These 3 component
mixtures were next cast into a flat bottomed open polyethylene
container and allowed to expand freely to produce the foams.

[0034] As the PBDMS has a very much higher viscosity than
either part A or part B, increasing the proportion of PBDMS
produced a reduction in density of the resulting foam. The
increased viscosity (melt strength) of the 3 component mix
restricted the expansion of the mix during reaction and cure
stage. To establish the effect of reducing the viscosity of the
PBDMS/part A pre-mix by heating this pre-mix an additional batch
of trial 3 was made with the pre-mix being heated to 65 degrees
Celsius before mixing with part B. This sample was then cast
immediately after mixing in the same way as previous specimens,
but with the mould pre-heated to 65 degrees Celsius also. The
resulting densities of foam were produced:

[0035] Trial 1-400 kg/m.sup.3

[0036] Trial 2-500 kg/m.sup.3

[0037] Trial 3 (65.degree. C. pre-heated)-380 kg/m.sup.3

[0038] The densities were measured simply by weighing the
samples and measuring the linear dimensions to establish the
total volume and dividing this by the weight of the samples.

EXAMPLE 2

[0039] The same technique as shown in Example 1 was applied to
the manufacture of PU foam containing Dow Corning 3179 silicone
dilatant. This dilatant is a filled PBDMS where the percentage
of PBDMS is 65% by weight. This renders 3179 stiffer and
stronger than the pure PBDMS. As a result of the presence of
these fillers 3179 would not mix with J-Foam part A even with
the assistance of an electric food blender. Using the electric
blender 50 g of 3179 was dissolved in 40 g isopropyl alcohol
(IPA), as solvent, then mixed with approximately 100 g of J-Foam
part A. This produced a creamy emulsion. In order to minimize
the amount of IPA present during the subsequent reaction with
J-Foam part B the blender was left switched on with the 3179 and
IPA and J-Foam part A mixture in a fume cupboard to encourage
evaporation of the IPA. This was left for 1 hour. The
evaporation of the IPA over this period of time caused the 3179
dilatant to come out of the solution and to form solid globules
of dilatant in the mix. The procedure was therefore repeated but
during the evaporation stage the blender was stopped at 10
minute intervals to observe visually the nature of the mixture.
After 40 minutes tiny particles of 3179 dilatant in suspension
were just detectable with the naked eye and at this stage part B
was introduced into the mixture by hand and cast into an open
container as before and again maintaining the 3 to 1 ratio of
part A to part B. The resulting foam had a measured density of
290 kg/m.sup.3 with a large closed cell structure (cell
diameters approximately 0.7 to 1.2 mm).

[0040] In order to increase the density of this foam the
procedure was repeated with the addition of 35 g of PBDMS during
the blending of the 3179 dilatant, IPA and J-Foam part A to
increase the viscosity of the mix. The resulting foam was of
much smaller cell size (cell diameters approximately 0.1 to 0.4
mm) and of higher density--640 kg/m.sup.3.

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**US Patent Application # 20070029690**

**Energy Absorbing Blends**

**Green; Philip ;   et al.**

**( February 8, 2007 )**

**Abstract**

A composite material which is elastic, which exhibits a
resistive load under deformation which increases with the rate
of deformation, which is unfoamed or foamed, comminuted or
uncomminuted and which comprises i) a first polymer-based
elastic material and ii) a second polymer-based material,
different from i), which exhibits dilatancy in the absence of i)
wherein ii) is entrapped in a solid matrix of i), the composite
material being unfoamed or, when foamed, preparable by
incorporating ii) with i) prior to foaming.

U.S. Current Class:  264/50; 264/349; 525/191   
U.S. Class at Publication:  264/050; 525/191; 264/349   
Intern'l Class:  B29C 44/34 20060101 B29C044/34; C08F 8/00
20060101 C08F008/00

**Description**

[0001] This invention relates to applications where rate
sensitivity can provide a performance advantage; e.g. energy
absorbent impact systems designed for the protection of humans,
animals or objects from damage by impact; these are referred to
hereinafter as impact protection systems.

[0002] Conventionally, impact protection systems have employed,
as the energy absorbing material, elastomeric foams or similar
relatively soft, resiliently compressible materials. However,
only limited protection is achieved thereby. In some systems,
this energy absorbing material is employed in combination with a
rigid member the purpose of which is to spread the impact force
over a greater area and therefore reduce its effect. However,
such systems tend to be inflexible and uncomfortable if in
contact with a human body. Most vulnerable areas of the body
which require protection, e.g. elbows and knees, undergo
significant changes in geometry and thus any attempt to match a
rigid load-spreading shape will usually fail. One solution is to
introduce articulation into the rigid element but this can
compromise performance and increases cost.

[0003] More recently, proposals have been made for the use of
strain-rate sensitive shear thickening silicone putty materials,
sometimes known as silicone dilatants, in or as energy absorbing
materials in impact absorption systems. By a strain-rate
sensitive shear thickening material or dilatant, we mean a
material which viscously flows at low rates of strain
deformation but, at an elevated strain rate of deformation
undergoes a substantial increase in viscosity with rate of
change of deformation. At significantly higher deformation
rates, such as those induced by a sudden impact, the material
becomes substantially stiff or rigid. For example, U.S. Pat. No.
5,599,290 describes a bone fracture prevention garment which
employs, as the dilatant or shear-thickening material, a
dispersion of solid particles in a viscous fluid. GB-A-2349798
describes an energy absorbing pad including a putty-like
dilatant. However, in both cases, the dilatant has to be
contained in an envelope because of its non self-supporting
nature. The products therefore tend to have limited flexibility,
are prone to damage by puncture, and require relatively complex
and expensive manufacturing processes. These products also tend
to be heavy due to the relatively high density of the dilatant,
which can be above 1000 kg/m.sup.3, and suffer from migration of
the dilatant within the envelope as the dilatant will exhibit
viscous flow at even very low levels of loading.

[0004] Other approaches for the utilisation of silicone
dilatants have been to combine this material with a resilient
carrier such as polyurethane foam.

[0005] In our copending International patent publication WO
03/055339 we have described and claimed a self supporting energy
absorbing composite comprising: [0006] i) a solid foamed
synthetic polymer matrix; [0007] ii) a polymer-based dilatant,
different from i), distributed through the matrix and
incorporated therein during manufacture of i); and [0008] iii) a
fluid distributed through the matrix, the combination of matrix
dilatant and fluid being such that the composite is resiliently
compressible; and a self supporting energy absorbing composite
comprising: [0009] i) a solid, closed cell foam matrix; [0010]
ii) a polymer-based dilatant, different from i), distributed
through the matrix; and [0011] iii) a fluid distributed through
the matrix, the combination of matrix dilatant and fluid being
such that the composite is resiliently compressible.

[0012] The present invention provides an energy absorbing
material suitable for use in or as an impact absorption
material; and which is self-supporting and wherein the density
can be tuned to specification applications; for example, from
about 1150 kg/m.sup.3 in the as blended condition and any
intermediate density down to 100 kg/m.sup.3 in the foamed form.

[0013] According to the present invention, there is provided a
composite material which is elastic, which exhibits a resistive
load under deformation which increases with the rate of
deformation, which is comminuted or uncomminuted and which
comprises i) a first polymer-based elastic material and ii) a
second polymer-based material, different from i), which exhibits
dilatancy in the absence of i) wherein ii) is entrapped in a
solid matrix of i), the composite material being unfoamed or,
when foamed, preparable by incorporating ii) with i) prior to
foaming.

[0014] It is preferred that the composite material is resistant
to permanent set under all types of loading; e.g. compression,
tension or shear or any combination thereof. By a solid matrix
is meant herein a matrix material which retains its own
boundaries without need of a container.

[0015] The composite material of this invention may be unfoamed
as such or as a precursor to a composite material which is
subsequently to be foamed (that is, foamed after ii) has become
entrapped in a solid matrix of i)).

[0016] Preferably, the first material i) and second material
ii) are in intimate admixture; for example, as attainable by
blending i) and ii) together. By blending is meant herein the
mixing together of polymer based constituents i) and dilatant
ii) in the semi-molten or molten state to form a composite
material wherein the first material i) and the second material
ii) are in intimate admixture.

[0017] In addition to being self-supporting, the composite
material of the invention offers a degree of impact protection
which can exceed that of current rigid systems and moreover, in
the preferred embodiment wherein it is both flexible and
resilient under all types of loading, it has the ability to
conform to the geometry of what it is designed to protect by
maintaining intimate contact through relatively large changes in
geometry. This is important for the design of protective
components because induced damage is a function of the maximum
force resulting from the impact divided by the area over which
this force is distributed. The composite material of the
invention enables both a reduction in the force and an increase
in the area on which the force acts or is reacted, thereby
significantly reducing the resulting pressure or stress
transmitted for a given impact event. It also offers the ability
to exhibit some conformity to the impactor and thus produce
additional force absorption as well as favourable geometry in
terms of abrasion resistance. By means of the invention, it is
also possible to achieve improved performance compared to the
use of an equivalent mass of dilatant when used on its own.

[0018] The first material i) may be one wherein the polymer
comprising the first material i) comprises EVA or an olefin
polymer, for example polypropylene or an ethylene polymer such
as high pressure polyethylene (LDPE), LLDPE or HDPE.

[0019] Preferably, the polymer comprising the first material i)
comprises an elastomer. While natural elastomers, e.g. latex
rubbers, may also be used, our preference is for synthetic
elastomers (such as neoprene), more preferably synthetic
thermoplastic elastomers such as thermoplastic polyesters.
Preferred classes of such elastomers include elastomeric
polyurethanes and elastomeric EVAs (ethylene/vinyl acetate
copolymers); others such as silicone rubbers and EP rubbers,
e.g. EPDM rubbers may also be suitable.

[0020] Other solid plastics materials may also be suitable for
use as the polymer constituent of the first material i) provided
that they too exhibit an appropriate level of resilience. Any
polymer-based material, different from i), which exhibits
dilatancy and can be incorporated into the chosen elastic
constituents) of first material i) may be used as second
material ii). By a polymer-based material which exhibits
dilatancy is meant a material in which the dilatancy is provided
by one or more polymers alone or by a combination of one or more
polymers together with one or more other components, e.g. finely
divided particulate material, viscous fluid, plasticiser,
extender or mixtures thereof, and wherein the polymer is the
principal component. In one preferred embodiment, the polymer
comprising the second material ii) is selected from silicone
polymers exhibiting dilatant properties. The silicone-based
polymer is preferably selected from borated siloxane polymers.
For example, the dilatant may be selected from filled or
unfilled polyborodimethylsiloxanes (PBDMSs) or any number of
polymers where PBDMS is a constituent. The dilatancy may be
enhanced by the inclusion of other components such as
particulate fillers.

[0021] The dilatant may be combined with other components in
addition to the components providing the dilatancy, e.g.
fillers, plasticisers, colorants, lubricants and thinners. The
fillers may be particulate (including microspheres or
microballoons) or fibrous or a mixture of particulate and
fibrous. One class of particularly preferred dilatants based on
PBDMS comprises the borated silicone-based materials that are
marketed under the generic name of silicone bouncing putties and
are produced by various manufacturers. These include those by
Dow Corning under product catalogue no. 3179; by Wacker GmbH
under product numbers M48 and M29 and by The Polish Chemical
Institute under the product name Polastosil AMB-12. Other
companies such as Rhodia, GE Plastics, ICI have also produced
these materials, and other polymer-based dilatant materials
having similar dilatancy characteristics, e.g. a similar modulus
at low rates of strain and a similar plot of modulus with
respect to the applied strain rate.

[0022] It is believed to be the presence of the borated
cross-link within the composite material which enables it to
exhibit a resistive load under deformation which increases with
the rate of deformation. This type of cross-link is considered
temporary because it is believed to form reversibly and only or
mainly during high rates of deformation of the polymer. In the
PBDMS polymer this effect inhibits the siloxane chains from
sliding during high rates of strain thus instantaneously
inhibiting viscous flow. In this condition the polymer will
therefore behave more like an elastomer. The composite material
of the invention also possesses the borated cross-links which
enable it to exhibit the aforementioned behaviour. Other
polymers that exhibit a temporary cross-link in the manner of
PBDMS may also be used.

[0023] The composite material of this invention is preferably
comminuted for ease of handling; for example, in transportation
or for moulding purposes.

[0024] In accordance with another aspect of this invention,
there is provided a process for the preparation of a composite
material according to the hereindescribed invention which
process comprises: [0025] a) melting the polymer intended to
comprise the first material i); and [0026] b) blending the
polymeric dilatant intended to comprise the second material ii)
therewith.

[0027] The polymer intended to comprise the first material i)
is as hereinabove defined and/or the polymeric dilatant intended
to comprise the second material ii) is as hereinabove defined.

[0028] Preferably, the polymeric dilatant is melted prior to
and/or during the blending step (b). Suitably, after blending
and cooling, the composite material so formed is c) comminuted.

[0029] One preferred method of forming the blend is first to
form microspheres of second material ii) coated, for example
with a polymer such as an elastomer, to prevent coalescence.
These coated microspheres are then introduced into the first
material i) which is either comminuted or in the melt.

[0030] This invention further provides a composite material
prepared by a hereindescribed process of this invention.

[0031] In accordance with an important aspect of this
invention, there is provided a composite material prepared by a
hereindescribed process of this invention which has subsequently
been foamed; suitably, the so-produced foam is a closed cell
foam. Suitably, at least part of the polymeric dilatant ii) is
included within cell walls of the foam.

[0032] It is preferred that the cells include, as pneumatogen,
a gas, vapour, supercritical liquid, or a precursor thereof; for
example, nitrogen or carbon dioxide. Usually, the gas or vapour
will be substantially uniformly dispersed throughout the matrix
but non-uniform dispersion may be desirable in certain cases.
The contribution of the gas or vapour to the resilient
compressibility may be due to redistribution of gas or vapour
within the matrix or compression of the gas or vapour (or,
indeed, both of these effects). The presence of the gas or
vapour within the composite material not only significantly
reduces the overall density of the composite but can also
provide an amount of damping within the system due to pumping
losses associated with a pneumatic effect. The compressive
resilience will also be enhanced by a pneumatic effect which
will increase with the ratio of closed to open cells in the
foam. An amount of pneumatic damping is desirable when
considering energy absorption during impact and will further
enhance the reactive nature of the composite.

[0033] An important property of the foam is the rate at which
it recovers after being subjected to deformation, especially
compression. Preferably, recovery is complete or substantially
complete within a few seconds, e.g. 5 seconds or less, more
preferably 2 seconds or less. In certain applications however a
slower rate of recovery may be desirable.

[0034] The foamed composite material of the invention may be
prepared by combining the polymer intended to comprise the first
material i); the polymeric dilatant intended to comprise the
second material ii); and the gas, vapour, supercritical liquid,
or precursor thereof, such that the dilatant and the gas or
vapour are distributed, generally substantially uniformly,
throughout the matrix to produce a resiliently compressible
material which exhibits a resistive load under deformation which
increases with the rate of deformation. Whatever process is
used, however, while the dilatant may be incorporated into the
structure of the foam it is important that it does not
completely displace the gas or vapour from the pores.

[0035] One such process comprises incorporating an unfoamed
composite material, or a mixture of i) and ii), according to the
hereindescribed invention in the barrel of an injection moulding
machine including means for supplying a pneumatogen thereinto;
bringing the material so defined to an elevated temperature and
an elevated pressure such that it is in molten form; supplying a
pneumatogen to the barrel; and reducing the pressure of the
heated composite material thereby causing foaming of the
composite material.

[0036] The pressure may be reduced in this process by injecting
the composite material into a mould or extruding the composite
material, suitably at ambient pressure. Such a process may be
operated on a continuous basis.

[0037] Preferably the weight ratio of ii) to i) is from 4 to
0.25, most preferably from 2.3 to 1. Preferably the elevated
temperature is from 150.degree. C. to 240.degree. C., most
preferably from 170.degree. C. to 210.degree. C. Preferably the
elevated pressure at which the pneumatogen is injected is from
1600 psi to 2000 psi, most preferably from 1700 psi to 1900 psi.

[0038] Another such process comprises incorporating an unfoamed
composite material, or a mixture of i) and ii), according to the
hereindescribed invention into a hermetic container including
means for supplying a pneumatogen thereinto; bringing the
composite material to an elevated temperature at an elevated
pressure; and injecting pneumatogen into the hermetic container.
Suitably, the interior of the container is formed as a mould.

[0039] Preferably the weight ratio of ii) to i) is from 4 to
0.25, most preferably from 2.3 to 1. Preferably the elevated
temperature is from 150.degree. C. to 240.degree. C., most
preferably from 170.degree. C. to 200.degree. C. Preferably the
elevated pressure is from 8000 psi to 12000 psi, most preferably
from 9000 psi to 11000 psi.

[0040] In such a process, the polymer-intended to comprise the
first material i) and the polymer-based dilatant intended to
comprise the second material ii) are combined to form an
intimate admixture, and the resultant mix is then foamed to form
the composite. The methods employed can be selected from a
number of recognized industrial processes such as the various
chemical or physical blowing methods. An additional preparatory
process using a very high pressure nitrogen environment is also
possible. This process uses a solid extruded section of the
blend which is cross-linked (chemically or by irradiation) then
subjected to a temperature and pressure cycle in an autoclave
which is charged with nitrogen. The temperature will soften the
material to aid solubility of the gas, which is at very high
pressure (10,000 psi). This process may take several hours
depending on the material and the thickness used. After this
first autoclave process the resulting material has tiny bubbles
of trapped nitrogen at very high pressure. A secondary lower
pressure/temperature cycle then allows the trapped nitrogen to
expand the surrounding material to form a foam. The exact
pressure and temperature cycle of this second process will
determine the final density of the foam produced. This process
is used by Zotefoams, Croydon, UK.

[0041] Another such process comprises incorporating with an
unfoamed composite material, or with one or both components of a
mixture of i) and ii), as hereinbefore defined microspheres
comprising a plastic shell which hermetically encapsulates a gas
or vapour; bringing the material so defined to an elevated
temperature and pressure; and reducing the pressure of the
heated composite material thereby causing the expansion of the
microspheres and foaming of the composite material. The pressure
may be reduced in this process by injecting the composite
material into a mould or extruding the composite material,
suitably at ambient pressure. Such a process may be operated on
a continuous basis.

[0042] In such a process according to the invention the foamed
composite material of the invention may be prepared using, as
pneumatogen, microspheres comprising a polymeric shell which
hermetically encapsulates a gas (EXPANCEL by Akzo Nobel, for
example). The microspheres may be mixed with the first material
i) or coated with the second material ii) (or, indeed, both)
before blending i) and ii). On heating the produced blend, the
gas in the microspheres expands (the expansion may be ca
40.times.) to create closed cells.

[0043] Preferably the weight ratio of ii) to i) is from 4 to
0.25, most preferably from 2.3 to 1. Preferably the elevated
temperature is from 160.degree. C. to 230.degree. C., most
preferably from 190.degree. C. to 210.degree. C. Preferably the
elevated pressure is from 5000 psi to 8000 psi, most preferably
from 6000 psi to 7000 psi, the autogenous pressure generated in
an injection moulding machine or extruder.

[0044] The composite material of the invention may include
components other than the polymer intended to comprise the first
material i), the polymer-based dilatant intended to comprise the
second material ii) and the gas or vapour; e.g., fibrous and/or
particulate fillers, plasticisers, lubricants, extenders,
pigments and dyes. If desired, the composite of the invention
may be incorporated within an envelope which may be rigid or
flexible, but it is valuable feature of the invention that such
containment is not essential.

[0045] Likewise, it may be associated with a rigid or semi
rigid component but this is not essential for the use of the
composite and may even compromise some of its properties for
certain applications.

[0046] Furthermore, it may also be associated with a textile
layer or similar where the textile has the facility to enhance
the abrasion performance and in some cases the resistance to
intrusion from sharp objects and/or assist in the attachment of
the composite material to other systems or products. A
stretchable textile backing will also serve to limit the
elongation of the material and thereby provide durability. The
textile may also serve as an antiballistic or stab-proof fabric
such as certain woven grades of KEVLAR.

[0047] In accordance with a further aspect of this invention,
the final properties of the composite material as
hereindescribed, such as resilience, strain rate sensitivity,
tensile strength, hardness, elastic modulus, and creep modulus,
may be carefully controlled by the use of compatibilisers or
crosslinking (or indeed both). Crosslinking may be chemical
crosslinking or physical crosslinking (such as by irradiating or
by entanglement polymerisation) and may be undertaken on first
material i) or the second material ii) (or, indeed, both). The
first material i) may be crosslinked to the second material ii).

[0048] In general, the composite material of the invention will
exhibit resistance to creep and compression set. A low creep
modulus of the composite modulus will be beneficial, but not
essential, to imparting resistance to compression set. In some
applications it may be preferred to allow the material to have
high creep characteristics; for example, for sound insulation
purposes.

[0049] The actual constitution of the composite material of the
invention will be influenced by the intended application.
Applications cover a wide range of uses and include impact
protection for objects, animals and humans. Potential
applications extend to any dynamic situation where the object
may already be in contact with a surface and the combination of
object and surface may undergo severe acceleration and/or
deceleration, e.g. as in packaging for delicate equipment or a
human body in a vehicle seat. Thus, the nature of the composite
material and the choice and blending ratio of the dilatant in
the composite material and, where foamed, the amount of gas or
vapour in the composite material, e.g. as indicated by the
required density of the composite material, will be determined
by the requirements of the protective system in which the
composite material is to be employed. In general, the dilatant
will form from 5 to 80%, preferably 10 to 50%, more preferably
15 to 40% by volume of the composite, and where foamed, the
amount of gas or vapour (in the preferred case where it is a
gas) will be such that the gas or vapour content of the
composite is preferably from 20 to 90%, more preferably from 30
to 80%, still more preferably from 40 to 70% by volume. It
should be noted that these proportions are excluding the use of
any fillers or other additional components.

[0050] Still further according to the invention there are
provided shaped articles, e.g. extruded articles such as films,
sheets, filaments and fibres, comprising the composite materials
of the invention. Shaped articles such as textured sheets of the
composite may have the texture geometrically configured such
that compressive deformation will advantageously deform the
elements comprising the texture to optimise the reactive nature
of the composite. This is particularly beneficial in closed cell
foam. The shaped article may, if desired, be produced in such a
way as to include regions or layers in which the ratio of
dilatant within the composite material differs from that in
other regions or layers. In this way the distortion of the
shaped article, e.g. fibre or filament, may be configured to
facilitate maximum shear deformation shearing of the dilatant
rich regions at the dilatant/matrix interface.

[0051] The fibres or filaments may be woven, knitted or
otherwise configured such as to incorporate air into the final
product. When such a material is subjected to impact, the
distortion of each fibre is facilitated by the air spaces to
provide a large number of localised bending deflections, which
is preferable for the efficient use of the composite material in
absorbing impact.

[0052] The choice and concentration of the first material i) is
preferably such as to allow the shaping of the composite
material e.g. into fibres or filaments. In low strain rate
movements, the flexibility of a textile comprising fibres or
filaments formed from the admixture composite blend may be
provided by choice of fibre weave or knit. Other fibres or
filaments may be included in the textile, if desired, e.g.,
elastic fibres and/or abrasion-resistant fibres.

[0053] The fibre which may be formed, for example, by extrusion
or spinning may have an even distribution of second material ii)
within first material i) or may be manufactured to create
regions or layers where the second material ii) is more
concentrated.

[0054] In accordance with a still further aspect of this
invention, there is provided a fibre which comprises a core of
second material ii) within a sheath of first material i),
wherein the first material i) and second material ii) are as
hereindefined. The core may be hollow, preferably coaxially
hollow. Such fibres may be made by coextrusion. Such a fibre is
depicted in FIG. 1 of the accompanying drawings in which 1 is a
core of second material ii), 2 is a sheath of first material i)
and 3 is a hollow containing a gas (air).

[0055] The energy absorbing composite material of the invention
may be employed in a wide variety of applications; for example
in protective pads or clothing for humans and animals, in or as
energy absorbing zones in vehicles and other objects with which
humans or animals may come into violent contact, and in or as
packaging for delicate objects or machinery. Specific examples
of applications are in headwear and helmets; protective clothing
or padding for elbows, knees, hips and shins; general body
protection, for example for use in environments where flying or
falling objects are a hazard; vehicle dashboards, upholstery and
seating. Other potential uses are in garments or padding to
protect parts of the body used to strike an object e.g. in a
sport or pastime; for example in footwear, such as running shoe
soles, football boots, boxing gloves and gloves used in the
playing of fives. The energy absorbing composite material of the
invention may also be employed in non-impact situations; for
example, in energy absorbing and damping materials such as
automotive mounts, vibration isolation and sound insulation.
This list is not intended to be exclusive and other potential
uses will occur to the reader.

[0056] Examples are depicted in FIGS. 2 and 4 inclusive of the
accompanying drawings.

[0057] FIG. 5 of the accompanying drawings illustrates an
example of use in footwear.

[0058] FIGS. 6 to 9 represent photomicrographs discussed in
more detail in Example 2;

[0059] FIGS. 10 and 11 represent photomicrographs discussed in
more detail in Example 3;

[0060] FIG. 12 represents diagrammatically the impact rig used
in Example 4; and

[0061] FIG. 13 depicts the results of Example 4.

[0062] In order to provide favourable pressure characteristics
and a greater level of support under shock loads transmitted
through the sole of the foot during any type of active
recreation, the composite material is utilised in the
construction in the soles of footwear, e.g. innersoles, midsoles
or outer soles. The example illustrates the use of the material
between the ,innersole (1) and the outersole (2), where the
interfaces between both the innersole and midsole (3) and the
outersole and midsole are favourably contoured or textured to
induce large amounts of shear deformation in the foamed
composite material of the invention. This type of construction
may be formed by incorporating the foamed composite material
into the cavity between the inner and outer sole such that the
resulting midsole solidifies and bonds to both the inner and
outer sole. A similar structure is achieved as a one-part
moulding whereby the material foams within a mould, the inner
and outer soles being formed by the "skin" produced at the mould
surfaces.

[0063] A coating may be applied to the composite if desired.

[0064] The following Examples illustrate the invention.

**EXAMPLE 1**

[0065] The elastic polymeric constituent material selected for
a precursor blend process evaluation was a linear low density
polyethylene (Flexirene MR5O by Europa Polymeri). Three dilatant
materials were selected for blending trials in different ratios.
The three dilatant materials were the Dow Corning silicone
dilatant 3179, Polastosil AMB-12 and pure PBDMS. These were
blended with the LLDPE MR50 using a Shaws K1 3 litre intermix.
The LLDPE was introduced into the mill in granular form first
where the temperature generated through shearing the material
rose to around 110.degree. C. The dilatant materials were then
fluxed into the internal mixer in the ratios as specified below:

1. 35% 3179 65% LLDPE by weight.

2. 50% 3179 50% LLDPE by weight.

3. 50% Polastosil ABM-12 50% LLDPE by weight.

4. 35% Polastosil ABM-12 65% LLDPE by weight.

5. 30% PBDMS 70% LLDPE by weight.

6. 35% PBDMS 65% LLDPE by weight.

The above material blends were then dump extruded through
4.times.2 mm diameter dies to form strands which were then
pelletised.

**EXAMPLE 2**

[0066] Having demonstrated the method of blending the dilatant
and a thermoplastic polymer using standard industrial equipment
in Example 1, Example 2 extends the processing route through the
realization of a closed cell structure.

[0067] One process found suitable for closed cell foam
manufacture is a high-pressure gas solution process. This
process subjects a block of solid polymer material to very high
pressure in a gas (for example, nitrogen) filled autoclave at a
controlled temperature to force the gas into the solid polymer.
This block is then foamed under controlled high pressure and
temperature, again using a gas filled autoclave. The advantage
of the process for foam manufacture is the uniformity of the
cellular structure and the lack of chemical deposition from
conventional blowing agents.

[0068] In order to confirm that such a manufacturing process is
suitable it is necessary to demonstrate that the mixture will be
stable at the elevated temperatures of the manufacturing
process. This is necessary in order to consider replacing the
polymer sheet or block in the experimental process with a
prepared sample containing both the dilatant and the matrix
material, as an intimate mix. The normal operating temperature
of the process is around 165.degree. C.

[0069] The polymer-based elastic matrix material chosen for an
initial trial was Hytrel G3548L, which is a polyester based
thermoplastic elastomer available from Du Pont. 50 grams of
Hytrel and an equal weight of 3179 dilatant compound (see
Example 1) were placed in a crucible in preparation of mixing at
high temperature. A laboratory oven was preheated to 220.degree.
C. and the crucible and contents placed in the oven and left for
30 minutes. The crucible was then removed and the contents
stirred with a metal spatula to mix the two materials. The
resulting mixture was next replaced in the oven and heat soaked
for a further hour at this temperature, before removing for
investigation. The two materials mixed very well to produce an
admixture that was solid at room temperature. The admixture was
heated to 165.degree. C. in a laboratory oven and was found to
be stable over a period of 8 hours, which is the duration of the
high-pressure nitrogen gas solution process. The results
indicate the potential suitability of the sample for foaming
using a high-pressure gas (such as nitrogen) process or indeed
other physical or chemical blowing processes.

[0070] Having established the ability of the two materials to
form an intimate admixture, the process was scaled to produce 30
kg batches on industrial equipment using the method as described
in Example 1.

[0071] Hytrel grade G3548L was blended with Dow Corning Silicon
dilatant 3179 to produce a precursor material. The two blend
ratios chosen were 35/65 dilatant to Hytrel by weight and 50/50
by weight, the blending process yielded around 30 kg of each
blend ratio.

[0072] As subsequent processing of these blends to produce
closed cell foams via physical or chemical blowing techniques
requires the material to be returned to the molten state a study
of the effect of this on the structure of the material was
undertaken.

[0073] The blend materials (now in pellet form) were put onto
non-stick vessels and subjected to a temperature of about
200.degree. C. The pellets were left for one hour, after which
time the material was molten; stirred; then left for an
additional hour before removal from the oven. On cooling the
mixes solidified.

[0074] The solid shapes were then examined under a scanning
electron microscope (SEM). To expose the structure of the
material two techniques were employed--cutting with a razor
blade and fracturing the samples by immersing them in liquid
nitrogen and fracturing them at a notch (cut by a razor blade).

[0075] The photomicrographs in FIGS. 6, 7, 8 and 9 represent,
respectfully, the structure of a 50/50 blend at 25.times.
magnification; the structure of a 50/50 blend at 83.times.
magnification; the structure of a 35/65 blend at 33.times.
magnification; and the structure of a 35/65 blend at 1200.times.
magnification. FIGS. 6 and 8 were obtained from cut surfaces
while FIGS. 7 and 9 were obtained from fractured surfaces.

[0076] In addition to the photomicrographs an electron probe
analysis was undertaken to establish the chemical make-up of the
phases observed.

[0077] The light areas shown in the photomicrographs are those
of higher density material (the specific gravities of Hytrel
G3548L and DC3179 are 1.15 and 1.14. However, the electron probe
analysis shows a higher silicon content in the lighter regions
and these are, therefore, assumed to be more chemically similar
to the DC3179 dilatant than the Hytrel. Some silicon was also
detected in the darker regions (assumed to be mainly made up of
the Hytrel) and, under further investigation, these included a
very fine dispersion of silicon based particles. These particles
were originally a constituent of the dilatant in the form of
crystalline silica (quartz) and so the original blend must have
been a very intimate mixture of the dilatant and the Hytrel
polyether ester copolymer.

[0078] The phase separation is almost certainly due to the
subsequent melting of the blend the higher the dilatant content
the more separation is occurring i.e. the regions of higher
density (dilatant) material in the 50/50 blend are much larger
and vary in size and shape compared to that of the 35/65 blend.
Both the cut and fractured sections (FIGS. 1 and 2) indicate
poor adhesion between the two phases due to the presence of
fissures at the interfaces between the phases.

[0079] The phases present in the 35/65 blend are considerably
finer (see FIG. 8). The second non-continuous phase is in the
form of spherical particles which are typically 3 to 10 .mu.m in
diameter (FIG. 9). The fracture has occurred across a plane
which follows the interface between the two phases which again
indicates poor adhesion between the phases.

[0080] From the analysis it can be concluded that the blend
materials before subsequent heating to the molten state were a
very intimate dispersion of one phase in the other. This being
indicated by the presence of crystalline silica in the Hytrel
phase of the blend. The separation of the phases evident in the
50/50 blend is due to the subsequent heating process. The amount
of separation for the 35/65 blend having had the same heat
treatment is considerably less and therefore phase separation
appears to be dependent on the ratio of dilatant to Hytrel--the
higher the dilatant content the greater the separation.

[0081] If a finer dispersion of dilatant within a second
material has advantages over a larger two phase structure
consideration of the blend ratio and processing time in the
molten state should be given. This is also the case if a
structure such as that seen in the 50/50 blend offers
advantages. The inference of this study is that the structure of
the phases can be controlled by the blend ratios and heat
treatments.

**EXAMPLE 3**

[0082] The two batches of blend materials (the 35/65 and the
50/50 blend) were further processed to produce a closed cell
foam using the Expancel process. The particular grade of
Expancel used was Akzo Nobel Expancel 092MB120 which was
masterbatched with the same Hytrel grade to give a high
concentration of Expancel in the masterbatch. The masterbatch
was then mixed with the two blends to give a final percentage by
weight of 8% of Expancel to the blend.

[0083] The blends, as well as pure Hytrel with the same content
of Expancel were then sheet extruded. This was done by using a
heated screw feeder fed by a hopper containing the material in
pellet form. As the pellets of material are screw fed down the
barrel of the machine the heaters raise the temperature of the
pellets to around 200.degree. C. which takes the material into
the molten state. This temperature also activates the Expancel
but the pressure in the barrel stops the material from forming
cells at this stage. The molten material was then injected
through an orifice around 4 mm wide by 180 mm long onto
non-stick polished steel rollers. As the molten material flowed
onto the rotating rollers to drop in pressure to atmospheric
enabled the material to foam under the action of the Expancel
system. The material was fed through another two rollers to
produce a solid foamed material around 6 mm thick with a density
of around 380 kg/m.sup.3. The final density and thickness are
influenced by the relationship between the speed of the screw
feeder and the rotational speed of the rollers. All three
materials--the pure Hytrel, the 35/65 blend and the 50/50 blend
felt relatively stiff.

[0084] As the dilatant material is soft and flowable it was
expected that the presence of this in the blends should have
imparted some softness to the final foamed blend when compared
to the foamed Hytrel material.

[0085] It was unexpectedly noticed, however, that during
subsequent repeated compression of the material that all of the
foamed materials became softer. By undertaking a controlled
amount of repeated compression on all materials the foams were
"worked" into their softest state. This was done by passing the
material through contra rotating steel rollers spaced at around
3 mm. This was done slowly, the rollers being turned by hand,
and repeated 20 times for each material. Softness measurements
were made before and after this process using a hand held ASTM
D2240 durometer to give a "Shore A" reading for the materials.
These are shown in Table 1. TABLE-US-00001 TABLE 1 HYTREL FOAM
35/65 BLEND FOAM 50/50 BLEND FOAM As extruded Softened As
extruded Softened As extruded Softened Shore a 52 33 52 27 52 25
hardness

[0086] An explanation as to why the materials became softer
after repeated compression is given by observing the structures
before and after this softening process with the aid of SEM. It
could be seen that it was the Expancel which was reinforcing the
blend material. The Expancel manifests as discrete, relatively
rigid, microballoons (FIG. 10: the internal structure was
exposed by tearing the sample). The Expancel microballoons can
be clearly seen intact. FIG. 11 shows the structure subsequent
to softening process. The Expancel microballoons have collapsed
to provide no cell reinforcement and so allowing the matrix
material to define the softness of the foam. This change in
structure was observed for all three materials.

[0087] This charge in softness according to the amount of
repeated compression of the material may provide benefits for in
service use of such a material e.g. for insoles where the high
pressure areas under feet will yield to allow the insole to
"mould" to the shape of the underside of the foot. The same
principle can be applied to ski boot liners.

**EXAMPLE 4**

[0088] In order to assess the effect the dilatant material has
on the impact properties of the Hytrel impact tests were
performed.

[0089] These tests were performed on a specially designed
pendulum impact rig which is illustrated in FIG. 12, and
essential features of which are listed in Table 2 below.
Briefly, the apparatus comprises a gallows-shaped rigid support
2 on the end of the horizontal arm 4 of which is freely
pivotally mounted a swing arm 6 which is pivoted to swing in a
vertical plane. On the free end of the swing arm is mounted an
impact head 8 to which weights 10 may be attached. Located on
the vertical arm of the rigid support at a position such that a
sample (not shown) mounted on it will be struck by the impact
head, is a hemispherical steel anvil 12. TABLE-US-00002 TABLE 2
Mass of swing arm assembly 4.055-9.247 Kg Radius of Swing arm
[From fulcrum 1.248 m centre to impact head centerline] Radius
of swing arm mass centre [From 0.852-1.05 m fulcrum to centre of
gravity of swing arm] Swing arm material Aluminium extrusion and
steel [bolted assembly] Anvil diameter 0.1 m Anvil material
Steel [welded assembly] Impact head dimensions 40 mm .times. 80
mm Mass of Impact head 0.25 Kg Material of Impact head Steel
Material of additional weight Steel Rigid support material Steel
[welded assembly]

[0090] Impact rigs are most commonly either of a drop weight
design or of a swing pendulum design. In this case the swing
pendulum design was chosen as it offers certain advantages for
the purpose of development testing. The applied impact load for
a pendulum rig is not followed by a residual creep load, as is
the case for a drop weight design, where the impact head remains
in contact with the tested sample after the impact event. This
is particularly relevant in respect of impact testing where the
use of pressure measuring devices are employed such as pressure
sensitive film. These record peak pressure during the impact and
any secondary strike or residual load may corrupt these
readings.

[0091] In any impact test the applied impact energy is equal to
the net kinetic energy of the impact head immediately prior to
impact, and in the case of a pendulum rig this is a function of
the impact head speed and the rotational mass of the system. The
impact rig was thus designed such that it was capable of
applying a range of impact speeds, by adjusting the inclined
angle of the pendulum prior to release and a range of rotational
mass, through the addition and subtraction of weights near the
impact head. The geometry of the impact head and anvil were
chosen to replicate the EN 1621-1 1997 standard test for
motorcycle body protection.

[0092] The test procedure was to apply the material samples to
the anvil in the orientation and position best representing the
material's use on the body as body protection, and to fix this
to the anvil with the use of adhesive tape. The impact swing arm
was then retracted to a prescribed angle before release. During
the impact event the force transmitted was measured dynamically
with a calibrated piezo-electric load cell and the peak force
recorded. This load cell is located behind the hemi-spherical
dome of the anvil. Preload of the piezoelectric load cell was
used according to best practice and reset to read zero.

[0093] Additionally the pressure transmitted to the anvil
during the impact was also recorded on Fuji pressure film
attached directly to the anvil and affixed with masking tape at
its edge. In order to simultaneously measure the pressure
transmitted at the different pressure ranges, medium (1400-7000
psi), low (350-1400 psi) and super low (70-350 psi) films were
placed on top of one another in a stack and affixed to the rig
simultaneously. All samples of film were pre cut to size and
measured 5 cm wide and 5.5 cm high. They were placed on the
anvil in a portrait orientation, with the masking tape applied
at the top and bottom only. Fuji pressure film serves as a
simple but effective way of indicating the peak pressure during
the impact over the contact area under investigation.

[0094] The standard EN 1621-1 test is not representative of
real impact events to the human body as the anvil is part of an
extremely rigid system and does not offer any compliance in the
manner of the body. The criterion for passing the EN1621-1 test
for motorcycle protection is that the peak load transmitted is
less than 35 kN for the impact speed of 4.3 m/s and an impact
energy of 50 J. However, a peak-transmitted force of 35 kN if
actually applied to the body would cause severe injury.

[0095] It is for these reasons that in addition to the
specified speed and energy level an impact speed of 3.9 m/s and
energy value of 20 J was also used. With the additional use of
Fuji pressure film, it is also relevant to define more fully the
performance of a material for which one of the proposed uses is
body protection systems used for a variety of sports e.g. snow
sports, skateboarding and downhill mountain biking.

[0096] To obtain the two energy levels additional mass was used
for the higher 50 J impact. This was added behind the striker so
in order to calculate the angle from which to release the arm
the new centre of mass was determined by measurement. This is
shown in Table 3. TABLE-US-00003 TABLE 3 Angle of Energy of
pendulum [deg] Impact Swing Arm Centre of Mass Impact (J) from
horizontal speed m/s mass (kg) Radius (m) 20 22 3.9 4.055 0.805
50 14.5 4.3 6.90 0.986

[0097] All three materials were tested as described above using
two layers of the extruded sheet material the force results in
both the as extruded and softened condition for the two impact
energy levels are shown below in Table 4. TABLE-US-00004 TABLE 4
HYTREL 35/65 Blend 50/50 Blend PROPERTY Hard Soft Hard Soft Hard
Soft Softness - shore a 52 33 52 27 52 25 hardness Force 20 J 7
9.6 4.9 9.1 6.7 8.7 Impact (kN) 50 J 18.6 19.1 15.9 16.1 16.9
16.6 Density S.G. 0.4 0.4 0.4 Thickness Mm 11 10 10

[0098] The performance of the materials with respect to
pressure for the 50 J impact are shown in FIG. 13.

[0099] From the results it has been shown that the blending of
a dilatant material has a beneficial effect on the impact
performance of the Hytrel polyester copolymer. The foamed blends
were measurably softer than the pure foamed Hytrel material yet
outperformed the Hytrel in terms of force and pressure
transmission during impact. Specifically the pure Hytrel
transmitted had a reduction of transmitted about 19% more force
than the 65/35 blend. Although difficult to quantify the
pressure signatures also show an improvement in performance; the
very sensitive superlow film shows the two blends to have an
increased area of contact, but for the less sensitive medium
film the contact area is smaller. This suggests that a lower
peak pressure was transmitted for the blends (less of the medium
film area being saturated) with a corresponding greater area for
the more sensitive film indicating that the blend material has
stiffened during impact to transmit the load through a greater
volume (and therefore area) of the material. It should also be
bome in mind that the softer blend materials had a thickness of
around 10% less than the pure Hytrel foam.

[0100] Without wishing to be bound by theory, it is believed
(though not ascertained) that because the second material ii)
(which exhibits dilatancy in the absence of the first material
i) is entrapped in the composite material of the invention in a
solid matrix of i) its ability to flow is inhibited such that at
high local deformation rate, its tendency to shear thicken is
efficiently imparted to the unfoamed composite material which
thereby exhibits a resistive load under deformation which
increases with the rate of deformation.

[0101] Furthermore, where the composite material is foamed the
gas or air within the cell will, by reason of its
compressibility, allow the composite material to undergo larger
amounts of local deformation thereby extending the opportunity
of the composite material to stiffen during impact. In the above
case where the cells are closed cells it is believed that
additional pneumatic stretching of the cell walls gives rise to
greater local elastic deformation.

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