阅读说明：本技术 熔融玻璃的运送装置、玻璃物品的制造设备以及玻璃物品的制造方法 (Molten glass conveying device, glass article manufacturing facility, and glass article manufacturing method ) 是由 五十岚仁 丹羽章文 于 2020-09-30 设计创作，主要内容包括：本发明涉及熔融玻璃的运送装置、玻璃物品的制造设备以及玻璃物品的制造方法。本发明提供一种能够长期使用的熔融玻璃的运送装置。一种运送装置,其为熔融玻璃的运送装置,其中,所述运送装置具有：导管构件；和第一陶瓷构件,所述第一陶瓷构件设置在所述导管构件的周围。所述第一陶瓷构件的1000℃下的线性热膨胀系数在8×10～(-6)/℃～12×10～(-6)/℃的范围内,并且所述第一陶瓷构件的1400℃下的抗压强度为5MPa以上,所述导管构件由在铂或铂合金的基材中分散有金属氧化物颗粒的增强铂材料构成,所述金属氧化物为选自由Al-2O-3、ZrO-2和Y-2O-3构成的组中的一种以上,在所述增强铂材料中以0.01质量％～0.15质量％的浓度含有所述金属氧化物颗粒。(The present invention relates to a molten glass conveying device, a glass article manufacturing facility, and a glass article manufacturing method. The invention provides a molten glass conveying device which can be used for a long time. A molten glass conveying device, comprising: a conduit member; and a first ceramic member disposed around the conduit member. The first ceramic member has a linear thermal expansion coefficient of 8X 10 at 1000 DEG C ‑6 /℃～12×10 ‑6 A compression strength at 1400 ℃ of the first ceramic member is 5MPa or more, the conduit member being composed of a reinforced platinum material in which metal oxide particles are dispersed in a base material of platinum or a platinum alloy, the metal oxide being selected from the group consisting of Al 2 O 3 、ZrO 2 And Y 2 O 3 And one or more metal oxide particles contained in the platinum reinforcing material at a concentration of 0.01 to 0.15 mass%.)

1. A molten glass conveying device, comprising:

a conduit member; and

a first ceramic member disposed around the conduit member; and is

The first ceramic member has a linear thermal expansion coefficient of 8X 10 at 1000 DEG C^-6/℃～12×10^-6In the range of/° C, and the compressive strength of the first ceramic member at 1400 ℃ is 5MPa or more,

the conduit member is composed of a reinforced platinum material in which metal oxide particles selected from the group consisting of Al are dispersed in a base material of platinum or a platinum alloy₂O₃、ZrO₂And Y₂O₃One or more of the group consisting of,

the metal oxide particles are contained in the platinum reinforcing material at a concentration of 0.01 to 0.15 mass%.

2. The delivery device of claim 1, wherein the reinforced platinum material has a creep rupture elongation at 1400 ℃ of 5% to 35%.

3. The conveyance device according to claim 1 or 2 wherein the metal oxide particles have an average particle diameter in the range of 5nm to 500 nm.

4. The conveyance device according to claim 1 or 2 wherein the conduit member has a joint portion, and

the joint has a creep rupture elongation at 1400 ℃ of 2% or more.

5. The conveyance device of claim 4 wherein the joint is a welded joint and/or a swaged joint.

6. The conveyance device according to claim 1 or 2, wherein the first ceramic member has a coefficient of linear thermal expansion within a range of 20 ℃ to 1000 ℃ that is within ± 15% of a coefficient of linear thermal expansion of the platinum reinforcing material at the same temperature.

7. The conveyance device according to claim 1 or 2, wherein the conveyance device further has a second ceramic member around the first ceramic member.

8. An apparatus for manufacturing a glass article, wherein the apparatus for manufacturing a glass article has:

a melting device that melts glass raw materials to form molten glass;

a fining device that refines the molten glass; and

a forming device that forms the refined molten glass and forms

There is also a conveying device for the molten glass between the melting device and the fining device and/or between the fining device and the forming device,

the conveyance device according to any one of claims 1 to 7.

9. A method for manufacturing a glass article, comprising:

a melting step of melting a glass raw material to form molten glass;

a fining process in which the molten glass is fined; and

a forming step of forming the clarified molten glass, and

a step of conveying the molten glass between the melting step and the fining step and/or between the fining step and the forming step,

the conveying device according to any one of claims 1 to 7 is used in the conveying step.

Technical Field

The present invention relates to a molten glass conveying device, a glass article manufacturing facility, and a glass article manufacturing method.

Background

Generally, a manufacturing apparatus of glass articles has a melting device, a fining device, and a forming device from an upstream side.

In the melting device, glass raw materials are melted, thereby forming molten glass. In addition, in the fining device, the molten glass is fined, and bubbles contained in the molten glass are removed. Further, the clarified molten glass is formed into a predetermined shape in a forming apparatus, thereby forming a formed glass.

The shaped glass is then slowly cooled, enabling the manufacture of glass articles.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/073594

Disclosure of Invention

Problems to be solved by the invention

In the manufacturing apparatus of glass articles as described above, conveying means for conveying molten glass is provided between the melting device and the fining device and between the fining device and the forming device.

Such a conveying device has a conduit for passing molten glass therethrough and insulating bricks disposed around the conduit. The insulating bricks are preferably disposed in contact with the entire outer circumferential portion of the duct. However, such a construction is not practical, and there is in fact a gap between the duct and the insulating brick.

Since the conduit needs to have corrosion resistance to the high-temperature molten glass, the conduit is usually made of platinum or a platinum alloy. However, from the viewpoint of cost, the duct is formed with a relatively thin thickness. Therefore, the conduit is likely to be deformed by creep and expand due to the high-temperature molten glass flowing through the conduit. Further, if such expansion of the catheter becomes significant, the catheter may be broken.

In order to prevent such breakage of the duct, it has been proposed to provide an amorphous ceramic material called a cement castable between the duct and the heat insulating bricks (patent document 1).

The cement castable is arranged in a manner of filling the gap between the guide pipe and the heat insulation brick, and can inhibit the expansion of the guide pipe at high temperature to a certain extent. Therefore, by using the cement castable, breakage due to expansion of the duct can be significantly suppressed.

However, even in the case where cement castable is present between the duct and the insulating brick, the inventors of the present application have often confirmed that the duct is cracked in a relatively short period of time.

The present invention has been made in view of such a background, and an object thereof is to provide a molten glass conveying apparatus that can be used for a long period of time. In addition, the invention aims to provide a glass article manufacturing facility with the conveying device. It is another object of the present invention to provide a method for manufacturing a glass article using such a conveying device.

Means for solving the problems

The present invention provides a molten glass conveying apparatus, comprising: a conduit member; and a first ceramic member that is provided around the conduit member and has a linear thermal expansion coefficient of 8 x 10 at 1000 ℃^-6/℃～12×10^-6A compression strength at 1400 ℃ of the first ceramic member is 5MPa or more, the conduit member being composed of a reinforced platinum material in which metal oxide particles are dispersed in a base material of platinum or a platinum alloy, the metal oxide being selected from the group consisting of Al₂O₃、ZrO₂And Y₂O₃And one or more metal oxide particles contained in the platinum reinforcing material at a concentration of 0.01 to 0.15 mass%.

Further, in the present invention, there is provided a glass article manufacturing apparatus, comprising: a melting device that melts glass raw materials to form molten glass; a fining device that refines the molten glass; and a forming device that forms the refined molten glass, and a conveying device for the molten glass is provided between the melting device and the refining device and/or between the refining device and the forming device, and the conveying device is a conveying device having the above-described features.

Further, the present invention provides a method for producing a glass article, comprising: a melting step of melting a glass raw material to form molten glass; a fining process in which the molten glass is fined; and a forming step of forming the refined molten glass, and further including a conveying step of conveying the molten glass between the melting step and the refining step and/or between the refining step and the forming step, wherein a conveying device having the above-described characteristics is used in the conveying step.

Effects of the invention

The present invention can provide a molten glass conveying apparatus that can be used for a long period of time. In addition, the present invention can provide a glass article manufacturing facility having such a conveying device. Further, the present invention can provide a method for manufacturing a glass article using such a conveying device.

Drawings

Fig. 1 is a conceptual diagram schematically showing the time-dependent behavior of the compression deformation of the castable in several delivery devices.

Fig. 2 is a view schematically showing a cross section of a molten glass conveying device according to an embodiment of the present invention.

Fig. 3 is a cross-sectional view schematically showing one configuration example of an apparatus for manufacturing a glass article according to one embodiment of the present invention.

Fig. 4 is a diagram schematically showing a flow of a manufacturing method of a molten glass conveying device according to an embodiment of the present invention.

Fig. 5 is a diagram schematically showing one structural example of a tube segment that can be used for the tube member.

Fig. 6 is a view schematically showing an example of a cylindrical segment formed of the pipe segments shown in fig. 5.

Fig. 7 is a view schematically showing an example of a duct constituted by the cylindrical segment shown in fig. 6.

Fig. 8 is a graph summarizing the measurement results of creep rupture elongation obtained using test pieces obtained from the main body of each sample.

Fig. 9 is a graph summarizing the measurement results of creep rupture elongation obtained using test pieces obtained from the welded portions of the respective samples.

Fig. 10 is a diagram collectively showing the structure of the test piece obtained from each sample before and after the heat treatment test.

Description of the reference symbols

100 first conveyance device

110 catheter member

112 lead-in part

114 discharge part

116 intermediate section

120 pipe section

122 side

124 side

126 cylindrical section

128 forge joint

130 welding part

132 catheter

140 first ceramic component

150 second ceramic component

201 first manufacturing facility

202A, 202B molten glass conveying device

212A, 212B inlet tube

214A and 214B discharge pipe

215A, 215B stirrer

216A, 216B accommodating part

260 melting device

262 burner

264 melting furnace

270 clarification device

272 clarifying tank

274 casing

276 inlet pipe

278 outlet pipe

290 forming device

G molten glass

Detailed Description

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

In one embodiment according to the present invention, there is provided a conveying device for molten glass, comprising: a conduit member; and a first ceramic member disposed around the conduit member; and the first ceramic member has a linear thermal expansion coefficient of 8X 10 at 1000 DEG C^-6/℃～12×10^-6A compression strength at 1400 ℃ of the first ceramic member is 5MPa or more, the conduit member being composed of a reinforced platinum material in which metal oxide particles are dispersed in a base material of platinum or a platinum alloy, the metal oxide being selected from the group consisting of Al₂O₃、ZrO₂And Y₂O₃And one or more metal oxide particles contained in the platinum reinforcing material at a concentration of 0.01 to 0.15 mass%.

In the molten glass conveying apparatus according to one embodiment of the present invention, the compressive strength of the first ceramic member at 1400 ℃ is 5MPa or more. Therefore, the first ceramic member provided around the conduit member can exert a certain degree of restraining force on the expansion of the conduit member that may occur during use of the transport apparatus.

In addition, the first ceramic member has a linear thermal expansion coefficient of 8X 10 at 1000 DEG C^-6/℃～12×10^-6In the range of/° c, the linear thermal expansion coefficient of the conduit member is relatively close.

Incidentally, in the molten glass conveying device, for example, in the case where the conduit member and the first ceramic member have complicated shapes, temperature distributions are liable to occur in the conduit member and in the first ceramic member. In this case, a large stress is locally applied to the duct member, and the duct member may be damaged.

Therefore, in the molten glass conveying apparatus according to one embodiment of the present invention, the linear thermal expansion coefficient at 1000 ℃ of the first ceramic member is adjusted as described above. Therefore, even in a structure in which a temperature distribution is likely to occur in the conduit member and the first ceramic member, local application of a large stress to the conduit member or breakage of the conduit member can be significantly suppressed.

Further, in the molten glass conveying apparatus according to one embodiment of the present invention, the conduit member is composed of a "ductility enhancing platinum material" in which metal oxide particles are dispersed.

Herein, in the present application, the "reinforced platinum material" refers to a platinum material having improved high-temperature creep strength by dispersing metal oxide particles selected from the group consisting of Al in a base material₂O₃、ZrO₂And Y₂O₃One or more of the group consisting of. By dispersing the metal oxide particles in the base material, the growth of crystal grains and the movement of dislocations (dislocations) can be inhibited, and thus good creep resistance can be obtained.

In addition, it is to be noted that the "reinforced platinum material" is a concept including not only platinum added with metal oxide particles but also a platinum alloy added with metal oxide particles.

In addition, the "ductility enhancing platinum material" particularly means an enhancing platinum material whose ductility is improved by setting the addition amount of the metal oxide particles in the range of 0.01 to 0.15 mass%.

When the conduit member is made of such a "ductile platinum-reinforcing material", the creep strength of the conduit member can be significantly improved even in an environment in which molten glass at 1400 ℃ flows inside. In addition, the creep rupture elongation of the conduit member can be significantly improved as compared with a conduit member made of a general "reinforced platinum material". Here, the creep rupture elongation is an elongation of a length (gauge length) of a reference portion when the test piece is ruptured in the creep test.

As a result of the above effects, in the molten glass conveying apparatus according to the embodiment of the present invention, the problem that the conduit member is damaged in a relatively short period of use is less likely to occur, and the conveying apparatus can be used stably for a long period of time.

Hereinafter, the features of the molten glass conveying apparatus according to one embodiment of the present invention will be described in more detail with reference to fig. 1.

Fig. 1 schematically shows the behavior over time of the compressive deformation (vertical axis) of the casting material at 1400 ℃ as assumed in several molten glass conveying devices.

During use of the transport device, the inner circumferential side of the potting compound is compressed as a result of the expansion of the duct element. In fig. 1, the compressive deformation of the casting compound on the longitudinal axis therefore corresponds to the expansion of the guide tube.

Three hypothetical curves are shown in fig. 1. The curve a represents the deformation behavior of the potting compound in the conveyor a, the curve B represents the deformation behavior of the potting compound in the conveyor B, and the curve C represents the deformation behavior of the potting compound in the conveyor C.

Here, it is assumed that the conveying device a has a duct member made of a "reinforced platinum material" and a "soft" castable material. Further, it is assumed that the conveyor B has a duct member composed of a "reinforced platinum material" and a "hard" castable material. The conveying device B corresponds to, for example, a conveying device described in patent document 1. On the other hand, it is assumed that the carrier C has a duct member composed of a "ductility enhancing platinum material" and a "hard" castable material (first ceramic member). The conveyance device C corresponds to a conveyance device according to an embodiment of the present invention.

In addition, in fig. 1, a horizontal line I indicates a risk band in which the duct member applied to the carrying device a and the carrying device B is expanded to be broken.

As can be seen from curve a in fig. 1, the compression of the casting compound in the conveyor a is changedThe amount of formation increases greatly over time. This is because: in the case of the conveyor device a, a soft potting compound is used, the radial thickness of which is drastically reduced as a result of the expansion of the duct element. As a result, curve A is plotted at time t_aIntersecting the horizontal line I. I.e. the duct member at time t_aFracture, time t_aThe life of the conveyor a.

Next, as can be seen from the curve B, in the conveying device B, the increase in the compression deformation amount of the castable is suppressed as compared with the conveying device a. This is because: in the conveying device B, a hard castable material that exerts a certain degree of restraining force against expansion of the duct member is used, and radial contraction of the castable material is suppressed.

However, even in the conveying device B, it is difficult to completely zero the expansion amount of the duct member with the castable. Thus, curve B is over time t_aAt a certain time t_bIntersecting the horizontal line I. I.e. the duct member at time t_bFracture, time t_bThe life of the conveyor B.

It can be seen that in the conveyor A, B, although there is a time difference, the life is determined by the horizontal line I.

Here, a horizontal line I corresponding to the creep rupture elongation at 1400 ℃ of the reinforced platinum material is present at a position of a lower height on the longitudinal axis. This is because: in the reinforced platinum material, the movement of dislocations is inhibited by the metal oxide particles dispersed in the matrix, and as a result, the creep rupture elongation is greatly reduced as compared with a "unreinforced platinum material", that is, a general platinum alloy material.

Even if the deformation speed can be reduced by increasing the hardness of the potting compound, as in the case of the conveying device B, the curve B will therefore finally intersect the horizontal line I at the corresponding time. Namely, the duct member is broken.

In contrast, in the transport apparatus C, a conduit member made of a "ductile reinforced platinum material" is used. In this case, the danger zone of the catheter member expanding to rupture moves from level I to level II. As a result, in the conveyor C, even when the same castable as that used in the conveyor B is used as the castableIn this case, the time at which the curve C intersects the horizontal line II also becomes t_c. Therefore, the conveyor C can significantly extend the life, i.e., the time for which the conduit member breaks, as compared to the conveyor B.

As can be seen, in the transport apparatus according to the embodiment of the present invention, the time until the catheter member is broken becomes longer than in the conventional transport apparatus, and the transport apparatus can be used for a long period of time.

(molten glass carrying apparatus according to one embodiment of the present invention)

Hereinafter, a configuration example of a molten glass conveying apparatus according to an embodiment of the present invention will be specifically described with reference to fig. 2.

Fig. 2 schematically shows a cross section of a molten glass conveying device (hereinafter referred to as "first conveying device") according to an embodiment of the present invention.

As shown in fig. 2, the first conveyance device 100 includes a duct member 110, a first ceramic member 140 provided around the duct member 110, and a second ceramic member 150 provided around the first ceramic member 140.

The conduit member 110 has an introduction portion 112 and a discharge portion 114 of molten glass and an intermediate portion 116 therebetween.

However, it should be noted that the structure of the duct member 110 shown in fig. 2 is merely an example. For example, the conduit member 110 may not have the intermediate portion 116 and be constructed of a single straight tube. Alternatively, the conduit member 110 may have more intermediate portions 116. In this case, the duct member 110 may further have a connecting portion between a certain intermediate portion and another intermediate portion.

The conduit member 110 is required to have corrosion resistance to molten glass and creep deformation resistance at high temperatures. Thus, the conduit member 110 is composed of the ductility enhancing platinum material described above. In the case of the ductility enhancing platinum material, by dispersing the metal oxide particles in the base material, even when used under a high temperature stress load environment, the movement of dislocations and the growth of crystal grains can be inhibited, and the creep strength can be improved.

The first ceramic component 140 is made of, for example, a cement casting compound. The second ceramic member 150 is made of, for example, refractory bricks.

As described above, the first ceramic member 140 has a linear thermal expansion coefficient of 8 × 10 at 1000 ℃^-6/℃～12×10^-6Within a range of/° C, and a compressive strength at 1400 ℃ of 5MPa or more.

When the first conveying device 100 is used as a molten glass conveying device, molten glass is supplied from the introduction portion 112 of the conduit member 110 to the first conveying device 100. The molten glass supplied to the first conveying device 100 passes through the intermediate portion 116 and is discharged from the discharge portion 114.

In a conventional conveyor, for example, as in the conveyor described in patent document 1, a reinforced platinum material is used for a duct member, and a cement castable is disposed around the duct member. However, in such a conveying device, a phenomenon in which the duct member is broken in a relatively short period of time is observed.

In contrast, in the first conveyance device 100, the conduit member 110 is made of a ductile reinforced platinum material. Therefore, in the first conveyor 100, the creep rupture elongation at high temperature of the duct member 110 can be significantly increased.

The first ceramic member 140 is configured to have a compressive strength of 5MPa or more at 1400 ℃. That is, the first ceramic member 140 has relatively high strength in a high temperature region. Therefore, the first ceramic member 140 can suppress expansion of the conduit member 110 to some extent. As a result, in the first conveyor 100, as shown by the curve C in fig. 1, the time during which the duct member 110 breaks can be significantly extended.

The first ceramic member 140 has a linear thermal expansion coefficient at 1000 ℃ of 8 × 10, which is a value close to the linear thermal expansion coefficient of the conduit member 110^-6/℃～12×10^-6In a range of/° c. Therefore, even in the case where a temperature distribution is generated in the conduit member 110 and/or the first ceramic member 140, the following problems can be significantly alleviated:since a large stress is locally applied to the duct member 110, the duct member 110 is broken in a relatively short period of time.

As a result of the above effect, the duct member 110 is less likely to be damaged in the first transport apparatus 100, and the first transport apparatus 100 can be used stably for a long period of time.

The molten glass conveying apparatus according to the present invention is not limited to the above-described embodiment, and may be used in the form of a stirring apparatus having a stirrer, as in the conveying apparatuses 202A and 202B of fig. 3, or may be used in the form of a fining apparatus as shown in fig. 3.

(constituent Member of a carrying device according to one embodiment of the present invention)

Next, each member included in the molten glass conveying apparatus according to one embodiment of the present invention will be described in more detail.

Here, the components of the first conveying device 100 will be described by way of example. Therefore, in explaining the respective members, reference numerals shown in fig. 2 are used.

(guide tube component 110)

The conduit member 110 is constructed of a ductile reinforced platinum material. In the case of the ductility enhancing platinum material, by dispersing the metal oxide particles in the base material, even when used under a high temperature stress load environment, the movement of dislocations and the growth of crystal grains can be inhibited, and the creep strength can be improved. In addition, the ductility-reinforced platinum material can significantly improve the creep rupture elongation compared to the reinforced platinum material.

The ductility enhancing platinum material may contain at least one of rhodium, gold, and iridium as a base material element in addition to platinum. When the base material contains these metal elements, the content ratio of platinum to these metal elements may be, for example, in the range of 95:5 to 80:20 in terms of mass ratio.

In addition, the ductility enhancing platinum material includes aluminum oxide (Al)₂O₃) Zirconium oxide (ZrO)₂) And yttrium oxide (Y)₂O₃) As metal oxide particles.

The metal oxide particles have an average particle diameter in the range of 5nm to 500nm, for example. When the average particle diameter is in the range of 5nm to 500nm, good creep resistance can be obtained, and breakage due to expansion of the catheter can be remarkably suppressed. The average particle diameter is preferably in the range of 10nm to 100 nm. The average particle diameter refers to the median diameter D50 of the particles. The median particle diameter D50 is the 50% particle diameter in the cumulative fraction determined by image processing TEM images of the ductility enhancing platinum material.

The metal oxide particles are contained in the base material in a range of 0.01 to 0.15 mass%. The content of the metal oxide particles is preferably in the range of 0.02 to 0.08% by mass.

By dispersing the metal oxide particles having the above particle diameter in the base material at the above content, the creep rupture elongation at 1400 ℃ of the ductility enhancing platinum material can be adjusted to, for example, 5% to 35%. When the creep rupture elongation is 5% or more, breakage due to expansion of the catheter can be significantly suppressed. When the creep rupture elongation is 35% or less, the growth of crystal grains and the movement of dislocations are inhibited, and thus a good creep resistance can be obtained. The creep rupture elongation is preferably in the range of 10% to 30%.

In the present application, the value of the creep rupture elongation is an average value of the results of 4 measurements.

Further, the ductility enhancing platinum material has a linear thermal expansion coefficient of, for example, 9X 10 at 1000 ℃^-6/℃～11×10^-6In the range/° c. In this case, the linear thermal expansion coefficient of the conduit member 110 can be made to match the linear thermal expansion coefficient of the first ceramic member 140, and the generation of the stress concentration portion can be suppressed significantly. The ductility enhancing platinum material preferably has a linear thermal expansion coefficient of 9.5X 10^-6/℃～10.5×10^-6In the range/° c.

The thickness of the duct member 110 is, for example, in the range of 0.8mm to 1.0 mm.

(Joint part)

In the case where the duct member 110 has a relatively large size, such a duct member 110 is constructed by joining a plurality of duct segments to each other.

It is to be noted that, as will be described in detail later, a forging method and/or a welding method are used in joining the plurality of pipe sections. I.e. the joint is a welded joint and/or a forged joint. For example, the forging method is used when opposite sides of a thin-plate-shaped ductility enhancing platinum material are joined to each other to form a cylindrical ductility enhancing platinum material (see fig. 5 and 6). For example, a welding method is used to form a longer cylindrical member by sequentially joining cylindrical platinum materials for ductility enhancement in the axial direction (see fig. 7).

As can be seen, the catheter member 110 typically has a junction. In general, it is known that the material properties of the joint portion are different from those of the non-joint portion, i.e., the main body portion. In particular, in the welding method, since heat is applied to the material during the joining, the material characteristics of the joint formed by welding sometimes differ significantly from those of the body portion as a result of thermal effects.

Therefore, in the present application, the above-described material characteristics mean the material characteristics of the main body portion of the duct member 110 unless otherwise specified.

However, it should be noted that in the first transport apparatus 100, relatively good material properties can be obtained even at the joint portion of the duct member 110. Specifically, the conduit member 110 has a creep rupture elongation at 1400 ℃ of 2% or more even at the joint, and has relatively good high-temperature ductility. The creep rupture elongation of the joint is preferably 3% or more, and more preferably 4% or more. If the creep rupture elongation at 1400 ℃ is 2% or more, even if the pipe member 110 is subjected to expansion deformation, cracks can be prevented from occurring in the joint.

The value of the creep rupture elongation at the joint represents the average of 4 measurements.

The duct member 110 has good material properties even at a joint portion where the material properties are relatively liable to be degraded. Therefore, the first conveying device 100 is less likely to generate mechanically weak portions, and can be used stably for a long period of time.

(first ceramic Member 140)

The first ceramic member 140 has a linear thermal expansion coefficient of 8X 10 at 1000 deg.C^-6/℃～12×10^-6Within a range of/° C, and a compressive strength at 1400 ℃ of 5MPa or more. The linear thermal expansion coefficient at 1000 ℃ is preferably 9X 10^-6/℃～11×10^-6In the range/° c.

The linear thermal expansion coefficient of the first ceramic member 140 in the range of 20 c to 1000 c is preferably within ± 15% of the linear thermal expansion coefficient of the ductility enhancing platinum material applied to the conduit member 110 at the same temperature. In this case, the expansion behavior between the duct member 110 and the first ceramic member 140 can be made uniform during the temperature rise of the first conveyor 100. In addition, this can further suppress breakage of the duct member 110.

The first ceramic member 140 may contain, for example, fine-grained zirconia (hereinafter, referred to as "first zirconia particles") and coarse-grained zirconia (hereinafter, referred to as "second zirconia particles"). The first ceramic member 140 may further include silica particles.

The content ratio of the first zirconia particles to the second zirconia particles is, for example, in the range of 3:10 to 3: 5.

When the first ceramic member 140 contains silica particles, the silica particles are preferably contained at a ratio of 0.05 to 0.2 in terms of mass ratio to the entire first ceramic member 140.

The first ceramic member 140 may be made of the same material as the first ceramic structure described in patent document 1.

The open porosity (open porosity) of the first ceramic member 140 is, for example, in the range of 25% to 50%. The open porosity is preferably in the range of 30% to 40%. In the present application, the open porosity can be determined by mercury intrusion.

The thickness of the first ceramic member 140 is not particularly limited, and is, for example, preferably in the range of 15mm to 50mm, and more preferably in the range of 25mm to 35 mm.

When the thickness of the first ceramic member 140 is 50mm or less, the temperature difference in the thickness direction can be suppressed.

The first ceramic member 140 is preferably disposed around the conduit member 110 so as to be in contact with the conduit member 110 with as little clearance as possible. Thereby, the expansion deformation of the conduit member 110 due to heating during use can be suppressed to some extent.

The maximum gap is preferably 2mm or less, and more preferably 1mm or less.

(second ceramic Member 150)

The second ceramic member 150 may be made of, for example, a heat insulating brick or the like.

The insulating brick may be an insulating brick mainly composed of at least one selected from the group consisting of alumina, magnesia, zircon and silica. Specific examples of the heat insulating brick include: silica-alumina insulating bricks, zirconia insulating bricks, magnesia insulating bricks and the like.

Commercially available products of the heat insulating brick include SP-15 (manufactured by Nikkiso Kabushiki Kaisha) and LBK3000 (manufactured by Ixolite Kaisha).

(first conveyance device 100)

The first conveyor 100 is applied to, for example, a glass article manufacturing facility or the like. In particular, the first conveying device 100 is preferably applied to a portion in which molten glass having a temperature of 1400 ℃ or higher flows.

(apparatus for manufacturing glass article according to one embodiment of the present invention)

Next, an apparatus for manufacturing a glass article according to an embodiment of the present invention will be described with reference to fig. 3.

Fig. 3 schematically shows the structure of a manufacturing apparatus for a glass article (hereinafter, referred to as "first manufacturing apparatus") according to an embodiment of the present invention.

As shown in fig. 3, the first manufacturing apparatus 201 has a melting device 260, a refining device 270, and a forming device 290.

The melting device 260 has a function of melting glass raw materials to form molten glass G. The melting apparatus 260 has a burner 262 that heats glass raw materials and a melting furnace 264 that receives molten glass G.

The fining device 270 has a function of removing bubbles contained in the molten glass G. The clarifying device 270 has: a clarifier 272 disposed with its extending axis oriented in the horizontal direction, and a housing 274 for accommodating the clarifier 272. An inlet pipe 276 and an outlet pipe 278 are connected to the bottom of the clearing sump 272. The forming device 290 has a function of forming the molten glass G into a formed glass.

Further, the first manufacturing apparatus 201 has a conveying device 202A of the molten glass G between the melting device 260 and the fining device 270. The first manufacturing facility 201 further includes a molten glass G conveyance device 202B between the fining device 270 and the forming device 290.

The conveyance device 202A has an introduction pipe 212A for supplying the molten glass G and a discharge pipe 214A for discharging the molten glass G. Further, an accommodating portion 216A accommodating the agitator 215A is provided between the introducing pipe 212A and the discharging pipe 214A.

Likewise, the conveyance device 202B has an introduction pipe 212B and a discharge pipe 214B. Further, an accommodating portion 216B accommodating the agitator 215B is provided between the introducing pipe 212B and the discharging pipe 214B.

The inner diameters of the introduction tubes 212A, 212B, the discharge tubes 214A, 214B, and the accommodation parts 216A, 216B are, for example, 50mm to 500 mm.

The clarifier 270 in fig. 3 is a vacuum degassing apparatus for reducing the pressure of the atmosphere in the clarifier 272. The vacuum degassing apparatus is excellent in degassing performance and suitable for clarifying molten glass having high viscosity at high temperature.

In manufacturing a glass article using the first manufacturing apparatus 201, glass raw materials are melted in the melting device 260 using the burner 262 or the like in the melting device 260. Thereby forming molten glass G.

Subsequently, the molten glass G is supplied to the conveying device 202A through the inlet pipe 212A. The molten glass G supplied to the conveyor 202A is stirred and homogenized in the containing portion 216A by the stirrer 215A. Then, the molten glass G is discharged from the conveying device 202A via the discharge pipe 214A, and is supplied to the inlet pipe 276 of the fining device 270.

The molten glass G supplied to the fining device 270 through the inlet pipe 276 is defoamed while flowing through the fining tank 272. The refined molten glass G is then discharged from the refining apparatus 270 through an outlet pipe 278.

Subsequently, the molten glass G is supplied to the conveying device 202B through the inlet pipe 212B. The molten glass G supplied to the conveyor 202B is stirred and homogenized in the containing portion 216B by the stirrer 215B. Then, the molten glass G is discharged from the conveying device 202B through the discharge pipe 214B and supplied to the forming device 290.

The molten glass G supplied to the forming device 290 is formed into a formed glass having a predetermined shape in the forming device 290. The shaped glass is then slowly cooled and cut as necessary.

Through such steps, a glass article is produced. When a glass plate is produced as a glass article, the molten glass G supplied to the forming device 290 is formed into a glass ribbon having a predetermined thickness in the forming device 290, and then the glass ribbon is slowly cooled and cut. Examples of the method for producing a glass sheet include a float method and a fusion method.

Here, the conveyance device 202A and the conveyance device 202B are constituted by a conveyance device according to an embodiment of the present invention. At least one of the conveyor 202A and the conveyor 202B may be constituted by the first conveyor 100.

Therefore, in the first manufacturing apparatus 201, the conveyance device 202A and the conveyance device 202B can be stably used for a long period of time. In addition, by using the first manufacturing apparatus 201, glass articles can be continuously and stably manufactured.

In place of the vacuum degassing apparatus, a high-temperature fining apparatus capable of raising the temperature of the molten glass in the fining tank to, for example, 1700 ℃ may be used as the fining apparatus.

The glass article of the present invention may be any of soda lime glass, alkali-free glass, mixed alkali glass, borosilicate glass, or other glass. Further, the use of the glass article includes various uses such as architectural use, vehicle use, flat panel display use, and others.

(method for manufacturing molten glass conveying apparatus according to one embodiment of the present invention)

Next, an example of a method for manufacturing a molten glass conveying apparatus according to an embodiment of the present invention will be described with reference to fig. 4 to 7.

Fig. 4 schematically shows a flow of a manufacturing method (hereinafter, referred to as a "first manufacturing method") of a molten glass conveying apparatus according to an embodiment of the present invention.

As shown in fig. 4, the first manufacturing method includes the steps of: the method includes the steps of forming a duct member (step S110), disposing a second ceramic member around the duct member with a gap therebetween (step S120), and disposing a first ceramic member in the gap (step S130).

Hereinafter, each step will be explained.

In the following description, for the sake of clarity, the first conveying device 100 described above is used as an example to describe a manufacturing method thereof. Therefore, the reference numerals shown in fig. 2 are used in representing the respective members.

(step S110)

First, the duct member 110 is formed. For example, the duct member 110 is formed by joining a plurality of duct segments to each other.

Fig. 5 schematically shows an exemplary embodiment of a pipe section.

As shown in fig. 5, the tube segment 120 has an approximately thin plate-like shape. The size of conduit section 120 is not particularly limited.

Edge 122 and edge 124 of tube section 120 are then joined to one another. A swaging method may be used in joining. Thereby, a cylindrical section is constructed.

Fig. 6 is a schematic perspective view showing an example of the cylindrical segment 126. The cylindrical section 126 has a swaged portion 128 parallel to the axial direction.

Next, as shown in fig. 7, a plurality of cylindrical segments 126 are stacked one on another in the axial direction and joined one on another, thereby forming a duct 132. A welding method may be used in the joining. The conduit 132 is constructed with a swage 128 parallel to the axial direction and a weld 130 perpendicular to the axial direction.

The conduit member 110 is formed by repeating such joining process.

Note that in the case where the introduction portion 112 and the discharge portion 114 of the duct member 110 shown in fig. 2 are formed, a cylindrical section 126 having an opening portion may be used. Then, another cylindrical section 126 is welded at the opening portion, whereby the introduction portion 112 and the discharge portion 114 can be formed.

(step S120)

Next, the second ceramic member 150 is prepared. The second ceramic member 150 is composed of the above-described insulating brick. The second ceramic member 150 is disposed around the pipe member 110 so as to form a predetermined gap.

The gap between the conduit member 110 and the second ceramic member 150 may be, for example, in the range of 0.1mm to 2 mm.

(step S130)

Next, a slurry for the first ceramic member 140 is prepared.

The slurry is prepared by adding zirconia particles, silica particles, a pH adjuster, an organic binder, and the like to ion-exchanged water. The silica particles and the organic binder may be omitted.

The zirconia particles include fine zirconia particles (first zirconia particles) and coarse zirconia particles (second zirconia particles).

The median diameter D50 of the first zirconium oxide particles is, for example, in the range of 0.2 μm to 10 μm. On the other hand, the median particle diameter D50 of the second zirconia particles is, for example, in the range of 0.2mm to 2 mm. The median particle diameter D50 of the first zirconium oxide particles is preferably in the range of 1 μm to 5 μm, more preferably in the range of 2 μm to 4 μm. The median particle diameter D50 of the second zirconium dioxide particles is preferably in the range from 0.25mm to 1.75mm, more preferably in the range from 0.5mm to 1.5 mm.

The first zirconia particles may be zirconia particles containing no stabilizer, and the second zirconia particles may be stabilized zirconia particles containing a stabilizer such as yttria.

The amount of the ion-exchange water added is, for example, in the range of 4 to 20 mass% with respect to the entire zirconia grains. The amount of ion-exchange water added is preferably in the range of 6 to 15 mass%, more preferably 8 to 12 mass%, based on the entire zirconia grains.

In the case of adding silica particles, the median particle diameter D50 of the silica particles is preferably in the range from 1 μm to 500. mu.m. The median particle diameter D50 of the silica particles is more preferably in the range of 10 to 300. mu.m, still more preferably in the range of 20 to 100. mu.m. Silica particles are added in a range of 0.05 to 0.2 mass% with respect to the mass of the entire zirconia particles.

The pH adjuster may be used to adjust the pH of the ion-exchanged water to be weakly basic (pH about 7 to about 9). As the pH adjuster, CaO, ammonia, potassium carbonate, or the like can be used. The amount of the pH adjuster added is preferably in the range of 0.01 to 0.2 mass%, more preferably 0.02 to 0.1 mass%, based on the total amount of the slurry.

An organic binder is added to improve the handleability of the slurry at ordinary temperature. As the organic binder, methylcellulose, liquid paraffin, polyethylene glycol, or the like can be used. As the organic binder containing methylcellulose as a component, there is, for example, methose, a product name of shin-Etsu chemical Co. The amount of the organic binder added is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.2% by mass or less, based on the entire slurry.

Next, the prepared slurry is filled into the gap between the duct member 110 and the second ceramic member 150, thereby constituting an assembly. After the slurry is sufficiently dried, the assembly is heat-treated at a temperature of 1300 to 1500 ℃ in the atmosphere. Thereby, the slurry is sintered to form the first ceramic member 140. The heat treatment temperature is preferably in the range of 1350 ℃ to 1450 ℃.

The first ceramic member 140 is sintered and shrunk by the heat treatment of the assembly, and a gap may be formed between the pipe member 110 and the first ceramic member 140.

However, such a gap disappears relatively quickly because the inner conduit member 110 expands during use of the first conveyance device 100.

The first conveyor 100 can be manufactured through the above steps.

[ examples ]

(evaluation of characteristics of conduit Member)

Various characteristics were evaluated using a catheter member that can be applied to the delivery device according to an embodiment of the present invention.

First, 3 kinds of samples a to C for catheter members, which were made of different platinum alloys, were prepared.

Sample a is composed of a so-called reinforced platinum material in which 0.2 mass% of zirconia particles is added to a platinum-rhodium alloy (in a mass ratio of 90: 10). Sample B was composed of a reinforced platinum material in which 0.07 mass% of zirconia particles was added to a platinum-rhodium alloy (in a mass ratio of 90: 10). In addition, sample C was composed of a reinforced platinum material in which 0.03 mass% of zirconia particles was added to a platinum-rhodium alloy (in a mass ratio of 90: 10). The mean particle diameter (nominal value) of the zirconia particles was 40nm in all samples.

Each of the samples a to C was formed by forging and welding a plurality of pipe sections.

(evaluation of creep Properties)

Test pieces for high-temperature creep test were obtained from the above samples A to C. The test piece was obtained from both the main body portion (non-joined portion) and the welded portion.

Hereinafter, the test piece of the main body portion obtained from sample a is referred to as "test piece a 1", and the test piece of the welded portion is referred to as "test piece a 2". Similarly, the test piece of the main body portion obtained from sample B was referred to as "test piece B1", and the test piece of the welded portion was referred to as "test piece B2". The test piece of the main body portion obtained from sample C is referred to as "test piece C1", and the test piece of the welded portion is referred to as "test piece C2".

High-temperature creep tests were carried out using these test pieces a1, a2, b1, b2, c1 and c 2.

A commercially available creep test apparatus (manufactured by eastern stretching industries, Ltd.) was used as the test apparatus. The test was carried out in an atmosphere at 1400 ℃. The gauge length of the test piece was 50mm, the load was in the range of 1MPa to 30MPa, and the displacement of the test piece was measured in a non-contact manner using a CCD camera. The number of N tested was 4.

Fig. 8 shows the results of measuring the creep rupture elongation of the test pieces a1 to c1 obtained from the main body of each sample. The creep rupture elongation was the average of 4 measurements.

As shown in fig. 8, the creep rupture elongation of the test piece a1 is 4% or less. In contrast, the creep rupture elongations of the test pieces b1 and c1 were more than 10%, and it was found that the creep rupture elongation was significantly improved compared to the test piece a 1.

Fig. 9 shows the results of measuring the creep rupture elongation of the test pieces a2 to c2 obtained from the welded portions of the respective samples. The creep rupture elongation was the average of 4 measurements.

As is clear from a comparison between fig. 8 and 9, in all the test pieces, the creep rupture elongation of the weld portion was lower than that of the main body portion. In particular, in test piece a2, the creep rupture elongation was reduced to 1% or less. However, in the test pieces b1 and c1, the creep rupture elongation was still more than 4%, and it was found that the respective elongations were maintained.

As can be seen, it was confirmed that: the creep rupture elongation of sample B and sample C for the duct member was significantly improved.

(evaluation of Heat resistance)

Test pieces for heat resistance evaluation test were obtained from the above samples B and C. Test pieces were obtained from 3 of the main body portion (non-joined portion), the welded portion, and the forged portion.

As described above, the test piece of the main body portion obtained from sample B was referred to as "test piece B1", and the test piece of the welded portion was referred to as "test piece B2". The test piece of the swaged portion obtained from sample B is referred to as "test piece B3". Similarly, the test piece of the main body portion obtained from sample C was referred to as "test piece C1", the test piece of the welded portion was referred to as "test piece C2", and the test piece of the swaged portion was referred to as "test piece C3".

The heat resistance was evaluated by using test pieces b1 to b3 and c1 to c 3.

The test was carried out by subjecting each test piece to a heat treatment at a high temperature in the air for a predetermined time. After the heat treatment, the structure was observed with an optical microscope to evaluate the change in the structure before and after the test. The heat treatment conditions are the following two: at 1350 deg.C for 24 hours and at 1450 deg.C for 100 hours.

Fig. 10 shows the results obtained for test pieces c1 to c 3. For comparison, fig. 10 also shows the results obtained for a typical platinum alloy material (Pt — Rh alloy material).

From the results, it is understood that in the case of the non-reinforced platinum material, the grain growth proceeds by the heat treatment, and the grains are significantly coarsened.

On the other hand, it is found that the grain growth is less significant in the case of the test pieces c1 to c3 composed of the platinum reinforcing material containing 0.03 mass% of zirconia grains. In particular, even in the welded test piece c2, the grain growth was significantly suppressed.

Although not shown in fig. 10, the same results as those of test pieces c1 to c3 were obtained for test pieces b1 to b 3.

As can be seen, samples B and C for the duct member were confirmed to have good heat resistance.

(evaluation of characteristics of first ceramic Member)

The first ceramic member was produced by the following method and the characteristics thereof were evaluated.

First, a slurry for a first ceramic member is prepared.

The mixture was prepared by adding fine-grained zirconia particles (first zirconia particles), a pH adjuster, and an organic binder in ion-exchanged water.

A mixed solution was prepared by adding a pH adjuster, an organic binder, and 76.85% of first zirconium oxide particles to 23% of ion-exchanged water by mass ratio. This mixed solution was mixed in a ball mill using zirconia balls and a container for 3 hours to prepare a slurry precursor.

The first zirconia particles were zirconia particles having a median particle diameter D50 of 0.96 μm. The pH adjuster was CaO, and the organic binder was METOLOSE (manufactured by shin-Etsu chemical Co., Ltd.).

Next, coarse zirconia particles (second zirconia particles) were added to the slurry precursor, and then mixed for 20 minutes to prepare a slurry.

The second zirconia particles are stabilized zirconia particles having a median particle diameter D50 of 420 μm. The second zirconia particles were added so that the mass ratio of the first zirconia particles to the second zirconia particles was 0.45.

Subsequently, the resulting slurry was filled into a cylindrical mold having an inner diameter of 25mm and a height of 30mm, dried in the atmosphere for 10 hours, and then further dried at 80 ℃ for 2 hours. Then, the obtained sample was taken out from the mold, and the sample was heat-treated at 1400 ℃ for 10 hours in the air.

Thus, a first ceramic member for evaluation (hereinafter referred to as "ceramic sample 1") was produced.

(measurement of high-temperature compressive Strength)

The determination of the high-temperature compressive strength was performed using the ceramic sample 1.

A gate type universal tester (manufactured by Shimadzu corporation: Autograph) was used for the measurement. Ceramic sample 1 was compressed by an alumina jig in a furnace heated to 1400 ℃. The moving speed of the crosshead was set to 2mm per minute. The measurement was carried out in the atmosphere. The highest load obtained during compression was taken as the high temperature compressive strength of ceramic sample 1.

As a result of the measurement, the high-temperature compressive strength of the ceramic sample 1 was 11.5 MPa.

(measurement of Linear thermal expansion coefficient)

The linear thermal expansion coefficient of the ceramic sample 1 was measured using TMA (manufactured by physical corporation).

The result of the measurement was that the linear thermal expansion coefficient at 1000 ℃ of the ceramic sample 1 was 10.5X 10^-6/℃。

(conclusion)

As described above, the molten glass conveying apparatus having the conduit member made of the platinum reinforcing material of sample B and sample C and the first ceramic member obtained by heat-treating the same slurry as that of ceramic sample 1 was evaluated as a molten glass conveying apparatus that can be used for a longer period of time.