Composite materials from a fiber and a

polymeric matrix

• Composite material (CM) the non-uniform, pseudo-

continuous material consisting of two or more components

with border of section between them. Mechanical properties

of the CM consisting of a fiber and a polymeric matrix

depend, basically, from properties of a fiber. The matrix

(polymer resin) provides teamwork of fillers. Delamination

of fibers in CM almost completely depends on properties of a

matrix. For additional hardening in a matrix short fibers,

various powders and nanoparticles can be added. The Overall

objective of any technology-provide necessary distribution of

a matrix between reinforcing elements.

Properties of resins of matrixes for

composite materials

Table1

Property Resin

Polyester Phenolic Epoxy Polyimide

Density,

kg/m31100-1460 1200-1760 1100-1400 1200-1450

Young's

modulus, GPa1.5-4,5 1,4-6,8 1,9-5,0 3,2-5,5

Tensile strength,

MPa23,5-28,5 22,5-78,3 27,4-140 90-95

Impact strength

kJ/m22-10,3 2-11,2 29-24,5 4,9-12,0

Marten’s heat

resistance °C60-80 140-180 140-190 250-370

Strength and the

elasticity module at a

tensile of various fibers

and a steel

Mechanical characteristics of a basalt fiber above, than at hight-modulus glass fiber S2 and ВМП (Russia),

which cost above 10 $/kg and slightly more low on the module to the

aramide fiber Kevlar, which cost above 20 $/kg.

Therefore, depending on success of realization of properties of a basalt

fiber in a composite material, it can be competitive at the price from 4 to 10

$/kg

Manufacturing of a composite material

by pultrusion, the most effective

process for products for building

Properties of some metals and the

composite materials (CM) produced

by pultrusion method Table 2

Property Fiber reinforcement epoxy resin CM Metal

E-Glass

fiber

Basalt

fiber

Aramid

fiber

Kevlar

Carbon

fiber

T300

Steel Aluminum

alloy**

(profil)

Density,

kg/m31900 2000 1400 1600 7800 2640

Young's

modulus,

GPa

40-50 60-85* 75 135 200 71

Tensile

strength,

MPa

1000 1000-

1800*

1300 1500 200-

400***

190***

* -depends on quality of basalt, ** -alloy aluminum 91,1-93,6% magnesium 5,8-6,8%*** -proportional limit σp

Typical Uniaxial Tensile of Prestressing

Tendons (CAN/CSA-S806-02)

from site www.isiscanada.com Table 3

Mechanical

Properties

Prestressing

Steel

AFRP CFRP GFRP

Tensile strength

(MPa)1379−1862 1200−2068 1650−2410 1379-1724

Elastic Modulus

(GPa)186−200 50−74 152−165 48-62

Rupture Strain

(%)>4 2−2.6 1−1.5 3-4.5

Density (kg/m3) 7900 1250−1400 1500−1600 1250-2400

A-aramid, C-carbon,-G-glass FRP (Fiber Reinforced Polymer)

Comparison steel and glass fiber reinforced

polymer deformation at a tensile

The steel should be maintained at

stress less than limit of

proportionality σp. Value of a

proportionality limit several times is

less ultimate stress σu. Typical value

σp for steels 200-400МПа

On the schedule results of measurements

are presented at a stretching of samples

of fiberglass cores with diameters from

4, 8, 12 and 20 mm. The proportionality

limit in all cases is more than 1000 Mpa

that is considerable above, than at a

steel.

Typical profiles from GFRR or

BFRR made by pultrusion for

constructions

For

The use of composite materials in

constructions

1. Bridges (ApATeCh, www.apatech.ru)

The use of composite materials in constructions

2. civil buildingShebanov S.M., Strebkov D.S., Goregliad V.V., Kogevnikov J.A. (Advances in

science and technology agricultural, 2011, in press )

The use of composite materials in

constructions3. Composite (GFRR or BFRR) rebar for concrete

• Composite rebar has advantages before metal

rebar in some important areas

• 1) Concrete with composite rebar is easier and

stronger, than with the metal. Perspective area -

building in seismodangerous zones.

• 2) The composite rebar isn't subject to

electrochemical corrosion. Concrete service life

can reach 100 and more years even near to the

sea.

• 3) Building of durable buildings and constructions

Samples Fiber Reinforced Polymer

(FRP) rebar

*- from site www.isiscanada.com

Advantages BFRP rebar as

compared with GFRP rebar

• 1) Basalt fiber for rebar is preferable to glass. Fiber E-glass

can lose strength in an alkaline environment, which is formed

during concrete hardening. Alkali-resistant glass fiber has a

high cost

• 2) Basalt widespread cheap raw materials (in 100 times is

cheaper than raw materials for glass fiber)

• 3) Mechanical properties of BFRP rebar is higher than the

properties GFRP rebar. Mechanical properties of BFRP rebar

can be equal to the properties of AFRP rebar, so the cost BFRP

may be higher than the GFRP.

Technical and economic the analysis

of use GFRP rebar for bridge deck.

• “The case study selected involves a deck

replacement for a specific bridge in Winnipeg,

Manitoba.

• The first design alternative was a standard steel-

reinforced concrete bridge deck. The second

alternative replaced steel in the deck with glass

FRP bar.”

• ISIS Canada Education. Module No7: An

introduction to Life cycle Costing

• From site www.isiscanada.com

The economic analysis of application

composite rebar at bridge building from site www.isiscanada.com Table 4

Parameter Metal rebar GFRP rebar

Deck area, sq m 6000 6000

Total Present WIC, $ 2275000 2669000

Annual WIC, $ 144336 162192

Total rebar cost, $ 150000 564000

Annual WMRC, $ 96602 12970

Total Annual WLCC, $ 251270 177468

Service life (years) 50 75

WIC -Worth of the Initial Cost,

WMRC -Worth of Maintenance and Repair Cost

WLCC-Worth of Life Cycle Cost

The relation of expenses for the bridge with

GFRP rebar to expenses for the bridge with

metal rebar (according to the table 4)

Comments

to the table 4 and the diagram A

• 1. The rebar from a carbonaceous steel is almost

always cheaper than rebar from composite materials.

• 2. The rebar from composite materials is favourable

for using from for big life service

• 3. In special conditions, for example, sea water or

salty water of mines, almost always rebar from

composite materials is more preferable metal.

Criteria for comparing the diameters

the FRP rebar and steel rebar in

concrete

The relation of diameters of rebars

from a steel and a composite material

Table 5

Material

E,

Gpa

σ,

MPa

ρ,

kg/c.m

d(CM)/d(Steel) Price

$ per kgCrit. 1 Crit. 2

Steel 200 400* 7900 0,6

GFRP 45 1000 1800 0,63 2,11 5

Nano** GFRP 60 1200 1900 0,57 1.83 7

BGRP 70 1500 1950 0,51 1,69 4,5

Nano**

BGRP90 1900 2100 0,48 1,49 7

d-diameter, * - proportionality limit, ** -added MWCNT 0,05-0,1 % ( S.

Shebanov Composite World n. 4, 2010). Nanocomposites and composites

were made at Stupino factory (Russia Moscow reg.)

Comments to table 5

• 1. By criterion 1 diameter rebar from a FRP compositematerial always is less, than at the metal. In this casealmost always composite rebar is more cheaply

than metal.

• 2. By criterion 2 diameter rebar FRP composite materialalways is more than at the metal. In this case almostalways metal rebar is more cheaply than composite.

• 3. The criterion choice depends on conditions in whichthe construction is maintained

Increase Total Present Worth of the Initial Cost

at use of composite rebar (according to the table 5).

Reduction the total Annual Worth of Life Cycle Cost the

bridge at use of rebar of concrete from composite

materials

(according to the table 4 and table 5)

Comments to the Diagram C

• 1. We have no experimental data about time of life of concrete and the

periods of repair with rebars from nanoGFRP, BFRP and nanoBFRP.

These are new materials. Therefore for an estimation given tables 4 for

GFRP have been accepted. Time of life of concrete with BFRP above,

than with GFRP.

• 2. FRP composite materials with MWCNT have very big life cycle at

cyclic loadings (to 100 times above, than FRP without MWCNT).

• Therefore we hope that terms between repairs at concrete with nanoGFRP,

BFRP and nanoBFRP rebars can be more, and the volume of repairs can

be less, than for concrete with GFRP rebars

• For the successful decision of all problems should unite efforts designers,

concretes technologists , composite and nanocomposite materials

technologists, economists and builders.

Intermediate conclusions

• Now there are no reliable experimental results for modeling of mechanical

properties of concrete with basalt armature. Therefore for the analysis

simple evident model (3) has been chosen. The parameter “X” equal 0,62

has been defined from the qualitative information from site

www.isiscanada.com only for GFRP. For other rebars value can be

another. It reduces reliability of conclusions. However economic

estimations at cost BFRP are made on the basis of a wide experience of

the organization of manufacture of a basalt fiber in Russia and release of

several experimental batches of composites and nanocomposites at

factory. The received information allows to draw a basic conclusion on

perspectivity and economic feasibility of use rebar from a basalt fiber

(with additives MWCNT and without) in concrete.

Perspective and expediency of use MWCNT

for increase in durability GFRR and BFRR

composite materials

• In the composite materials made pultrusion it is not possible to

realize completely mechanical properties of a fiber. Even along a

direction of fiber the module of the composite material made

pultrusion , usually doesn't exceed 60-70 %, and ultimate tensile

strength 50 % from values of a used fiber. It is shown (S. Shebanov

Composite World n. 4, 2010) that addition of 0,1 % and less

multilayered carbon nanotube (MWCNT) in GFRP can increase the

Young's module of a composite material to 90 % from value for a

fiber. In this case nanoBFRR will have the Young's module above,

than at an aluminum profile. As the constructional material

nanoBFRP will surpass aluminum in the mechanical characteristics

and on corrosion firmness.

MultiWalled Carbon NanoTubes (MWCNT)

Tensile individual MWCNT SEM MWCNT

Our technology for manufacturing

nanocomposites, nanoGFRP or nanoBFRP

• 1. Manufacturing MWCNT by method CVD

• 2. Oxidation of surface MWCNT by acids

• 3. Dispersion of MWCNT in the resin using ultrasonic

cavitation

• 4. Use of resin with MWCNT in technology pultrusion.

Manufacturing rebar or a profile from nanocomposite

material, nanoGFRP or nanoBRFP.

Ultrasonic dispersion MWCNT in epoxy

resinCavitation in resin MWCNT in resin after dispersion

Result of addition MWCNT: increase in mechanical

characteristics and change of character of deformation

of resin and FRP a composite material

Compression epoxy resin Bending of rebars

Intermediate summary

• Composition reinforcement has advantage over the metal one being used

in concrete where metal is prone to corrosion. Concrete with the

composite reinforcement is more durable. It is known that corrosion

becomes more aggressive under the influence of humidity and ground

electrical currents. Correspondingly the most promising areas of use are

sea shore constructions, mines, foundation of overhead transmission line

structures and constructions in the damp climate.

• The basalt fibers composition reinforcement is more promising than glass

fiber compositions. The basalt fibers have more advanced mechanical

properties and are more stable to alkaline solution which results by

concrete maturing. The basalt and glass fiber technologies are close

but basalt itself is much cheaper than the input materials for the glass

fiber. As a result, the commercial production of basalt fibers (which does

not exist at present) will be considerable cheaper than production of the

glass fiber.

The average time between repairs

(TBR) oil pumps in the U.S. increased

from 472 to 675 days for 5 years(Poddubnij J. from site www.eng.rpi-inc.ru)

1. Optimization of work of

the pump

Decrease in power inputs on 15-

40 %

Increase in efficiency on 20 – 40

%

2. Equipment upgrade

Increased TBR in 1,5 –

2 timescontinuous sucker rods

GFRP sucker rods

Application of electric motors

with 500 rpm Power consumption decrease on

30-45 %Increase in length of stroke

At oil recovery FRP composite

materials can be used in the most

various places. These are various

pipes, capacities, lungs and

buildings. In our opinion use

nanoGFRP and nanoBFRP for sucker

rods of oil pumps can be very

favourable. In this case, the unique

properties of nanocomposite materials

can be most fully realized. According

to a table 6, increase of TBR in 2

times on condition of the use of

continuous rods and/or GFRP rods

and also by measures related to them.

GFRP sucker rods are produced in the

USA, Canada, Japan, China and

Russia.

Perspective of use nanoFRP of

composite materials at oil recovery

Table 6

GFRP it was offered to use in pumps for oil

recovery for a long time. One of early variant of use GFRP sucker rod is resulted, for example,

in the US patent 3889579, 17 June, 1975

For

A serious problem is connection of GFRP rod with

a metallic tip.The fittings illustrated in FIGS. 7 and 8 are intended as merely illustrative of the types

which may be used and selection of a particular design depends on the environment

and circumstances of use. (from US patent 3889579)

“ In FIG. 7, the rod 80 extends into a cylindrical

connector 82 which is threaded at one end and

tapered at the other. The rod is held in the connector

by a plurality of wedges illustrated at 84 and 86

which are pressed against the rod by the conical

configuration of the cylinder 82. A potting compound,

such as an epoxy thermosetting resin, indicated at 88

bonds the end of the rod in the cylinder and bonds the

wedges in the cylinder to the cylinder and to the rod.”

“In FIG. 8, the rod 90 is held in the cylinder 92

simply by a potting compound 94. The potting

compound would typically be an epoxy or other

thermosetting adhesive resin. The thickness of the

potting compound in 94 is exaggerated in FIG. 8 for

illustrative purposes”

Comment • 1. Advantages GFRP in comparison with metal:

• -smaller weight (the GFRP density is four times less than steel density)

• -higher durability

• -flexibility of GFRP. Rod, as well as rebar can be transported on reels

• 2. Disadvantages GFRP in comparison with metal :

• -low value of the Young's module (45 GPa for GFRP and 200 GPa for a

steel)

• - the probability of delamination of fibers

• Maximize the advantages and minimize the disadvantages will allow the

use of nanotechnology:

• -earlier been shown that the use of CNT increases all the mechanical

properties of GFRP and BFRP

• - further we will show influence CNT on the fatigue characteristic and

delamination of FRP composite materials

Increase in delamination resistance of a FRP

composite material as a result of MWCNT additionRate of growth of a crack in resin with

MWCNT (a matrix of a composite material)

can be to 100 more low, than in pure resin.

( W. Zhang , etc. Small, 2009)

Interlaminar shear of FRP composites with

CNT increased by 20-40%

(S.Shebanov, etc., 2005) Table 7

FiberInterlaminarshear, MPa

Increase in %Without

MWCNT

With 0.001-

0,1%

MWCNT

Aramid 30,4 35,4 16

E-glass 41 54 24

Carbon 63 87 38

Comments

to the diagram D and the table 7

• According to diagram D and table 7 we expect

increase of resistance to delamination at nanoFRP

composite materials in comparison with FRP in real

designs.

• According to it life cycle time of designs with

nanoFRP composite materials can be considerable

above.

Summary

• We expect improvement in characteristics of nanoGFRP and nanoBGFRP compared

with GFRP and BFRP materials under the simultaneous action of cyclic loading in

axial and longitudinal direction. This effect is very important for any FRP composite

materials. It isn’t important when you will use FRP composite materials.

• The increase of price of nanoGFRP and nanoBGFRP compared with GFRP and BFRP

materials depend on the price of MWCNT. The most of the commercial activity

involves the use of hollow multi-wall carbon nanotubes MWCNTs. Increased demand

for MWCNT stimulates the creation of new industries. For example, Bayer plans to

bring the total production of CNT to 3000 tons per year, company CNano (U.S.) by

mid-2009 completed the construction of a large factory in China, with capacity of 500

tons per year and it plans to build another plant. The company Arkema (France) plans

to increase the production of CNT to 550 tons per year. Showa Denko (Japan) plans to

increase the production of CNT to 650 tons per year, Nanocyl (Belgium) - up to 150

tons per year. Due to the expansion of applications for 2014, the market for CNT can

make more than $ 1 billion. We can expect significant price reductions on CNT with

such volume of production.

• Falling prices of MWCNT makes nanoGFRP and nanoBGFRP very promising

materials for the construction and engineering industries.

• Presented results reduced the risk for the promotion of these materials

in the industry. Also results prepared a basis for tests of materials in real

structures.

Acknowledgements

• The author expresses deep gratitude to all thanks to

which it was possible to finish the presented work.

They are employees of the D. Mendeleev University

of Chemical Technology of Russia, Moscow State

University, Semenov Institute of Chemical Physics

RAS, polytechnical college № 8, all Moscow.

Personally to Streltsova Ye., Streltsov A., Serbin V.,

Kogevnikov J., Goregliad V., Tarakanov P.