JPH0360441A - Production of raw stone for art glass - Google Patents

Abstract

PURPOSE:To obtain raw stone for art glass suitable to seed stone for terrazzo with good workability at a low cost by melting a raw material incorporating slag and adding the prescribed amount of ZnO as a colorant to the obtained melt having specified composition and melting the mixture and solidifying it. CONSTITUTION:In order to low the viscosity of melt and to make removal of foams easy, Na2CO3 and CaF2, etc., are added to slag such as blast-furnace slag and ferroalloy slag and the mixture is heated and melted. Thereby melt consisting of 40-60% SiO2, 5-15% Na2CO3, 3-20% CaF2 and <=1% (FeO+MnO) is produced. Furthermore raw stone for art glass is obtained by adding at least 5-15 parts ZnO as a colorant for 100 parts melt and melting the mixture and thereafter solidifying it. Thereby when ZnO is independently added, the raw stone shows achromatic transparency or opaque white. When cobalt oxide is utilized in combination with ZnO, it shows blue. When chromium oxide is utilized in combination with ZnO, it shows green. When copper oxide is utilized in combination with ZnO, a product colored in red is produced.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method of producing raw glass for craft glass, particularly for use in so-called terrazzo, which is a polished concrete panel used for interior and exterior walls or floors. This article relates to a method for producing raw seed stones.

(Prior Art) Conventionally, crushed natural colored raw stones such as marble and granite have been used as so-called seed stones scattered on the surface of terrazzo, and there have been limits to their use as landscape materials. For example, in the case of natural raw stone, the color may not be vivid, it may not have a glass-like luster, the surface may have moisture, lumps, etc.
The problem is that the appearance changes due to the absorption of dust and the like.

Therefore, recently, slag (mine slag) generated during metal smelting
For example, attempts have been made to make colored craft glass by applying glass manufacturing methods using mineral slag, such as blast furnace slag and ferroalloy slag, as raw materials.

However, this method is similar to the so-called general glass manufacturing method, and uses the following methods: Sin□, Cab, Na, 0. AZ, 0
3 as the main component, the viscosity when dissolved is quite high, and 14
There are 15 or more voids at 00'C, and therefore it is difficult to remove the bubbles present in the melt, and it is necessary to float and remove them by heating and holding for a long time. In addition, in order to obtain the desired colored craft glass, Fe contained in the raw materials,
It is necessary to bleach the dark black color caused by impurities such as Mn and use the colorant in a state where the color is transparent or milky white.

Zinc (metal or oxide) is used as the decolorizing agent, but these increase the viscosity of the melt in the temperature range of about 1400"C, and when metallic zinc is used, gas generation becomes active. In addition to the above-mentioned floating removal of air bubbles, it is inevitable that high temperature maintenance for a longer period of time (3 to 4 hours) is required.Maintaining high temperature consumes thermal energy and requires time. This will increase manufacturing costs accordingly.In addition, the decolorizing effect of zinc may disappear if kept at high temperatures for a long time (the maximum time is about 2 hours depending on the dissolution method), so from this point of view, There are problems with time management, etc.

(Problems to be Solved by the Invention) In the conventional manufacturing method, since the viscosity at the time of melting is high as described above, it is necessary to heat and maintain the melt at a high temperature for a long time in order to remove the bubbles present in the melt. This tendency is more pronounced when zinc is added for coloring.

Holding the melt at high temperatures for a long period of time increases manufacturing costs and makes the quality of the manufactured glass raw stone unstable.

The present invention solves the problems of the prior art, and aims to provide a method for manufacturing raw glass for craft glass that uses simple means to lower the viscosity of the melt and facilitate the removal of air bubbles. .

(Means for Solving the Problems) The method for producing raw craft glass of the present invention is obtained by melting raw materials containing slag. Sing: 40-60% NFltCOs: 5-15% CaF2: 3-20% FeO+MnO: 1 % of dissolved matter: at least Z as colorant per 100 parts
It is characterized by adding 5 to 15 parts of nO, dissolving it, and solidifying it.

In addition to zinc, colorants used in the present invention include chromium, copper,
Oxides or sulfides of metals such as cobalt, nickel, and manganese are used. In other words, when zinc is added alone as ZnO, it becomes colorless and transparent or milky white; for example, when cobalt oxide is added together with Zr+0, it becomes blue, when chromium oxide is added together with ZnO, it becomes green, and when copper oxide is added with Zr+0, it becomes green.
When added with nO, it becomes red. Note that when ZnO is added together with other colorants, ZnO is Fed, M
It acts as a decolorizing agent for the dark black color caused by impurities such as nO.

(for production) Let's explain the ingredients.

SiO2 has the effect of increasing the gloss of the fractured surface when the solidified material is crushed by cooling in the atmosphere, and stabilizing the tendency of vitrification. However, when the content increases, the solubility deteriorates, and the viscosity of the dissolved product also increases, slowing down the upward dispersion of bubbles. The content of St in the effective solution is 40
~60%.

NazCoff is effective in adjusting the viscosity of the melt and floating bubbles. However, when the content exceeds a certain value, the solidity of the coagulated material becomes weaker and there is a tendency for cracking to occur more easily. Furthermore, in the case of melting in a resistance electric furnace using graphite electrodes, it serves to increase the electrical conductivity of the molten salt. N in effective melt
a, CO1 content is 5-15%.

CaPz has the effect of lowering the viscosity of the melt, but when the content exceeds a certain value, it reduces the gloss of the fractured surface of the coagulated product and makes it brittle and easily chipped. Cab in the effective lysate, the content is 3-20%.

That is, the main component 5t (h is a necessary component for vitrification of the coagulated material, but as the content increases, the viscosity of the melt increases and the fluidity becomes poor, and therefore the air bubbles contained in the melt are removed. In order to solve this problem, the melted material was kept at high temperature for a long time, which is not economical because it consumes a large amount of thermal energy. By adding and containing a predetermined amount of CaF2 and Na2CO= in the melt, the viscosity of the melt can be controlled, lowering the viscosity and promoting the floating removal of air bubbles contained therein, resulting in complete dissolution of the raw material. This allows immediate access to hot water in stages.

Since the raw materials contain small amounts of iron and manganese that interfere with color development, ZnO is added in order to cancel out these interferences. Depending on the content of FeO + MnO in the melt, the required amount of ZnO to make the color of the melt solidified colorless and transparent or milky white changes, and as the amount of interfering components increases,
It is necessary to increase ZnO accordingly. However, when FeO+MnO exceeds 1%, decolorization becomes difficult and a gray color remains on the fractured surface of the solidified product. Also, FeO+ Mn
It has been found that even if O is 1% or less, complete decolorization cannot be achieved if the amount of ZnO added is insufficient. Furthermore, since ZnO is an ultrafine powder with a particle size of 0.2 μm or less, it becomes a white fume during dissolution and easily scatters into the atmosphere, so the amount of ZnO added is limited. Based on the above background, the amount of ZnO added was set to a maximum of 15 parts per 100 parts of the melt. It was also found that interfering components are contained in small amounts (~0.1%) in natural raw materials other than slag, and complete decolorization cannot be achieved unless ZnO is used. Therefore, a minimum of ZnO of 100
It was concluded that it was necessary to add at least 5 parts per part.

(Example) Examples of the present invention are shown below. The melting method was carried out in a resistance electric furnace using a graphite electrode.

In the present invention, as a means of obtaining the necessary components, mineral slag, such as blast furnace slag and ferroalloy slag, which are cheaper and industrial by-products, are used as part of the raw material. An example of the chemical composition of blast furnace slag and ferroalloy slag is shown in Table 1, and the blending ratio of the raw materials used is shown in Table 2.

Table 1 Blast furnace slag and ferroalloy slag (Fe-Ni
Tables 3, 4, 5 and 6 show examples of SiO2, NazCO:+, Ca in the melt, respectively.
By changing the component content of Fz and FeO + MnO,
The range of each component to obtain desired characteristic values was investigated.

The investigation method is to confirm with the naked eye that the molten metal has fallen in the furnace, that is, that the surface of the molten metal is completely melted, and then to
5US3 when held at 0~400°C for 10 minutes
The evaluation was made by inserting a 04 stainless steel round rod into hot water, pulling it up, solidifying it in the atmosphere, and observing the appearance of deposits. That is, if there are no bubbles in the glassy covering formed on the surface of the round bar and the state of decolorization by ZnO is colorless and transparent or milky white, it is considered that the desired characteristics have been exhibited.

In order to investigate the decolorizing effect of ZnO, the deficiency of FeO in the raw materials used was compensated for by adding a predetermined amount of mill scale.

From the investigation results shown in Tables 3 to 6, in order to obtain a craft glass rough having the characteristics desired by the present invention, it is necessary to contain 40 to 60% of Sin and 5 to 15% of NagCOi in the melt.
, CaF, in an amount of 3 to 20%, and FeO and MnO
It was concluded that it is necessary to limit the amount of ZnO to 1% or less and to add at least 5 to 15 parts of ZnO as a coloring agent to 100 parts of the dissolved material.

In the above example, ZnO was used alone as a coloring agent to make the color tone of the craft glass raw stone colorless and transparent or milky white, but of course other colorants could be added in addition to ZnO to create the desired color tone (blue, green, green, etc.). Red, brown, yellow, etc.) can also be obtained. ZnO in this case is FeO
+ Acts as a decolorizer for the dark black color caused by MnO. That is, the coloring agent is applied in a state that is colorless and transparent or milky white due to ZnO.

(Effects of the Invention) According to the method for producing craft glass raw stone according to the present invention, instead of holding the melt at a high temperature (1400°C) for a long time (3 to 4 hours) to lower the viscosity of the melt, NazCO
The viscosity can be lowered in a short time (about 10 minutes) by simply incorporating S and Cab into a predetermined M solution, which is economical without consuming a large amount of thermal energy. As a result, air bubbles contained in the melt can be floated and removed in a short time. FeO also interferes with color development.
→-MnO is suppressed to 1% or less, and 5 to 15 parts of ZnO is added to 100 parts of the melt, so it becomes sufficiently colorless and transparent or milky white, so the coloring agent works effectively to produce raw craft glass of the desired color. Obtainable.

In addition, the raw craft glass obtained by the production method of the present invention has a bright color and luster on the fractured surface of the solidified product, so it can be used as seed stone for high-grade terrazzo, etc. to provide a unique landscape material. I can do it.

Procedural amendment (voluntary) August 17, 1990

Claims (1)

[Claims] SiO_2 obtained by melting raw materials including slag: 40-60% Na_2CO_3: 5-15% CaF_2: 3-20% FeO+MnO: 1% or less of dissolved material: Colorant per 100 parts as at least Z
A method for producing craft glass raw stone, which comprises adding 5 to 15 parts of nO, dissolving and solidifying it.