JP2548083B2 - Structural material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structural material using waste glass.

[0002]

A large amount of glass is used in various directions such as building windows, automobile windows, bottles, etc. When these are discarded, a large amount of glass must be disposed of. Of course, in some cases, it may be recycled, but the amount is known.

From such a point of view, a method of utilizing various kinds of waste (waste glass) such as plate glass used in buildings, plate glass used in automobiles, bottle glass, etc. has been proposed. For example, a method for producing an artificial ultralight aggregate in which limestone powder and water glass are added to glass powder, clay powder, and volcanic ash, which is mixed, granulated, and fired has been proposed (Japanese Patent Publication No. 62-45187). In addition, building materials for structures have been proposed in which clay minerals such as kaolin and montmorillonite are added to waste glass, molded, and fired.

However, the structural material thus obtained has never been satisfactory.

[0005]

DISCLOSURE OF THE INVENTION It is an object of the present invention that a large amount of waste glass can be used, that is, waste glass can be effectively disposed of,
And it is to provide a technology capable of converting into a material having an excellent function as a structural material. The object of the present invention is to have an expansion coefficient of 35 × 10 ^{−6 to} 25 × 10 ⁻⁶ / ° C.
Glass foam particles on the surface, the expansion coefficient of 20 × ^{10 -6} ~
It is achieved by a structural material characterized in that it is provided with a powder of 5 × 10 ⁻⁶ / ° C.

The expansion coefficient is 20 × 10 ^{−6 to} 5 × 10.
^The expansion coefficient of the powder of ⁻⁶ / ° C. attached to the surface is 35.
× 10 ^{−6 to} 25 × 10 ⁻⁶ / ° C. glass foam particles are
It is achieved by a structural material characterized by being molded and fired. In the above structural material, Gala
Foam granules (hereinafter also simply referred to as glass granules
There is. ) Has a coefficient of expansion of 33 × 10 ^{−6 to} 27 × 1.
Preferably of the 0 ^-6 / ° C., and the glass
The expansion coefficient of the powder attached to the surface of the foamed granules is 1
It is preferably 5 × 10 ^{−6 to} 9 × 10 ⁻⁶ / ° C.

Further, the ratio of the glass granules and the powder applied to the surface of the glass granules (volume cc / weight g) is 10
0:50 to 100: 20, preferably 100: 45 to 1
It is preferably 00:30. In addition, the powder attached to the surface of the glass granules has a Zegel formula of KNa ₂ O 0.3 to 0.55 CaO 0.4 to 0.6 Al ₂ O ₃ 0.2 to 0.5 SiO ₂ It is preferably adjusted to a range of 2.0 to 4.0 B ₂ O ₃ 0 to 0.10. More preferably, the formulation has a Zegel formula of KNa ₂ O 0.30 to 0.55 CaO 0.45 to 0.60 Al ₂ O ₃ 0.20 to 0.50 SiO ₂ 2.0 to 4.0 B ₂ O. ₃ It was adjusted in the range of 0.02 to 0.10.

The powder applied to the surface of the glass granules has a size of 325 mesh and a residue of 0.5-0.5.
0.1%, preferably 325 mesh sieve with no residue.
It is preferably 2 to 0.1%. Then, the powder having the above characteristics is the same material as the glass granules (glass foam granules) to be the core material, that is, the waste glass and the clay minerals (for example, calcined wollastonite, bentonite, raw elutriated clay, It can be obtained by using a desired amount of frog eye clay, calcined cholemannite, etc. in combination.

Further, the size of the glass foam particles is 2.5 to
It is preferably 0.3 mm, preferably 1.2 to 0.3 mm. Then, the structural material constituted as described above, especially the structural material formed and fired,
Powder having a small expansion coefficient of 20 × 10 ^{−6 to} 5 × 10 ⁻⁶ / ° C. intervenes like a three-dimensional network structure, and the expansion coefficient of 35 × 10 ^{−6 to} 25 × 10 ⁻⁶ / It has a structure in which glass with a large expansion coefficient of ℃ is isolated, and even if it is formed into a plate-like one, it has little distortion, especially little cooling distortion, and it has a good mechanical strength. Was becoming. Therefore, structural materials used in various applications such as building materials and building materials were obtained.

Moreover, in this structural material, a large amount of glass can be blended, so that waste glass can be effectively disposed, which is preferable from the viewpoint of resource saving. Hereinafter, the present invention will be described in detail. Waste glass is generally soda-lime glass, and its maximum expansion coefficient is as large as 28.5 × 10 ⁻⁶ / ° C., so that cooling cracks frequently occur in the firing process in the case of commercialization, and the yield is increased. Is decreasing. As measures against this problem, it is possible to take measures such as lengthening the cooling zone of the firing furnace and taking more time to cool it, or improving the structure of the cooling zone, but it is important to study the raw material composition using waste glass. is there. As a result of earnestly promoting such studies, glass particles having a large expansion coefficient, particularly glass foam particles, can be coated with powder having a lower expansion coefficient than glass foam particles to provide a stable material without cooling cracks. We have found that

That is, foamed particles composed of powder having a low expansion coefficient and waste glass having a maximum expansion coefficient of 28.5 × 10 ⁻⁶ / ° C. (the raw material waste glass is 28.5 × 10 ^{−). 6}
Even if the expansion coefficient is / ° C, the expansion coefficient of this expanded granule is 3
3 × 10 ⁻⁶ / ° C.), a glass with a low expansion powder coated with a low expansion powder having a maximum expansion coefficient of 15 × 10 ⁻⁶ / ° C. or less. When the foamed particles are put into a mold and pressure-molded, the coating powder has a three-dimensional network structure along the grain boundaries, and each high expansion glass foamed particle has a low-expansion structure. It becomes like being held by a fine powder.

In the fired body having such a structure, since each of the highly expanded glass foam particles is like a structure held by a low expansion powder having a network structure, cooling distortion is caused. It was thought that there is little and that it is rich in mechanical strength. On the other hand, when glass foam particles that are not coated with low-expansion powder are put into a mold and pressure-molded, high-expansion glass foam particles are fused together into a single plate, and the strain of the plate is It is conceivable that it will be large and will cause cooling cracks, and that it will be inferior in mechanical strength as a structural material.

The glass foam particles have a softening point of waste glass of 6
Since the temperature is as low as 25 ° C, foaming particles can be obtained by adding a foaming agent and a binder for granulation to glass powder, granulating and firing. Dolomite, sodium nitrate, silicon carbide, etc. are used as the foaming agent, and bentonite, clay, etc. are used as the granulation binder. As the granulation binder, CMC liquid, sugar-tight, water glass, monard gum, PVA, etc. are used. After granulation, powder of kaolin, alumina, silica sand, etc. is adhered to the surface of the granule as an anti-adhesion agent, and the external heating rotary kiln is used. Light-weight foamed granules can be obtained by firing at. The firing foaming temperature is also good in the low temperature range of 800 to 950 ° C. because the softening point of the main raw material is low, and hard foamed granules can be produced.

Foamed granules of waste glass are lightweight and have high strength, and unlike perlite and pearlite foamed granules, they have sufficient strength to withstand extrusion molding of a clay extruder and pressure press molding, and are used as lightweight aggregates for building materials. Is also the best foam granule. Although the elements capable of forming glass are extremely diverse, silicic acid (SiO ₂ ), alumina (Al ₂ O ₃ ), boric acid (B ₂
O ₃ ), soda (Na ₂ O), and lime (CaO) are the main components of [SiO ₂ ] silicate glass, which is the most used in the glass raw materials and has high chemical durability, low expansion, and high Gives strength and hardness. [Al ₂ O ₃ ] Glass normally contains about 1 to 7%, but generally increases chemical durability, elasticity, hardness, and lowers thermal expansion coefficient. [B ₂ O ₃ ] Reduces the coefficient of thermal expansion and improves chemical durability. It also promotes melting and fining of the glass. [Na ₂ O] It plays an important role in melting and refining of glass, but it lowers chemical durability and increases thermal expansion coefficient and electric conductivity. [CaO] The main component of soda and lime glass,
The plate and bottle glass contain about 4 to 15%. Provides low expansion and high chemical durability.

In addition, calcined wollastonite, bentonite,
Within the group of raw elutriated clay, frog eye clay, calcined colemanite, etc.
Clay minerals selected from waste glass (especially SiO₂And
Al ₂O₃Against waste glass, which has a relatively low content of ingredients
And add the desired amount, and the coefficient of expansion is small and stable
A powder having the Zegel formula in the above range is obtained.

Then, a binder solution is added to the waste glass foam granules to wet the surface thereof, and powder having a Zegel formula prepared in the above range is dropped onto the surface of the waste glass foam granules to roll the powder. A glass granule having a powder having a coefficient of expansion attached to the surface thereof is obtained, and by molding and firing this, a structural material having excellent mechanical properties can be obtained.

The present invention will be described below with reference to specific examples.

[0018]

[Glass Foamed Particles] Mixed waste glass cullet is roughly crushed with an aero-fractron (diameter 0.5 mm or less), and 90% by weight of this crushed glass, 5% by weight of sodium nitrate, and 5% by weight of bentonite are mixed. The product was placed in a pot mill, and a steel ball having a diameter of 10 mm was placed in the pot mill, followed by rotary grinding for 6 hours. The particle size of this pulverized raw material was as fine as 95% as a pass at 325 mesh.

The powder obtained as described above was put into a pan-type granulator and tumbled while spraying a waste sugar-concentrated 15% liquid to obtain particles having a diameter of 0.4 to 1.2 mm. After natural drying, fine alumina powder was sprinkled on the surface of the particles, and the particles were placed in a retort of an external heat type rotary kiln set to an internal temperature of 870 ° C. and tumbled to obtain expanded particles. The expanded beads obtained were hard expanded beads having an expansion coefficient of 33 × 10 ⁻⁶ / ° C., a particle size of 0.5 to 2.0 mm, and a bulk specific gravity of 0.28.

The mixed waste glass (G) used in this example
The chemical composition of is shown in Table-1. In addition, the chemical composition of calcined wollastonite (A), bentonite (B), raw elutriated clay (C), frog eye clay (D), and calcined colemanite (E) described later is also shown in Table 1. Show. Table-1 GABCDE SiO ₂ 71.6 50.17 65.0 51.23 51.75 7.88 Al ₂ O ₃ 1.9 − 12.0 32.29 33.50 − Fe ₂ O ₃ 0.19 0.12 1.0 1.17 2.70 − TiO ₂ 0.06 − − 1.03 − − CaO 11.2 46.48 1.0 − − 32.5 MgO 0.39 − 1.5 − − − K ₂ O 1.07 − 0.5 1.08 − − Na ₂ O 13.0 − 2.0 − − − B ₂ O ₃ − − − − − 58.4 IgLoss 0.16 0.65 6.0 11.89 11.71 (Glass foam surface Powder (coating material) attached to] mixed waste glass (G), calcined wollastonite (A), bentonite (B), raw elutriated clay (C), frog eye clay (D), shown in Table 1 Powder (coating material) having a coefficient of expansion smaller than the coefficient of expansion of the glass foam particles, prepared by using calcinated colemanite (E) and compounding as shown in Table-2a (the Zegel formula according to the compounding is shown in Table-2b). Got

Table-2a (mixing ratio) No1 No2 No3 No4 No5 No6 Mixed waste glass (G) 62 parts 64 parts 62 parts 60 parts 64 parts 64 parts Calcined wollastonite (A) ---- 10 parts --- Bentonite (B) 4 parts 4 parts −10 parts 7 parts − Raw water elutriated clay (C) − − − 20 parts − − Frog eye clay (D) 31 parts 31 parts 35 parts − 28 parts 35 parts Calcined colemanite (E) 3 Part 1 Part 3 Part-1 Part 1 Table-2b (Zegel formula) No1 No2 No3 No4 No5 No6 KNa ₂ O 0.492 0.513 0.492 0.409 0.513 0.513 CaO 0.507 0.486 0.508 0.590 0.486 0.486 Al ₂ O ₃ 0.424 0.430 0.454 0.233 0.407 0.461 SiO _{2 3.772 3.903 3.755 3.171 3.927 3.876 B} 2 O 3 0.089 0.030 0.090 - 0.030 0.030 [foamed particles of the coating and molding, baking] the above particle size was made in the waste glass 0.5~1.5mm Glass-made foamed particles] To 100 ml, CMC2.5% solution 10 g was added, and well stirred to wet the surface of glass-made foamed particles, and the powders attached to the surface of the above-mentioned [glass-made foamed particles] No. 1 to No6 (Coating material), the residue was 0.1% on a 325-mesh sieve, and 45 g of the residue was rolled down to allow the coating powder to uniformly adhere to the surface of the glass foam particles.

After being dried so that the water content of the foamed glass beads attached with the wet coating powder is 8%, 5.0 ×
It was filled in a 5.0 cm die and pressure-molded at 58 kg / cm ² , and then a 5.0 × 5.0 × 0.8 cm plate was taken out of the die. The bending strength of the wet plate in this demolded state is the green strength in Table-3. After drying a molded plate with a green strength of about 2 kg / cm ² or more, put it in an electric furnace and 900 ° C for 60 minutes
The temperature was raised to, and a test piece was obtained.

The physical properties of this test piece were investigated, and the results are shown in Table-3. [Manufacture of lightweight roof tile] 2 L of the above glass foam particles made of waste glass and having a particle size of 0.5 to 1.5 mm were put in a mixer, and the CMC 2.
200g of 5% solution was added and mixed well, and it was confirmed that the surface of each grain was wet.
With a 5 mesh screen, add 900 g of the residue (0.1% residue),
The mixture was stirred to obtain 2.8 L of coated granules.

1.4 L of the coated granulated product was dried in a rotary kiln to a water content of 1.0%, and the mixture was mixed with the remaining 1.4 L and cured for 4 hours. In addition, this is because the granulated product has excessive water content and easily adheres to the mold.
%) For adjustment. That is, the total amount of water is 6 to 7%.
It is difficult to perform stable drying, and it is easier to completely dry and dry half of the mixture, and it is easier to stabilize the water content.

46.0 mounted on press machine
The coating granules, which had been stably dried with the water content of 6 to 7%, were placed in a die of a flat tile having a size of 30.6 cm and a depth of 3.0 cm, and molded with a pressure of 58 kg / cm ² , and then with a suction cup. It was taken out, received in a plate, put in a drying oven at 120 ° C., dried for 10 hours, sprayed with glaze, put on a shelf assembled in a gas furnace, heated, baked, rapidly cooled, and taken out from the oven. .

The roof tile surface was a red semi-glazed black semi-matte surface, and was a heavy roof tile. On the other hand, a 30 × 30 cm plate made only of glass foam balloons and glass powder required 6 to 7 hours for firing and cooling, but with the present invention, it can be manufactured in an extremely short time and will be lightweight in the future. It can greatly contribute to the production of ceramic plates. Table showing physical properties of various lightweight roof tiles
4 shows.

[0027] Table -4 NoA NoB NoC NoD NoE water absorption *% - - - 4.0 0.83 Water absorption **% 44.46 38.88 25.14 22.6 2.6 saturation coefficient - - - 0.18 0.32 Bending strength ^{kg / cm 2 75.75 73.57 75.93 120.0} 130.0 bulk density 0.98 1.01 1.13 1.2 1.25 * Water absorption is 24h water absorption ** Water absorption is 2h boiling water absorption NoA firing condition is 40 minutes over 20 minutes using a gas furnace.
Hold at 0 ° C., 920 ° C. over 100 minutes, and 920 ° C. for 20 minutes, then cool over 60 minutes.

The firing conditions for NoB were 20 using a gas furnace.
Hold at 400 ° C. over minutes, 940 ° C. over 80 minutes, and 940 ° C. for 20 minutes, then cool over 60 minutes. N
The firing conditions for oC are 400 for 30 minutes using a gas furnace.
To 940 ° C over 150 minutes and 2 at 940 ° C.
Hold for 0 minutes, then cool over 60 minutes. The firing conditions for NoD are: using a gas furnace, maintaining at 400 ° C. for 20 minutes, at 950 ° C. for 80 minutes, and at 950 ° C. for 30 minutes, and then cooling for 70 minutes.

The firing conditions for NoE were 20 using a gas furnace.
Hold at 400 ° C. over minutes, 970 ° C. over 80 minutes, and 970 ° C. for 30 minutes, then cool over 70 minutes.

[0030]

[Effect] It is possible to effectively dispose of waste glass and obtain a structural material having excellent functions.

Claims (7)

(57) [Claims] 1. A coefficient of expansion of 35 × 10 ^{−6 to} 25 × 10.
^The expansion coefficient is 20 × on the surface of the glass foam particles of ⁻⁶ / ° C.
A structural material comprising a powder of 10 ^{−6 to} 5 × 10 ⁻⁶ / ° C. attached. 2. A coefficient of expansion of 20 × 10 ^{−6 to} 5 × 10.
^The expansion coefficient of the powder of ⁻⁶ / ° C. attached to the surface is 35.
× 10 ^{−6 to} 25 × 10 ⁻⁶ / ° C. glass foam particles are
A structural material characterized by being molded and fired. 3. The expansion coefficient of the glass foam particles is 33.
× 10 ^{−6 to} 27 × 10 ⁻⁶ / ° C. , glass
The expansion coefficient of the powder attached to the surface of the foamed granules is 1
The structural material according to claim 1 or 2, wherein the structural material is 5 × 10 ^{−6 to} 9 × 10 ⁻⁶ / ° C. 4 . 4. The ratio (volume / weight) of the glass foam particles and the powder attached to the surface of the glass foam particles is 10.
It is 0: 50-100: 20, The structural material in any one of Claims 1-3 characterized by the above-mentioned. 5. The powder attached to the surface of the foamed glass granules has a Zegel formula of KNa ₂ O 0.3 to 0.55 CaO 0.4 to 0.6 Al ₂ O ₃ 0.2 to 0. 0.5 SiO ₂ 2.0 to 4.0 B ₂ O ₃ 0 to 0.10. The structural material according to any one of claims 1 to 4, wherein the material is adjusted. 6. The powder applied to the surface of the glass foamed granules , the size of which is 325 mesh, and the residue is 0.5 to
Claims 1 to 5 have, which is a 0.1%
A little structural material. 7. The glass foam particles have a size of 2.5.
~ 0.3mm is a claim 1 to claim characterized in that
6 Any structural material.