CN1167640C - Microcrystalline foam glass wall material and its preparation method - Google Patents

Abstract

The present invention discloses a wall material of microcrystal foam glass. The present invention is characterized in that the wall material of microcrystal foam glass comprises glass powder, pulverized coal ash and nonmetal minerals, wherein the particle size d(0.9) of the glass powder is smaller than 130 meshes, the particle size d(0.9) of the pulverized coal ash is smaller than 120 meshes, and the particle size d(0.9) of the nonmetal minerals is smaller than 230 meshes. A preparation method of the present invention comprises: the glass powder, the pulverized coal ash and nonmetal mineral powder which are milled are mixed after water is added in, are baked after being shaped by pressing under the condition of containing water, and are fired in a kiln; the fired blanks are shaped by cutting. The present invention has the advantages that the wall material of microcrystal foam glass contains no clay, has superior performance than aeroconcrete with the same volume density, and conforms to the technological process of industrialized mass production. The pilot production of the wall material of microcrystal foam glass is performed in a factory scale, and continuous heating curve technology with constant speed of the wall material of microcrystal foam glass can be completely adapted to the requirement of industrialized continuous mass production.

Description

Microcrystalline foam glass wall material and its preparation method

1. Technical field

The invention relates to a wall material, in particular to a glass-ceramic foam glass wall material between glass-ceramics and foam glass in terms of structure and performance and a preparation method thereof.

2. Background technology

The research, development and application of various glass-ceramics in the world have a history of at least 50 years. The domestic research has begun since the 1980s, and some products have come out. Glass-ceramics has high density (≥2700kg/m ³ ), corrosion resistance, wear resistance, non-conductivity, non-magnetism, and high mechanical strength. It is widely used in non-construction industries. When made into a thin sheet with a smooth surface, it is mainly used as a decorative veneer material, which is expensive.

Foam glass has been developed abroad since the 1930s, and it has been introduced and developed domestically since the late 1980s. It uses finely ground glass powder as the main raw material, adds a foaming agent, and is processed by melting and foaming, annealing and cooling. It has an independent bubble structure, a small bulk density, and a small thermal conductivity. It is 0.052w/m.k at room temperature. Good thermal insulation, but low compressive strength (average 0.7Mpa) and low flexural strength (average 0.5Mpa), so it is mainly used as a thermal insulation component of composite wall materials.

3. Contents of the invention

1. Purpose of the invention: The purpose of the present invention is to utilize the advantages of high mechanical strength of glass-ceramic, light foam glass, good thermal insulation, heat insulation and sound-absorbing performance; to propose a non-clay, waste-saving, energy-saving micro-ceramic foam glass that is environmentally friendly Type wall materials and their preparation methods.

2. Technical scheme: in order to achieve the above object, the microcrystalline cellular glass wall material of the present invention is characterized in that its components are glass powder, fly ash and non-metallic minerals, and the particle size d (0.9) of the glass powder is less than 130 mesh, the particle size d(0.9) of fly ash is less than 120 mesh, and the particle size d(0.9) of non-metallic ore is less than 230. The total proportion (% by weight) of glass powder and fly ash is 90-97%, and that of non-metallic minerals is 3-10%.

In the mixture of glass powder and fly ash, the proportioning (weight %) of main oxide is:

SiO ₀ : 62.43-76.80, Al ₂ O ₃ : 5.41-10.55, CaO: 5.43-14.89, MgO: 1.64-3.75, FeO+Fe ₂ O ₃ : 0.75-3.30, Na ₂ O+K ₂ O : 9.20-14.95 .

The non-metallic mineral is one or more of alkaline feldspar, silica sand, wollastonite, soda ash (Na ₂ CO ₃ ) and calcite. The weight ratio (%) of the alkaline feldspar is 1-5%, that of the calcite is 1-2%, that of the wollastonite is 1-2%, and that of the soda ash is 1-5%.

The glass powder is tempered glass powder, plate glass powder or beer bottle glass powder.

The preparation method of microcrystalline cellular glass wall material of the present invention is characterized in that:

1) Mix the ground glass powder, fly ash and non-metallic ore powder into water;

2) Pressing and molding under the condition of containing moisture, and then drying;

3) put into kiln and burn;

4) Cutting the fired blank into shape. In the second step, the moisture content (weight %) is 6-8%. In the third step firing process, the heating rate in the kiln is 1-5°C/min, and the temperature is lowered to 915-925°C , the cooling rate is the same as the heating rate, and it is naturally cooled after reaching 400 °C.

The main raw materials of the new wall material of microcrystalline foam glass are cullet, fly ash, and non-metallic ore. After grinding, mixing and adding foaming agent, sintering and foaming, it is made into a porous and microcrystalline reinforced glass with independent bubble structure. The foam glass material, that is, a glass crystal interweaving structure composed of a large number of interwoven wollastonite, soda wollastonite and acicular crystals in a glassy matrix, increases the strength and toughness of the material. According to the changes in the composition and content of the added fly ash and non-metallic minerals, the density, thermal conductivity, and mechanical strength of the microcrystalline foam glass body are in a relationship of mutual growth and decline, thus becoming the corresponding building materials that can be used in different parts of the wall.

The raw materials of glass-ceramic foam glass mainly include broken glass powder and fly ash, followed by alkaline feldspar (potassium feldspar, albite), silica sand, wollastonite, soda ash (Na ₂ CO ₃ ) and calcite. The cullet and fly ash account for more than 90%wt of the total weight of the raw materials. The particle size of the cullet is preferably d(0.9)=130-250 mesh, and the particle size of the power plant fly ash is d(0.9)=120-150 mesh. It can be used directly, and the particle size of other raw materials is d(0.9)=230-325 mesh.

Glass powder can be processed and ground into powder by tempered glass, flat glass and beer bottle glass waste. Its chemical composition is shown in Table 1. Among them, the chemical composition of wine bottle glass varies greatly with different types of wine bottles. When preparing the raw materials of microcrystalline foam glass, it is necessary to adjust the composition according to the tempered glass or flat glass that has successfully made the product, and adjust the composition by changing the amount of other components. Positive, such as appropriate addition and subtraction of silicon powder and alkali, etc.

Table 1 Chemical composition of various glass powders sample name Famous tempered glass plate glass beer bottle glass SiO ₂ 69.50 70.88 69.86 69.90 70.40 71.37 68.39 TiO ₂ 0.02 0.02 0.03 0.01 0.05 0.07 Al ₂ O ₃ 2.24 2.24 2.58 2.59 2.21 1.43 4.22 _{Fe2O3 _} 0.18 0.26 0.30 0.31 T0.18 0.14 T0.41 FeO 0.15 0.08 0.04 0.09 MnO 0.01 0.01 0.01 0.01 0.01 0.02 MgO 3.47 3.43 3.57 3.57 3.35 3.67 1.96 CaO 8.49 8.49 8.27 8.14 8.19 7.70 8.08 Na ₂ O 11.38 11.15 11.10 11.38 13.69 }13.98 13.10 K ₂ O 2.72 2.82 2.97 3.02 0.80 1.31 P ₂ O ₅ 0.10 0.10 0.08 0.07 0.01 Trace Loss on ignition 1.21 0.44 0.54 0.29 0.92 1.02 sum 99.47 99.92 99.35 99.38 99.81 98.29 98.58

The particle size of power plant fly ash can generally be used directly, and its composition also varies with the composition of raw coal. The chemical composition of the fly ash used in the microceramic foam glass we have successfully produced is shown in Table 2. If other power plant fly ash is used, it needs to be used accordingly. The success criteria are adjusted and standardized. The fly ash used to make the product needs to be radioactively tested to see if it meets environmental protection standards, because the radioactive content of the finished product mainly comes from coal mines.

The combination of silica sand, alkaline feldspar, calcite and soda ash Na ₂ CO ₃ can increase the amount of synthetic glass in the matrix of microcrystalline foam glass, thereby increasing the number of closed pores of the product and increasing the mechanical strength of the product.

When using silica sand, alkaline feldspar, calcite and soda ash _Na2CO3 , the content of glass powder and fly ash _should be appropriately reduced to balance the chemical composition. The amount of feldspar and soda ash is 1-5%, and the amount of calcite is 1-2%. It is matched with an appropriate amount of silica sand to replace the corresponding component quantity of glass powder + fly ash.

Table 2 Chemical composition of fly ash sample 2A 3A 4A 5A L-1 SiO ₂ 44.84 45.12 47.74 47.59 56.01 TiO ₂ 0.89 1.11 1.11 0.98 Al ₂ O ₃ 26.37 25.58 26.05 26.50 29.62 _{Fe2O3 _} 2.11 2.46 1.79 2.52 }4.56 FeO 1.16 0.91 1.00 0.58 MnO 0.02 0.04 0.04 0.03 MgO 0.86 0.74 0.72 0.77 0.92 CaO 15.07 14.49 13.64 13.58 2.92 Na ₂ O 0.46 0.48 0.48 0.47 }1.31 K ₂ O 0.89 0.96 0.96 0.93 P ₂ O ₅ 0.17 0.24 0.21 0.20 Loss on ignition 6.48 7.20 5.69 5.16 sum 99.32 99.33 99.43 99.31

The chemical compositions of silica sand, feldspar and calcite are shown in Table 3.

Table 3 Chemical composition of other non-metallic mineral raw materials raw material name silica sand Potassium feldspar Calcite SiO ₂ 99.14 99.10 64.64 72.52 0.00 TiO ₂ 0.02 0.00 0.00 _Al2O3 0.21 0.21 13.43 15.21 0.32 _{Fe2O3 _} 0.00 0.18 0.09 0.04 0.03 FeO 0.04 0.11 0.07 MnO 0.01 0.02 0.00 MgO 0.00 0.00 0.10 0.00 0.20 CaO 0.00 0.08 6.51 0.30 55.52 Na ₂ O 0.00 }0.36 2.64 } 11.22 0.00 K ₂ O 0.06 7.02 0.07 P ₂ O ₅ 0.05 0.06 0.04 Loss on ignition 0.17 5.10 43.45 sum 99.78 99.72 99.70

In addition to acting as a flux, soda ash also has a foaming effect. It decomposes at about 850 ° C to produce gas CO ₂ , and its Na ₂ O component is composed of nascent crystals, soda wollastonite and nascent glass. Calcite decomposes at 800-920°C to generate gas CO ₂ , so it is the main foaming agent of the product of the present invention (heating > 900°C), and the CaO formed by its decomposition is also a component of nascent glass.

The dosage of wollastonite is 1-2%, which mainly plays the role of promoting crystallization and microcrystalline strengthening. Glass powder, fly ash, wollastonite, soda Na ₂ CO ₃ , calcite, or glass powder, fly ash, (alkaline feldspar + silica sand + soda ash), wollastonite, calcite and other raw materials are mechanically mixed Evenly, under the condition of water content of 6-8%, press molding, after drying, enter the kiln for roasting, after foaming and sintering, cut and shape, and then make finished bricks.

According to the above-mentioned components (multiple formulations can be formed) and production methods, a variety of glass-ceramic foam products can be obtained. Among them, lightness and strength are a pair of contradictions in the relationship of mutual depletion. When the amount of fly ash or (silica sand + feldspar + alkali) is increased in the composition, and the amount of glass powder is reduced, the strength and bulk density will increase. The main physical properties of the foamed glass-ceramics obtained by the present invention are compared with those of relevant wall materials as shown in Table 4 and Table 5.

Table 4 Comparison of the physical and chemical properties of microfoam glass wall materials and similar products Product name Product density (kg/m ³ ) Cubic compressive strength (MPa) Flexural strength (MPa) Thermal conductivity (w/m·k) Freeze Resistance (15 charges) Drying shrinkage(mm/M) Operating temperature °C Microcrystalline cellular glass type I type II sample 433-451 average 411 average 750 3.5-4.1 average 3.890-17.0 average 10.7 2.0 0.137-0.139 After freezing, the strength is 3.0MPa and the mass loss is 0.7%. 0.05 >900 Autoclaved aerated concrete (GB/T11968-1997) 400500600700 Average≥2.0≥2.5-3.5≥3.5-5.0≥5.0-7.5 0.120.140.16/ 1.6MPa2.0MPa2.8MPa mass loss after freezing≤5.0 0.80 Not resistant to high temperature Autoclaved aerated concrete (Nanjing Jiantong) 547 2.7 0.12 2.7MPa after freezing 0.70 Foam glass (Wall Material Manual 2001.6) 130-160 Average 0.7 0.052 <430 Aerated Glass, Foam Glass(545) 300-500 0.116-0.163 Foam Concrete (Wall Material Handbook 2001.6) 300-1000 0.7-3.5 0.07-0.15 antifreeze 0.6-1.0 Foam Concrete(547) 400-800 0.151-0.291 Sintered hollow brick (handbook of wall materials 2001.6) 800-1100 Large noodles 2.0-5.0 noodles 1.6-3.4 23 hole brick 0.3825 hole brick 0.51 Various hollow bricks 1000-1500 0.465-0.64 ordinary brick 1800-1900 MU10 Average 10.0 pumice 1000 0.372

Table 5 Comparison of sound absorption and sound insulation performance between microcrystalline foam glass wall materials and similar products material name Thickness cm Sound absorption coefficient (when the frequency is below Hz) Sound insulation performance 125 250 500 1000 2000 4000 Remark 100-3150Hz Microcrystalline foam glass (reverberation chamber method) GBJ47-83 5.5 0.24 0.55 0.70 0.66 0.69 0.70 100-5000Hz average 0.61 Average sound insulation 39.1dB (wall thickness 13cm) Autoclaved Aerated Concrete(307) Average 38.8-43dB (wall thickness 7.5-15cm) Brick (clear water surface)(551) / 0.02 0.03 0.04 0.04 0.05 0.05 On concrete (Luming)(551) / 0.35 0.25 0.18 0.12 0.02 0.04 Foam cement (close to the wall) 5 0.32 0.39 0.48 0.49 0.47 0.54 Foam Glass(552) 5.3 0.23 0.69 0.57 0.46 0.49 0.55 board 2 0.16 0.15 0.10 0.10 0.10 0.10

3. Beneficial effects: Compared with the prior art, the present invention has the remarkable advantages of:

(1) Does not contain any clay. The "Tenth Five-Year Plan" of the national building materials industry pointed out that in 170 large and medium-sized cities, the use of solid clay bricks is completely prohibited within a transition period of 3 years. Wall materials should focus on the development of non-clay hollow products, concrete blocks, etc. Focus on the development of aerated concrete block production lines with an annual output of 100,000 to 200,000 m ³ , the production line of sintered hollow bricks with an annual output of more than 60 million pieces, and promote the new technology of high permeability of waste slag. Even so, due to the weak historical foundation, by 2005 it was only possible to reduce the annual land consumption from 660,000 mu in 2001 to 460,000 mu. Because hollow clay bricks still use a large amount of clay, and most parts of the country cannot ban the use of clay solid bricks. And the present invention can not use clay.

(2) It has better performance than air-entrained concrete with the same bulk density. The "Tenth Five-Year Plan" mentioned that the focus should be on the development of autoclaved aerated concrete block production lines. And the microcrystalline foam glass wall body material produced by the present invention, under the same volume density condition, index such as mechanical property is obviously better than air-entrained concrete. The product of the present invention has a similar application to the air-entrained concrete. That is, a lightweight, insulating, sound-absorbing wall material, but with better performance.

my country started research on air-entrained concrete in 1958, carried out industrial tests and applications in 1963, and introduced a complete set of technology and equipment from the Swedish Siporex company in 1965, and then successively introduced them from Poland, Romania, Germany, and Japan. Key technologies and equipment. By 1999, about 200 aerated concrete production lines had been established. Up to now, the overall technical level is still very low, and the qualification rate of the whole product is not high. It mainly produces aerated concrete blocks with a compressive strength of 2.5Mpa to 3.5Mpa.

The microcrystalline foam glass wall material produced by the invention can already produce products with a compressive strength of 3.5Mpa to 17Mpa.

(3) It conforms to the technological process of industrialized mass production. The present invention has been produced in a factory scale pilot test. Its continuous and uniform heating curve technology fully meets the needs of industrialized continuous mass production.

4. Specific implementation

Embodiment 1: The main raw material is a mixture of glass powder and fly ash accounting for more than 90%wt of the total weight. The weight percentage of each oxide in its chemical composition is SiO ₂ 66.24, TiO ₂ 0.18, Al ₂ O ₃ 6.50, Fe ₂ O ₃ 0.65, FeO0.12, MnO0.01, MgO3.10, CaO9.03, Na ₂ O9 .36, K ₂ O 2.81, P ₂ O ₅ 0.10, loss on ignition 1.30, together with soda ash Na ₂ CO ₃ , calcite and wollastonite accounting for less than 10%wt of the total raw material weight. The particle size of the raw material components is as described in the preceding paragraph of the specification. After being uniformly mixed mechanically, it is pressed into shape under the condition of water content of 6-8%wt. After drying, it is fired in a kiln. The heating rate in the kiln is 1-1.5°C/min. Cooling down to 915-925°C, the cooling rate is the same as the heating rate, and natural cooling after reaching 400°C, all of which are automatically carried out in the kiln at a uniform speed. Leave the kiln at about 60°C, cool to room temperature and cut into finished products.

The main properties of the product in this embodiment are bulk density ≤ 450kg/m ³ , cubic compressive strength 3.5-4.1Mpa.

Embodiment 2: a mixture of glass powder and fly ash accounting for more than 90%wt of the total weight. The weight percent of each oxide in its chemical composition is: SiO ₂ 65.35, TiO ₂ 0.24, Al ₂ O ₃ 7.41, Fe ₂ O ₃ 0.62, FeO0.28, MnO0.02, MgO3.0, CaO9.28, Na ₂ O9.14, K ₂ O2.60, P ₂ O ₅ 0.1, loss on ignition 1.4. It is mixed with soda ash Na ₂ CO ₃ , calcite and wollastonite accounting for ≤10%wt of the total raw material weight. The particle size of the raw material is the same as that described in the preceding paragraph of the description. After being uniformly mixed mechanically, it is pressed into shape as in Example 1, fired in a kiln, cooled and cut into finished products.

The main properties of the product in this example are five groups of 15 samples with an average bulk density of 750kg/M ³ and an average cubic compressive strength of 10.7Mpa.

Claims (6)

1, a kind of foamed glass ceramic material for wall, it is characterized in that its component is glass powder, flyash and nonmetalliferous ore, the granularity d of glass powder (0.9) is less than 130 orders, and the granularity d of flyash (0.9) is less than 120 orders, and the granularity d of nonmetalliferous ore (0.9) is less than 230 orders;

Wherein: the total amount proportioning (weight %) of glass powder and flyash is 90-97%, and nonmetalliferous ore is 3-10%;

In the mixture of described glass powder and flyash, the proportioning of main oxides (weight %) is: SiO ₂: 62.43-76.80, Al ₂O ₃: 5.41-10.55, CaO:5.43-14.89, MgO:1.64-3.75, FeO+Fe ₂O ₃: 0.75-3.30, Na ₂O+K ₂O:9.20-14.95;

Described nonmetalliferous ore is alkali feldspar, silica sand, wollastonite, soda ash (Na ₂CO ₃) and calcite in one or more.

2, foamed glass ceramic material for wall according to claim 1 is characterized in that the weight proportion (%) of described alkali feldspar is 1-5%, and calcite is 1-2%, and wollastonite is 1-2%, and soda ash is 1-5%.

3, foamed glass ceramic material for wall according to claim 1 is characterized in that described glass powder is toughened glass powder, sheet glass powder or beer bottle glass powder.

4, the method for making of foamed glass ceramic material for wall according to claim 1 is characterized in that:

1) will mix behind the glass powder, flyash and the nonmetal breeze adding water that grind;

2) containing compression moulding under the condition of moisture, then oven dry;

3) putting into kiln fires;

4) the blank excision forming after will firing.

5, the method for making of foamed glass ceramic material for wall according to claim 4 is characterized in that the content of moisture (weight %) is 6-8% in the 2nd step.

6, the method for making of foamed glass ceramic material for wall according to claim 4, it is characterized in that the heat-up rate in kiln is 1-5 ℃/minute, to 915-925 ℃ of cooling in the 3rd step sintering procedure, rate of temperature fall is identical with temperature rise rate, naturally cooling after 400 ℃.