18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

THERMOPHYSICAL PROPERTIES OF WOVEN FABRICS REINFORCED GEOPOLYMER COMPOSITES

Xiem Nguyen Thang1, Petr Louda2 & Dora Kroisova3
Abstract: The aim of this study is to determinate thermophysical properties (thermal diffusivity, thermal conductivity, specific heat and thermal expansion) of geopolymer composites reinforced with different types of woven fabrics. Many reinforcements and geopolymer matrices are now available, but our work was focused on geopolymer matrix Q13K1, which involved common of thermal silica, kaolin, and potassium water glass; and combination with fabric E-glass, basalt and carbon fibers were also investigated. The samples were prepared using a standard vacuum bagging technique. The fabrics were impregnated with the matrix by-hand, stacked together and placed in the vacuum bag. Thermophysical properties were determined in accordance with national and international standards such as ASTM E-1461, DIN 30905, DIN EN 821, DIN 53752, etc.

INTRODUCTION

Since the chemistry of geopolymer materials was discovered, geopolymer has emerged as a promising new material with environmentally sustainable properties. And they are also still considered as a new material for coatings and adhesives, a new binder for fiber composites, and new cement for concrete [1-3]. Geopolymers are chains or networks of amorphous mineral molecules linked together through covalent bonds. Geopolymerization involves the chemical reaction of alumino-silicate oxides (Al+3 in IV-fold coordination) with alkali polysilicates yielding polymeric Si-O-Al bonds; the amorphous to semi-crystalline three dimension silico-aluminate structures are of the Poly(sialate) type (-Si-O-Al-O-), the Poly(sialate-siloxo) type (-Si-O-Al-O-Si-O-), the Poly(sialate-disiloxo) type (-Si-O-Al-O-SiO-Si-O-) [4-6]. Generally, any mineral clay that contains high concentration of silica and alumina can be diluted into strongly alkaline solutions (such as NaOH or KOH) to make an exothermal reaction polycondensation process of geopolymerization to form geopolymers [1-4]. In this paper, we recommended an application of thermal silica-based geopolymer with nanosized amorphous silica as a main component for fiber fabric reinforced (E-glass, basalt, and carbon) composites. Table 1 shows all kinds fiber fabric. E-glass and basalt are a bidirectional fabric made by interweaving direct roving in plain weave pattern. And carbon fiber fabric used in this study is a type of biaxial fabric.

Ing. Xiem Nguyen Thang; Department of Material Science, Faculty of Mechanical Engineering, Technical University of Liberec, Studentsk 2, 461 17 Liberec, Czech Republic, Thangxiemctm@yahoo.com.
2

Prof. Ing. Petr Louda, CSc; Department of Material Science, Faculty of Mechanical Engineering, Technical University of Liberec, Studentsk 2, 461 17 Liberec, Czech Republic.

Doc. Ing. Dora Kroisov, PhD; Department of Material Science, Faculty of Mechanical Engineering, Technical University of Liberec, Studentsk 2, 461 17 Liberec, Czech Republic.

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

Table 1: Main properties of woven fabrics Density [g/m2] Extensile strength resistance [MPa] 1900 Thermalconductivity coefficience (w/m.K) 800

Name

Model

Picture

12K Carbon fiber fabric Basalt fiber fabric E-glass fiber fabric

Biaxial

400

Plain

200

1870

0.03 0.038

Plain

486

2200

0.05 0.08

The thermal diffusivity and specific heat were measured using a NETZSCH model LFA 447 NanoFlash diffusivity apparatus. In Fig. 1 presents the schematic design of this new container system. The unit used in this work was equipped with a furnace, capable of operation from 25 to 300C. The system is equipped with a software-controlled automatic sample changer allowing measurement of up to 4 samples at the same time. The temperature rise on the back face of the sample is measured using an InSb detector. Data acquisition and evaluation are accomplished using a comprehensive 32-Bit MS-WindowsTM software package. Various analysis models are integrated in the software. The data can be corrected for finite pulse and (2-dimensional) heat loss effects. The data evaluation software also allows 2and 3-layer calculations as well as the evaluation of the contact resistance. The instrument is designed to carry out tests fully automatically. The LFA 447 operates in accordance with national and international standards such as ASTM E-1461, DIN 30905 and DIN EN 821.

Figure 1. Schematic design of the LFA 447 NanoFlash The thermal expansion was measured using a NETZSCH model 402 C pushrod dilatometer (see in Fig. 2). This dilatometer was equipped with a SiC furnace capable of operation between room temperature and 1600C. The system is a vacuum tight, allowing measurement

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

to be carried out in pure inert or oxidizing atmospheres, as well as under vacuum. A set of primary standards, including fused silica, sapphire, platinum, tungsten, etc., is available for the length calibration. The expected expansion of the specimen and the temperature range of the measurement, of course, dictate which standard should be used. Data acquisition and evaluation, as well as instrument control, are accomplished with a MS-WindowsTM Thermal Analysis software package. The software includes semi-automatic routines for correction of the sample holder expansion as well as computation of the expansion coefficients, onset and peak temperatures, inflection points, rate of expansion, etc. The dilatometer DIL 402 C works according to national and international standards like ASTM D 696, - E 228, - E 831, - E 1363, - E 1545, - E 1824 as well as DIN 53752.

Figure 2: Schematic design of the NETZSCH Dilatometer 402 C

2
2.1

EXPERIMENTAL
Material

In the synthesis of geopolymer resins, there are essentially two types of raw materials, the aluminosilicate-containing solids and alkaline-silicate solutions. The results of EDX investigations highlighted are summarized in Table 2. The element (%) and atomic (%) of the pure geopolymer are in good agreement with those of their respective components. We can see that pure geopolymer Q13K1 is an inorganic material containing mostly silicon, potassium, and aluminum. Table 2: Quantitative elemental analysis data of pure geopolymer Q13K1 matrix Element Aluminium (Al) Silicon (Si) Phosphorus (P) Potassium (K) Oxygen (O) Element [%] 3.70 35.60 1.94 13.11 45.66 Atomic [%] 2.94 27.23 1.34 7.20 61.29

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

2.2

Specimen preparation

The geopolymer fabric composites were prepared by wet hand lay-up technique. The fabric laminates were impregnated with the matrix by-hand, layer by layer until desire thickness. Each layer was consolidated by a roller, ensuring that the resin impregnates the fiber and that any air bubbles were removed. Then the saturated fabrics were covered by a peel ply fabric and suction tissue then placed into a sealed plastic bag. The laminates were cured in a vacuum bag with 1 atm pressure at room temperature (about 25oC) for 1 hour. Next the bag was placed in a heated press at -1atm in the furnace at 80oC for 2 hours more. The laminates were then removed from the vacuum bag and inserted into a furnace for final curing at 80oC for 20 hours or until a constant mass was achieved. The dimension of all the laminates were approximately (200 x 200 x 3.5) mm. The small samples were cut from the laminate using a high speed diamond blade. The volume fraction of reinforcement was approximately 50%. 2.2.1 Thermal conductivity The samples were tested with the LFA 447 between room temperature (25C) and 250C. Standard sample holders (12.6 x 12.6 mm) were used. The samples were coated with graphite in order to increase the absorption of flash light on the front surface and to increase the emissivity on the back surface. The samples were measured five times at each temperature. The specific heat was measured with the LFA 447 by a comparative method. For this, the system was calibrated with a Cp reference sample (Pyroceram 12.6 mm in diameter, 2.5 mm thick). The density of the samples at room temperature was determined by measuring of mass and volume. 2.2.2 Thermal expansion The dilatometer measurements were carried out using the following parameters: Table 3: Measurement parameters DIL 402 CD Sample holder Sample thermocouple Pushrod force Atmosphere Calibration standard Temperature program Sample length Fused Silica Type E 25 cN Argon at 50 ml/min Al2O3* RT to 800C at 5 K/min 20.40 mm (Q13K1-Basalt) 20.27 mm (Q13K1-Carbon) 20.08 mm (Q13K1-Eglass) *The system influence was recorded by the measurement of a calibration standard with well known expansion behavior. The calibration run was, of course, carried out under the same conditions as used for the samples.

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

2.3

Measurements The measured data was used to compute the thermal conductivity by following equation: = . Cp . a with: is thermal conductivity, W/(m.K) is bulk density, g/cm3 Cp is specific heat, J/(g.K) a is thermal diffusivity, mm2/s (1)

3
3.1

RESULTS
Thermal conductivity

Fig. 3 presents the thermophysical properties of sample Q13K1-Eglass. For thermal conductivity slight decreasing values were detected up to 250C. The specific heat increases with temperature as expected from Debye theory. Only slight changes were detected for thermal conductivity. Similar dependencies were detected for sample Q13K1-Basalt. Table 4: Thermophysical properties of geopolymer composite Q13K1-Eglass Density (25oC): 1.612 g/cm3 ; Thickness (25oC): 2.210 mm Temperature [oC] 25 100 150 200 250 Thermal Diffusivity [mm2/s] 0.278 0.242 0.227 0.213 0.207 Specific Heat [J/(g.K)] 0.942 1.080 1.137 1.180 1.211 Thermal Conductivity [W/(m.K)] 0.422 0.421 0.416 0.405 0.404

Figure 3: Thermophysical properties of sample Q13K1-Eglass

Figure 4: Thermophysical properties of sample Q13K1-Basalt

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

Table 5: Thermophysical properties of geopolymer composite Q13K1-Basalt Density (25oC): 1.934 g/cm3 ; Thickness (25oC): 3.490 mm Temperature [oC] 25 100 150 200 250 Thermal Diffusivity [mm2/s] 0.334 0.242 0.210 0.197 0.191 Specific Heat [J/(g.K)] 0.952 1.105 1.217 1.292 1.313 Thermal Conductivity [W/(m.K)] 0.615 0.517 0.494 0.492 0.485

Figure 5: Thermo-physical properties of sample Q13K1-Carbon

Figure 6: Thermal expansion of sample Q13K1-Basalt, Q13K1-Carbon and Q13K1-Eglass

Table 6: Thermophysical properties of geopolymer composite Q13K1-Carbon Density (25oC): 1.517 g/cm3 ; Thickness (25oC): 2.270 mm Temperature [oC] 25 100 150 200 250 Thermal Diffusivity [mm2/s] 0.415 0.346 0.311 0.281 0.268 Specific Heat [J/(g.K)] 1.055 1.272 1.432 1.568 1.633 Thermal Conductivity [W/(m.K)] 0.664 0.668 0.676 0.668 0.664

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

However the thermal conductivity is on a higher level most probably due to different composition and structure of samples. The stronger decrease of thermal conductivity between room temperature and 100C might be due to the influence of drying of sample. The thermophysical properties of sample Q13K1-Carbon can be seen in Fig. 5. For the thermal conductivity higher values were detected compared to other samples most probably due to carbon content. The standard deviation (thermal diffusivity) of five shots at each temperature was less than 1%. Tables 4 to 6 contain the values for thermophysical properties. 3.2 Thermal expansion The thermal expansion of samples Q13K1-Basalt, Carbon and E-glass are shown in Fig. 6. Q13K1-Basalt: In the beginning the sample increased to 99C (extrapolated peak), and then expanded up to the maximum sample length which was detected at 439C with an expansion of 0.06%. Further on the sample length decreased till the end of measurement. During this decrease two steps were observed in the thermal expansion at 634C and 731C (extrapolated onsets). Q13K1-Carbon: In the beginning the sample length expanded up to the maximum sample length which was detected at 54.5C with an expansion of 0.01%. Further on the sample length decreased down to a minimum at 336C. During this decrease three step s were observed in the thermal expansion at 124C (extrapolated onset) and between 249C (minimum) and 262C (maximum). Above 336C the sample length increased till the end of measurement. Q13K1-Eglass: In the beginning the sample length expanded up to the maximum sample length which was detected at 370C with an expansion of 0.07%. Further on till the end of the measurement shrinkage of 1.6% was detected. At 713C (extrapolated onset) a step was observed in the thermal expansion. The values for the thermal expansion of all samples are summarized in Table 7. Table 7: Values for the thermal expansion of sample Q13K1-Basalt, Q13K1-Carbon, and Q13K1-Eglass Temp [oC] 40 60 80 100 120 140 160 180 Thermal expansion [%] Q13K1 Basalt 1.23E-02 2.68E-02 3.81E-02 4.21E-02 4.01E-02 3.55E-02 2.80E-02 2.48E-02 Q13K1 Carbon 8.68E-03 1.00E-02 -1.54E-03 -3.94E-02 -8.02E-02 -0.10605 -0.13893 -0.15793 Q13K1 Eglass 1.22E-02 2.27E-02 2.99E-02 3.43E-02 3.68E-02 3.76E-02 3.50E-02 3.40E-02 440 460 480 500 520 540 560 580 Temp [oC] Thermal expansion [%] Q13K1 Basalt 6.31E-02 6.10E-02 5.62E-02 4.97E-02 4.09E-02 2.85E-02 1.64E-02 5.68E-03 Q13K1 Carbon -0.17931 -0.17757 -0.17517 -0.17209 -0.16885 -0.16572 -0.16204 -0.15761 Q13K1 Eglass 5.48E-02 4.75E-02 3.37E-02 1,37E-02 -1.03E-02 -4.14E-02 -7.12E-02 -9.68E-02

18th International Conference Structure and Structural Mechanics of Textiles

December 2011 TU Liberec, Czech Republic

200 220 240 260 280 300 320 340 360 380 400 420

2.58E-02 2.80E-02 3.14E-02 3.56E-02 3.99E-02 4.44E-02 4.81E-02 5.00E-02 5.16E-02 5.41E-02 5.78E-02 6.15E-02

-0.16982 -0.17696 -0.18090 -0.18010 -0.18108 -0.18274 -0.18466 -0,18547 -0.18463 -0.18390 -0.18278 -0,18109

3.63E-02 3.99E-02 4.42E-02 4.89E-02 5.37E-02 5.85E-02 6.26E-02 6.53E-02 6.66E-02 6.67E-02 6.57E-02 6.13E-02

600 620 640 660 680 700 720 740 760 780 800

-4.15E-03 -1.26E-02 -1.87E-02 -2.32E-02 -5.18E-02 -0.13112 -0.22751 -0.29617 -0.34282 -0.38374 -0.42550

-0.15293 -0.14843 -0.14378 -0.13894 -0.13421 -0.13005 -0.12633 -0.12194 -0.11678 -0.11121 -0.10542

-0.12454 -0.15224 -0.18010 -0.20877 -0.23992 -0.29931 -0.46712 -0.76533 -1.10384 -1.37768 -1.56621

CONCLUSIONS

In this work, the thermal diffusivity, thermal conductivity, specific heat and thermal expansion of the ber fabric reinforced composites was investigated. As a result, geopolymer carbon fabric composite showed the highest thermal conductivity to the reinforcements. On the other hand, thermal expansion of geopolymer composite reinforced carbon fabric is smaller than the types of rest. The results indicate that the geopolymer fabric composites can apply in industries, such as hot piping, chimney, exhaust systems, heat equipment, and insulator wall in building industry.

ACKNOWLEDGEMENT

The authors wish to thank A. Lindemann, D. Kwiryn (NETZSCH-Gertebau GmbH, Wittelsbacherstr. 42, 95100 Selb, Germany) for helping with the dilatometric measurements. And the present work was supported by the Project FT-TA4/068 and Project MSMT 4674788501. References [1.] Hardjito H, Rangan RV. Development and properties of low-calcium fly ash based geopolymer concrete. Research report GC1. Perth, Australia: Faculty of Engineering, Curtin University of Technology, 2005. [2.] Shuzheng Zhang, et al., Novel modification method for inorganic geopolymer by using water soluble organic polymers, Lsevier B.V, Vol. 58, Issues 7-8, p. 1292 1296, 2004. [3.] Joseph Davidovits, Geopolymer chemistry & application, Second Edition, Institute Gopolymr France, 2008, ISBN: 2-95148201-9. [4.] Duxson, et al., The role of inorganic polymer technology in the development of green concrete, Cement and Concrete Research 37, p. 1590 1597, 2007.