THE EFFECT OF FIBER ADDITION ON LOW CEMENT CASTABLES

Hamed Samadi* Sales Engineering Dept., PARS Refractories Co. Tehran, Iran hamed_samadi@iranscholarship.net F. Golestani Fard Dept. of Metals & Materials Engineering Iran University of Science & Technology Narmak, Tehran I6844 Iran

1. INTRODUCTION 1.1. LOW CEMENT CASTABLES Refractory Castables are classified according to their hydraulic bonds. A castables ingredients are: AluminaCalcium cement, filler, aggregate, fibers and additives. Raw materials, formulation and installation affect castable properties 1). According to ASTM C401, low cement castable has 1 to 2.5 wt. % CaO. In LCC refractories, a kind of filler is present. Filler plays an important role in castables performance. In traditional (regular) castables, as there is no filler between aggregates, water fills the porosities (Fig. 1) and this leads to an increase in water amount. A LCC refractory has 5-15% of different kinds of fillers including reactive Alumina, micro silica and chrome oxide. Chrome oxide is not used according to environmental hazards. Micro silica is an ideal filler because of being reachable, feasible and environmental friendliness. But when comes to high temperature performance and Alumina based castables, reactive Alumina would be the first choice. Filler decreases the water amount by 5-10 %, and the porosity decreases respectively.

may be used to increase HMOR; polymer fibers are used to increase heating rate and steel fibers are used to increase toughness. For toughening a refractory by fibers, the cracks must be stopped. Generally there are two mechanisms to stop a crack. A crack should be stopped or its direction should be changed 2). There are three factors which affect the fibers functions: fibers length, orientation and amount. Fibers orientation and amount are in connection and both affect strength and composite properties. Steel fibers are developed in 1910 as an additive in portland cement. In last 1960s these fibers have been used in refractory monolithics and today it is considered as a normal ingredient of monolithic refractories 3). Adding fibers to cement castable makes a reinforced structure with advanced properties comparing with regular castables 4). There are different ways to make steel fibers: steel wire cut, shearing thin steel plate, shaving thick steel plate and melt extract 3). By using melt extract (ME) method the achieved fibers have the following advantages 5): - Because of the high cooling rate, the fibers have microcrystalline structure and high mechanical strength as a result. - As an adaptable method, different additives can be added to make alloy steel. - The specific area of fibers are very high (Fig.3) and this leads to excellent fiber/ refractory bonding. - There is no need to equip the mixing apparatus with extra equipment.

Fig.1 Water settlement in regular castables

1.2. Fibers Despite high temperature resistance and chemical stability, refractories are brittle against thermal and mechanical shocks and this is because of rigid bonds in ceramics. As rigidity is in inherent of ceramics, the only way of solving this problem is increasing the materials toughness. There are different ways of toughening a brittle material. Only two ways can be used in castables: Fiber reinforcement and pore dispersion. Fibers are widely used in castables. Ceramic fibers

Fig.2 Meltex fiber micrograph and its high surface area Despite the above mentioned advantages, if a proper fiber type and amount according to manufacturers data sheet is not chosen, no increase in refractory

service life will be found and it may result in some performance problems. On the other hand the best performance is reachable when at least 50% of the refractory lining has a temperature below 1200C. Practically, when the temperature of lining exceeds 1150C, the fibers lose their ability. 2. EXPERIMENTAL APPROACH 2.1. RAW MATERIALS The consumed materials are as followed: Tabular Alumina (ALUFIN, Germany), cement-Secar 71 (LAFARGE, France), reactive AluminaRA15 (ALCAN, UK), steel fiber- ME 466 (FIBERTECH, UK), additivesSodium Tri Poly Phosphate and Citric Acid (MERCK, Germany). The physical and chemical properties of the raw materials are in Tables 1~3. Table 1. General characteristics of tabular alumina CHEMICAL ANALYSIS PHYSICAL PROPERTIES Oxide % Apparent density 3.7 gr./cc Al2O3 SiO2 Fe2O3 Na2O CaO 99.5 0.03 0.02 0.3 0.01 Bulk density App. Porosity Water adsorption 3.6 gr./cc 4% 1.5 %

2.2. FORMULATION A formulation based on Alumina low cement castable was developed according to Size Dist software version 1.1 by ELKEM (Norway). All affecting matters like water and additive amounts are the same in all batches. Two, three and four weight percent of steel fibers were added due to different sources advised using fibers in this range mostly. 2.3. TESTS The following tests have been done according to ASTM. As some non-standard tests were needed some tests were designed solely as a measurement. Flowability (ASTM C230), MOR and CCS (ASTEM C133), HMOR (ASTM C583), bulk density and apparent porosity (ASTM C20), permanent linear change (ASTM C113), thermal shock resistance, fiber oxidation (designed). For measuring thermal shock resistance there are different ways, which are based on crack propagating. A test was designed on MOR decrease after thermal shock being applied. In this test, samples being fired at 1400C are heated up to 1200C for 15 minutes in a gas furnace. Gas furnace is chosen for higher gradient in temperature. Then the samples are put in water for 10 minutes. After drying samples for 30 minutes, the procedure would be repeated for 2 more times. Then the MOR test is done based on ASTM C133-91 and the MOR decrease is reported. For measuring fiber oxidation, 10 grams of fibers are put in an Alumina crucible (fired in 1000C and cooled in a dry place). The crucible is measured by a sensitive balance (sensitivity 0.0001gr is enough). The crucible is then heated up in an electric furnace up to 1200C and 1400C. The new weights should be measured by the same balance after cooling in a dry area. 3. RESULTS 3.1. Flow Decay With increasing fiber amount the vibration flow amount is decreased according to the needle shaped fibers. Besides, the castable workability is decreased (Fig. 3).
100 90 80

Table 2. General characteristics of filler, RA15 CHEMICAL PHYSICAL PROPERTIES ANALYSIS Oxide % Specific area 3.7 sq. m/gr. Al2O3 SiO2 Fe2O3 Na2O CaO LOI 99.5 0.04 0.02 0.06 0.03 0.20 . d50 Density @ 1650 C Water adsorption

2.7 micron 3.6 gr./cc 11 gr./100gr

Table 3- General characteristics of fibers, ME466 CHEMICAL ANALYSIS Element % C 0.10 Si Cr Ni Fe 0.30 25 0 74 PHYSICAL PROPERTIES
VIBRAFLOW (% )

70 60 50 40 30 20 10 0 0 2 3 4

Melt temp. Thermal exp. Coe. @ 870C Resistance to: Oxidation Carbonization Sulfur Nitrizidation Hydrogen Reduction

1500 C 13.1 x 10E-6 / C Excellent Fair Excellent Fair Excellent Excellent

15

30 TIME (m in)

45

60

Fig.3 Flow Decay 3.2. Strength MOR and CCS are increased due to crack stopping mechanisms. By increasing fiber amount, as the possibility of facing a fiber for a crack increases, the strength increases. Considering MOR and CCS increased percent (Fig.4~5), it can be seen that strength increase is

more obvious in 110C than in 1400C. This is because of fiber oxidation, which makes the fiber more brittle, and it fails to absorb crack energy. Comparing MOR and CCS, it can be seen that MOR is more affected by fiber reinforcement than CCS and this is because of its sensitivity to crack growth. Fiber addition has no obvious effect on HMOR.
140

3.5. Permanent Linear Change PLC is positive in Alumina based LCCs. By fiber addition the PLC increased. The exact reason for this increase is unknown but can be referred to two things. At first fiber oxidation in the sample expands the fiber volume and a compressive stress is formed in the matrix and an increase in PLC. Secondly some expanding phases may be formed with the newly made iron oxide (Fig.7).
0.9

120

100 MOR INCREASE (%)

80

110 1000

0.7

60

1400

PLC (%)

0.5

40

1000 1400

20

0.3

0 2 3 FIBER ADDITION (%) 4

0.1

Fig.4. Fiber addition shows a significant MOR increase

1 00 90 80 70 CCS INCREASE (% ) 60 50 40 30 20 10 0 2 3 4 1 10 1 000 1 400

-0.1 0 2 FIBER ADDITION (%) 3 4

Fig. 7. PLC results 3.6. Fiber Oxidation Melt Extract steel fibers are the most resistant steel fibers (Fig.8). This is because of their being quenched while manufacturing which leads to a microcrystalline structure.
70 60

FIBER ADDITION (% )

50 WEIGHT GAIN (%)

Fig.5. CCS increase percent after adding fibers 3.3. Bulk Density and Apparent Porosity Fiber addition does not affect bulk density and apparent porosity. 3.4. Thermal Shock Resistance There are two active mechanisms in fiber-reinforced castables. The positive mechanism is increasing in resistance according to the crack stopping mechanisms. The negative one is crack development due to the difference in fiber and matrix thermal expansion coefficient. What is practically occurred in the samples was a result of both. Up to 3wt% the positive mechanism stopped the cracks and after that the negative one propagates new cracks and decreases the strength (Fig.6).
100 90 80 70 DECREASE (%) 60 50 40 30 20 10 0 0 2 FIBER ADDITION (% ) 3 4 MOR CCS

40

MELT EXTRACT CUT WIRE

30

SLIT STEEL

20

10

0 1000 1200 FIRING TEMERATURE (^C) 1400

Fig. 8. Oxidation test result 4. Microstructure Observation 4.1. Samples preparation Samples are cut with high-speed cutter. In cutting samples, a large volume of coolant liquid is used and the cutting speed is low for preventing samples destruction. Then a layer of PVA is coated on samples for increasing the strength. If the strength is not enough the SEM picture would be unstable while observation. The fired sample in 1400C has the sufficient strength and there is no need to coat the PVA layer on it. After these operations a coated layer of gold is deposited on the samples. 4.2. Results Sample 110 dried in 110C. Fig.9 is a fiber with in the matrix. Fig.10 shows a fiber/matrix interface. The gap between fiber and the matrix helps pull out effect. When the growing crack faces a fiber, the fiber is pulled out because of the crack surrounds it.

Fig. 6. MOR and CCS decrease after thermal shock test

Fig. 12 Fig. 9 5. CONCLUSION With increasing fiber amount, - Flow ability and workability decreases. - MOR and CCS increase. - HMOR does not change. - Bulk density and apparent porosity make no change. - PLC increases. - Thermal shock resistance increases up to 3 wt. % and then decreases. Considering all aspects of fiber reinforced castables installation and usage mainly workability, thermal shock resistance and economy, 3 weight percent of fibers is shown to be ideal for most castables. AKNOWLEDGEMENTS The authors wish to thank G-Jey Refractories, Materials and Energy Research Center, Prof. F.Moztar Zadeh and Mr. A.Souri for their support in the experimental works. REFERENCES: 1) W.D.J. Callister: Materials Science and Engineering, John Wiley & Sons Inc., 3rd edition, USA (1994) pp. 514-525. 2) A.Nishikawa, Technology of Monolithic Refractories, Plibrico Japan co. (1984) pp. 110-158. 3) A. Souri, MSc Thesis, Iran Univ. of Sci. and Tech. (1997) pp. 10-40. 4) B.Mirhadi, H.Samadi, C.Khezri, N.Razavi, M.Bavand, S. Mehr Aein, Refractory Materials (Translated from English by G.Routoschka), Iran University of Sci. and Tech. Publications (1998) pp. 182-185. 5) H.Samadi, The Effect of Steel Fibers in Improving the Service Life of Refractories used in Metallurgical Furnaces, Refractory Materials and Technology Workshop, Iran Univ. of Sci. and Tech., IRAN (1998). 6) Fiber Technology technical brochure, FIBRETECH (1997). 7)C.Parr, T.A.Bier, N.E.Bunt, E.Sprafico, Calcium Aluminate Cement Based Castables for Demanding Applications, Proceeding of International Seminar on Monolithic Refractory Materials (1997) IRAN, pp.141152.

Fig. 10 Sample 1000 is fired at 1000C. Fig. 11 shows developing bonds between matrix and fibers. This interface is a semi-brittle phase due to iron oxide formation on fibers. Sample 1400 is fired at 1400C. The interface is completely dense and the gap between fiber and matrix is filled. As Fig. 12 illustrates the fibers oxide totally in the surface. This forms a semi uniform matrix, which decreases the fibers crack stopping effect.

Fig. 11