JP2006095847A - Manufacturing method for sulfur-containing material molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a sulfur-containing material molded body which is hard to be affected by the shape or the size of a mold when a sulfur-containing material molded body is manufactured, can sufficiently perform an air bubble removal in a molten sulfur-containing material, is excellent in strength, and also, by which a more uniform strength can easily be obtained, and in addition, which is excellent in a surface state as well. <P>SOLUTION: By this manufacturing method for the sulfur-containing material molded body, after a vibration is applied to the molten sulfur-containing material which has been poured into the mold of a specified shape by using a vibrating device, the sulfur-containing material is molded and solidified. The vibration is performed by using the vibrating device equipped with a bar-like vibrating section under a state in which the external surface temperature of the vibrating section is kept at 120 to 160°C by inserting the vibrating section in at least one place of the molten sulfur-containing material which is poured into the mold. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a sulfur-containing material molded body that is not easily affected by the form and size of a mold when producing a sulfur-containing material molded body, is excellent in strength, and provides a more uniform strength.

In recent years, a large number of sulfur-containing materials that are excellent in acid resistance, mechanical strength, water shielding, etc. have been proposed as civil engineering and construction materials that replace concrete, and using these sulfur-containing materials, panels, tiles, flooring materials, fish reefs, It has been proposed to manufacture various blocks, earth retaining walls, retaining walls, L-shaped walls, civil engineering works such as sheet piles, and molded articles for construction.
In order to produce a molded body of such a sulfur-containing material, since the melting temperature of the sulfur-containing material is usually 120 ° C. or higher, the molten sulfur-containing material maintained at about 120 to 160 ° C. is poured into a predetermined formwork. A method of forming and solidifying is employed.
At this time, in order to improve the strength of the obtained molded body, for example, Patent Documents 1 and 2 disclose that the amount of sulfur in the molten sulfur-containing material and the amount of mineral powder or aggregate are set to a predetermined ratio, A method of forming a molten sulfur-containing material while applying vibration is disclosed.
In Patent Documents 1 and 2, as the method for applying the vibration, a table vibrator using an eccentric weight rotation type vibration motor is used to apply vibration to the mold and vibrate the molten sulfur-containing material. Only the method of addition is described. In short, Patent Documents 1 and 2 only describe a method of indirectly applying vibration to a molten sulfur-containing material via a mold.
However, in such a method, the ratio control between the amount of sulfur in the molten sulfur-containing material and the amount of mineral powder or aggregate is likely to be complicated, and the formwork form is complicated when the formwork size becomes somewhat large. In some cases, it is not sufficient to remove bubbles that have entered the molten sulfur-containing material at the time of pouring into the mold, and the desired strength is not always obtained. May occur.
JP 2000-281425 A JP 2001-30213 A

  The problem of the present invention is that it is hardly affected by the form and size of the mold when producing a sulfur-containing material molded body, can sufficiently remove bubbles in the molten sulfur-containing material, has excellent strength, and more It is an object of the present invention to provide a method for producing a sulfur-containing material molded body that can easily obtain uniform strength and is excellent in surface condition.

  According to the present invention, there is provided a method for producing a sulfur-containing material molded body that is molded and solidified after applying vibration to a molten sulfur-containing material poured into a mold of a predetermined form using a vibration device, Then, using a vibration device including a rod-shaped vibration part, the vibration part is inserted into at least one place in the molten sulfur-containing material that is poured into the mold in a state where the outer surface temperature of the vibration part is maintained at 120 to 160 ° C. The method for producing a sulfur-containing material molded body is provided.

  Since the manufacturing method of the present invention uses a vibration device that can maintain the outer surface temperature of the rod-shaped vibration part at 120 to 160 ° C., it can be directly inserted into the molten sulfur-containing material to apply vibrations. According to the size and form, vibration can be applied at multiple locations, so it is not easily affected by the form and size of the mold, can sufficiently remove bubbles in the molten sulfur-containing material, has excellent strength, And more uniform intensity | strength is obtained, Furthermore, the sulfur containing material molded object of various uses which is excellent also in the surface state can be obtained simply.

Hereinafter, the present invention will be described in more detail.
In the manufacturing method of the present invention, a vibration device provided with a rod-shaped vibration portion is used to form and solidify a molten sulfur-containing material poured into a mold of a predetermined form after vibration is applied using a vibration device. The vibration part is inserted into at least one place in the molten sulfur-containing material that is poured into the mold in a state where the outer surface temperature of the vibration part is maintained at 120 to 160 ° C.
The size and form of the formwork are not particularly limited, and uses of the sulfur-containing material molded body to be produced, such as panels, tiles, flooring, fish reefs, various blocks, retaining walls, retaining walls, L-shaped walls, sheet piles, etc. It can be manufactured according to the size and form of civil engineering such as construction and molded articles for construction. The material of the mold is not particularly limited as long as the material is not eroded by the molten sulfur-containing material.

The molten sulfur-containing material used in the production method of the present invention is preferably a non-hazardous material to be verified by a small gas flame ignition test when solidified, and a specific proportion of aggregate and modified What contains the sulfur material which consists of sulfur is preferable.
The modified sulfur is, for example, a natural product or sulfur or the like produced by desulfurization of petroleum or natural gas, and is preferably a reaction product of sulfur and a sulfur modifier.

Examples of the sulfur modifier include olefin compounds such as dicyclopentadiene (DCPD), tetrahydroindene (THI), or DCPD and cyclopentadiene oligomer (2 to 5 mer mixture), dipentene, vinyltoluene, and dicyclopentene. The mixture with 1 type, or 2 or more types of a kind is mentioned.
As the DCPD, in addition to the simple substance of DCPD, a mixture mainly composed of 2-5 pentamers of cyclopentadiene can be used. Examples of the mixture include those having a content of DCPD of 70% by mass or more, preferably 85% by mass or more, and many commercially available products called dicyclopentadiene can be used.
As the THI, in addition to THI alone, one or more selected from the group consisting of THI, DCPD alone, a polymer of cyclopentadiene and butanediene, and a cyclopentadiene dimer to pentamer. It is also possible to use a mixture of those composed mainly of The THI content in the mixture is usually 50% by mass or more, preferably 65% by mass or more. As the mixture, many commercially available products called tetrahydroindene and by-product oil discharged from an ethyl norbornene production plant can be used.

The modified sulfur can be obtained by melt-mixing sulfur and a sulfur modifier. Under the present circumstances, the usage-amount of a sulfur modifier is 0.1-30 mass% normally with respect to the total amount of sulfur and a sulfur modifier, and the ratio of 1.0-20 mass% is especially preferable.
The melt mixing can be performed using, for example, an internal mixer, a roll mill, a drum mixer, a pony mixer, a ribbon mixer, a homomixer, a static mixer, or the like.

When the modified sulfur is produced using a mixer, sulfur and the sulfur modifier are melt-mixed in the range of 120 to 160 ° C in the mixer, and the viscosity at 140 ° C is 0.05 to 3.0 Pa · s. A method of staying until it becomes is preferable. The melt mixing temperature in the mixer is usually 130 to 155 ° C, particularly preferably 130 to 150 ° C, so that sulfur can be efficiently modified.
The initial reaction between sulfur and the sulfur modifier generated in the mixer is an exothermic reaction in which a modified sulfur precursor is generated by the reaction between sulfur and the sulfur modifier. For this reason, it is preferable to continuously stir while confirming that no sudden heat generation occurs in the mixer and to gradually raise the temperature to 130 to 160 ° C. in the mixer.
When reacting sulfur with a sulfur modifier in a mixer, a modified sulfur precursor having a molecular weight of 150 to 500 as measured by gel permeation chromatography (GPC) is generated, and the modified sulfur is produced in the reaction system. It is preferable to produce the precursor in an amount of 0.1 to 45% by mass, particularly 1 to 40% by mass.
The molecular weight can be measured by GPC by dissolving sulfur added with a sulfur modifier in carbon disulfide or toluene. The measurement can be performed, for example, by using a calibration curve measured with polystyrene using a UV254Nm detector at a room temperature using a chloroform solvent at a flow rate of 1 ml / min and a carbon disulfide 1 mass / vol% concentration sample solution. it can.

The residence time in the mixer varies depending on the amount of sulfur modifier used and the melting temperature, but is about 1 minute to 24 hours.
The reaction end time for sulfur reforming can be determined by the viscosity of the melt. For example, the viscosity at 140 ° C. is preferably in the range of 0.05 to 3.0 Pa · s. From the viewpoint of the strength of the obtained sulfur solidified base material and the workability of the manufacturing process, the viscosity at 140 ° C. is 0.05 to The range of 2.0 Pa · s is optimal overall.

  In the molten sulfur-containing material, the content of the modified sulfur is usually 15 to 400 parts by mass, preferably 20 to 300 parts by mass with respect to 100 parts by mass of the aggregate described later. If it is less than 15 parts by mass, uniform kneading with the aggregate is not sufficient, and if it exceeds 400 parts by mass, the modified sulfur and the aggregate are separated and it is difficult to obtain a uniform material.

The aggregate that can be included in the molten sulfur-containing material is not particularly limited as long as it can be used as an aggregate, but is generally an aggregate used in concrete, such as natural stone, sand, rubble, dredged sand, steel slag, ferro One or more selected from the group consisting of nickel slag, copper slag, by-products generated during metal production, coal ash, fuel incineration ash, electrostatic dust ash, molten slag, shells and mixtures thereof Can be mentioned. Silica fume, alumina, quartz powder, quartz rock, clay mineral, activated carbon, glass powder, and inorganic and organic fine powders that do not contain the same harmful substances can also be used. Among these fine powders, the group consisting of coal ash, silica sand, silica fume, quartz powder, sand, glass powder, and electrostatic precipitating ash is easy in obtaining a large amount of uniform and uniform particle size distribution. One or more selected from the above are preferred.
Further, even when industrial waste is used as the fine powder, it can be rendered harmless by the sulfur material described above.

As the aggregate, it is usually preferable to include a fine aggregate having a particle size of 5 mm or less, preferably 1 mm or less, but can be appropriately selected depending on the application.
In addition to the modified sulfur and fine aggregate, the molten sulfur-containing material includes, for example, light aggregates such as pumice, vinylon fibers, perlite, various coarse aggregates, fibrous fillers, fibrous particles, flakes Particles and the like can be contained.
Examples of the fibrous filler include carbon fiber, glass fiber, steel fiber, amorphous fiber, vinylon fiber, polypropylene fiber, polyethylene fiber, aramid fiber, or a mixture thereof.
The fiber diameter of the fibrous filler varies depending on the material, but is usually preferably 5 μm to 1 mm. The fiber form may be either a short fiber or a continuous fiber, but in the case of a short fiber, the fiber length is preferably 2 to 30 mm and easy to uniformly disperse. The continuous fiber may be in a lattice shape with a gap through which aggregates can pass, and may have either a woven structure or a non-woven structure.
Examples of the fibrous particles include wollastonite, bauxite, mullite and the like having an average length of 1 mm or less.
Examples of the flaky particles include mica flakes, talc flakes, vermiculite flakes and alumina flakes having an average particle size of 1 mm or less.
In addition to the above, other components may be blended with the molten sulfur-containing material as necessary, as long as the desired effects of the present invention are not impaired.

Preparation of the molten sulfur-containing material is, for example, a method in which a molten material of the modified sulfur kept at 120 to 160 ° C. is charged into and mixed with a solid material including aggregate preheated to 120 to 160 ° C. Or it can carry out by the method etc. which throw and mix the solid material containing the aggregate etc. which were preheated at 120-160 degreeC to the said melt | dissolution of the modified sulfur hold | maintained at 120-160 degreeC.
The mixing is preferably performed while maintaining the viscosity of the modified sulfur in the molten state at 140 ° C. within the range of 0.05 to 3.0 Pa · s. Since the viscosity of the modified sulfur increases with time due to the progress of the polymerization of sulfur, it is preferable that the modified sulfur has an optimum viscosity range that is easy to handle. If the viscosity is less than 0.05 Pa · s, the strength of the obtained sulfur-solidified base material is lowered, and the modification effect by the modified sulfur becomes insufficient. On the other hand, as the viscosity increases, the effect of improving the strength also increases. However, if it exceeds 3.0 Pa · s, stirring in the melt mixing becomes difficult and workability is remarkably deteriorated.
The mixer used for the mixing is not particularly limited as long as the mixing can be sufficiently performed, and preferably for solid-liquid stirring. For example, a paddle mixer, internal mixer, roll mill, ball mill, drum mixer, screw extruder, pug mill, pony mixer, ribbon mixer, kneader and the like can be used.

  The vibration device used in the manufacturing method of the present invention is a throwing-type vibration device including a rod-shaped vibration portion that can sufficiently remove bubbles in the molten sulfur-containing material poured into a mold, for example, the vibration A device equipped with a heating means such as a heater that can hold and control the surface temperature of the part at 120 ° C. or higher, or a device formed with a material having an excellent heat holding ability at the outer surface of the vibration part of 120 ° C. or higher, etc. Can be mentioned.

In the production method of the present invention, in order to apply vibration to the molten sulfur-containing material poured into the mold using the vibration device, for example, the outer surface temperature of the vibration part in the vibration device is 120 to 160 ° C., preferably melt reforming. To keep sulfur from adhering to the vibrating part, keep it near the temperature of the melt-modified sulfur when it is poured into the mold, and insert the vibrating part into the molten sulfur-containing material that has flowed into the mold to apply vibration. Can be performed. At this time, the surface temperature of the vibration part is maintained by, for example, the method of controlling by the above-described heating means, or preheating the outer surface to 120 to 160 ° C. before inserting the vibration part into the molten sulfur-containing material. It can be performed by a method or the like.
The time during which the vibration is applied can be appropriately determined according to the amount of the molten sulfur-containing material and the like so that bubbles can be sufficiently removed. In addition, since the vibration device used in the present invention is a throw-in type, for example, depending on the size and form of the formwork, the place where vibration is applied is not necessarily limited to one place, and can be implemented at a plurality of places as appropriate. .

  In the production method of the present invention, after completion of the vibration, a desired molded product can be obtained by solidifying the molten sulfur-containing material according to a known method and removing the mold.

Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to this.
Example 1
73.6 parts by mass of steelmaking slag heated to 140 ° C. after drying, 8.8 parts by mass of coal ash heated to 140 ° C. after drying and 17.6 parts by mass of molten modified sulfur at 140 ° C. modified with a sulfur modifier The mixture was kneaded and poured into a 1000 mm × 1000 mm × 450 mm square form by the following method to solidify.
While pouring the kneaded material into the mold, a throwing-type vibrating rod having a rod-shaped vibrating portion provided with a heater on the surface is inserted into the kneaded material, and pouring is completed over 5 minutes while applying vibration. Then, it was allowed to stand at room temperature and gradually cooled and solidified. The outer surface temperature of the vibrating rod was controlled to about 140 ° C. while being inserted into the kneaded product.
Three specimens were prepared by the above method. As a result, in any case, the kneaded material did not adhere to the vibrating rod during the placement on the mold, and the placement was possible with good workability from beginning to end. Moreover, there was little roughness on the surface of the casting. When the core of 100 mmΦ × 200 mmH was removed from the obtained molded body and observed, almost no voids due to air bubbles were found in all three specimens. Further, the compressive strength of the obtained specimen was measured. The results are shown in Table 1.
From Table 1, each specimen prepared in this example had little variation in compressive strength, and the average compressive strength was as high as 80.5 MN / m ² .

Comparative Example 1
A kneaded material was prepared in the same manner as in Example 1 and poured into a mold similar to that in Example 1 set on a vibration table, and the vertical vibration (30 Hz) with an amplitude of 0.30 mm was applied to the mold for 5 minutes. In addition, internal bubbles were removed from the kneaded product. Subsequently, it was allowed to stand at room temperature and gradually cooled and solidified.
Three specimens were prepared by the above method, and the core was extracted and observed in the same manner as in Example 1. As a result, it seemed that the removal of bubbles from the kneaded material was performed well, but in each of the cores, there were some voids due to bubbles. In addition, the compression strength of the obtained three specimens was measured. The results are shown in Table 1.
From Table 1, there was some variation in the compressive strength of each specimen. Further, the average compressive strength was 78.2 MN / m ² , which was lower than that of Example 1.

Comparative Example 2
Each specimen was prepared in the same manner as in Example 1 except that the surface of the vibrating bar was not heated while the vibrating bar was inserted into the kneaded product.
As a result, when the melt-modified sulfur was cooled by the vibrating rod during placement on the mold, the kneaded material adhered to the rod and the workability decreased. In addition, the surface of the obtained casting was rough. Furthermore, when the core was removed from the molded body in the same manner as in Example 1, many voids due to bubbles were observed in any specimen. Furthermore, the compressive strengths of the three specimens were varied, and the average compressive strength was 74.7 MN / m ² , which was lower than that of Comparative Example 1.

Example 2
35.8 parts by mass of No. 3 silica sand heated to 140 ° C. after drying, 35.7 parts by mass of No. 7 silica sand heated to 140 ° C. after drying, 9.5 parts by mass of coal ash heated to 140 ° C. after drying, and a sulfur modifier 19.0 parts by mass of 140 ° C. melt-modified sulfur modified by the above was kneaded, and the kneaded product was poured into a 1000 mm × 1000 mm × 450 mm square form by the following method to solidify.
While pouring the kneaded material into the mold, a throw-type vibrating rod whose rod-shaped vibrating portion was heated to 140 ° C. or higher in advance was inserted into the kneaded material, and pouring was completed over 5 minutes while applying vibration. Then, it was allowed to stand at room temperature and gradually cooled and solidified. The outer surface temperature of the vibrating rod was maintained at about 140 ° C. while being inserted into the kneaded product.
Three specimens were prepared by the above method. As a result, in any case, the kneaded material did not adhere to the vibrating rod during the placement on the mold, and the placement was possible with good workability from beginning to end. Moreover, there was little roughness on the surface of the casting. When the core of 100 mmΦ × 200 mmH was removed from the obtained molded body and observed, almost no voids due to air bubbles were found in all three specimens. Further, the compressive strength of the obtained specimen was measured. The results are shown in Table 2.
From Table 2, each specimen prepared in this example had little variation in compressive strength, and the average compressive strength was as high as 58.0 MN / m ² .

Comparative Example 3
A kneaded material was prepared in the same manner as in Example 2 and poured into a mold similar to that in Example 2 set on a vibration table, while vertical vibration (30 Hz) with an amplitude of 0.30 mm was applied to the mold for 5 minutes. In addition, internal bubbles were removed from the kneaded product. Subsequently, it was allowed to stand at room temperature and gradually cooled and solidified.
Three specimens were prepared by the above method, and the core was extracted and observed in the same manner as in Example 2. As a result, it seemed that the removal of bubbles from the kneaded material was performed well, but in each of the cores, there were some voids due to bubbles. In addition, the compression strength of the obtained three specimens was measured. The results are shown in Table 2.
From Table 2, there was some variation in the compressive strength of each specimen. Further, the average compressive strength was 54.9 MN / m ² , which was lower than that of Example 2.

Comparative Example 4
Each specimen was prepared in the same manner as in Example 2 except that the outer surface of the vibrating rod was not heated in advance.
As a result, when the melt-modified sulfur was cooled by the vibrating rod during placement on the mold, the kneaded material adhered to the rod and the workability decreased. In addition, the surface of the obtained casting was rough. Further, when the core was removed from the molded body in the same manner as in Example 2, many voids due to bubbles were observed in any specimen. In addition, the compressive strength of the three specimens was varied, and the average compressive strength was 51.2 MN / m ² , which was lower than that of Comparative Example 3.

Claims (3)

A method for producing a sulfur-containing material molded body that is molded and solidified after applying vibration to a molten sulfur-containing material poured into a mold of a predetermined form using a vibration device,
At least one location in the molten sulfur-containing material in which the vibration is poured into a mold in a state where the outer surface temperature of the vibration portion is maintained at 120 to 160 ° C. using a vibration device including a rod-shaped vibration portion. A method for producing a sulfur-containing material molded body, which is performed by inserting the material into a sulfur-containing material.   The manufacturing method according to claim 1, wherein the rod-shaped vibrating portion includes a heating unit capable of maintaining and controlling the surface temperature at 120 ° C. or more.   2. The rod-shaped vibrating portion is inserted into at least one location in the molten sulfur-containing material to apply vibration, and the outer surface temperature of the vibrating portion is heated to 120 ° C. or higher in advance. The manufacturing method described.