U.S. patent number 3,603,221 [Application Number 04/771,993] was granted by the patent office on 1971-09-07 for multilayered structure.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Robert Hall Barton, Martin Luther Brown, Andrew Mitchell.
United States Patent |
3,603,221 |
Barton , et al. |
September 7, 1971 |
MULTILAYERED STRUCTURE
Abstract
A multilayered structure comprising a base support, an
unvulcanized elastomeric membrane at least 0.05 inch thick
overcoated with an exposed cover layer. This structure is useful in
roadway construction with particular application to bridge decks
where vibration tends to accelerate crack formation allowing water
to penetrate the roadbed where it freezes and thaws resulting in
structural damage to conventional roadways. The membrane prevents
water from penetrating the roadbed. As a bridge deck the base
support is normally Portland cement concrete, the intermediate
layer is the elastomeric membrane and the exposed cover layer is
asphaltic concrete.
Inventors: |
Barton; Robert Hall (Ridgewood,
NJ), Brown; Martin Luther (Elkton, MD), Mitchell;
Andrew (Newark, DE) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
25093564 |
Appl.
No.: |
04/771,993 |
Filed: |
October 30, 1968 |
Current U.S.
Class: |
404/31 |
Current CPC
Class: |
C08K
3/04 (20130101); C08K 5/09 (20130101); C08L
23/16 (20130101); C08L 91/00 (20130101); C08K
3/013 (20180101); E01C 7/325 (20130101); C08K
3/22 (20130101); E01C 7/32 (20130101); C08K
3/013 (20180101); E01D 19/083 (20130101); C08K
3/04 (20130101); C08L 23/16 (20130101); C08L
91/00 (20130101); C08L 2666/02 (20130101); C08L
23/16 (20130101); C08K 3/22 (20130101); C08K
5/09 (20130101); C08L 2666/02 (20130101) |
Current International
Class: |
E01C
7/32 (20060101); E01D 19/00 (20060101); E01C
7/00 (20060101); E01D 19/08 (20060101); C08L
23/00 (20060101); C08K 3/00 (20060101); C08L
23/16 (20060101); E01c 007/18 () |
Field of
Search: |
;94/7,9,10,22,24,4,3
;14/73 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Nackenoff; Jacob L.
Claims
We claim:
1. A multilayered structure consisting essentially of
a. a base layer,
b. an intermediate unvulcanized elastomeric membrane at least
0.05-inch thick, resistant to oxygen degradation and having a
brittle point of less than 0.degree. C., said elastomer being a
polymer from the group of ethylene/propylene copolymers and
ethylene/propylene/diene terpolymers,
c. an exposure layer.
2. A multilayered structure according to claim 1 wherein the base
layer is Portland cement concrete.
3. A multilayered structure according to claim 1 wherein the
exposure layer is asphalt.
4. A multilayered structure according to claim 1 wherein a plastic
film is interposed between the unvulcanized membrane and the
exposure layer.
5. A multilayered structure according to claim 1 wherein the
elastomeric membrane has at least 100 to 500 parts of filler per
100 parts of elastomer and at least 100 to 300 parts of
plasticizing oil per 100 parts of elastomer.
6. A multilayered structure according to claim 1 wherein the
elastomeric membrane is made from a copolymer of ethylene,
propylene and at least one nonconjugated diene having only one
polymerizable double bond.
7. A multilayered structure according to claim 1 wherein the
copolymer is ethylene/propylene.
8. A multilayered structure according to claim 6 wherein the
copolymer is ethylene/propylene/1,4-hexadiene.
9. A multilayered roadway comprising essentially
a. a base layer of Portland cement concrete;
b. an intermediate unvulcanized elastomeric membrane at least
0.05-inch thick, resistant to oxygen degradation and having a
brittle point of less then 0.degree. C. wherein the elastomeric
membrane is 100 parts ethylene/propylene copolymer, 100-500 parts
filler, and 100- 300 parts plasticizing oil; and
e. an exposure layer of asphalt.
10. A multilayered roadway according to claim 9 wherein a plastic
film is interposed between the unvulcanized membrane and the
exposure layer of asphalt.
Description
FIELD OF THE INVENTION
This invention relates to the use of elastomers in a multilayered
structure particularly useful in highway and bridge
construction.
BACKGROUND OF THE INVENTION
In the construction and maintenance of bridge decks and roadways,
one problem that exists is cracking and spalling of the structure
due to water penetration into the roadbed. The water freezes,
expands and causes cracking then thaws leaving a damaged
roadbed.
Another situation that is damaging to a roadbed is heaving of the
soil below the roadbed caused by water penetrating the roadbed into
the soil below the roadbed followed by freezing of the water. The
resultant expansion often breaks the roadbed.
Some methods of alleviating these problems are disclosed in the
art. U.S. Pat. No. 1,512,125 discloses a process of making a
monolithic roadbed by cleaning, drying and heating the substratum,
covering the substratum with a film of soft pitch and laying down a
wearing surface over the soft pitch thereby effecting a knitting
together of three layers into one monolithic mass.
U.S. Pat. No. 2,183,253 discloses a method of road construction
wherein the grade line is established, a water soluble electrolyte
is mixed into the soil below the grade line to constitute a subbase
with waterproof material to prevent escape of the electrolyte and
thereafter overcoating with a wearing surface.
In "Restoring Salt-Damaged Highway Bridges," by R. J. Walsh, Civil
Engineering, May 1967, the following process of bridge restoration
is disclosed: The damaged wearing surface of the bridge is removed
exposing the subsurface. The subsurface is then primed and coated
with a layer of coal tar pitch emulsion. Into the emulsion is
placed a layer of a glass-fibered cloth called Fiberglas, a
trademark of Owens-Corning Fiberglas Corp. This forms a
waterproofed membrane which is then overcoated with a wearing
surface.
The prior art does not provide a method of protecting roadways and
bridges that is economical, easy to construct, and durable over a
long period of time while subjected to varied weather conditions
and constant use.
SuMMARY OF THE INVENTION
This invention provides a multilayered roadway comprising
essentially;
A. a base support,
B. an intermediate unvulcanized elastomeric membrane at least 0.05
-inch thick, resistant to oxygen degradation and having a brittle
point temperature of about 0.degree. C. or less, and
BRIEF DESCRIPTION OF THE DRAWING
The drawing shows a typical embodiment of this invention in which
an uncured elastomeric membrane is sandwiched between a base layer
and a traffic-bearing layer of concrete.
DETAILS OF THE INVENTION
The multistructure element of this invention comprises a base
support, an elastomeric membrane, and a traffic-bearing layer.
The attached drawing shows a typical embodiment of this invention
in which the base support 1 is Portland cement concrete and
intermediate layer 2 is an uncured elastomeric membrane and the
traffic-bearing layer 3 is asphalt cement concrete.
The base support can be any flat surface such as a concrete bridge
deck or roadbed that has been leveled by a roller. In the case of a
roadway the base support can be asphalt, gravel, broken stone where
the voids are filled with sand, a bituminous concrete base course,
or an already existing road. In the case of a bridge, the base
support is generally Portland cement concrete either precast or
poured in place.
The elastomeric membranes of this invention should exhibit the
following characteristics. The membrane must not become so brittle
that in cold weather it will crack and fail. The term "cold
weather" is meant to include the winter conditions found in the
North and South Temperate Zones. Accordingly, the desired brittle
point of the membrane should be 0.degree. C. or less as measured by
the solenoid brittle point test described in ASTM D-746.
The thickness of the membrane should be at least 0.05 inch to
provide the necessary structural integrity for installation. The
maximum thickness is a matter of economics and it has been found to
be uneconomical and unnecessary to use a membrane more than 0.5
-inch thick. Membranes 0.10 to 0.25 inch are preferred since they
provide the best balance between economics and structural
integrity.
The membrane should be self-healing. This is accomplished by
preparing and using the membrane is an unvulcanized state.
Therefore, no sulfur or other vulcanizing agents are used in the
mix, nor any agent that might cross-link the polymers. The membrane
should desirably be very resistant to oxidative degradation. This
is accomplished by using an elastomeric material that in itself is
practically immune to oxidative degradation or an elastomeric
material subject to oxidative degradation compounded with an
antioxidant.
Elastomers which best meet the above requirements are the saturated
and low unsaturated elastomers such as ethylene/propylene (EP)
copolymers, ethylene/propylene/diene (EPDM) terpolymers, butyl
rubber, chlorinated polyethylenes, and the like. Natural rubber,
styrene/butadiene rubber and the neoprenes can be employed when
compounded with antioxidants. For economy and maximum resistance to
degradation, the EP or EPDM elastomers are preferred.
EP elastomeric copolymers useable in this invention are those
having at least one .alpha.-monoolefin with the structure R--CH
Ch.sub.2 where R is H or C.sub. 1 -C.sub.16 alkyl. Representative
copolymers include: ethylene/propylene, which is preferred;
ethylene/1-butene; propylene/1-butene;
ethylene/5,5-dimethyl-1-octene; 1-hexene/1-decene,
ethylene/propylene/1-octadene; propylene/5-methyl-1-heptene; and
1-hexene/1-dodecene. The ethylene copolymers should contain about
25 to 75 weight percent ethylene monomer units.
Representative procedures for making such copolymers are given in
U.S. Pat. Nos. 3,000,867 and 2,975,159.
EPDM terpolymers that are useful are made from at least one .alpha.
-monoolefin and at least one nonconjugated diene having only one
polymerizable double bond. The .alpha.-monoolefins have the
structure R--CH CH.sub.2 where R is H or C.sub.1 -C.sub.16 alkyl
and are preferably straight-chained. Representative nonconjugated
hydrocarbon dienes include: open-chain C.sub.6 -C.sub.22 dienes
having the structure ##SPC1##
wherein R.sub.1 is an alkylene radical; R.sub.4 is H; R.sub.2,
R.sub.3 independently selected from the group consisting of
hydrogen and alkyl radicals; dicyclopentadiene; 5 -methylene-
2-norbornene; 5-ethylidene 2-norbornene; 5-alkenyl- 2-norbornene;
2-alkyl- 2,5-norbornadiene; cyclopentadiene; and
1,5-cyclooctadiene. EPDM terpolymers and procedures for making them
are given in U.S. Pat. Nos. 2,933,480; 3,000,866; 3,063,973;
3,093,620; 3,093,621; 3,260,708 and French Pat. No. 1521,726. When
cyclic nonconjugated dienes are employed, it is preferred that the
resultant copolymer contain ethylene and at least one other .alpha.
-monoolefin, e.g., propylene. The ethylene copolymers should
contain about 20 to 70 weight percent ethylene monomer units.
Representative EPDM copolymers include: ethylene/1,4 -hexadiene;
ethylene/propylene/1,4-hexadiene;
ethylene/propylene/dicyclopentadiene;
ethylene/propylene/5-methylene- 2-norbornene;
ethylene/propylene/2-ethyl- 2,5-norbornadiene;
ethylene/propylene/5ethylidine- 2-norbornene; and
ethylene/propylene/1,5-cyclooctadiene.
Elastomers that are useful, provided they are compounded with an
antioxidant, are neoprenes and SBR (styrene(butodiene) rubber.
Neoprenes are polymers and copolymers of chloroprene. These are
well known and fully described in many U.S. Patents and various
texts such as Introduction to Rubber Technology, edited by M.
Morton, Reinhold Publishing Corp. New York, 1959, and The
Neoprenes, R. M. Murray and D. C. Thompson, published by E. I. du
Pont de Nemours and Co., Wilmington, Delaware, 1963.
Chlorosulfonated saturated aliphatic hydrocarbon polymers are best
exemplified by chlorosulfonated polyethylenes. These elastomeric
materials are well known and can be prepared in a number of ways as
shown in U.S. Pat. Nos. 2,212,786; 2,586,363; 2,879,251 and
2,982,759. These chlorosulfonated polymers contain at least 20
percent chlorine and at least 0.5 percent sulfur by weight.
Representative preferred polymers contain about 20 to 40 percent
chlorine and about 1 to 1.5 percent sulfur by weight. The
polyethylene before chlorosulfonation is frequently a linear type
having a density greater than 0.94 and a melt index of about 0.2 to
200.
Neoprenes can be made by polymerizing chloroprene or copolymerizing
chloroprene with up to about 50 percent of another ethylenically
unsaturated copolymerizable monomer, e.g., acrylonitrile, styrene,
acrylic and methacrylic acids and esters, 1,3-butadiene isoprene
and 2,3-dichlorobutadiene- 1,3. These are also useable.
SBR rubbers which can be used are characterized in the publication
entitled Rubber: Natural and Synthetic by H. J. Stern, second
edition, 1967.
Antioxidants, to be compounded with SBR rubber, neoprenes and
natural rubber fall into three (1) secondary amines, (2) phenols,
and (3) phosphites. Useable amines are phenyl-alpha- and
phenyl-beta-naphthylamines; useable phenols are those alkylated
with isobutylene; and useable phosphites are those of the alkylated
phenol phosphite class. These antioxidants are well known to the
art.
The elastomeric composition can contain relatively large
proportions of filler which should be of the type that has a
limited tendency to absorb water. Carbon black, whiting (calcium
carbonate) and baryta (barium sulfate) are suitable fillers. At
least 100 parts of filler per 100 parts of elastomeric is suggested
for use. However, as much as 500 parts can be used. Preferably 200
to 400 parts are used to give the best workable consistency to the
membrane.
Although not necessary for obtaining the benefits provided by the
present invention, a petroleum oil is usually included in the
present elastomeric membrane composition in order to lower the
materials cost and to improve the ease of processing. Plasticizing
oils can be used at concentrations of 100 to 300 phr (parts per
hundred parts of elastomer by weight). These oils should be a
permanent nonvolatile type compatible with the particular elastomer
used. Aromatic and naphthenic petroleum oils have been found
useful.
Stabilizing agents such as metal oxides, or extrusion aids such as
waxes and stearic acid can be employed if desired.
In the manufacture of the elastomers of this invention, industrial
processing internal mixers such as Banbury mixers are frequently
used to compound the elastomer and a membrane is formed by
conventional calendering or extrusion techniques. When it has an
inherently sticky nature, the membrane must be protected by a
release paper or plastic film if it is to be stored or transported.
The plastic film may be polyethylene terephthalate, polypropylene
or the like. It is sometimes desirable to leave the plastic film in
place as part of the finished structure. During construction it can
be used as a walking surface for workmen and it protects the
membrane until the cover layer is applied. For large scale
installations it is practical to extrude the membrane directly into
the base layer of the roadway or bridge during construction.
The traffic-bearing layer can be any of the conventional types
known to the art of highway and bridge construction. Some examples
are sheet asphalt, a dense mix of bituminous concrete or Portland
cement concrete pavement The traffic-bearing layer is applied over
the membrane by conventional methods known in the art of highway
and bridge construction.
It is sometimes necessary to roll or compress the traffic-bearing
layer particularly when it is asphalt. During the compression
operation aggregate may be forced into the membrane and perhaps
rupture it. Due to the self-Healing qualities of the membrane it
seals around the aggregate maintaining its protective shield.
The multilayered structure of this invention has been particularly
defined in terms of its use as a roadway or bridgedeck.
Nevertheless, with a few simple modifications it can be adapted to
other uses. It can be used as a roof wherein the base layer is
wood, plastic, paper, cloth, metal plating, etc.; the intermediate
layer is the unvulcanized elastomeric membrane described above; and
the exposure layer is conventional roofing such as pebbles, tile,
etc. This membrane would keep water from penetrating the roof and
should a crack develop, e.g., from settling of the structure or
someone walking on the roof, the self-healing healing properties of
the membrane would operate to seal itself and prevent leakage or
damage from the weather.
Another use may be weather guarding for basement walls where the
base layer is cinder block, concrete, or brick; the intermediate
layer is the membrane described above and the outer layer can be
wood, sheet metal, gravel drain or the earth. Still other uses may
be in sidewalls, racetracks or athletic fields.
This invention is illustrated by the following examples.
EXAMPLE I
The following ingredients are compounded in a Banbury mixer:
---------------------------------------------------------------------------
Ingredients Parts by Weight
__________________________________________________________________________
EPDM Copolymer 100 Zinc oxide 5 Stearic acid 3 FEF carbon black 150
Austin Black 100 Sundex 790 175
__________________________________________________________________________
The EPDM copolymer is made by copolymerizing ethylene with
propylene and 1,4-hexadiene in solution in tetrachloroethylene in
the presence of a coordination catalyst in accordance with the
general procedures of U.S. Pat. No. 2,933,480. Hydrogen
modification is employed during the preparation in accordance with
U.S. Pat. No. 3,051,690. This copolymer has a Mooney viscosity of
about 45 (ML- 4/250.degree. F.) and contains about 0.33 g.-mol of
ethylenic unsaturation per kilogram. The following monomer unit
composition is present by weight: 63 percent ethylene, 33 percent
propylene, 4 percent 1,4 -hexadiene. The inherent viscosity is
about 2.2.
FEF Carbon Black is characterized in the ASTM manual under Standard
Specifications for Carbon Blacks Used in Rubber Products. This
material is identified as ASTM: D-1765-.GAMMA., Type FEF 30.
Austin Carbon Black is a finely pulverized bituminous coal of
specific gravity 1.25, containing 77 percent carbon and 17 percent
volatile components. It is commercially available from the Chemical
Products Division of Slab Fork Coal Company, Slab Fork, West
Virginia.
Sundex 790 is a process oil sold commercially by the Sun Oil
Company. Its standard designation is ASTM D-2226, Type 102. This
oil is characterized as follows: specific gravity at 60.degree. F.
of 0.9806; density 0.9769; molecular weight 37.5 and a
viscosity-gravity constant of 0.932.
After mixing, the composition is calendered into a sheet 50 inches
wide and 0.100-inch thick. It is installed as the sealing membrane
on a heavily traveled bridge deck, over an 8-inch thick Portland
cement concrete base, and under a 11/2-inch thick asphaltic
concrete traffic bearing layer. After 6 months of service the
membrane is intact and is giving full protection to the Portland
cement concrete base layer. Core borings are taken and analyzed.
The structural integrity of the roadway is as good as it was in the
beginning.
EXAMPLE II
A multilayered structure comprising a base layer of Portland cement
concrete, and intermediate layer of elastomeric membrane prepared
as described in Example I and a top layer of amesite is constructed
in the following manner. A concrete slab having a surface area of 8
.times.16 inches is poured and curved according to conventional
methods. An elastomeric membrane is placed on top of the concrete
slab with the ends turned up to form a pan. Hot amesite, 2 inches
thick, is placed in the pan and compressed under a 200 p.s.i.
hydraulic press to complete the structure.
The structure is cracked in half, the pan formed by the elastomeric
membrane is filled with salt solution and multilayered structure is
placed on a vibrator to flex the joint. Electrodes are placed
between the concrete slab and the elastomeric membrane. The sample
is vibrated and if the crack causes rupture of the membrane to
allow salt solution to reach the concrete the electrical resistance
of the electrodes will drop. After one week of flexing the crack by
continuous vibration, the electrical resistance of the electrodes
remains the same indicating the self-healing elastomeric membrane
is still containing the salt solution.
* * * * *