KR101974334B1 - Method for manufacturing glassbead - Google Patents

Abstract

A process for producing glass beads is provided. A method of manufacturing glass beads according to an embodiment of the present invention includes the steps of charging alloy crucibles, fluxes, fluxes, and oxidants into a crucible, heating the crucibles to perform primary oxidation, cooling the crucibles, A step of adding a potassium solution, a step of secondary oxidation by heating the crucible, and a step of charging the melt formed in the crucible into a mold and cooling the glass to form glass beads.

Description

[0001] METHOD FOR MANUFACTURING GLASSBEAD [0002]

One embodiment of the present invention relates to a method of manufacturing glass beads, and more particularly, to a method of manufacturing glass beads for fluorescent X-ray analysis.

During the steelmaking process, alloy iron is added to the molten metal for the purpose of adjusting the elements of the steel or deoxidizing steel. At this time, knowing precisely the content of elemental iron in the alloy iron can accurately calculate the amount of trace element in the steel and control the steel properties. Therefore, rapid and accurate component analysis of ferroalloys to produce high quality steels is very important.

As shown in FIG. 1, the chromium (Cr) component analysis method is a titration method, the silicon (Si) component analysis method is gravimetric analysis, and the phosphorous (P) component analysis method is a spectrophotometric method. However, this method is complicated because the preprocessing process is different for each element. In addition, it is time-consuming and difficult to utilize rapid analysis data. In addition, since an acidic solvent (hydrochloric acid, nitric acid, etc.) which is harmful to the human body is used in the dissolving process, there is a possibility that the working environment is contaminated and the health of the analyst is damaged.

One embodiment of the present invention is to provide a method of manufacturing glass beads.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned here can be understood by those skilled in the art from the following description.

A method of manufacturing a glass bead according to an embodiment of the present invention includes the steps of charging alloy crucible, flux, flux, and oxidizer into a crucible, heating the crucible to perform primary oxidation, air cooling the crucible, A step of adding a potassium iodide solution to the crucible, a step of secondary oxidizing the crucible by heating, and a step of filling the melt formed in the crucible into a mold and cooling the glass to form a glass bead.

In the step of adding the potassium iodide solution to the crucible, the amount (ml) of the potassium iodide solution added to the crucible may be 2.9 to 7.5 times the weight (g) of the ferroalloy.

In the step of adding the potassium iodide solution to the crucible, the potassium iodide solution may be a solution containing 0.5 to 0.7 Kg of potassium iodide based on 1 L of the total volume of the potassium iodide solution.

The method may further include heating and drying the crucible prior to the step of adding the potassium iodide solution to the crucible and then heating the crucible and performing the second oxidation.

The step of performing the primary oxidation by heating the crucible may be a stepwise raising from the first temperature region to the second temperature region at a temperature interval of 40 to 60 占 폚.

The second oxidizing step includes a step of raising the temperature from the third temperature region to the fourth temperature region, holding the material in the fourth temperature region for a predetermined time, raising the temperature from the fourth temperature region to the fifth temperature region, Temperature region for a certain period of time.

The step of charging the molten material formed in the crucible into the mold and cooling the molten material to form glass beads is performed by cooling the molten material for 2 to 3 minutes until the molten material reaches 150 to 200 DEG C and then cooling the molten material at 150 to 200 DEG C to 25 to 40 DEG C It can be to cool the fan until it reaches.

The step of charging the alloy iron, the flux and the oxidizing agent into the crucible includes the steps of charging the crucible with a flux and forming a groove, charging the mixture with the oxidizing agent, the ferroalloy and the fluidizing agent, and mixing the oxidizing agent, And the step of covering the iron and flux mixture with the flux.

The ferroalloy may be Fe-Cr alloy iron, the oxidant may be strontium nitrate (Sr (NO3) 2), the fluxing agent may be sodium carbonate (Na2CO3), and the flux may be lithium tetraborate (Li2B4O7).

The oxidizing agent is charged at a weight of 23 to 60 times the weight of the alloy iron and the flux is charged at a weight of 2.9 to 15 times the weight of the alloy iron and the flux is 44 to 85 times Lt; / RTI > weight.

According to one embodiment of the present invention, a glass bead for rapidly and accurately analyzing the components of ferroalloys can be produced. In addition, compared to the conventional wet method, the time required for analysis is significantly reduced, and the health of workers is protected. In addition, it is possible to analyze the components that can ensure high accuracy regardless of the skill of the operator. Also, it is possible to solve the problem of alloying of alloyed iron and platinum material crucible generated in the process of producing glass beads of ferroalloy.

The various and advantageous advantages and effects of the present invention are not limited to the above description, and can be more easily understood in the course of describing a specific embodiment of the present invention.

1 is a flowchart showing a conventional wet analysis method
FIG. 2 is a flowchart showing a method of manufacturing a glass bead according to an embodiment of the present invention
3 is a view for explaining the process of charging the glass bead material into the crucible;
4 is a view showing an electric furnace that can be applied in the primary oxidation step
5 is a view showing an electric furnace that can be applied in the step of drying the crucible
6 is a view for explaining the alternating speed and the alternating angle;
7 is a view showing a bead manufacturing apparatus that can be applied in the secondary oxidation step and the cooling step
FIG. 8 is a view showing an analysis apparatus that can be applied in fluorescence X-ray analysis
9 is a view showing a device that can be applied when cleaning crucibles and molds used after bead preparation

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the embodiments of the present invention are not intended to be limited to the specific embodiments but include all modifications, equivalents, and alternatives falling within the spirit and scope of the embodiments.

Terms including ordinals, such as first, second, etc., may be used to describe various elements, but the elements are not limited to these terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the embodiments, the second component may be referred to as a first component, and similarly, the first component may also be referred to as a second component. And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the embodiments of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

In the description of the embodiments, in the case where one element is described as being formed "on or under" another element, the upper (upper) or lower (lower) or under are all such that two elements are in direct contact with each other or one or more other elements are indirectly formed between the two elements. Also, when expressed as "on or under", it may include not only an upward direction but also a downward direction with respect to one element.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings, wherein like or corresponding elements are denoted by the same reference numerals, and redundant description thereof will be omitted.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

In this specification, when an element is referred to as being on another element, it may be directly formed on another element, or a third element may be interposed therebetween. Further, in the drawings, the thicknesses of shapes and sizes are exaggerated for an effective description of the technical content.

Also, while the terms first, second, third, etc. in the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components. The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms such as " comprises " or " having " are intended to specify the presence of stated features, integers, Should not be understood to exclude the presence or addition of one or more other elements, elements, or combinations thereof. Also, in this specification, the term " connection " is used to include both indirectly connecting and directly connecting a plurality of components.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

2 is a flowchart showing a method of manufacturing glass beads according to an embodiment of the present invention. Referring to FIG. 2, a method of manufacturing a glass bead according to an embodiment of the present invention includes the steps of charging alloy crucible, flux, flux, and oxidizer into a crucible, firstly oxidizing the crucible by heating, Adding a potassium iodide solution to the crucible, heating the crucible to secondary oxidation, and charging the melt formed in the crucible into a mold and cooling the glass bead to form a glass bead.

First, alloyed iron, a flux, a fluidizing agent and an oxidizing agent, which are materials of glass beads, are prepared. Here, the alloy iron to be subjected to the component analysis may be Fe-Cr alloy iron. 0.1 to 0.17 g of ferroalloy may be charged. If the amount of the alloy iron is less than 0.1 g, the reproducibility of the analysis data is deteriorated. If the amount is more than 0.17 g, the alloy iron may not be completely melted.

The flux is not particularly limited as long as it has a melting point lower than that of the alloy iron so that the melting point of the alloy iron can be lowered. However, lithium tetraborate (Li2B4O7) which absorbs moisture and does not form a film on the surface after the production of the glass bead can be used as a flux .

The amount of flux to be charged may be in the range of 44 to 85 times the weight of the ferroalloy. For example, when 0.1 to 0.17 g of ferroalloy is charged, 7.5 to 8.5 g of flux may be charged. If the amount of the flux to be charged is less than 44 times the weight of the alloy iron, the meltability of the alloy iron is lowered. If the amount of the flux is over 85 times, the melt may be overfilled after the melt is charged into the mold. There may be an error in the component analysis due to a decrease in the number of components.

The oxidizing agent for oxidizing ferroalloy is not particularly limited as long as it is a material capable of oxidizing ferroalloy at a temperature lower than the melting point of the flux, but strontium nitrate (Sr (NO3) 2) can be used.

The amount of the oxidizing agent to be charged can be in the range of 23 to 60 times the weight of the ferroalloy. For example, when 0.1 to 0.17 g of the iron alloy is charged, 4 to 6 g of the oxidizing agent may be charged. If the amount of the oxidizing agent to be charged is less than 23 times the weight of the iron alloy, the melting property of the iron alloy may be deteriorated. If the amount of the oxidizing agent is more than 60 times, the analytical component may be volatilized.

The fluidizing agent may be sodium carbonate (Na2CO3), and the amount of the fluidizing agent charged may be 2.9 to 15 times the weight of the alloyed iron. For example, when 0.1 to 0.17 g of the iron alloy is charged, 0.5 to 1.5 g of the fluidizing agent may be charged. When the amount of the fluidizing agent is less than 2.9 times as much as the weight of the alloy iron, the meltability of the alloy iron may be lowered. If the amount of the fluxing agent is more than 15 times, the melt may overflow during the cooling after charging the mold into the mold.

In addition, in one embodiment of the present invention, charging the alloy iron, flux, and oxidizer into the crucible includes the steps of charging the crucible with a flux and forming a groove, charging the crucible with an oxidizing agent, Mixing the oxidizing agent, the ferro-alloy and the flux mixture with a flux.

As the crucible for manufacturing glass beads, a container made of platinum may be used. The platinum component of the crucible may react with the metal component of the ferroalloy during the glass bead manufacturing process, and the crucible may be damaged, and the reaction with the metal component of the ferroalloy may make it difficult to produce an accurate sample.

In order to prevent this, in an embodiment of the present invention, the flux 101 is first charged into the crucible 10 as shown in FIG. 3A, and a groove is formed in the upper central portion of the flux.

3 (b), the oxidizing agent 102, the fluidizing agent 103, and the alloyed iron 104 are charged into the grooves formed in the flux, and the oxidizing agent 102, the fluidizing agent 103, The iron (104) is mixed to form the mixture (105). Alternatively, a mixture 105 in which the oxidizing agent 102, the fluidizing agent 103, and the ferroalloy 104 are mixed and mixed may be charged into the groove formed in the flux 101.

3 (c), the mixture 105 is covered with the flux 101 to prevent the alloy iron 104 from contacting the crucible 10, and the alloy iron 104 and the platinum crucible 10 Allowing the oxidation reaction of the ferroalloy and the oxidizing agent to occur while maintaining the non-contact state.

3 (d), the potassium iodide solution 106 may be added to the upper portion of the mixture 105 covered with the flux 101. [

The amount (ml) of the potassium iodide solution added at this time may be added from 0.29 to 2.5 times the weight (g) of the ferroalloy charged into the crucible. For example, when 0.1 to 0.17 g of ferroalloy is charged, 0.05 to 0.25 ml of potassium iodide solution may be added. The added potassium iodide solution may be a solution of potassium iodide in an amount of 0.5 to 0.7 Kg based on 1 L of the total potassium iodide solution. If the potassium iodide solution is less than 0.5 Kg based on the total volume of 1 L of the solution, the resulting beads may be broken during the cooling process and the beads of homogeneous components may not be produced. When the potassium iodide solution has a volume of 1 L If it is more than 0.7 g as a standard, it may overflow during cooling after charging the melt into the mold, and beads of a homogeneous component may not be produced.

After the crucible is placed on the tray, the tray is placed in an electric furnace and heated to primary oxidation of the ferroalloy.

The primary oxidizing step may be a stepwise raising from the first temperature region to the second temperature region at a temperature interval of 40 to 60 占 폚.

For example, the primary oxidizing step may be a stepwise raising from 530 to 570 캜 to 930 캜 to 970 캜 at a temperature interval of 40 to 60 캜. Also, each temperature step can be maintained for 20 minutes to 40 minutes.

Specifically, the primary oxidizing step includes heating at 530 to 570 캜 for 20 minutes to 40 minutes, heating at 580 to 620 캜 for 20 to 40 minutes, at 630 to 670 캜 for 20 to 40 minutes Heating at 680 to 720 ° C for 20 minutes to 40 minutes, heating at 730 to 770 ° C for 20 minutes to 40 minutes, heating at 780 to 820 ° C for 20 minutes to 40 minutes, Heating at 830 to 870 캜 for 20 to 40 minutes, heating at 880 to 920 캜 for 20 to 40 minutes, and heating at 930 to 970 캜 for 20 to 40 minutes have. By raising the temperature stepwise in the primary oxidation step as described above, it is possible to prevent the phenomenon that the ferroalloy and the flux are scattered.

In the first oxidation step, an apparatus as shown in Fig. 4 can be used.

4, the tray 200 on which the crucible 10 is mounted includes a handle 201 formed on one side of the tray, so that the tray heated to a high temperature in the electric furnace can be stably taken out and stably cooled . In addition, the refractory plate 202 may be attached to the lower part of the tray 200 to prevent heat from being transmitted.

The electric furnace 300 to which the tray 200 is charged is provided with an on / off function of the electric furnace power source and an on / off function of the heater in the furnace. The electric furnace 300 has an automatic temperature And may be an electric furnace having a function.

When the primary oxidation step is completed, the crucible is taken out of the electric furnace and air-cooled to room temperature.

When the air cooling is completed, 0.5 to 0.75 ml of potassium iodide solution is added to the crucible.

The amount (ml) of the potassium iodide solution added at this time may be 2.9 to 7.5 times the weight (g) of the ferroalloy charged into the crucible. For example, when 0.1 to 0.17 g of ferroalloy is charged, 0.5 to 0.75 ml of potassium iodide solution may be added. The potassium iodide solution may be a solution of potassium iodide in an amount of 0.5 to 0.7 Kg based on 1 L of the total potassium iodide solution.

If the potassium iodide solution added to the crucible is less than 2.9 times as large as the weight (g) of the ferroalloy charged into the crucible, the resulting beads may break during the cooling process, and if it exceeds 7.5 times the flowability is increased, It can overflow during cooling. If the potassium iodide solution is less than 0.5 Kg based on 1 L of the total volume of the solution, the resulting beads may be broken during the cooling process, the beads of the homogeneous component may not be formed, and the potassium iodide solution may have a volume If it is more than 0.7 g based on 1 L, the molten material may overflow during cooling after charging the mold, and beads of homogeneous components may not be produced.

After the step of adding the potassium iodide solution to the crucible, the crucible can be heated and dried at 230 to 270 ° C. When moisture is present in the crucible by the potassium iodide solution, the sample in the crucible may be scattered in a high-temperature atmosphere during the secondary oxidation.

In the step of heating and drying the crucible at 230 to 270 캜, the electric furnace 400 as shown in Fig. 5 may be used. 5, when the crucible is charged after the control unit 401 is operated to set the temperature in the electric furnace 400 to 230 to 270 ° C, and the drying is completed, the crucible can be taken out and air-cooled.

After the moisture drying in the crucible is completed, the crucible is heated to secondary oxidation.

The second oxidizing step includes a step of raising the temperature from the third temperature region to the fourth temperature region, holding the material in the fourth temperature region for a predetermined time, raising the temperature from the fourth temperature region to the fifth temperature region, Temperature region for a certain period of time.

For example, first, a furnace is heated to 640 to 660 DEG C, and then a dried crucible is charged into a furnace. Then, the furnace is heated from 1140 to 1160 ° C for 5 minutes to 15 minutes, and then maintained at 1140 to 1160 ° C for 2 to 10 minutes. Thereafter, the temperature is raised from 1140 to 1160 占 폚 to 1180 to 1200 占 폚 for 30 seconds to 2 minutes, and then maintained at 1180 to 1200 占 폚 for 5 to 10 minutes. By raising the temperature stepwise in the secondary oxidation step as described above, it is possible to prevent the phenomenon that the ferroalloy and the flux are scattered.

Further, in the step of holding at 1180 to 1200 ° C for 5 to 10 minutes, the components of the melt can be homogenized by alternating the crucibles. The alternating angle? May be 20 ° to 28 °. If the alternating angle? Is less than 20 °, the homogeneity of the beads may be deteriorated, and if it exceeds 28 °, the melt may spill from the crucible. Alternatively, the alternating speed may be alternated by alternating speeds of 1 to 2 seconds for 3 to 7 minutes, and alternately by alternating speeds of 4.5 to 9 seconds for 2 to 3 minutes thereafter. Here, the alternating speed refers to the time taken for the reciprocating pendulum movement from b to c to b to a to b in FIG. 6, and the alternating angle (?) Means the moving angle during the reciprocating pendulum motion. By controlling the alternating speed in two steps in the step of maintaining at 1180 to 1200 ° C for 5 to 10 minutes, beads of a homogeneous component can be produced.

When the secondary oxidation is completed, the molten material present in the crucible is charged into the mold and cooled to prepare glass beads. The process of charging the molten material into the mold and cooling the molten material is air-cooled for 2 to 3 minutes until the melt reaches 150 to 200 DEG C, and then cooled for 3 to 5 minutes at 150 to 200 DEG C until reaching 25 to 40 DEG C It can be fan cooling. If the air cooling time is less than 2 minutes, the produced glass bead may be broken. If the air cooling time is more than 3 minutes, the homogeneity of the component of the glass beads may be lowered.

Fe-Cr alloy iron has a high melting point, and unlike other ferro-alloys such as Fe-P, Fe-Si, and Fe-Mn, complete oxidation and melting do not occur in a single oxidation step. Therefore, in one embodiment of the present invention, the crucible may be first oxidized, then air-cooled, potassium iodide may be added, and then secondary oxidation may be performed.

Further, in the secondary oxidation step and the cooling step, an apparatus as shown in Fig. 7 can be used. Referring to FIG. 7, the bead manufacturing apparatus 500 may have an automatic temperature function in which the temperature in the furnace is maintained at a preset temperature at a predetermined time. The bead manufacturing apparatus 500 may include a seating portion 501 on which a crucible is seated. The seating part 501 may have a function of stirring the material in the crucible by a motor connected to the seating part. When the crucible is placed on the seating part 501, the controller 502 of the bead manufacturing apparatus sets the temperature with time. When the temperature in the furnace 503 of the bead manufacturing apparatus reaches 640 to 660 占 폚, the seat part is charged into the furnace 503, and the secondary oxidation is performed according to the predetermined temperature and time conditions. Thereafter, when the secondary oxidation is completed, the mounting portion is taken out from the furnace 503 and the melt in the crucible is injected into the mold 504.

After the cooling of the bead is completed, the beads are removed and the beads are mounted on the holder of the fluorescent X-ray analyzer, and chromium (Cr), phosphorus (P) and silicon (Si) components are analyzed. An apparatus as shown in Fig. 8 can be used for fluorescence X-ray analysis. 8, the glass bead is mounted on the bead holder 601, and then the holder is passed through the fixture 602 for confirming whether or not the holder is properly mounted.

9, the crucible 10 and the mold 504 used after the bead preparation are immersed in an aqueous hydrochloric acid solution and then heated in the electric heater 700 for 30 to 60 minutes to remove foreign substances, washed with pure water, It is possible.

The embodiments of the present invention have been described in detail with reference to the accompanying drawings.

It will be apparent to those skilled in the art that various modifications, substitutions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. will be. Therefore, the embodiments disclosed in the present invention and the accompanying drawings are intended to illustrate and not to limit the technical spirit of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments and the accompanying drawings . The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

10: Crucible
101: Flux
102: oxidizing agent
103: Fluidizer
104: Alloy iron
105: mixture
200: Tray
201: Handle portion
202: Refractory pallet
300: Electric furnace
400: Electric furnace
401:
500: bead manufacturing apparatus
501:
502:
503: furnace
504: mold
601: Bead holder
602: jig
700: Heater

Claims (10)

Charging alloys of iron, fluxes, fluxes and oxidants into the crucible;
Heating the crucible to perform primary oxidation;
Cooling the crucible;
Adding a potassium iodide solution to the crucible;
Heating the crucible to perform secondary oxidation; And
Charging a molten material formed in the crucible into a mold and cooling the molten material to form glass beads,
In the step of adding the potassium iodide solution to the crucible,
The potassium iodide solution to be added to the crucible is a solution containing 0.5 to 0.7 Kg of potassium iodide based on 1 L of the total volume of the potassium iodide solution,
Further comprising heating and drying the crucible at 230 to 270 캜 before the step of adding the potassium iodide solution to the crucible and heating the crucible and performing the second oxidation. delete delete delete The method according to claim 1,
The step of primary oxidation of the crucible by heating comprises:
And raising the temperature stepwise from the first temperature region to the second temperature region at a temperature interval of 40 to 60 占 폚. 6. The method of claim 5,
Wherein the secondary oxidation comprises:
Raising the temperature from a third temperature region to a fourth temperature region;
Maintaining in a fourth temperature zone for a period of time;
Raising the temperature from the fourth temperature region to the fifth temperature region; And
And maintaining the glass bead for a predetermined time in a fifth temperature region. The method according to claim 6,
The step of charging the molten material formed in the crucible into the mold and cooling the molten material to form glass beads may be performed by air cooling the molten material for 2 to 3 minutes until the molten material reaches 150 to 200 ° C, And cooling the glass bead until it reaches a predetermined temperature. 8. The method of claim 7,
The step of charging the alloy iron, flux, and oxidizer into the crucible includes:
Filling the crucible with a flux and forming a groove;
Charging the grooves with an oxidizing agent, an alloyed iron and a fluidizing agent, and then mixing the grooves; And
And covering the mixture of oxidizer, ferroalloy and fluidizer with a flux. 9. The method of claim 8,
The alloy iron is Fe-Cr alloy iron,
The oxidant is strontium nitrate (Sr (NO3) 2)
The flow agent is sodium carbonate (Na2CO3)
Wherein the flux is lithium tetraborate (Li2B4O7). 10. The method of claim 9,
The oxidizing agent is charged at a weight of 23 to 60 times the weight of the alloy iron, and the flux is charged at a weight of 2.9 to 15 times the weight of the alloy iron,
Wherein the flux is charged at a weight of 44 to 85 times the weight of the ferroalloy.

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