U.S. patent application number 14/459259 was filed with the patent office on 2014-11-27 for biocomposite material.
The applicant listed for this patent is CELLUCOMP LIMITED. Invention is credited to David HEPWORTH, Eric WHALE.
Application Number | 20140350144 14/459259 |
Document ID | / |
Family ID | 33548684 |
Filed Date | 2014-11-27 |
United States Patent
Application |
20140350144 |
Kind Code |
A1 |
HEPWORTH; David ; et
al. |
November 27, 2014 |
BIOCOMPOSITE MATERIAL
Abstract
A biocomposite material (1) and methods of production thereof
are described. The biocomposite material (1) exhibits a physical
stiffness, strength and toughness comparable to known glass fibre
composites while its composition makes it inherently impermeable to
water. A general formulation for the biocomposite material (1) is
given by the expression: Cel.sub.(1-x-y)HPI.sub.x HPO.sub.y where
"Cel" represents cellulose fragments (2), "HPI" represents
hydrophilic binders (4), "HPO" represents hydrophobic binders (5)
and (x) and (y) quantify the percentage by weight of the
hydrophilic (4) and hydrophobic binders (5) present within a
material, respectively. The described properties of the
biocomposite material (1) are achieved when (x) is within the range
of from 0.05 to 0.55 and (y) is within the range of from 0.05 to
0.65.
Inventors: |
HEPWORTH; David; (Fife,
GB) ; WHALE; Eric; (Fife, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CELLUCOMP LIMITED |
Fife |
|
GB |
|
|
Family ID: |
33548684 |
Appl. No.: |
14/459259 |
Filed: |
August 13, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11791221 |
May 22, 2007 |
8834980 |
|
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PCT/GB2005/004322 |
Nov 10, 2005 |
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14459259 |
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Current U.S.
Class: |
524/35 ; 156/60;
162/60; 162/70; 264/257 |
Current CPC
Class: |
Y10T 428/1352 20150115;
C08L 1/02 20130101; Y10T 428/1348 20150115; C08J 2301/02 20130101;
D21H 11/20 20130101; D21C 9/002 20130101; C08J 5/12 20130101; Y10T
156/10 20150115; D21H 27/34 20130101; Y10T 428/1359 20150115; Y10T
428/139 20150115; C08J 5/045 20130101; D21C 9/10 20130101; Y10T
428/2929 20150115; D21C 5/005 20130101; Y10T 428/1303 20150115;
Y10T 428/13 20150115 |
Class at
Publication: |
524/35 ; 162/70;
162/60; 156/60; 264/257 |
International
Class: |
C08J 5/04 20060101
C08J005/04; D21C 5/00 20060101 D21C005/00; C08J 5/12 20060101
C08J005/12; D21C 9/10 20060101 D21C009/10 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 23, 2004 |
GB |
0425691.3 |
Claims
1. A method for producing cellulose fragments comprising a network
of cellulose microfibrils, the method comprising: treating a plant
material to obtain a first pulp of the plant material; mixing the
first pulp with a bleach solution so that a quantity of pectins and
hemicelluloses present within the plant material are dissolved
within a resultant solution; producing a second pulp by removing
the bleach from the resultant solution; and reducing the water
content present within the second pulp.
2. The method of claim 1, wherein the step of treating the plant
material comprises: heating the plant material to obtain a softened
plant material; blending the softened plant material with water to
obtain a blended resultant residue; and adding a micro-organism to
the blended resultant residue to aid the breakdown of the plant
material.
3. The method of claim 2, further comprising filtering any
resultant liquid from the softened plant material.
4. The method of claim 2, wherein the micro-organism is bacterium
or yeast.
5. The method of claim 1, wherein the step of producing a second
pulp comprises homogenising the resultant solution and then washing
and filtering the homogenised resultant solution to remove the
bleach.
6. The method of claim 1, wherein the step of reducing the water
content present within the second pulp results in the second pulp
comprising at least 40% water by weight.
7. A method for producing a biocomposite material comprising:
producing a plurality of cellulose fragments, comprising a network
of cellulose microfibrils; incorporating a hydrophilic binder
within the network of cellulose microfibrils; and encapsulating the
plurality of cellulose fragments within a hydrophobic binder.
8. The method of claim 7, wherein the step of producing the
plurality cellulose fragments comprises: treating a plant material
to obtain a first pulp of the plant material; mixing the first pulp
with a bleach solution so that a quantity of pectins and
hemicelluloses present within the plant material are dissolved
within a resultant solution; producing a second pulp by removing
the bleach from the resultant solution; and reducing the water
content present within the second pulp.
9. The method of claim 7, wherein the step of incorporating the
hydrophilic binder within the network of cellulose microfibrils
comprises: re-hydrating the cellulose fragments with the
hydrophilic binder and water so as to produce a paste; and removing
excess water and excess hydrophilic binder from the paste.
10. The method of claim 9, wherein the re-hydrating step comprises
re-hydrating the cellulose fragments with a first emulsion
comprising the hydrophilic binder so as to produce a paste.
11. The method of claim 7, wherein the step of encapsulating the
plurality of cellulose fragments comprises: mixing the hydrophobic
binder and the paste containing the hydrophilic binder so as to
produce a composite paste material; removing water from the paste
material; and curing the dried paste material.
12. The method of claim 11, wherein the step of encapsulating the
plurality of cellulose fragments further comprises Applying
pressure to the paste material.
13. The method of claim 12, wherein the mixing step further
comprises producing a second emulsion comprising the hydrophobic
binder; and mixing the second emulsion and the paste containing the
hydrophilic binder so as to produce a composite paste material.
14. The method of claim 13, wherein the production of the second
emulsion involves mixing the hydrophobic binder with a surfactant
and water.
15. The method of claim 14, wherein the surfactant is
non-ionic.
16. The method of claim 13, wherein the production of the second
emulsion comprises: obtaining a sample of individual cellulose
fibrils and microfibrils derived from the plant material; and
mixing the hydrophobic binder with the sample.
17. The method of claim 16, wherein the sample of individual
cellulose fibrils and microfibrils derived from the plant material
is obtained from a method comprising: producing a first pulp of the
plant material; mixing a first pulp with a bleach solution so that
a quantity of pectins and hemicelluloses present within the plant
material are dissolved within a resultant solution; producing a
second pulp by removing the bleach from the resultant solution; and
homogenising the second pulp so as to reduce the cellulose in the
second pulp to individual cellulose fibrils and microfibrils.
18. The method of claim 17, wherein the sample of individual
cellulose fibrils and microfibrils derived from the plant material
is obtained from a method comprising: producing a first pulp of the
plant material; mixing a first pulp with a bleach solution so that
a quantity of pectins and hemicelluloses present within the plant
material are dissolved within a resultant solution; homogenising
the resultant solution so as to reduce the cellulose in the second
pulp to individual cellulose fibrils and microfibrils; and removing
the bleach from the homogenised solution.
19. The method of claim 17, wherein the homogenising is carried out
using high shear mixing.
20. The method of claim 17, wherein the homogenising is carried out
using high pressure homogenisation up to 1000 bar.
21. The method of claim 11, wherein the homogenising is carried out
using high pressure homogenisation up to 1000 bar.
22. The method of claim 11, comprising a method of obtaining a
sample of individual cellulose fibrils and microfibrils derived
from the plant material which comprises: producing a first pulp of
the plant material; mixing a first pulp with a bleach solution so
that a quantity of pectins and hemicelluloses present within the
plant material are dissolved within a resultant solution; producing
a second pulp by removing the bleach from the resultant solution;
and homogenising the second pulp so as to reduce the cellulose in
the second pulp to individual cellulose fibrils and
microfibrils.
23. The method of claim 11, comprising a method of obtaining a
sample of individual cellulose fibrils and microfibrils derived
from the plant material which comprises: producing a first pulp of
the plant material; mixing a first pulp with a bleach solution so
that a quantity of pectins and hemicelluloses present within the
plant material are dissolved within a resultant solution;
homogenising the resultant solution so as to reduce the cellulose
in the second pulp to individual cellulose fibrils and
microfibrils; and removing the bleach from the homogenised
solution.
24. The method of claim 22, wherein the homogenising step is
carried out using high shear mixing.
25. The method of claim 21, wherein the homogenising is carried out
using high pressure homogenisation up to 1000 bar.
26. The method of claim 13, wherein the ratio of the hydrophobic
binder to the water within the second emulsion is between 10:1 and
1:5.
27. The method of claim 26, wherein the ratio of the hydrophobic
binder to the water within the second emulsion is between 10:1 and
5:1.
28. The method of claim 13, wherein the step of removing water from
the paste material comprises applying a vacuum to the paste.
29. The method of claim 27, wherein the step of removing water
further comprises air drying the paste at a temperature below
120.degree. C.
30. The method of claim 13, wherein the curing of the dried paste
material comprises a first curing of the dried paste material at a
temperature within the range from ambient to 80.degree.-160.degree.
C.
31. The method of claim 30, wherein the step of curing of the dried
paste material further comprises a second curing of the dried paste
material at a temperature within the range 120.degree.-180.degree.
C.
32. The method of claim 30, wherein the step of curing of the dried
paste material further comprises a second curing of the dried paste
material at a temperature within the range 120.degree.-180.degree.
C.
33. The method of claim 7, wherein the hydrophilic binder comprises
a hydrophilic or substantially hydrophilic polymer selected from
the group consisting of hemicellulose, an acrylic resin, a
partially hydrolysed polyvinyl acetate and a biological hydrophilic
polymer.
34. The method of claim 7, wherein the hydrophobic binder is
selected from a member of the group consisting of a hydrophobic
polymer, polyurethane, phenolic resin, acrylic, epoxy resin and
siloxane.
35. A method for producing a laminate structure, comprising:
applying a hydrophobic resin to preformed sheets of biocomposite
material, stacking the sheets on top of one another and applying
pressure.
36. A method for producing a laminate structure comprising two or
more layers wherein at least one layer comprises a biocomposite
material, said method comprising: preparing the biocomposite
material according to the method of claim 11.
37. A method of claim 36, wherein the laminate structure forms a
tubular structure.
38. A method of claim 37, wherein the laminate structure is a
fishing rod, bicycle frame, ski pole, sail spar or a mast.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a division of U.S. application Ser. No.
11/791,221, filed Nov. 10, 2005, which is a National Stage Entry of
International Application No. PCT/GB2005/004322, filed Nov. 10,
2005, which claims the benefit of GB Application No. 0425691.3,
filed Nov. 23, 2004. The entire contents of the above-identified
applications are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to the field of biocomposite
materials and in particular to biocomposite materials produced
through the extraction of cellulose from plants.
[0003] The use of plant based long fibres such as hemp, flax,
kanaf, cotton, jute, sisal and coconut fibre mats as reinforcement
for polymer matrices such as polypropylene and epoxy resins are
well known to those skilled in the art. These composites utilise
fibres which are typically several centimetres long and hundreds of
micrometers wide (usually in the form of bundles of several bast
fibre cells). Primarily these plant based long fibres have found
applications in the automotive industry, but only for
non-structural applications such as door liners and parcel shelves,
due in part to the poor surface finish achieved with these
materials, but mainly because of their reduced toughness when
compared to glass fibre reinforced polymers (GFRP). These materials
are also known to exhibit inherent problems with water absorption
and odour release.
[0004] Shorter plant fibres, mainly derived from wood pulp, have
also been used by those skilled in the art as reinforcements for
plastics. Traditional materials made from these fibres include
Formica, medium density fibre board (MDF) and high density fibre
board (HDF). However, these materials suffer from similar problems
to the long plant fibre composites, being either brittle and water
proof (e.g. Formica) or alternatively tough but water absorbent
(e.g. MDF).
[0005] Recently it has been discovered that high performance
materials can be produced by impregnating mats of fibrillated wood
pulp fibres with phenolic resin (see Nakagaito et al "The Effect Of
Morphological Changes From Pulp Fiber Towards Nano-Scale
Fibrillated Cellulose On The Mechanical Properties Of High-Strength
Plant Fibre Composites" Applied Physics A: Materials Science &
Processing Vol. 78 Page 547-552 (2004) and Yano et al
"Bio-Composites Produced From Plant Microfiber Bundles With A
Nanometer Unit Web-Like Network" Journal Materials Science Vol. 39
Page 1635-1638 (2004)). The fibrillation of the wood fibres acts to
partially separate cellulose microfibrils within the cell walls so
that the wood fibres become more absorbent and the surface
`roughened` so that there is a greater surface area for interaction
with other fibres and binders. In general these materials are stiff
and strong but only achieve toughness equal to or greater than
glass fibre if the resin content is kept to less than 3%, so
resulting in a highly hygroscopic material which losses strength as
it absorbs water. Also the method of manufacturing the materials,
which involves impregnating sheets of dry fibres with dilute resin
and then stacking many thin (<0.5 mm) sheets of impregnated
material on top of one another and hot pressing at high pressure,
is a very time consuming process, taking over 100 hours. This
severely increases manufacturing time compared to GFRP and so
greatly limits the potential range of applications for these
materials.
[0006] U.S. Pat. No. 4,609,431 in the name of Congoleum Corporation
teaches of a tough, water proof material produced by mixing lower
quantities of wood pulp fibres (less than 30%) with glass fibres
and thereafter embedding these within a complex of rubber materials
and inorganic fillers. However, these materials exhibit a lower
stiffness than GFRP which limits their applications to surface
finishes. Furthermore, such materials can only be classified as a
partial biocomposite material due to the significant proportion of
GFRP present.
[0007] A further method of forming composite materials is described
by Matsumura et al "Cellulosic Nanocomposites I Thermally
Deformable Cellulose Hexanoates From Heterogeneous Reaction" J.
Applied Polymer Science Vol. 78 Page 2242-2253 (2000). This method
involves the chemical treatment of the surface of wood fibres so as
to cause esterification of the wood fibres. The esterified fibres
are then hot pressed together to form consolidated sheets. Although
these materials are water resistant they exhibit only limited
modulus and strength.
[0008] The prior art also teaches that it is possible to completely
separate cellulose microfibrils from animal and bacterial sources
which are much smaller and thinner than the previously discussed
plant fibres (being 5-20 nm in diameter), see PCT Application No.
PCT/NL92/00206 in the name of DSM N. V. and PCT Application No.
PCT/US89/02355 in the name of Brown, respectively. Composite
materials made from these animal and bacterial cellulose
microfibrils have been shown to exhibit high stiffness and good
strength but have inherently low failure strains which results in
them being brittle in nature.
[0009] Improvements to these composite materials have been achieved
by mixing the cellulose microfibrils with low modulus
resins/binders so as to produce a tougher composite material.
However, the tensile modulus of these composite materials is less
than 5 GPa, which is no better than the levels achieved within
non-reinforced plastics, and is too low to allow them to be
employed within many structural applications.
[0010] Within these composite materials it is also desirable to
achieve high volume fractions of the cellulose microfibrils within
the finished composites. However, this in itself is problematic
because even when a few percent, by weight, of free cellulose
microfibrils are added to a liquid, the viscosity of the liquid
increases dramatically. Indeed the liquid quickly becomes a gel if
the cellulose microfibrils begin to interact with one another (at
less than 15% microfibril content).
[0011] To date the only way to achieve the high volume fractions,
which are necessary to produce high stiffness, high strength
composite materials, has been to employ a method described by
Nakagaito et al "Bacterial Cellulose: The Ultimate Nano-Scalar
Cellulose Morphology For The Production Of High-Strength
Composites" Applied Physics A: Materials Science & Processing
DOI: 10.1007/s00339-004-2932-3 (2004). This method involves the
formation of mats of the cellulose microfibrils by precipitation
from water, drying off of the water (or sequential replacement of
the water with an organic solvent) and then impregnating the
resultant material with a resin (often under high pressure). This
is a complex and time consuming process involving many individual
manufacturing steps and so the composite materials produced by this
route consume large amounts of energy during manufacturing and
therefore are not economical for commercial scale production.
[0012] It is also known to those skilled in the art that cellulose
microfibrils can be found within almost all plant cell walls.
Indeed Dufresne et al "Mechanical behaviour of sheets prepared from
sugar beet cellulose microfibrils" J Appl Polym Sci Vol. 64 Page
1185-1194 (1997) teach that these cellulose microfibrils can be
extracted from these plant cells using a combination of chemical
degradation of plant material and high pressure homogenisation. The
cellulose microfibrils can then be used to produce composite
materials, in a similar way to those described previously in
connection with animal and bacterial cellulose microfibrils, as
described in Dufresne A et al "Cellulose Microfibrils From Potato
Tuber Cells Processing And Characterisation Of Starch-Cellulose
Microfibril Composites" J. Applied Polymer Science Vol. 76 Page
208-2092 (2000). To date the composite materials produced by this
method exhibit very poor mechanical properties with low stiffness
and poor strength. This is partly due to the low upper limit of 15%
of the cellulose microfibrils that can be mixed with the liquid
resin, before it becomes a solid gel, as discussed above.
[0013] It is therefore an object of an aspect of the present
invention to provide a biocomposite material that exhibits a
physical stiffness, strength and toughness comparable to known
glass fibre composites but which is also inherently impermeable to
water.
[0014] It is a further object of an aspect of the present invention
to provide a biocomposite material that exhibits the above
properties and which can be produced economically on a commercial
scale.
[0015] For clarity purposes it should be noted that the stiffness
of a material is quantified by the Young's modulus exhibited by the
material while the toughness of a material is quantified by the
amount of energy absorbed per unit volume of the material up to the
point of failure. Furthermore, an impermeable material is defined
as a material that has a significantly slower rate of water uptake
when completely immersed in water when compared to cellulose or
previously known cellulose composites.
[0016] In the following formulations "Cel" represents cellulose
fragments, "HPI" represents hydrophilic binders, "HPO" represents
hydrophobic binders and x and y quantify the percentage by weight
of the hydrophilic and hydrophobic binders present within a
material, respectively.
SUMMARY OF THE INVENTION
[0017] According to a first aspect of the present invention there
is provided a biocomposite material comprising a plurality of
cellulose fragments made up of a network of cellulose microfibrils,
a plurality of hydrophilic binders located within the network of
cellulose microfibrils and a plurality of hydrophobic binders
arranged to interact with the hydrophilic binders so as to
encapsulate the plurality of cellulose fragments.
[0018] The above arrangement ensures good stress transfer from the
hydrophobic binders through the hydrophilic binders to the
cellulose microfibrils so providing the biocomposite material with
the desired stiffness, strength and toughness. By arranging the
hydrophobic binders so as to encapsulate the cellulose fragments,
the biocomposite material is also rendered impermeable to
water.
[0019] Most preferably the biocomposite material of the first
aspect of the present invention has the general formulation
Cel.sub.(1-x-y) HPI.sub.x HPO.sub.y where x is within the range of
from 0.05 to 0.55 and y is within the range of from 0.05 to
0.65.
[0020] According to a second aspect of the present invention there
is provided a biocomposite material that is impermeable to water
comprising a plurality of cellulose fragments made up of a network
of cellulose microfibrils, a plurality of hydrophilic binders and a
plurality of hydrophobic binders having the general formulation
Cel.sub.(1-x-y) HPI.sub.xHPO.sub.y where x is within the range of
from 0.05 to 0.55 and y is within the range of from 0.05 to
0.65.
[0021] Preferably the plurality of hydrophilic binders are located
within the network of cellulose microfibrils and the plurality of
hydrophobic binders are arranged to interact with the hydrophilic
binders so as to encapsulate the plurality of cellulose
fragments.
[0022] Most preferably the biocomposite material of the first and
second aspects of the present invention exhibits a stiffness in the
range from 5 GPa to 90 GPa.
[0023] According to a third aspect of the present invention there
is provided a biocomposite material that is impermeable to water
and which exhibits a stiffness in the range from 5 GPa to 90
GPa.
[0024] Preferably the biocomposite material of the third aspect of
the present invention comprises a plurality of cellulose fragments
made up of a network of cellulose microfibrils, a plurality of
hydrophilic binders located within the network of cellulose
microfibrils and a plurality of hydrophobic binders arranged to
interact with the hydrophilic binders so as to encapsulate the
plurality of cellulose fragments.
[0025] Preferably the biocomposite material of the third aspect of
the present invention has the general formulation
Cel.sub.(1-x-y)HPI.sub.xHPO.sub.y where x is within the range of
from 0.05 to 0.55 and y is within the range of from 0.05 to
0.65
[0026] Most preferably the cellulose fragments of the various
aspects of the present invention are arranged in a randomly
orientated manner.
[0027] Most preferably the biocomposite material of the various
aspects of the present invention exhibit a tensile strength in the
range from 60 MPa to 1 GPa.
[0028] Most preferably the biocomposite material of the various
aspects of the present invention exhibit a bending strength in the
range from 60 MPa to 600 MPa.
[0029] Most preferably the biocomposite material of the various
aspects of the present invention exhibits a stiffness in the range
from 14 GPa to 21 GPa.
[0030] Most preferably the biocomposite material of the various
aspects of the present invention exhibits a strength in the range
from 200 MPa to 300 MPa.
[0031] Most preferably the biocomposite material of the various
aspects of the present invention exhibit a toughness in the range
from 3 MJm.sup.-3 to 10 MJm.sup.-3.
[0032] Preferably the hydrophilic binders comprise a hydrophilic or
substantially hydrophilic polymer. The hydrophilic polymer may
comprise a hemicellulose, an acrylic resin or alternatively a
partially hydrolysed polyvinyl acetate. Optionally the hydrophilic
polymer comprises a biological hydrophilic polymer e.g. gelatine
and guar gum.
[0033] Optionally the hydrophobic binders comprise a hydrophobic
polymer. The hydrophobic polymer may comprise an epoxy such as a
bisphenol-A or a modified bisphenol A epoxy.
[0034] Alternatively the hydrophobic binders comprises a binder
selected from the group comprising polyurethanes, phenolic resins,
acrylics and siloxanes.
[0035] According to a fourth aspect of the present invention there
is provided a monolithic structure comprising two or more layers
wherein at least one layer comprises a biocomposite material in
accordance with any of the first to third aspects of the present
invention.
[0036] The formation of a monolithic layered structure provides a
structure within which the mechanical properties can be gradated,
as appropriate. As curing results in there being no distinct
interfaces between the layers, these monolithic structures
experience no compromise to their mechanical properties.
[0037] Optionally the monolithic structure comprises at least one
layer of a plastic material. Preferably the plastic material
comprises a carbon fibre reinforced material.
[0038] According to a fifth aspect of the present invention there
is provided a laminate structure comprising two or more layers
wherein at least one layer comprises a biocomposite material in
accordance with any of the first to fourth aspects of the present
invention.
[0039] Optionally the laminate structure comprises at least one
layer of a plastic material. Preferably the plastic material
comprises a carbon fibre reinforced material.
[0040] Preferably the laminate structure comprises one or more
layers of resin located between the two or more layers of the
structure.
[0041] Preferably the one or more layers of resin comprise a
hydrophobic resin such as epoxy or polyurethane.
[0042] According to a sixth aspect of the present invention there
is provided a tube, suitable for use in a fishing rod, the tube
comprising a biocomposite material in accordance with the first to
fifth aspects of the present invention.
[0043] According to a seventh aspect of the present invention there
is provided a method of producing cellulose fragments, comprising a
network of cellulose microfibrils, from a plant material comprising
the steps of:
[0044] 1) Producing a first pulp of the plant material;
[0045] 2) Mixing a first pulp with a bleach solution so that a
quantity of pectins and hemicelluloses present within the plant
material are dissolved within a resultant solution;
[0046] 3) Producing a second pulp by removing the bleach from the
resultant solution; and
[0047] 4) Reducing the water content present within the second
pulp.
[0048] Optionally the first pulp is filtered and washed in water
before mixing with the bleach solution; Preferably the step of
producing the first pulp comprises the steps of:
[0049] 1) Heating the plant material so as to soften the plant
material;
[0050] 2) Filtering any resultant liquid from the softened plant
material; and
[0051] 3) Blending the resultant residue with water.
[0052] Optionally the step of producing the first pulp further
comprises chopping of the plant material before heating.
[0053] Preferably the plant material is heated to temperature
between 85.degree. C. and 120.degree. C. at atmospheric
pressure.
[0054] Optionally the blended resultant residue and water is
allowed to stand for a period of at least one day. Optionally a
micro-organism is added to the blended resultant residue so as to
aid the breakdown of the plant material. The micro-organism
optionally comprises bacterium or yeast.
[0055] Preferably the mixture of the first pulp and the bleach
solution is allowed to stand for a period of at least thirty
minutes so as to form the resultant solution. This has been found
to have the effect of aiding the reduction of the particle size
produced.
[0056] Preferably the step of producing a second pulp comprises
washing and filtering the resultant solution so as to remove the
bleach and so produce a second residue.
[0057] Optionally the step of producing the second pulp further
comprises the step of homogenising the second residue.
[0058] Preferably the second residue is homogenised by mixing the
second residue within a high shear mixing process. Alternatively
the second residue is homogenised by pressurising the second
residue at a pressure between 500 and 1000 bar.
[0059] Alternatively, the step of producing a second pulp comprises
homogenising the resultant solution and then washing and filtering
the homogenised resultant solution so as to remove the bleach.
[0060] Preferably the step of reducing the water content present
within the second pulp comprises pressing the second pulp.
[0061] Most preferably the pressing of the second pulp results in
the second pulp comprising at least 40% water by weight.
[0062] According to an eighth aspect of the present invention there
is provided a method of producing a biocomposite material that is
impermeable to water comprising the steps of:
[0063] 1) Producing a plurality of cellulose fragments, comprising
a network of cellulose microfibrils;
[0064] 2) Incorporating a plurality hydrophilic binders within the
plurality of cellulose fragments; and
[0065] 3) Encapsulating the plurality of cellulose fragments and
the plurality of hydrophilic binders within a plurality of
hydrophobic binders.
[0066] Most preferably the step of producing the plurality
cellulose fragments comprises the method of the seventh aspect of
the present invention.
[0067] Preferably the step of incorporating the plurality
hydrophilic binders within the cellulose fragments comprises:
[0068] 1) Re-hydrating the cellulose fragments with a first
emulsion comprising the hydrophilic binders so as to produce a
paste; and
[0069] 2) Removing excess water and excess hydrophilic binders from
the paste.
[0070] Preferably the step of encapsulating the plurality of
cellulose fragments and the plurality of hydrophilic binders
comprises:
[0071] 1) Producing a second emulsion comprising the plurality of
hydrophobic binders;
[0072] 2) Mixing the second emulsion with the paste containing the
hydrophilic binder so as to produce a composite paste material;
[0073] 3) Applying pressure to the composite paste material;
[0074] 4) Removing water from the composite paste material; and
[0075] 5) Curing the dried composite paste material.
[0076] Preferably the production of the second emulsion involves
mixing the hydrophobic binders with a surfactant and water.
[0077] Most preferably the surfactant is non-ionic.
[0078] Alternatively the production of the second emulsion
comprises the steps of:
[0079] 1) Obtaining a sample of the second pulp;
[0080] 2) Homogenising the sample so as to reduce the plurality of
cellulose fragments to individual cellulose fibrils and
microfibrils; and
[0081] 3) Mixing the hydrophobic binders with the homogenised
sample.
[0082] Preferably the ratio of the hydrophobic binders to the water
within the second emulsion is between 10:1 and 1:5. Most preferably
the ratio is between 10:1 and 5:1.
[0083] Preferably the step of removing water further comprises air
drying the composite paste material at a temperature below
120.degree. C. Optionally the step of removing water from the
composite paste material comprises applying a vacuum to the
paste.
[0084] Preferably the curing of the dried composite paste material
comprises a first curing of the dried composite paste material at a
temperature within the range from ambient to 180.degree. C. but
ideally in the range 80-160.degree. C.
[0085] Optionally the curing of the dried composite paste material
further comprises a second curing of the dried composite paste
material at a temperature within the range 120-180.degree. C.
BRIEF DESCRIPTION OF THE DRAWINGS
[0086] Aspects and advantages of the present invention will become
apparent upon reading the following detailed description and upon
reference to the following drawings in which:
[0087] FIG. 1 presents a series of schematic representations of the
structure of a biocomposite material in accordance with aspects of
the present invention;
[0088] FIG. 2 presents a schematic representation of the chemical
structure of a cellulose fragment employed within the biocomposite
material of FIG. 1;
[0089] FIG. 3 presents a flow chart of the method for producing the
biocomposite material of FIG. 1;
[0090] FIG. 4 presents a flow chart of the method for producing
cellulose fragments as employed within the method of FIG. 3;
[0091] FIG. 5 presents a schematic representation of a monolithic
structure in accordance with an aspect of the present invention;
and
[0092] FIG. 6 presents a schematic representation of a laminate
structure in accordance with an aspect of the present
invention;
DETAILED DESCRIPTION OF THE INVENTION
[0093] A detailed description of a biocomposite material 1 in
accordance with aspects of the present invention shall now be
described with reference to FIGS. 1 and 2.
[0094] From FIG. 1 the biocomposite material 1 can be seen to
comprise a plurality of cellulose fragments 2 in the form of a
network of cellulose microfibrils 3. The cellulose fragments 2 can
be seen to be infiltrated with a hydrophilic (or substantially
hydrophilic) binder 4 and encapsulated within a hydrophobic binder
5. In practice the cellulose fragments 2 can range from comprising
a mix of individual cellulose microfibrils (typically .about.20 nm
in diameter) to sections of cellulose cells typically .about.50
.mu.m in length and breadth and less than 1 .mu.m in thickness
themselves made up of a number of cellulose microfibrils 3. A
schematic representation of the chemical structure of cellulose is
presented in FIG. 2.
[0095] In the present embodiment the hydrophilic binder 4 comprises
partially hydrolysed polyvinyl acetate. Partially hydrolysed
polyvinyl acetate is known by those skilled in the art to be a
substantially hydrophilic polymer that readily forms micelles in
water. The diameter and nature of the partially hydrolysed
polyvinyl acetate particles is such that they locate within the
cellulose fragment 2, as shown in FIG. 1(b).
[0096] In the present embodiment the hydrophobic binder 5 comprises
an epoxy resin. Cured epoxy resins are known by those skilled in
the art to be hydrophobic in nature. The uncured epoxy resin is
therefore formed into micelles with a typical diameter of
.about.0.5-2 .mu.m. The diameter and nature of the epoxy particles
is such that these particles cannot locate within the cellulose
fragments 2. In the cured material, FIG. 1(c), the polymer
particles fuse and the epoxy interacts with the partially
hydrolysed polyvinyl acetate with the result that there is a
transfer of stress from the cured epoxy matrix via the partially
hydrolysed polyvinyl acetate to the cellulose fragments 2. This
interaction provides the composite material with the physical
parameters as detailed in Table 1 below which relates in particular
to a material that comprises 25% partially hydrolysed polyvinyl
acetate by weight and 25% epoxy by weight and in which the
cellulose fragments are randomly orientated throughout the
composite material. For comparison purposes Table 1 also includes
typical results for alternative materials known to those skilled in
the art i.e. GFRP and so called waterproof hemp (hemp with a 30%
polypropylene fibre content).
[0097] A further function of the epoxy is that it effectively
encapsulates the cellulose fragments 2 and hence the partially
hydrolysed polyvinyl acetate located therein, so rendering the
biocomposite material 1 impermeable to water.
[0098] The precise physical properties of the biocomposite material
1 outlined in Table 1 can be varied by altering the relative
proportion by weight of both the partially hydrolysed polyvinyl
acetate and the epoxy. It has been found that a biocomposite
material that is impermeable to water can be produced when the
partially hydrolysed polyvinyl acetate comprise between 5% and 55%
of the total weight of the material while the epoxy can be varied
within a range of 5% to 65% of the total weight of the material. It
has been possible to produce these biocomposite materials in
samples in excess of 4 mm thick.
[0099] Methods for producing the biocomposite material 1 shall now
be described in detail, a flow chart for which is presented in FIG.
3.
[0100] The first stage of this process involves the production of
the cellulose fragments 2, comprising a network of cellulose
microfibrils 3 which provides the framework for the biocomposite
material 1. The production of the cellulose fragments 2 is achieved
by the following process, a flow chart for which is provided in
FIG. 4:
[0101] 1) A plant material is coarsely chopped into a plurality of
pieces. In this particular example the plant material comprises
chopped carrot.
[0102] 2) The coarsely chopped carrot is then hydrothermally
treated, at a temperature between 85-120.degree. C. at atmospheric
pressure, until it begins to soften. Optionally steam and pressures
above atmospheric pressures may be utilised to soften the
carrots.
[0103] 3) The resultant cooking liquid is then drained off from the
softened coarsely chopped carrot.
[0104] 4) Fresh water is then added to the residue material and
this material is then processed in high speed blender for
approximately 3-5 minutes so as to increase the available surface
area of the material.
[0105] 5) Optionally, the material can then be immediately used as
described below. Alternatively, the material can be allowed to
stand for a period of time before use with or without the addition
of a micro-organism e.g. bacteria or yeast. Such additional steps
further assist in the breakdown of the carrot material.
[0106] 6) The resultant pulp produced by the blending process may
then be filtered and washed with clean water.
[0107] 7) Next the residue Produced within the previous stage is
mixed with a concentrated bleach solution and thereafter allowed to
stand for 30 minutes, although longer time periods may be employed.
The addition of bleach acts to kill of any unwanted micro-organisms
while ensuring that a significant quantity of the pectins and
hemicelluloses present within the original carrot material is
dissolved within the resultant solution.
[0108] 8) The bleach is then removed by washing and filtering.
Thereafter, water is added to the residue which is then homogenised
by passing through a high shear in-line mixer or a high shear batch
mixer. This involves the passing of the residue through a fine mesh
under high shearing conditions so as to break down the cellular
material in the residue so as to produce a pulp containing a range
of cellulose fragments i.e. sized from individual cellulose
microfibrils (on a scale of 20 nm in diameter) up to sections of
cellulose cells typically 50 .mu.m in length and breadth and less
than 1 .mu.m in thickness depending on the precise processing
conditions.
[0109] 9) It is then required to reduce the water content within
the resultant pulp. This is achieved by wrapping the pulp in a fine
meshed bag and then pressing within a standard mechanical press.
The resulting pressed pulp provides the required cellulose
fragments 2 and in particular comprises 1-30% cellulose by weight,
and so behaves as a solid, feeling dry to the touch. It is
essential that there remains enough water present within the
cellulose fragments 2 so as to prevent the cellulose fragments 2
from interacting too strongly and therefore forming a rigid
solid.
[0110] Although the above stage employs carrot plant material, a
range of alternative plant materials may equally well be employed
in order to obtain cellulose fragments 2, comprising the network of
cellulose microfibrils 3. These include, but are not limited to
turnip, swede, apple, sugar beet, beetroot and onions.
[0111] As an alternative to hydrothermally treating the coarsely
chopped carrot, as outlined within step 2 above, the chopped carrot
may simply be heated in a microwave or infrared heater until the
required softening occurs.
[0112] As an alternative to the homogenisation process of step 8
above, the homogenised filtrate may be produced by subjecting the
filtrate to a single pass through a high pressure homogeniser (at
between 500-1000 bar).
[0113] In a further alternative to the above step 8 a sample of the
homogenised pulp is taken before the water content within the pulp
is reduced by pressing. This sample of pulp is then available for
employment within a later stage of the process, as described in
detail below.
[0114] The second stage of the process for producing the
biocomposite material 1 involves the incorporation of a hydrophilic
(or substantially hydrophilic) binder 4 within the cellulose
fragments 2. This can be achieved by the following process:
[0115] 1) The cellulose fragments 2, comprising a network of
cellulose microfibrils 3 are re-hydrated with an emulsion or a
particulate suspension of hydrophilic matrix material, namely PVA
which exhibits high strains to failure (greater then 6%) and a low
modulus of between 200-1000 MPa when formed into a solid. Depending
upon the particular requirements of the biocomposite material 1 the
emulsion produced at this stage can comprise between 5 and 60%
resins (and/or glues) by weight and between 40 and 95% water. For
the biocomposite material detailed within Table 1 the proportion of
total resin (and/or glues) by weight was within the range of
45-55%.
[0116] 2) The final step of this stage involves any excess water
and PVA material that has not penetrated into the cellulose matrix
being removed. This is achieved by pressing the material (under a
significant pressure) over a filter means. A soft smooth paste is
then produced.
[0117] Although the above stage employs PVA as the hydrophilic
binder any other hydrophilic binding material that can be
incorporated within the cellulose fragments 2 may equally well be
employed. Suitable alternative hydrophilic binding materials
include acrylic resins and biological hydrophilic polymers such as
gelatines and gaur gum.
[0118] The final stage of the process for producing the
biocomposite material 1 involves the encapsulation of the cellulose
fragments 2 and the PVA particles with a hydrophobic binder 5. This
can be achieved by the following process:
[0119] 1) An emulsion is formed by adding an epoxy resin to water
through the employment of a non-ionic surfactant (e.g.
Triton.RTM.-X octyl phenol ethoxylate). Typically the ratio of the
epoxy particles to water is between 10:1 and 1:5. For the
biocomposite material detailed in Table 1 the ratio of the epoxy
particles to water was 1:1.
[0120] 2) The emulsion is then added to the soft smooth paste
produced within the second stage of the process so as to produce a
thick smooth paste of uncured wet materials.
[0121] 3) Pressure is then applied to the thick smooth paste so as
to ensure that the cellulose fragments are forced together and that
there is some mixing of the materials at the nanoscopic level.
[0122] 4) Residual water is then removed from the thick smooth
paste by air drying at a temperature up to 110.degree. C.
[0123] 5) The dried material is then subjected to post drying
curing in an oven at between 80-160.degree. C.
[0124] A further improvement in the stiffness and strength of the
biocomposite material 1 can be achieved by employing a second post
drying curing cycle in an oven at between 120-180.degree. C.
[0125] Although the above stage employs an epoxy (e.g. bisphenol-A
or a modified bisphenol A epoxy) as the hydrophobic binding
material any other hydrophobic binding material that acts to
encapsulate the cellulose fragments 2 and the hydrophilic binders 4
may equally well be employed. Suitable alternative hydrophobic
binding materials include but are not limited to polyurethanes,
phenolic resins, acrylics and siloxanes.
[0126] The step of the removing the residual water from the thick
smooth paste may be achieved through the application of a vacuum,
in conjunction with, or as an alternative to the process of air
drying.
[0127] An alternative method for producing the cellulose fragments
2 from carrots shall now be described. The alternative method
comprises the steps of:
[0128] 1) Hydro thermally treating whole carrots at a temperature
between 85.degree. C. and 120.degree. C. at atmospheric pressure
until they soften. Optionally steam and pressures above atmospheric
pressure may be used to soften the carrots.
[0129] 2) The resultant cooking liquid is then drained off from the
carrots.
[0130] 3) Fresh water is then added to the residue material and
this material is then processed in a high shear mixer for a period
of between 5 minutes and 4 hours, although longer process times are
possible.
[0131] 4) The resultant residue produced by the shear mixing
process can be taken to the next stage immediately or alternatively
the material can be left to stand in a container, ideally for 12-14
days although shorter or longer times are possible. Optionally when
left to stand a micro-organism (e.g. bacteria or yeast) can be
added to the residue, as previously described.
[0132] 5) Optionally the resultant residue is then filtered and
washed with clean water.
[0133] 6) The residue produced within the previous stage is then
mixed with a bleaching solution ideally of the concentration 0.5%
and is allowed to stand for up to 15 hours. This ensures that an
effective quantity of pectins and hemicellulose present within the
original carrot material is dissolved within the resultant
solution.
[0134] 7) A number of options are available at this stage. The
first option is to remove the bleach by filtering and washing the
resultant solution. Optionally, if further reduction in the
particle size of the material is desired then further processing of
the material can take place either using a high shear mixer or
through a high-pressure homogeniser. A final alternative is to
initially homogenise the residue and to thereafter remove the
bleach by filtering and washing the resultant solution. In practice
the resultant biocomposite material appears to relatively
independent of the particular order of this step of the
process.
[0135] 8) The water content within the resultant pulp is then
reduced, as previously described, so as to provide the required
cellulose fragments, which preferably comprises 1%-30% cellulose by
weight.
[0136] An alternative for forming the hydrophobic polymer emulsion
comprises the employment the sample taken of pulp produced from the
high pressure homogeniser. This process involves the steps of:
[0137] 1) Passing the sample through the homogeniser a number of
times so as to reduce the cellulose fragments to individual
cellulose fibrils and microfibrils. This material is then retained
in liquid form.
[0138] 2) The epoxy particles are then mixed directly with this
liquid so as to produce an emulsion comprising the epoxy particles
and the cellulose fibrils and microfibrils. Similar ratios to those
previously described are again employed.
[0139] An alternative for forming the hydrophilic polymer solution
comprises the employment of the sample taken of the pulp from the
homogeniser. This process involves the step of:
[0140] 1. Passing the sample through the homogeniser a number of
times so as to reduce the cellulose fibrils and microfibrils. This
material is retained in the liquid form.
[0141] 2. The hydrophilic polymer (e.g. PVA) is then mixed directly
with this liquid to form a solution comprising PVA particles and
the cellulose fibrils and microfibrils. This is then used as
previously described.
[0142] A number of examples of uses of the described biocomposite
materials 1 shall now be described. In the first instance the
biocomposite material 1 can be used to produce a monolithic
structure 6 through which the mechanical properties are graded.
Essentially a multi layer structure can be formed within which
there exist no internal interfaces to compromise the overall
structure. This is achieved by laying down a layer of the uncured
material with the correct formulation for the mechanical properties
required (this layer can be several mm thick) before a second layer
of uncured material with a different mechanical property is laid
down on top of the first. Repeating this step a number of times
results in structure with different mechanical properties layers.
Once the required number of layers has been reached the composite
material is then pressed and cured to form the monolithic structure
6, as appropriate. It will be readily apparent that each of the
layers may in fact exhibit the same, or similar, mechanical
properties.
[0143] By way of example this method can be employed to produce a
ski in which an extremely tough layer 7 is initially prepared, upon
which a stiffer layer 8 is then laid, followed by a layer of
intermediate properties 9 at the core with a layer of stiff 8 and
then tough material 7 completing the structure. Such a structure is
presented schematically in FIG. 5.
[0144] Alternatively, the biocomposite material 1 can be used
within a more conventional lamination process so as to form a
laminate structure 10, see FIG. 6. The laminate structure 10 can be
employed to produce thick flat items such as skis, snow boards,
surf boards, skate boards etc or tubular items such as fishing
rods, bicycle frames, ski poles, sail spars, masts etc. This is
achieved by dipping pre-formed sheets of the biocomposite material
1 in a hydrophobic resin 11, stacking the sheets on top of one
another and thereafter pressing under high pressure. When the
hydrophobic resin 11 has cured the laminate structure 10 is removed
from the press and if necessary given an extra coating surface of a
finishing material.
[0145] It will be apparent to those skilled in the art that the
laminate structure 10 may comprise one or more layers of materials
already known in the art e.g. plastics and/or carbon fibre
reinforced plastic materials. A known problem of prior art laminate
structures that comprise carbon fibre reinforced plastic materials
is the large difference in stiffness between the fibres and
plastic. Carbon fibres have Young's modulus in the range 150-600
GPa where as plastic materials such as epoxy resin, typically have
moduli of between 2-8 GPa. This can cause problems of delamination
when different layers of carbon fibre composites are bonded
together with resins. Furthermore, it also means that
unidirectional carbon fibre materials have very low stiffness and
strength at right angles to the fibre direction.
[0146] Incorporation of one or more layers of the biocomposite
material 1 provides a means for alleviating this problem. The
advantage of using the biocomposite material to form the laminate
structure is that it can increase stiffness, strength and toughness
in certain directions, for certain orientations of the layers. For
example a laminate made from a layer of unidirectional carbon
fibres in epoxy resin and a layer of biocomposite material has
higher stiffness and strength, when tested in tension in the
direction of the carbon fibre axis, than a laminate made from two
layers of carbon-epoxy with fibre directions at right angles.
Although the stiffness is lower when the laminate is tested in
tension at right angles to the carbon fibre axis, the stiffness in
this direction is still more than adequate for certain applications
e.g. hollow tubular rods where the highest stiffness is required
along the axis of the rod, with just sufficient stiffness and
strength in the hoop direction to prevent crushing and ovalisation
during mechanical loading of the rod.
[0147] The above described laminate structure may be formed in a
number of ways. The first method comprises applying a layer of
biocomposite paste to a pre-cured layer of high stiffness fibre
reinforced composite. The biocomposite paste layer is then dried
and cured by heating. Pressure need not be applied to the laminate
during curing, but can be advantageous in reducing imperfections in
the cured biocomposite. Several layers can be built up by this
method (e.g. composite/paste/composite/paste) before drying and
curing, or each paste layer can be cured first before the addition
of further layers.
[0148] An alternative method involves applying an uncured high
stiffness fibre reinforced plastic to a layer of cured biocomposite
material 1. The high stiffness fibre reinforced plastic is then
cured. Pressure may need to be applied to the laminate during
curing. Several layers can be again be built up employing this
method (e.g. paste/composite/paste/composite) before drying and
curing, or each paste layer of paste and composite can be cured
first before the addition of further layers.
[0149] A further alternative method comprises the pressing of
layers of precured biocomposite material 1 and high stiffness fibre
reinforced plastic together with an adhesive. Pressure is sustained
until the adhesive has cured.
[0150] The biocomposite material 1 is also found to increase the
toughness of carbon fibre structures when applied as a surface
finish i.e. a lamination of carbon fibre-biocomposite. This is
because certain formulations of the biocomposite material 1 have
higher failure strains than the carbon fibre, while still retaining
good strength.
[0151] A further example application of the biocomposite material 1
is in the production of tubular sections which are suitable for use
within a fishing rod. The biocomposite material 1 is initially
prepared as described above. Before curing however the biocomposite
material 1 is placed into a porous mould or a mould which contains
a porous liner (e.g. ceramic, clay or open celled foam) and formed
round a waxed tapered mandrel of the required dimensions. The
biocomposite material 1 is then air dried to remove water. Next the
tapered tube of the biocomposite material 1 is removed from the
mandrel and preferably heated to a temperature of around
120.degree. C. Finally the tube is post cured at temperatures of up
to 180.degree. C.
[0152] The biocomposite material described above exhibits several
unique features over those materials described in the prior art. In
the first instance the biocomposite material exhibits stiffness and
tensile strength parameters that are favourably comparable with any
previously described material. In addition these parameters are
achieved without any compromise on the toughness of the material
and so the described composite material is not brittle like many of
the previously described biocomposite materials. Typically the
composite materials produced exhibit a bending strength in the
range of 60 MPa to 600 MPa.
[0153] Furthermore, the described material has the significant
advantage that it is also impermeable to water so allowing its
range of applications to be extensively increased. In particular,
the described material may be employed to produce skis, snow
boards, surf boards, skate boards etc or tubular items such as
fishing rods, bicycle frames, ski poles, sail spars, masts. However
it is envisaged that wherever there is a requirement for a strong
flat material, that is impermeable to water, then the described
biocomposite material would provide an ideal solution.
[0154] Since the described extraction process of cellulose
fragments from the plant material requires relatively little energy
the method of manufacture is more amenable to be employed on a
commercial scale. In addition, the manufacturing process is less
complex than those previously described in the art to produce
composites from wood fibres or bacterial cellulose. A particular
advantage to the described method is that it does not require the
employment of an organic solvent.
[0155] As a result a new composite material with a unique
combination of physical properties has been produced from a
sustainable resource and manufactured by a relatively low energy,
non polluting process. In fact the biocomposite material produced
appears to be many times tougher than any waterproof cellulose
based composite produced to date.
[0156] The foregoing description of the invention has been
presented for purposes of illustration and description and is not
intended to be exhaustive or to limit the invention to the precise
form disclosed. The described embodiments were chosen and described
in order to best explain the principles of the invention and its
practical application to thereby enable others skilled in the art
to best utilise the invention in various embodiments and with
various modifications as are suited to the particular use
contemplated. Therefore, further modifications or improvements may
be incorporated without departing from the scope of the invention
as defined by the appended claims.
TABLE-US-00001 TABLE 1 Stiffness Toughness (Young's Tensile (Energy
Modulus Strength Absorbed to Material GPa) (MPa) failure
MJm.sup.-3) Biocomposite 18 250 10 Material GFRP 12 160 4 e.g.
Chopped Strand Mat Waterproof Hemp 7 50 1 (30% Polypropylene fibre
content
* * * * *