论文部分内容阅读
Abstract: The previous laboratory studies on the geopolymer matrix have resulted in the semi-industrial production of selected geopolymer goods. This technology exploits the basic properties of the geopolymer matrix (high strength, volume stability, heat resistance and the possibility to be filled by different materials). Large-size polished boards have been offered for the kitchen countertops. The variations on them have involved the production of very thin inset tiles. Both types with dimensions of 1,000 × 500 mm have been filled with stone powder, waste glass and mirror shreds, which creates an excellent shiny effect when polished. The subsequent task was to take advantage of the excellent heat resistance of the geopolymer composites and develop heating panels. Combinations of experience with polished panels and different fillers improving the thermal conductivity have provided multiple functions: heating and decorative panels.
Key words: Geopolymer, semi-industrial, production.
The geopolymer technique and technology were developed in France in the second half of the 20th century [1]. The laboratory of the Institute of Rock Structure and Mechanics of the Academy of Sciences of the Czech Republic (IRSM, ASCR) participates in the applications of this technology from one main point of view: The identification of the raw-material quality and its ability to form a geopolymer matrix [2-4].
The advantage of the Czech Republic’s kaolin deposits lies in their variety in many localities, but the experience and knowledge of many ways is at the same time a disadvantage. The laboratory beneficiation of the material (washing, drying, milling and thermal treatment) does not take into consideration the pricing in a semi-industrial operating unit, hence the “best”
resonance analysis. The 27Al MAS-NMR (Magic Angle Spinning, Nuclear Magnetic Resonance) pattern depicts the shift of the natural hexa-coordinated aluminum ion to its new five and four coordination to the oxygen.
In the chemistry of alumina-silicates, it is well known that only in this changed coordination of the aluminum ions is it possible to reach the chaining of aluminum and silica ions. The connection is made by oxygen bridges through the alkalization of thermally treated material. A geopolymer is generally an amorphous complex of 3D netting in a whole volume of the reacting clayed material forming solid matter. Transforming this common natural act from the chemical laboratory to the semi-industrial level means first of all is choosing the most economic way of preparing a geopolymer matrix. During the five years of the cooperation between the scientific laboratory of the Academy of Sciences and the Czech Development Agency production unit, it has, among others, been found that the best result of the thermal treatment is when the layer of the material in the kiln is only 15-20 cm thick.
Both cooperating parties have also prepared matrixes from waste clay materials (e.g., clay washed out of a sandstone deposit and “white waters” from the porcelain industry) [8, 9]. To find the most economic way and assure the constant quality of the raw material was a major problem for both participants. The resulting issues of all these tests and proof have shown that the quality and utility of the product is the most important.
Even if the economy permits higher costs of material treatment, the principal question still to be resolved was a constant quality of the incoming clayed material. Once again, it should be mentioned that laboratory experience and industrial reality are two different things. Beside the manipulation and preparation of aqueous alkali solutions, there are differences in mixing devices, the treatment of cast products and their final elaboration-polishing. The presented article will
The experimental part at the industrial level starts with a selected and laboratory-proven raw material, kaolin from the Kaznejov deposit, West Bohemian Region (Czech Republic). Having gone through all the necessary beneficiation and resolved the problem with the recommended maximum layer by a special kiln furniture construction, the semi-production unit had to focus also on the kaolin particle size. The importance of the minimum clay particles was published in 2002 [2], and after the firing procedure a milling was applied.
The selection of the product, after all kinds of laboratory testing, was focused on the big countertops exploiting the wonderful behavior of the geopolymer matrix, encapsulation of a large amount of fillers and the possibility of coloring the matrix with inorganic additives. The combination of both was applied on the designed desks, where the effects of the different color layers in combination with glass and mirror shreds were used. The face board was polished by an ordinary stone polishing machine with a rotated head cooled by water. Despite the fact that there were three or four different material hardness’s (glass, mirror, stone and the geopolymer matrix), the surface was glittering with small colored particles of glass shreds and reflecting the light through the mirror particles. The thickness of the table was about 25 mm and 1000 × 500 mm in dimension while the weight exceeded 40 kilograms.
The advantage of this kaolin lies in its light white-yellowish color, but the preparation of the matrix with all the treatment work and other complications(mixing and casting difficulties owing to the low casting flow when filled) does not permit a future, truly industrial use.
Looking for a similar, lightly colored material for the matrix, a material generated from so-called “white waters” was later used. This specific clayed material is
exploitation of its very low viscosity when alkalized, it was possible to augment the quantities of the additives and choose their best proportions for a different type of usable product. The combination of this new quality of the matrix and previously tested composition with different types of fabrics opened a new field- highly filled thin tile. Apart from heavy countertop, it was now possible to produce very thin (3-7 mm) tiles in dimensions of 500 × 1,000 mm with the same effect of shining glass and mirror shreds incorporated into the light gray matrix.
On the one hand, this matrix permitted the production of decorative inset tiles and at the same time opened another door: The light, relatively thin (14mm thick) anti-fire protective plates made from three layers of sandwiched matrix, supported on the outside by fabrics and filled inside with a powdered-mica waste.
The combination of the fully filled geopolymer matrix with waste basalt in three different grain sizes and glass/mirror shreds converted the obtained composite into a well heat-conductive matter. There was then only a small step to find an electric cable and all the other electrical components and open a new production division, heat geopolymer panels with a shiny polished surface.
The results presented in Table 1 compare the chemical composition of all the above-mentioned materials tested for the semi-industrial unit operated by the Czech Development Agency. The comparative table demonstrates the difference in treatments, the first three were analyzed in the natural state and the last one with very low L.O.I. was thermally treated by a supplier. The analyses in oxides were recalculated from the results in the elements obtained by the XRF method. The industrially thermally treated material contains a small amount of organic matter (gray color of the supplied material), but when the L.O.I. was identified at a temperature of 1,000 °C with a ten-minute dwell,
The policy of the semi-industrial unit is not in the inspection and testing of the incoming materials but in the application of the one selected and exploits its behavior with respect to the demanded products. The most important part of the know-how comes in when the mixing of a huge amount of alkalized material starts with its filling (e.g., the time of mixing and the revolution of the mixing paddle) of different sorts of additives. Apart from that, an exceptional knowledge should be mentioned of how and from which material the molds in light of their resistance to alkalis and production turnover could be prepared. It means at the same time resolving the problem of separators and all kinds of mold maintenance (cleaning, stocking, etc.).
All this specific and very costly knowledge collected through the fabrication of countertops and thin large dimensioned tiles was applied on the preparative steps before the first heating panels were made.
The division of heating panels today represents the most complex knowledge of geopolymer application: How to prepare the best composite, how, when and which coloring agents should be added, how to apply the prepared mixture into the molds avoiding air bubbles even when the used mass is very viscose. The maintenance of the panel made and the hardening time before it could be polished differs from all laboratory knowledge and experience.
Fig. 1 shows a heating panel (600 mm × 900 mm ×65 mm) fabricated from a basalt/glass/mirror geopolymer composite.
This article clarifies important points in the processes of knowledge transfer between the chemical laboratory and industrial unit. The difficulties in material selection which could be resolved by a laboratory equipped with all facilities are not effective on the industrial level, where the energy and manpower costs must be very well judged. The product itself must be evaluated on the market by its high value added through its novelty and qualities. As shown, each fabricated product needs a specific technology timing, which in the case of heating panels is converted into real production know-how.
[11] T. Hanzlicek, M. Steinerova, P. Straka et al., Reinforcement of the terracotta sculpture by geopolymer composite, Materials and Design 30 (8) (2009) 3229-3234.
[12] I. Perna, T. Hanzlicek, M. Steinerova, P. Straka, Acoustic Absorption of geopolymer/sand mixtures, CeramicsSilikáty 53 (1) (2009) 48-51.
[13] T. Hanzlicek, I. Perna, The alumina-silicates in stabilization process in fluidized-bed ash, Ceramics-Silikáty 55 (1) (2011) 94-99.
[14] T. Hanzlicek, I. Perna, Thermal resistance of foamed fluidized bed ashes, Acta Geodynamica et Geomaterialia 8(2) (2011) 115-122.
[15] T. Hanzlicek, I. Perna Z. Ertl, The Influence of temperature and composition on modeled mortars, International Journal of Architectural Heritage 6 (2012) 359-372.
Key words: Geopolymer, semi-industrial, production.
The geopolymer technique and technology were developed in France in the second half of the 20th century [1]. The laboratory of the Institute of Rock Structure and Mechanics of the Academy of Sciences of the Czech Republic (IRSM, ASCR) participates in the applications of this technology from one main point of view: The identification of the raw-material quality and its ability to form a geopolymer matrix [2-4].
The advantage of the Czech Republic’s kaolin deposits lies in their variety in many localities, but the experience and knowledge of many ways is at the same time a disadvantage. The laboratory beneficiation of the material (washing, drying, milling and thermal treatment) does not take into consideration the pricing in a semi-industrial operating unit, hence the “best”
resonance analysis. The 27Al MAS-NMR (Magic Angle Spinning, Nuclear Magnetic Resonance) pattern depicts the shift of the natural hexa-coordinated aluminum ion to its new five and four coordination to the oxygen.
In the chemistry of alumina-silicates, it is well known that only in this changed coordination of the aluminum ions is it possible to reach the chaining of aluminum and silica ions. The connection is made by oxygen bridges through the alkalization of thermally treated material. A geopolymer is generally an amorphous complex of 3D netting in a whole volume of the reacting clayed material forming solid matter. Transforming this common natural act from the chemical laboratory to the semi-industrial level means first of all is choosing the most economic way of preparing a geopolymer matrix. During the five years of the cooperation between the scientific laboratory of the Academy of Sciences and the Czech Development Agency production unit, it has, among others, been found that the best result of the thermal treatment is when the layer of the material in the kiln is only 15-20 cm thick.
Both cooperating parties have also prepared matrixes from waste clay materials (e.g., clay washed out of a sandstone deposit and “white waters” from the porcelain industry) [8, 9]. To find the most economic way and assure the constant quality of the raw material was a major problem for both participants. The resulting issues of all these tests and proof have shown that the quality and utility of the product is the most important.
Even if the economy permits higher costs of material treatment, the principal question still to be resolved was a constant quality of the incoming clayed material. Once again, it should be mentioned that laboratory experience and industrial reality are two different things. Beside the manipulation and preparation of aqueous alkali solutions, there are differences in mixing devices, the treatment of cast products and their final elaboration-polishing. The presented article will
The experimental part at the industrial level starts with a selected and laboratory-proven raw material, kaolin from the Kaznejov deposit, West Bohemian Region (Czech Republic). Having gone through all the necessary beneficiation and resolved the problem with the recommended maximum layer by a special kiln furniture construction, the semi-production unit had to focus also on the kaolin particle size. The importance of the minimum clay particles was published in 2002 [2], and after the firing procedure a milling was applied.
The selection of the product, after all kinds of laboratory testing, was focused on the big countertops exploiting the wonderful behavior of the geopolymer matrix, encapsulation of a large amount of fillers and the possibility of coloring the matrix with inorganic additives. The combination of both was applied on the designed desks, where the effects of the different color layers in combination with glass and mirror shreds were used. The face board was polished by an ordinary stone polishing machine with a rotated head cooled by water. Despite the fact that there were three or four different material hardness’s (glass, mirror, stone and the geopolymer matrix), the surface was glittering with small colored particles of glass shreds and reflecting the light through the mirror particles. The thickness of the table was about 25 mm and 1000 × 500 mm in dimension while the weight exceeded 40 kilograms.
The advantage of this kaolin lies in its light white-yellowish color, but the preparation of the matrix with all the treatment work and other complications(mixing and casting difficulties owing to the low casting flow when filled) does not permit a future, truly industrial use.
Looking for a similar, lightly colored material for the matrix, a material generated from so-called “white waters” was later used. This specific clayed material is
exploitation of its very low viscosity when alkalized, it was possible to augment the quantities of the additives and choose their best proportions for a different type of usable product. The combination of this new quality of the matrix and previously tested composition with different types of fabrics opened a new field- highly filled thin tile. Apart from heavy countertop, it was now possible to produce very thin (3-7 mm) tiles in dimensions of 500 × 1,000 mm with the same effect of shining glass and mirror shreds incorporated into the light gray matrix.
On the one hand, this matrix permitted the production of decorative inset tiles and at the same time opened another door: The light, relatively thin (14mm thick) anti-fire protective plates made from three layers of sandwiched matrix, supported on the outside by fabrics and filled inside with a powdered-mica waste.
The combination of the fully filled geopolymer matrix with waste basalt in three different grain sizes and glass/mirror shreds converted the obtained composite into a well heat-conductive matter. There was then only a small step to find an electric cable and all the other electrical components and open a new production division, heat geopolymer panels with a shiny polished surface.
The results presented in Table 1 compare the chemical composition of all the above-mentioned materials tested for the semi-industrial unit operated by the Czech Development Agency. The comparative table demonstrates the difference in treatments, the first three were analyzed in the natural state and the last one with very low L.O.I. was thermally treated by a supplier. The analyses in oxides were recalculated from the results in the elements obtained by the XRF method. The industrially thermally treated material contains a small amount of organic matter (gray color of the supplied material), but when the L.O.I. was identified at a temperature of 1,000 °C with a ten-minute dwell,
The policy of the semi-industrial unit is not in the inspection and testing of the incoming materials but in the application of the one selected and exploits its behavior with respect to the demanded products. The most important part of the know-how comes in when the mixing of a huge amount of alkalized material starts with its filling (e.g., the time of mixing and the revolution of the mixing paddle) of different sorts of additives. Apart from that, an exceptional knowledge should be mentioned of how and from which material the molds in light of their resistance to alkalis and production turnover could be prepared. It means at the same time resolving the problem of separators and all kinds of mold maintenance (cleaning, stocking, etc.).
All this specific and very costly knowledge collected through the fabrication of countertops and thin large dimensioned tiles was applied on the preparative steps before the first heating panels were made.
The division of heating panels today represents the most complex knowledge of geopolymer application: How to prepare the best composite, how, when and which coloring agents should be added, how to apply the prepared mixture into the molds avoiding air bubbles even when the used mass is very viscose. The maintenance of the panel made and the hardening time before it could be polished differs from all laboratory knowledge and experience.
Fig. 1 shows a heating panel (600 mm × 900 mm ×65 mm) fabricated from a basalt/glass/mirror geopolymer composite.
This article clarifies important points in the processes of knowledge transfer between the chemical laboratory and industrial unit. The difficulties in material selection which could be resolved by a laboratory equipped with all facilities are not effective on the industrial level, where the energy and manpower costs must be very well judged. The product itself must be evaluated on the market by its high value added through its novelty and qualities. As shown, each fabricated product needs a specific technology timing, which in the case of heating panels is converted into real production know-how.
[11] T. Hanzlicek, M. Steinerova, P. Straka et al., Reinforcement of the terracotta sculpture by geopolymer composite, Materials and Design 30 (8) (2009) 3229-3234.
[12] I. Perna, T. Hanzlicek, M. Steinerova, P. Straka, Acoustic Absorption of geopolymer/sand mixtures, CeramicsSilikáty 53 (1) (2009) 48-51.
[13] T. Hanzlicek, I. Perna, The alumina-silicates in stabilization process in fluidized-bed ash, Ceramics-Silikáty 55 (1) (2011) 94-99.
[14] T. Hanzlicek, I. Perna, Thermal resistance of foamed fluidized bed ashes, Acta Geodynamica et Geomaterialia 8(2) (2011) 115-122.
[15] T. Hanzlicek, I. Perna Z. Ertl, The Influence of temperature and composition on modeled mortars, International Journal of Architectural Heritage 6 (2012) 359-372.