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RUREDIL

Via B. Buozzi 1 -20097 San Donato Milanese

Fiber Reinforced Cementitious Matrix (FRCM) New Developments -

Ruredil X Mesh Gold

Ultra high mechanical performance Polyparaphenylene benzobisoxazole (PBO) fibre mesh, with a stabilised inorganic matrix, for structural reinforcement of concrete.

Technical Management October 2006

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Introduction

Ruredil was the first company in the world to develop, patent, produce and market a fibrereinforced composite material in which epoxy resin is replaced by stabilised inorganic material (cement mortar) binding carbon fibres with the concrete or masonry substrate.

In this innovative line of research aimed at coming up with new FRCM (Fiber Reinforced Cementitiuos Matrix) methods, Ruredil has developed a structural compound with a stabilised inorganic matrix known as RUREDIL X MESH GOLD, consisting of a Polyparaphenylene benzobisoxazole (PBO) fibre mesh offering exceptional mechanical performance, equivalent to the performance of conventional carbon fibre FRP with an epoxy binder.

This document looks at the chemical/physical properties and mechanical performance of the new FRCM, comparing it with a conventional CFRP (carbon fibre-reinforced polymer) .

The report also describes the results of qualification tests conducted on the new compound at IUAV in Venice.

An international patent is pending for the material.

-31Physical and mechanical properties of PBO fibre

PBO fibres represent the new generation of superfibres with ultra high resistance and a modulus of elasticity double that of aramidic fibres. PBOs decomposition temperature is 100C higher than that of aramidic fibres. The table below shows the principal properties of PBO fibre - Table 1 Density (g/cm3) Tensile strength (GPa) Modulus of elasticity (GPa) Ultimate elongation (%) Decomposition temperature (C) Thermal dilation coefficient (10-6 C-1) 1.56 5.8 270 2.1 650 -6

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Mechanical properties: comparison with other structural fibres

The mechanical properties of PBO fibre were compared with the fibres most commonly used in FRPs (see Tab-2). The comparison reveals that PBO normally has a modulus of elasticity of 270 Gpa, comparable to that of carbon fibre (240-270 GPa), but a much higher tensile strength: 5.8 GPa as compared to 4.1 GPa for carbon.( fig.1) These mechanical properties and the particular mechanism of adhesion between the fibre and the inorganic binder explain the excellent performance of FRCM composite used as reinforcement for reinforced concrete structures. Comparison of mechanical properties with other types of fibre - Table 2
Type of fibre Tensile strength (MPa) Modulus of elasticity (GPa) 270 240 109 17 206 80 Ultimate deformation (%) 2.5 1.6 2.4 2.2 20-30 4.5 Density 3 (g/cm ) Resistance to heat (C) 650 1400 550 400 -1200 Coef. of thermal dilation 6 1 ( 10 C ) -6 -1.45 -2 -2 +10.4 +5.4

PBO Carbon (high strength) Aramidic (high modulus) Aramidic Construction steel Glass

5800 4100 2800 650 250-400 (yield) 350-600(breakage) 3500

1.56 1.75 1.45 1.38 7.8 2.5

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Com parison of stru ctu ral fibres: respon se to m on oaxial ten sile stress
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FORCE (GPa)

PBO
Carbonio
Aram idica
Vetro

0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Deform ation(% )

Comparison of structural fibres: response to monoaxial tensile stress Figure 1

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The new PBO fibre: interaction with the inorganic matrix

The new RUREDIL X MESH GOLD mesh is made by weaving a Polyparaphenylene benzobisoxazole (PBO) mesh. This synthetic polymer has the molecular structure shown in fig.2.

Figure 2

There are numerous active sites in this structure (atoms of nitrogen, carbon, oxygen) capable of establishing chemical bonds with hydrated compounds in a special inorganic binder by means of a hydraulic reaction (Ruredil X Mesh M750) The formation of these chemical (interphase) bonds between fibre (dispersed phase) and matrix (continuous phase) helps determine the mechanical properties of the new FRCM (fig.3)

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Contttiinuous phase Con in uous phase Con nuous phase Ruredil X Mesh M750 IIIntterrphase n te rp hase n e phase Chemical bonds Dispersed phase Ruredil X Mesh Gold

Figure 3 In a conventional FRP, the matrix and the fibre adhere by means of a third component which is normally applied to the surface of the fibre in a very thin layer (interphase), where it acts as a bridge to which the epoxy resin is attached. In the new PBO fibre, the interphase is an integral part of the polymer, because it consists of atoms of carbon, nitrogen and oxygen in the polymers own molecular structure. Adhesion between fibre and matrix is therefore not indirect through a third component (interphase) which in turn adheres to the carbon fibre as a result of a process of dressjng the fibre. The new mechanism for adhesion of the inorganic matrix with the fibre and the high mechanical performance of PBO fibre are the two factors explaining the excellent mechanical performance of the new FRCM-RX MESH GOLD compound, which, as we will see later, rivals the performance of a conventional Carbon Fibre Reinforced Polymer (CFRP)

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Comparison with other FRCMs

FRCMs are compounds made with high performance structural fibres immersed in an inorganic cement matrix. On the basis of our current knowledge, it is possible to reinforce the bending strength of specimens of concrete with FRCM, varying the type of fibre and the inorganic matrix. We have created FRCMs using the following fibres: Ruredil X MeshC10(C-FRCM) Glass (G-FRCM) Aramidic fibres (A-FRCM) Polypropylene(PP-FRCM) Carbon/aramidic fibres (CA-FRCM) Carbon/polyester (CP-FRCM) Ruredil XMESH GOLD (PBO-FRCM) This study aims to identify the structural behaviour of concrete specimens reinforced with each of these different FRCMs.

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Description of the test 5 concrete specimens were made for each type of FRCM, measuring 600x150x75 (l x d x h), which were cut along their midline to a depth of 5 mm before being flex reinforced. The experimental campaign was conducted by performing flex tests on four points (with a blade centre-to-centre space of 450 mm and a top blade centre-to-centre span of 100 mm) while controlling shift with a speed of travel of 0.01 mm/min.

Results 1. The concrete specimens flex-reinforced with polypropylene fibre mesh fig.4 revealed that the fibre has practically no ability to increase ultimate tensile strength after the first cracks appear.

Figure 4 2. Specimens reinforced with aramidic fibre and fibreglass, shown in Fig. 5 and 6 respectively, reveal some increase in ultimate tensile strength; but the mesh visibly came away from the matrix and rapidly became ineffective, as shown by the drop in the curve.

Figure 5

Figure 6

-73 Specimens reinforced with carbon fibre mesh (X MESH C10/M50) turned out to be much more efficient that those tested so far fig. 7

Figure 7 4

Figure 8

Lastly, specimens made with the new Ruredil X MESH GOLD (PBO-FRCM) mesh collapse at a load more than 40% greater than carbon-reinforced specimens. Comparison of the areas shown in the diagrams demonstrate that Ruredil X Mesh Gold (PBO-FRCM) reinforcement also considerably increases the specimens flexibility fig. 8.

Diagram summarising tests conducted on various different FRCMs

9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 1 2 freccia (mm 3 4
X MESH GOLD X MESH C10 POLIPROPILENE
ARAMIDE VETRO

-85Comparison of the performance of CFRP (Ruredil X Wrap 310) and PBO-FRCM (Ruredil X Mesh Gold)

The experiments were conducted in the Construction Science Laboratory of IUAV University in Venice under the direction of Prof. Angelo Di Tommaso. The tests were conducted to assess the effectiveness of the new PBO-FRCM (Ruredil X Mesh Gold) flex reinforcement technique in comparison with specimens with no reinforcement and specimens reinforced with CFRP (Ruredil X Wrap 310).

Geometric and mechanical properties of PBO-FRCM (Ruredil X Mesh Gold) Table 3 shows the geometric and mechanical properties of Ruredil X MESH Gold mesh and Ruredil X MESH GOLD M750 mortar, while fig. 9 depicts the mesh.

Geometric properties of RUREDIL X MESH GOLD Warp Equivalent dry fabric thickness
Weft

0.0450 mm 0.0225 mm 261.0 kN/m 130.5 kN/m 28 MPa 4 MPa 7500 MPa

Maximum load per unit of width

Warp Weft

Mechanical properties of RUREDIL X MESH M750 28 days Compression strength 28 days Flex fatigue 28 days Modulus of elasticity

-9Experimental programme Description of the specimens 6 reinforced concrete beams with the geometric properties shown in figure 10 were used in the tests.

Figure 10

6 of these beams were not reinforced (BC1 BC2)

Figure 11

- two were reinforced with 2 layers of Ruredil X Mesh Gold on the intrados and U-shaped shearing reinforcements at the ends (AC1a and AC1b-fig.12)

Figure 12

- 10 - two were reinforced with 1 layer on the intrados and a continuous U-shaped layer of Ruredil X Mesh Gold and shearing reinforcements at the ends (CC1a and CC1b-fig.13)

Figure 13

- two were reinforced with 1 layer of Ruredil X Wrap 310 on the intrados and U-shaped shearing reinforcements at the ends (EC1 and EC2-fig.14)

Figure 14

A flex test was conducted at three points on all specimens, acquiring load and camber at the mid-line as shown in the diagram in fig.15)

Figure 15

At loads of 30 kN and 70 kN the beams were released from their loads and then subjected to the loads again.

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Analysis of Results The load-camber diagrams for the experiments are shown in figures 16 - 19. (For easier reading, the figures do not show the points at which the load was removed and replaced.)

Figure 16

Figure 17

Figure 18

Figure19

Collapse loads for all specimens. Average values - Table 4. Specimen BC AC CC EC Maximum load 255.86 319.33 311.98 321.09 Camber at maximum load 14.52 17.19 19.61 13.76

Comment on the results of the experiment The load-camber diagrams for the unreinforced specimens reveal a phase without cracking (first segment), a phase with cracking in which the steel is still elastic (up to the knee point, corresponding to the yield point of the tense steel) and a phase in which the steel has yielded, in which the load is increased (moderately) as the steel hardens and the arm of internal torque increases. The diagrams for the reinforced specimens are the same as for the unreinforced specimens up to the steels yield point; after this event load can still be increased considerably thanks to the

- 12 linear elastic behaviour of the fibre reinforcement up to the breakage point, in which tensile stress continues to grow with curvature. As compared to the unreinforced specimens, all the reinforced specimens revealed an increase in the steels yield strength (due to the contribution of the reinforcement, which absorbs part of the tensile stress) and an increase in the collapse point. In all cases, once the effect of reinforcement had been annulled, the load-shift diagrams were the same as for unreinforced specimens. Crisis was more ductile in the case of specimens reinforced with PBO-FRCM (Ruredil X Mesh GOLD) than in the case of specimens reinforced with C-FRP (Ruredil X Wrap 310) because the former revealed a gradual release of the reinforcement (due to slip between the matrix and the fibre), while the latter demonstrated sudden detachment of the entire reinforcement. This difference in behaviour appeared systematically in all the specimens tested: after the peak, the load-camber curves for specimens reinforced with PBO-FRCM gradually return to the same line as unreinforced specimens, while the load-camber curves of specimens reinforced with CFRP reveal a sudden drop in load after the peak. The increase in collapse load obtained wtih Ruredil X Mesh GOLD is the same as for Ruredil X Wrap 310. And in fact tab.3 reveals that the maximum loads are 321.09kN and 319.33kN for Ruredil X Wrap 310(EC) and Ruredil X Mesh GOLD(AC) respectively. In particular, note that the reinforcement configurations adopted correspond to a 42.5 mm2 section in the case of Ruredil X Wrap and a 30.6 mm2 section for Ruredil X Mesh Gold. These results on the beams confirm the results obtained with specimens of smaller section, in which comparison of different FRCMs (fig.4-8) revealed the superior performance of RUREDIL X MESH GOLD over all other FRCMs.

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Fire resistance

Ruredil X Mesh Gold is a compound consisting of a stabilised cement inorganic matrix which, like all cement conglomerates, is fire-resistant thanks to its low conductivity and high specific heat. The effect of high temperatures and fire on the mechanical properties of concrete is quite complex, because it depends on the water to cement ratio, the type of inert material used, the type of cement, the load conditions the material is subject to during the fire, etc. In the case of reinforced concrete, the literature reveals that at temperatures of over 500C steel loses its mechanical properties, while concrete maintains its performance practically unaltered up to temperatures of 650C. The inorganic matrix of Ruredil X Mesh M750 mortar resists high temperatures without suffering significant degradation, and therefore preserves its adhesion with the Ruredil X MESH GOLD mesh and the concrete substrate. The PBO fibre the mesh is made of breaks down at 650C. In the case of FRPs, the literature reports numerous studies attesting to the scarce resistance to high temperatures as a result of use of a resin (organic polymer). For all resins have a glass transition temperature or Tg, which is from 80 to 120C in the case of epoxy-based resins which harden with heat. Above these temperatures resin loses its adhesive and mechanical properties as it passes from a rigid, fragile state to a viscous, rubbery state and finally burns and is totally broken down by high temperatures. Dynamic mechanical analysis (DMA) a technique involving simultaneous application of an oscillating sinuosidal load and a controlled temperature programme has revealed that at temperatures approaching Tg (80-120C) modulus of elasticity is decreased by up to 3 orders of magnitude. FRP systems subjected to temperatures even a few degrees above the resins glass transition temperature will therefore be subject to a drastic reduction of strength, rigidity and adhesion to the concrete or masonry substrate. In order to reveal just how important it is to consider the effect of temperature on the performance of FRPs after their application to the substrate, let us quote the entire text of point 3.6 -Limits on reinforcement in the event of exposure to fire of document CNR-DT 200/2004 (Guide for the Design and Construction of Externally Bonded FRP Systems for Strengthening Existing Structures)

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3.6 Strengthening limitations in case of fire

(1) Composite fibre-reinforced materials are particularly sensitive to exposure to high temperatures, a circumstance which may arise, for instance, in the event of fire. When the ambient temperature exceeds the resins glass transition temperature (or melting temperature, in the case of semi-crystalline materials), the resistance and rigidity of the FRP system are drastically decreased. If the FRP is applied outside the concrete or masonry element, exposure to high temperatures will also produce rapid deterioration of the FRPs adherence to the substrate, resulting in delamination of the composite and loss of the reinforcements effectiveness. (2) In the event of exposure to fire, the mechanical properties of FRP-based systems applied to exteriors may be significantly improved by increasing the thickness of the protective layer applied. Use of coatings which reduce propagation of flame and production of smoke is suggested. In all cases, use of certified insulation systems is recommended. Further specifications for application of productive systems are contained in points 4.8.2.3 and 5.8.2.3 (3) In the event of exposure to fire, to prevent collapse of FRP-reinforced structures, until further information is available on the actual behaviour of coatings and of different types of resins under these conditions, the contribution required of the reinforcement should prudentially be limited. (4) The combination of actions under exceptional circumstances (fire), as defined by current standards, should refer to the situations listed below, in which the calculated effect of indirect thermal action is denoted with the symbol Ed. Exceptional situation in the presence of reinforcement (Ed 0), if the reinforcement itself is designed for a predetermined time of exposure to fire. In this case the actions exerted on the structure due to the frequent combination should be considered. The elements capacity, appropriately reduced to take into account the time for which they are exposed to fire, is calculated using partial coefficients pertaining to the exceptional circumstances, as stated by current standards (for fibre-reinforced composite, =1). Situation following the exceptional event (Ed = 0), in the absence of reinforcement. In This case it is necessary to take into consideration the effect on the structure of the almost permanent combination. The elements capacity, appropriately reduced to take into account he time for which they are exposed to fire, is calculated using partial coefficients pertaining to the exceptional circumstances.

Comments The results of the experiments reveal the dependability of the new Ruredil X Mesh Gold reinforcement method for keeping mechanical properties and adhesion to the substrate practically unaltered even in the presence of high temperatures and fire. FRP composites in which adhesion is entrusted to an organic resin lose their structural reinforcement properties at temperatures of 80 to 120C because the resin constituting the binder of the composite suffers chemical and physical alteration at these temperatures (glass transition temperature or Tg) which reduces or eliminates their ability to adhere to the fibre and the substrate. This behaviour drastically reduces the structural reinforcement features designed with FRP, compromising the safety of the restoration work. Ruredil X Mesh Gold is therefore a compound for reinforcement of concrete and reinforced concrete constructions, to be applied to structures that may be simultaneously affected by high temperatures associated with a seismic event or unforeseen load.

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Humidity of the substrate

The humidity of the concrete or masonry substrate also has an effect on mechanical properties and adhesion in that, in the case of FRPs, if we alter the catalysis process in the resin, Tg and therefore adhesion to the fibre and the substrate will be reduced. In the case of RUREDIL X MESH GOLD, on the other hand, the binder (inorganic material stabilised in relation to hydraulic reactions) requires water in the mix: It therefore does not suffer from humidity in the substrate, which on the other hand favours its adhesion.

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Durability

The new Ruredil X Mesh Gold reinforcement technique offers excellent durability in the presence of the aggressive chemicals most commonly present in the natural and industrial environments. And in fact the Ruredil X Mesh M 750 inorganic matrix is not only pozzolanic in nature but contains special additives capable of reducing microporosity and therefore making it impermeable to aggression from chemicals such as chlorides, sulphates, nitrates, organic and inorganic acids, etc. In addition, the PBO fibre making up the Ruredil X Mesh Gold mesh does not suffer chemical and physical deterioration in any aggressive environment. The Ruredil X Mesh Gold technique can therefore be used effectively in situations requiring not only structural reinforcement but high resistance to aggressive chemical agents in the environment (chemical industries, ports, viaducts and bridges near the sea, etc.)

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Applications

Ruredil X Mesh Gold offers the same performance as conventional FRP techniques, so that it may be used for static consolidation of reinforced concrete or pre-compressed reinforced concrete structures, including those which could be subject to the simultaneous action of high temperatures. Ruredil X Mesh Gold is specifically used on reinforced concrete and pre-compressed reinforced concrete structures for: Flex reinforcement Shearing reinforcement Torsion reinforcement Confinement of beam columns with low eccentricity Confinement and longitudinal reinforcement of beam columns with high eccentricity

Ruredil X Mesh Gold is suitable for work in seismic zones for: increasing resistance to simple flex fatigue or combined pressing and bending action increasing resistance to shear stress with the mesh arranged at right angles to the axis of the architectural element increasing the flexibility of the terminal portions of beams and pillars by binding increasing the resistance to tensile stress of the panels of beam-pillar nodes with fibres aligned with tensile stress isostatics.