WO2011110965A1 - Humidity regulating material and production method thereof - Google Patents

Humidity regulating material and production method thereof Download PDF

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Publication number
WO2011110965A1
WO2011110965A1 PCT/IB2011/050672 IB2011050672W WO2011110965A1 WO 2011110965 A1 WO2011110965 A1 WO 2011110965A1 IB 2011050672 W IB2011050672 W IB 2011050672W WO 2011110965 A1 WO2011110965 A1 WO 2011110965A1
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Prior art keywords
humidity
humidity regulating
regulating material
production method
sepiolite
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PCT/IB2011/050672
Other languages
French (fr)
Inventor
Ferhat Kara
Gunes Korc
Alpagut Kara
Original Assignee
Seramik Arastirma Merkezi Anonim Sirketi
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Publication of WO2011110965A1 publication Critical patent/WO2011110965A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/042—Magnesium silicates, e.g. talc, sepiolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4591—Construction elements containing cleaning material, e.g. catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00267—Materials permeable to vapours or gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the present invention relates to a humidity regulating material and production method thereof which is used as a wall, ceiling coating material and controls the humidity of the environment wherein it is used and also eliminates offensive odors in the environment.
  • humidity regulation is the characteristic of condensing the moisture in capillary pores on material surface when the humidity ratio in air is high whereas releasing the condensed moisture to air when the humidity ratio in air is low.
  • Sepiolite which is one of the natural porous materials, is a clay mineral exhibiting adsorption - desorption characteristic owing to the fact that it has a high surface area and a large proportion of pore volume thereof is composed of pores under 50 nm. Therefore, natural sepiolite raw material exhibits high-humidity control characteristic by itself.
  • the material should be strengthened in order to produce wall/ceiling tile having humidity control characteristic from sepiolite raw material. Thus, heat treatments are applied at temperatures above 600°C.
  • US20010181134 discloses increasing decorativeness and staining resistance of humidity-controlling building material by glazing.
  • Humidity-adjusting granules in this fire proof, humidity-adjusting building material consist of hydraulic binding materials. These granules are one or several of diatomaceous earth, silica gel, zeolite, sepiolite, apataljite, calcium silicate, allophane materials.
  • hydraulic material is one or several of cement, slag, gypsum, calcium carbonate, magnesium carbonate and calcium silicate.
  • JP2004269282 discloses obtaining a material which has high humidity absorption-desorption performance, can be used as humidity control material, has excellent physical properties and structure stability.
  • JP2000110300 discloses obtaining a porous material which is obtained from natural materials, not easily affected by environmental conditions and capable of controlling the moisture. Sepiolite, slaked lime, natural reinforced fiber and water are treated at a certain temperature in order to form this material.
  • the objective of the present invention is to realize a humidity regulating material and production method thereof without need for carrying out heat treatment at high temperatures using sepiolite raw material by geopolymerization method.
  • Another objective of the present invention is to realize a humidity regulating material and production method thereof wherein natural humidity regulation characteristic of sepiolite is maintained to a great extent.
  • a further objective of the present invention is to realize a humidity regulating material and production method thereof having decorative feature by being coloured with inorganic pigments.
  • a still further objective of the present invention is to realize a humidity regulating material and production method thereof which is partially coated with frits melting at low temperature and humidity regulation characteristic of which is maintained.
  • a yet further objective of the present invention is to realize a humidity regulating material and production method thereof having sufficient strength for wall, ceiling applications using geopolymerization method.
  • Figure 1 is the process flowchart of production of humidity regulating material.
  • Figure 2 is the view of adsorption-desorption behaviors of humidity regulating material samples in cycles 5 and 9 at 40-80% relative humidity range.
  • Figure 3 is the view of adsorption-desorption behaviors of humidity regulating material samples in cycle 2 at 40-80% relative humidity range.
  • Figure 4 is the view of humidity regulation performance within relative humidity ranges varying at 40-50%, 40-60%, 40-70% and 40-80% ranges in cycle 4.
  • Figure 5 is the view of humidity regulation kinetic within range of 40-80% relative humidity of sepiolite + metakaoline + alkaline solution (SM-A) humidity regulating samples.
  • SM-A sepiolite + metakaoline + alkaline solution
  • alkaline solution obtained from sodium hydroxide (NaOH), potassium hydroxide (KOH) or sodium hydroxide/potassium hydroxide mixtures in ratios ranging between 10-90%) by weight and alkaline silicate (sodium and/or potassium silicate) solutions are used.
  • Alkaline solution which will be used in granulation are prepared by mixing these solutions (3).
  • the granules are kept in an indoor environment between 1-2 hours for humidity homogenization.
  • the granules then are shaped (5) with dry press.
  • Samples pressed from granule state to desired dimensions (5) and shaped by this means are subjected to heat treatment at room temperature (25 °C) within the temperature range of 250°C maximum in relative humidity environment of 80- 100% by being kept in time interval of 2-24 hours, i.e geopolymerization reaction occurs (6). Reaction time shortens as the temperature increases during geopolymerization (6).
  • Decoration is performed on the surface (8) so as to create decorative effect in SM- A humidity regulating products.
  • structure of the whole inventive material can be coloured (811) by making addition of inorganic colorant (pigment) to the starting compositions depending on desired color intensity.
  • colouring (811) can be performed only in surface by making addition of inorganic pigments to the geopolymer composition.
  • frits of alkaline/alkaline earth alumina borosilicate having characteristic of maturing at low temperature can be applied to the surfaces of the material partially (812). Frits of alkaline/alkaline earth alumina borosilicate are sintered at the surfaces of the materials at 650°C. After sintering, partial glazing (812) is performed on the surface. The glazing process is applied partially such that the surface will be coated approximately in the ratio of 70-90%. After glaze application, materials stated as humidity regulating SM-A650 are obtained by applying heat treatment at 650°C in order to melt the glaze and enable it to adhere to the surface.
  • humidity regulating material is obtained (7) having desired strength at low temperatures such as 25-250°C by applying geopolymerization method differently from tile production processes known in the state of the art.
  • sepiolite provides humidity regulating characteristic in the material produced.
  • Geopolymers are ceramic-like materials resulting from alkaline activation of reactive alumina silicates.
  • Alkaline activation is a process which is carried out by mixing alumina silicate based raw materials with alkaline solutions prepared in certain stochiometric ratios. Hardening reaction occurs upon the paste obtained is kept at a certain temperature and in a humidity-controlled environment.
  • Reaction product formed in the stated system is an amorphous alumina silicate mineral which is three dimensional and gel-like. The material which is formed depending on raw material selection and process conditions exhibits high compressive strength, high acid resistance, high heat resistance and low thermal conductivity.
  • metakaoline is used as alumina silicate source in the inventive production method (10).
  • Mole ratios of the oxides present at the material structure in the geopolymerization are: Si0 2 /Al 2 0 3 : 2-8, Na 2 0+K 2 0 /Si0 2 : 0,20-0,50, H 2 0/Na 2 0+K 2 0: 11-18, (Na 2 0,K 2 0)/Al 2 0 3 : 1-1,5.
  • mole ratios which are stated are prepared depending on metakaoline amount in the composition and the reactive alumina silicate amounts in the metakaoline.
  • SK-75-650 Mixture of 75% sepiolite + 25% clay was subjected to heat treatment for 5 min. at 650°C with 10°C/min. heating rate.
  • SK-50-650 Mixture of 50%> sepiolite + 50%> clay was subjected to heat treatment for 5 min. at 650°C with 10°C/min. heating rate.
  • SK-75-850 Mixture of 75 %> sepiolite + 25 %> clay was subjected to heat treatment for 5 min. at 850°C with 10°C/min. heating rate.
  • SK-50-850 Mixture of 50%> sepiolite + 50%> clay was subjected to heat treatment for 5 min. at 850°C with 10°C/min. heating rate.
  • SKF-20-850 Mixture of 75% sepiolite + 5% clay + 20% frit was subjected to heat treatment for 5 min. at 850°C with 10°C/min. heating rate.
  • Humidity regulating materials are produced in order that known conventional ceramic tile production methods and the inventive one are compared by preparing sepiolite and clay mixtures under conditions stated in the above codings. These materials were pressed in 5x10 cm dimensions and subjected to heat treatment at high temperatures such as 650 and 850°C. Consequently, SK-75-650 and SK-75- 850 coded samples were obtained. In addition, SKF-20-850 coded samples were obtained using frit in the ratio of 20% in the composition. Humidity regulating performances and strength values of the humidity regulating materials obtained were measured.
  • Humidity adsorption-desorption behavior of humidity regulating materials was carried out at a constant temperature of 25°C and changing humidity ratios in air conditioner (humidity). Humidity regulation performances of the materials were determined in the experiment. Each adsorption-desorption process realized at constant temperature of 25°C, time interval of 24 hours and within the range of 40% (low) to 80% (high) relative humidity is called as a "cycle”. Following processes were carried out respectively in the experimental study performed:
  • the samples were kept at 25°C and 40% (low) humidity medium for 24 hours and weight changes thereof were measured.
  • the samples were kept for 24 hours by setting the humidity device to 80%> relative humidity at 25°C again and adsorbed humidity amount was determined by measuring the sample weights.
  • the samples were kept for 24 hours by setting the humidity device to 40%> relative humidity at 25°C again and desorbed humidity amount was determined by measuring the sample weights.
  • Humidity regulation performances of the samples within the range of 40-80% relative humidity were determined by completing 5-10 cycles in the humidity device. (Table 4, Figure 2 and Figure 3).
  • Adsorption-desorption isotherms of the humidity regulating materials, natural sepiolite and a commercial product in the state of the art were obtained at 77K temperature and N 2 atmosphere in Autosorp-1 device.
  • BET method was used for surface area from adsorption-desorption isotherms and Monte-Carlo method for pore dimension and distribution. Values obtained by these methods are given in Table 3.
  • Humidity regulation characteristic of humidity regulating materials is provided by dimension and distribution of the pores present in the structure.
  • Surface area and pore volume of the material which is a humidity regulating material (SM-A) and treated at 650°C decrease significantly after geopolymerization process acting as inorganic binder and heat application.
  • pore volumes and meso-pore volumes between 2-10nm determining humidity regulation capacity are observed to be higher in proportion to the commercial product in SM-A and SM-A650 samples (Table 3).
  • Humidity adsorption-desorption behavior of the samples was measured in relative humidity medium of 40% and 80% at 24 hours intervals. Average adsorption and desorption amounts obtained after 9 cycles were determined for unit volume (Table 4).
  • Humidity regulation performance of the material (SM-A650) obtained after partial frit coating for decorative purpose and sintering at 650°C is in the value of 0,037g/cm 3 (Table-4 and Figure 2-3).
  • SM-A Blue Ceramic material coloured with blue
  • SM-A Pink Ceramic material coloured with pink
  • Adsorption-desorption values of the SM-A coded humidity regulating material at different relative humidity ranges are given in Table 5.
  • the amount of humidity adsorbed increases with increase in the relative humidity increases ( Figure 4).
  • SM-A 0,010 0,023 0,040 0,064 Three-point bending strength of the humidity regulating materials are given in Table 6.
  • 0,064 g/cm moisture is adsorbed on average when the inventive materials are kept for 24 hours in relative humidity medium of 80% ratio.
  • the humidity amount is decreased to 40% from 80% and kept for 24 hours the ceramic materials desorb the humidity that they have adsorbed (0,063 g/cm ) again (Table 5, Figure 4).
  • Humidity regulation kinetics of the SM-A materials are determined by making measurement at 24 hours intervals under same experimental conditions. Adsorption starts as soon as it is started to keep the inventive ceramic materials in 80% relative humidity medium and adsorb 80% of the humidity that they have adsorbed in 24 hours in first 8 hours. Whereas in 40%> relative humidity values, they desorb approximately 80% of the humidity that they have adsorbed in the first 4 hours ( Figure 5).
  • the inventive humidity regulating materials have characteristics such that they can control moisture content of the environment where they are located at especially highly-humid regions as wall and ceiling coating material in indoors.

Abstract

The present invention relates to a humidity regulating material and production method thereof which can be used as a wall, ceiling coating material and control the humidity of the environment wherein it is used and also eliminate offensive odors in the environment. The objective of the said invention is to obtain a humidity regulating material whereby there is no need for heat treatment at high temperature by geopolymerization method and thus natural humidity control characteristic of the sepiolite is maintained to a great extent and has sufficient strength for applications. The material can gain decorative feature by being coloured with inorganic pigments or partially coated with frits melting at low temperature.

Description

HUMIDITY REGULATING MATERIAL AND PRODUCTION METHOD
THEREOF
Field of the Invention
The present invention relates to a humidity regulating material and production method thereof which is used as a wall, ceiling coating material and controls the humidity of the environment wherein it is used and also eliminates offensive odors in the environment.
Background of the Invention
In ceramic materials, humidity regulation is the characteristic of condensing the moisture in capillary pores on material surface when the humidity ratio in air is high whereas releasing the condensed moisture to air when the humidity ratio in air is low.
Sepiolite, which is one of the natural porous materials, is a clay mineral exhibiting adsorption - desorption characteristic owing to the fact that it has a high surface area and a large proportion of pore volume thereof is composed of pores under 50 nm. Therefore, natural sepiolite raw material exhibits high-humidity control characteristic by itself. The material should be strengthened in order to produce wall/ceiling tile having humidity control characteristic from sepiolite raw material. Thus, heat treatments are applied at temperatures above 600°C.
In the United States patent document no. US6472061 it is stated that sepiolite maintains its humidity control characteristic and has sufficient strength for applications after heat treatment at high temperatures such as 650-850°C, by being mixed with clay or glass binders. The United States patent document no. US2002031656 discloses obtaining a building material which adsorbs hazardous substances, has decorative feature and high resistance to staining.
The United States patent document no. US20010181134 discloses increasing decorativeness and staining resistance of humidity-controlling building material by glazing.
The Japanese patent document no. JP2002293600 discloses obtaining a fire proof and humidity-adjusting, by absorbing and desorbing moisture, building material. Humidity-adjusting granules in this fire proof, humidity-adjusting building material consist of hydraulic binding materials. These granules are one or several of diatomaceous earth, silica gel, zeolite, sepiolite, apataljite, calcium silicate, allophane materials. Whereas hydraulic material is one or several of cement, slag, gypsum, calcium carbonate, magnesium carbonate and calcium silicate.
The Japanese patent document no. JP2004269282 discloses obtaining a material which has high humidity absorption-desorption performance, can be used as humidity control material, has excellent physical properties and structure stability.
The Japanese patent document no. JP2000110300 discloses obtaining a porous material which is obtained from natural materials, not easily affected by environmental conditions and capable of controlling the moisture. Sepiolite, slaked lime, natural reinforced fiber and water are treated at a certain temperature in order to form this material.
In the state of the art, geopolymerization method is widely used in building material production. However, production of resistant material by maintaining humidity control characteristic of sepiolite clay mineral in this method is not present in the state of the art. Summary of the Invention
The objective of the present invention is to realize a humidity regulating material and production method thereof without need for carrying out heat treatment at high temperatures using sepiolite raw material by geopolymerization method.
Another objective of the present invention is to realize a humidity regulating material and production method thereof wherein natural humidity regulation characteristic of sepiolite is maintained to a great extent.
A further objective of the present invention is to realize a humidity regulating material and production method thereof having decorative feature by being coloured with inorganic pigments.
A still further objective of the present invention is to realize a humidity regulating material and production method thereof which is partially coated with frits melting at low temperature and humidity regulation characteristic of which is maintained.
A yet further objective of the present invention is to realize a humidity regulating material and production method thereof having sufficient strength for wall, ceiling applications using geopolymerization method.
Detailed Description of the Invention
The inventive "humidity regulating material and production method thereof realized to fulfill the objective of the present invention is illustrated in the accompanying figures, in which:
Figure 1 is the process flowchart of production of humidity regulating material. Figure 2 is the view of adsorption-desorption behaviors of humidity regulating material samples in cycles 5 and 9 at 40-80% relative humidity range.
Figure 3 is the view of adsorption-desorption behaviors of humidity regulating material samples in cycle 2 at 40-80% relative humidity range.
Figure 4 is the view of humidity regulation performance within relative humidity ranges varying at 40-50%, 40-60%, 40-70% and 40-80% ranges in cycle 4.
Figure 5 is the view of humidity regulation kinetic within range of 40-80% relative humidity of sepiolite + metakaoline + alkaline solution (SM-A) humidity regulating samples.
The production steps of the humidity regulating material and production method thereof realized to fulfill the objective of the present invention are numbered step by step and the parts of the product are numbered individually, where the numbers refer to the following:
10. Humidity regulating material and production method thereof
1. Mixing starting powders
2. Grinding and homogenization
3. Preparation of alkaline solution
4. Obtaining granule via dry granulation
5. Shaping (pressing)
6. Heat treatment humidity-controlled environment (geopolymerization)
7. Obtaining humidity regulating material
8. Decoration process
811. Colouring
812. Partial glaze application In the inventive humidity regulating material and production method thereof (10), natural sepiolite which is humidity regulating main constituent and alumina silicate powder are used as starting powders. Alumina silicates such as metakaoline, meta-clays, fly ash, slag are especially preferred for geopolymerization. Reactive alumina silicate powder and natural sepiolite that can provide geopolymerization reaction are mixed (1). Sepiolite in the ratio of 50-90% by weight and reactive alumina silicate in the ratio of 50-10% by weight are used for mixture.
Grinding and homogenization are carried out (2) in order that the mixed powders are brought into a certain dimension and there is powder having same characteristic in every part of the powder mixture.
On the other hand, in preparation of alkaline solution; alkaline solution obtained from sodium hydroxide (NaOH), potassium hydroxide (KOH) or sodium hydroxide/potassium hydroxide mixtures in ratios ranging between 10-90%) by weight and alkaline silicate (sodium and/or potassium silicate) solutions are used. Alkaline solution which will be used in granulation are prepared by mixing these solutions (3).
By spraying alkaline solution onto the mixture obtained after powder mixing (1), grinding and homogenization (2) processes, it both mixed and granule is obtained (4). Granules obtained after granulation (4), which is a process of turning into granule, are sieved through a sieve of 1mm.
The granules are kept in an indoor environment between 1-2 hours for humidity homogenization. The granules then are shaped (5) with dry press.
Samples pressed from granule state to desired dimensions (5) and shaped by this means are subjected to heat treatment at room temperature (25 °C) within the temperature range of 250°C maximum in relative humidity environment of 80- 100% by being kept in time interval of 2-24 hours, i.e geopolymerization reaction occurs (6). Reaction time shortens as the temperature increases during geopolymerization (6).
After geopolymerization process, humidity regulating material is obtained (7). In order that this material stated as SM-A (sepiolite + metakaoline + alkaline solution) is used in applications, its strength should be high enough.
Decoration is performed on the surface (8) so as to create decorative effect in SM- A humidity regulating products.
In an embodiment of decorating (8), structure of the whole inventive material can be coloured (811) by making addition of inorganic colorant (pigment) to the starting compositions depending on desired color intensity.
Apart from that, colouring (811) can be performed only in surface by making addition of inorganic pigments to the geopolymer composition.
Whereas in another embodiment of decoration (8), frits of alkaline/alkaline earth alumina borosilicate having characteristic of maturing at low temperature can be applied to the surfaces of the material partially (812). Frits of alkaline/alkaline earth alumina borosilicate are sintered at the surfaces of the materials at 650°C. After sintering, partial glazing (812) is performed on the surface. The glazing process is applied partially such that the surface will be coated approximately in the ratio of 70-90%. After glaze application, materials stated as humidity regulating SM-A650 are obtained by applying heat treatment at 650°C in order to melt the glaze and enable it to adhere to the surface.
In production of the inventive humidity regulating materials (10), humidity regulating material is obtained (7) having desired strength at low temperatures such as 25-250°C by applying geopolymerization method differently from tile production processes known in the state of the art. In production (10), sepiolite provides humidity regulating characteristic in the material produced.
Geopolymers are ceramic-like materials resulting from alkaline activation of reactive alumina silicates. Alkaline activation is a process which is carried out by mixing alumina silicate based raw materials with alkaline solutions prepared in certain stochiometric ratios. Hardening reaction occurs upon the paste obtained is kept at a certain temperature and in a humidity-controlled environment. Reaction product formed in the stated system is an amorphous alumina silicate mineral which is three dimensional and gel-like. The material which is formed depending on raw material selection and process conditions exhibits high compressive strength, high acid resistance, high heat resistance and low thermal conductivity.
Preferably metakaoline is used as alumina silicate source in the inventive production method (10). Mole ratios of the oxides present at the material structure in the geopolymerization are: Si02/Al203: 2-8, Na20+K20 /Si02: 0,20-0,50, H20/Na20+K20: 11-18, (Na20,K20)/Al203: 1-1,5. In the method (10), considering that the reactive silicon and the aluminum in the composition come from metakaoline, mole ratios which are stated are prepared depending on metakaoline amount in the composition and the reactive alumina silicate amounts in the metakaoline.
Experimental Study
In experimental study, some experiments were carried out in terms of firstly comparing samples which are produced using in the state of the art method (prior art) and the products which are obtained by the inventive method.
Materials to be used in the experiment ant their codings are as follows: SK-75-650 : Mixture of 75% sepiolite + 25% clay was subjected to heat treatment for 5 min. at 650°C with 10°C/min. heating rate.
SK-50-650 : Mixture of 50%> sepiolite + 50%> clay was subjected to heat treatment for 5 min. at 650°C with 10°C/min. heating rate.
SK-75-850 : Mixture of 75 %> sepiolite + 25 %> clay was subjected to heat treatment for 5 min. at 850°C with 10°C/min. heating rate.
SK-50-850 : Mixture of 50%> sepiolite + 50%> clay was subjected to heat treatment for 5 min. at 850°C with 10°C/min. heating rate.
SKF-20-850 : Mixture of 75% sepiolite + 5% clay + 20% frit was subjected to heat treatment for 5 min. at 850°C with 10°C/min. heating rate.
Humidity regulating materials are produced in order that known conventional ceramic tile production methods and the inventive one are compared by preparing sepiolite and clay mixtures under conditions stated in the above codings. These materials were pressed in 5x10 cm dimensions and subjected to heat treatment at high temperatures such as 650 and 850°C. Consequently, SK-75-650 and SK-75- 850 coded samples were obtained. In addition, SKF-20-850 coded samples were obtained using frit in the ratio of 20% in the composition. Humidity regulating performances and strength values of the humidity regulating materials obtained were measured.
When the test results were examined it is seen that adsorption and desorption amounts in materials produced by conventional ceramic tile production method (prior art) and obtained after heat treatment at high temperature are substantially decreased in comparison to natural sepiolite mineral (Table 1). Except for the frit- applied samples, strength of all other samples remained at low levels. It is not possible to use the material obtained with these strength values in practice (Table 2). Although sufficient strength is obtained for frit-applied samples it is observed that humidity regulation performance is low (Table 1 and Table 2). In addition, surface decoration was not applied to the said samples. After surface decoration process, humidity control values are expected to fall to some extent. In the experiments, it is observed that the moisture regulation performance of sepiolite is not utilized effectively in this method.
Table 1. Humidity regulation capacity of sepiolite-clay mixtures produced by conventional ceramic tile production method (prior art) and subjected to heat treatment at 650°C and 850°C
Figure imgf000011_0001
Table 2. Strength values of sepiolite-clay mixtures produced by conventional ceramic tile production method (prior art) and subjected to heat treatment at 650°C and 850°C
Samples Three-point bending strength
(N/mm2)
SK-75-650 0,98
SK-75-850 2,14
SK-50-650 0,84
SK-50-850 1,74
SKF-20-850 6,84
Humidity adsorption-desorption behavior of humidity regulating materials was carried out at a constant temperature of 25°C and changing humidity ratios in air conditioner (humidity). Humidity regulation performances of the materials were determined in the experiment. Each adsorption-desorption process realized at constant temperature of 25°C, time interval of 24 hours and within the range of 40% (low) to 80% (high) relative humidity is called as a "cycle". Following processes were carried out respectively in the experimental study performed:
Firstly, the samples were kept at 25°C and 40% (low) humidity medium for 24 hours and weight changes thereof were measured.
The samples were kept for 24 hours by setting the humidity device to 80%> relative humidity at 25°C again and adsorbed humidity amount was determined by measuring the sample weights.
The samples were kept for 24 hours by setting the humidity device to 40%> relative humidity at 25°C again and desorbed humidity amount was determined by measuring the sample weights.
Humidity regulation performances of the samples within the range of 40-80% relative humidity were determined by completing 5-10 cycles in the humidity device. (Table 4, Figure 2 and Figure 3).
By measuring humidity adsorption-desorption amounts of SM-A and commercial product (known product) at the same time and different humidity ranges, their humidity regulation performances were determined under similar experimental conditions.
It is aimed to keep adsorption-desorption amount and behavior of natural sepiolite mineral and develop a material having high humidity regulation performance in the inventive humidity regulating material production (10). In order to realize this, geopolymerization technique was used. Thus, sufficient strength value is obtained for practical applications and humidity regulation performance of the sepiolite is kept since high temperature was not applied.
Adsorption-desorption isotherms of the humidity regulating materials, natural sepiolite and a commercial product in the state of the art were obtained at 77K temperature and N2 atmosphere in Autosorp-1 device. BET method was used for surface area from adsorption-desorption isotherms and Monte-Carlo method for pore dimension and distribution. Values obtained by these methods are given in Table 3.
Humidity regulation characteristic of humidity regulating materials is provided by dimension and distribution of the pores present in the structure. Surface area and pore volume of the material which is a humidity regulating material (SM-A) and treated at 650°C decrease significantly after geopolymerization process acting as inorganic binder and heat application. Whereas pore volumes and meso-pore volumes between 2-10nm determining humidity regulation capacity are observed to be higher in proportion to the commercial product in SM-A and SM-A650 samples (Table 3).
Table 3. BET surface area and pore volume distribution
Total pore
Surface area Meso pores Micro pores Pores volume
(m2/gr) (2-50nm) (0-2nm) 2-10 nm
(cm3/gr)
Sepiolite 369,6 0,6411 0,55 0,066 0,137
SM-A 98,33 0,2666 0,21 0,011 0,051
SM-A650 54,94 0,2084 0,19 0,0002 0,035
Commercial
32,60 0,0878 0,071 0,0 0,033 Product
SM-A Humidity regulating material
Humidity regulating material subjected to heat treatment at SM-A650 °C
Humidity adsorption-desorption behavior of the samples was measured in relative humidity medium of 40% and 80% at 24 hours intervals. Average adsorption and desorption amounts obtained after 9 cycles were determined for unit volume (Table 4).
It is seen that humidity regulating performances of the inventive SM-A coded humidity regulating material and the decorative SM-A humidity regulating materials coloured with blue and pink colors in the ratio of 5% are approximately the same with natural sepiolite mineral (0,063gr/cm ). Humidity regulation performance of the material (SM-A650) obtained after partial frit coating for decorative purpose and sintering at 650°C is in the value of 0,037g/cm3 (Table-4 and Figure 2-3).
Table 4. Adsorption-desorption behavior of the samples at 40-80% relative humidity
Figure imgf000014_0001
Commercial Product 0,015 0,014
SM-A Blue: Ceramic material coloured with blue
SM-A Pink: Ceramic material coloured with pink
Adsorption-desorption values of the SM-A coded humidity regulating material at different relative humidity ranges are given in Table 5. The amount of humidity adsorbed increases with increase in the relative humidity increases (Figure 4).
Table 5. Humidity regulation performance at different relative humidity ranges
Adsorption-Desorption (g/cm3)
Sample 40-50% 40-60% 40-70% 40-80%RH
SM-A 0,010 0,023 0,040 0,064 Three-point bending strength of the humidity regulating materials are given in Table 6. Strength values of the SM-A which is produced by geopolymerization technique and colored by pigment additions, and the SM-A650 coded humidity regulating materials which are glaze-applied and subjected to heat treatment at 650°C change between 7-14MPa depending on preparation conditions and microstructure homogeneity (Table 6). The obtained strength values are sufficient for wall/ceiling applications.
Table 6. Strength values of the humidity regulating materials
Figure imgf000015_0001
Commercial Product 5-8
0,064 g/cm moisture is adsorbed on average when the inventive materials are kept for 24 hours in relative humidity medium of 80% ratio. When the humidity amount is decreased to 40% from 80% and kept for 24 hours the ceramic materials desorb the humidity that they have adsorbed (0,063 g/cm ) again (Table 5, Figure 4).
Humidity regulation kinetics of the SM-A materials are determined by making measurement at 24 hours intervals under same experimental conditions. Adsorption starts as soon as it is started to keep the inventive ceramic materials in 80% relative humidity medium and adsorb 80% of the humidity that they have adsorbed in 24 hours in first 8 hours. Whereas in 40%> relative humidity values, they desorb approximately 80% of the humidity that they have adsorbed in the first 4 hours (Figure 5). The inventive humidity regulating materials have characteristics such that they can control moisture content of the environment where they are located at especially highly-humid regions as wall and ceiling coating material in indoors.
Within the framework of these basic concepts, it is possible to develop a wide variety of embodiments of the inventive "humidity regulating material and production method thereof. The invention cannot be limited to the examples described herein; it is essentially according to the claims.

Claims

1. A humidity regulating material and production method thereof (1) characterized by steps of:
- mixing starting powders (1),
grinding and homogenization (2),
preparation of alkaline solution (3),
obtaining granule via dry granulation (4),
shaping (pressing) (5),
heat treatment in humidity-controlled environment (geopolymerization) (6),
obtaining humidity regulating material (7),
decoration process (8),
colouring (811),
partial glaze application (812).
2. A humidity regulating material and production method thereof (1) according to Claim 1, characterized by sepiolite in the ratio of 50-90% by weight and reactive alumina silicate in the ratio of 50-10% by weight in step of mixing starting powders (1).
3. A humidity regulating material and production method thereof (1) according to Claim 1 to 2, characterized by metakaoline, meta-clays, fly ash, slag as alumina silicate source.
4. A humidity regulating material and production method thereof (1) according to Claim 1 to 3, characterized in that alkaline solution is used in step of obtaining granule via dry granulation (4).
5. A humidity regulating material and production method thereof (6) according to Claim 1 to 4, characterized by 25-250°C, 80-100% relative humidity, keeping in time interval of 2-24 hours.
6. A humidity regulating material and production method thereof (1) according to Claim 1 to 5, characterized by mole ratios of Si02/Al203: 2-8, Na20+K20 /Si02: 0,20-0,50, H20/Na20+K20: 11-18, (Na20,K20)/Al203: 1-1,5 in composition geopolymerization (6).
7. A humidity regulating material which is produced according to any of the above steps.
8. A humidity regulating material according to Claim 7, which is used as wall and ceiling coating material at highly-humid regions in indoors.
PCT/IB2011/050672 2010-03-11 2011-02-17 Humidity regulating material and production method thereof WO2011110965A1 (en)

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WO2022005432A1 (en) * 2020-07-02 2022-01-06 Kaleserami̇k Çanakkale Kalebodur Serami̇k Sanayi̇ Anoni̇m Şi̇rketi̇ Moisture regulating material and production method thereof

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