JPWO2014203834A1 - GLASS CONVEYING ROLL, PROCESS FOR PRODUCING THE SAME, AND METHOD FOR PRODUCING PLATE GLASS USING THE SAME - Google Patents

Abstract

In a roll for glass conveyance, the surface of which is made of a metal roll and coated with a ceramic spray coating, which is often used at high temperatures, particles fall off from the ceramic spray coating, and the ceramic spray coating itself peels off. Further suppression. A glass roll having a metal roll base material coated with a ceramic spray coating, wherein the linear thermal expansion coefficient of the roll base material in the temperature range of 500 to 750 ° C. is αs, and the ceramic spray coating Αs−αc ≦ 2 × 10 −6 / ° C., 8 × 10 −6 / ° C. ≦ αc ≦ 14 × 10 −6 / ° C., and The elongation due to thermal expansion from room temperature to 750 ° C. is 0.6 to 1.05%, the thickness of the ceramic sprayed coating is 100 to 500 μm, and the porosity of the ceramic sprayed coating is 2 by the cross-sectional image analysis method. % Or less glass roll.

Description

  The present invention relates to a glass conveying roll used for conveying glass in a high temperature state in the production of plate glass, a method for producing the same, and a method for producing plate glass using the glass conveying roll.

  Conventionally, in the process of producing plate glass by the float method, a lift-out roll for lifting a continuous layer of high-temperature glass called glass ribbon that has flowed over the top surface of molten tin from the tin bath, or moving the glass ribbon Many glass transport rolls such as rare rolls for gradually cooling while being used are used.

Therefore, a glass conveying roll has been proposed in which a ceramic spray coating is coated on the surface of a roll base material made of metal, and a metal layer or a cermet spray coating is provided as an underlayer between the roll base material and the ceramic spray coating. Yes.
For example, Patent Document 1 describes a transport roll in which a ceramic sprayed coating is formed on the surface of an iron-based alloy roll base material and a base film made of cermet is provided between the ceramic sprayed coating and the base material. ing.
Further, in Patent Document 2, a ceramic thermal spray coating is provided on the surface of the metal base material of the roll body portion, and the linear thermal expansion coefficient is between the metal base material and the ceramic thermal spray coating. A roll for producing float glass provided with a metal spray coating is described.

  If the surface of the roll is made of a ceramic spray coating as in Patent Documents 1 and 2, adhesion of glass residues and tin aggregates is difficult to occur. Moreover, peeling of the ceramic sprayed coating resulting from the difference in a linear thermal expansion coefficient can be suppressed by providing a base film between this ceramic sprayed coating and a roll base material.

However, a conventional transport roll having a base layer made of metal or cermet on the surface of a roll base material and laminated with a ceramic spray coating thereon has a high temperature at least when used in a plate glass production line. When the roll atmosphere temperature is 550 ° C. or higher, fine cracks on the surface of the ceramic sprayed coating are inevitable, so the particles constituting the ceramic sprayed coating drop off and adhere to the glass being conveyed. Inconvenience is likely to occur.
Further, in the glass ribbon transport process, in order to prevent scratches due to friction between the transport roll and the ribbon, a high temperature and corrosive gas is often used. In many cases, the thermal spray coating itself peels off.

In order to solve the above-described problems in the prior art, the applicant of the present application is to use ceramics in a roll for glass conveyance, which is often used at high temperatures, in which a base layer and a ceramic spray coating are laminated on the surface of a roll base material. In order to suppress the drop-off of particles from the sprayed coating and the peeling of the sprayed coating itself, a roll for transporting glass described in Patent Document 3 is proposed.
In the glass transport roll described in Patent Document 3, a first thermal spray coating made of cermet or metal is provided on the surface of a roll base material, and a second thermal spray coating made of ceramics is provided on the first thermal spray coating. It is the roll for glass conveyance provided, Comprising: This 2nd thermal spray coating is a sealing process using the silica precursor solution.
In the roll for glass conveyance described in Patent Document 3, in the roll for glass conveyance in which the base layer and the ceramic spray coating are laminated on the surface of the roll base material, the particles fall off from the ceramic spray coating and the interface between the base layer and the ceramic surface layer. Peeling of the ceramic spray coating that occurs from the vicinity can be remarkably suppressed. For this reason, it is hard to produce the particle adhesion to the glass in conveyance, and quality improvement of glass can be implement | achieved.

  However, in order to satisfy the demand for higher quality of the plate glass, it is required to further suppress the particle drop of the ceramic sprayed coating from the glass transport roll and the peeling of the ceramic sprayed coating.

Japanese Unexamined Patent Publication No. 2004-277828 Japanese Laid-Open Patent Publication No. 4-260623 International Publication No. 2009/113638

  In the present invention, in order to solve the above-mentioned problem, in a roll for conveying a glass, which is often used at a high temperature, the surface of a metal roll base material is coated with a ceramic spray coating, particles from the ceramic spray coating It aims at further suppression of falling off and peeling of the ceramic sprayed coating itself.

In order to achieve the above-mentioned object, the present invention is a roll for transporting glass in which a metal roll base material surface is coated with a ceramic spray coating,
Α _s −α _c ≦ 2 × 10 ⁻⁶ when α _s is the linear thermal expansion coefficient of the roll base material and α _c is the linear thermal expansion coefficient of the ceramic sprayed coating in the temperature range of 500 to 750 ° C. / ° C., 8 × 10 ⁻⁶ / ° C. ≦ α _c ≦ 14 × 10 ⁻⁶ / ° C.
Elongation due to thermal expansion from room temperature to 750 ° C. of the ceramic sprayed coating is 0.6 to 1.05%,
The ceramic sprayed coating has a thickness of 100 to 500 μm,
Provided is a glass transport roll, wherein the ceramic sprayed coating has a porosity of 2% or less by a cross-sectional image analysis method.

In addition, the present invention provides a surface of a roll base material having a linear thermal expansion coefficient α _s in a temperature range of 500 to 750 ° C. of 10 × 10 ⁻⁶ / ° C. ≦ α _s ≦ 16 × 10 ⁻⁶ / ° C. 7 to 23 wt. A film forming step of forming a ceramic sprayed coating comprising stabilized zirconia containing,
An impregnation step of impregnating the ceramic sprayed coating with a silica precursor solution;
Provided is a method for producing a glass transport roll, comprising a curing step of curing the silica precursor solution to seal a ceramic sprayed coating.

In addition, the present invention provides a metal on the surface of a roll base material having a linear thermal expansion coefficient α _s in a temperature range of 500 to 750 ° C. of 10 × 10 ⁻⁶ / ° C. ≦ α _s ≦ 16 × 10 ⁻⁶ / ° C. Or a first film forming step of forming a thermal spray base film made of cermet;
7 to 23 wt. A second film forming step of forming a ceramic sprayed coating made of stabilized zirconia containing,
An impregnation step of impregnating the ceramic sprayed coating with a silica precursor solution;
Provided is a method for producing a glass transport roll, comprising a curing step of curing the silica precursor solution to seal a ceramic sprayed coating.

  Moreover, this invention provides the manufacturing method of plate glass which has the process of conveying glass using the roll for glass conveyance of this invention.

ADVANTAGE OF THE INVENTION According to this invention, in the roll for glass conveyance by which the metal roll base material surface was coat | covered with the ceramic sprayed coating, particle | grain omission from this ceramic sprayed coating and peeling of this ceramic sprayed coating itself can be suppressed significantly. .
Further, in the glass transport roll of the present invention, when a base film made of cermet or metal is formed between the roll base material and the ceramic spray coating, in the presence of corrosive gas such as sulfur oxide. When the transport roll is used, corrosion of the roll base material due to the corrosive gas that has passed through the ceramic spray coating can be suppressed.
High quality plate glass can be provided by the manufacturing method of plate glass and tempered plate glass using the roll for glass conveyance of the present invention.

FIG. 1 is a schematic diagram showing a test apparatus used for evaluating the adhesion of particles to a glass plate. FIG. 2 is a graph showing the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 6.

The roll for glass conveyance of the present invention is a roll for glass conveyance in which a metal roll base material surface is coated with a ceramic spray coating,
Α _s −α _c ≦ 2 × 10 ⁻⁶ / ° C. where α _s is the linear thermal expansion coefficient of the roll base material and α _c is the linear thermal expansion coefficient of the ceramic spray coating in the temperature range of 500 to 750 ° C. 8 × 10 ⁻⁶ / ° C. ≦ α _c ≦ 14 × 10 ⁻⁶ / ° C.
The elongation due to thermal expansion of the ceramic sprayed coating from room temperature to 750 ° C. is 0.6 to 1.05%,
The thickness of the ceramic sprayed coating is 100 to 500 μm,
The ceramic sprayed coating has a porosity of 2% or less by a cross-sectional image analysis method.

<Roll base material>
The material of the roll base material is not particularly limited as long as it is made of metal, but the linear thermal expansion coefficient α _s of the roll base material in the temperature range of 500 to 750 ° C. is equal to the linear thermal expansion coefficient α _c of the ceramic spray coating. In relation, it is required to satisfy α _s −α _c ≦ 2 × 10 ⁻⁶ / ° C.
Hereinafter, in this specification, when describing as linear thermal expansion coefficient (alpha) _s , (alpha) _c , the linear thermal expansion coefficient in the temperature range of 500-750 degreeC is pointed out. The linear thermal expansion coefficient α _c can be measured by the following method. For the ceramic spray coating, raw materials were mixed at a specified ratio, and a sintered body having a diameter of 20 mm and a length of 20 mm was produced by using a spark plasma sintering (SPS) method. The linear thermal expansion coefficient in the temperature range of 20 to 750 ° C. of the sintered body was measured with a push-rod dilatometer (TD5000SA manufactured by NETZSCH) of the horizontal suggestion detection method, and the linear heat in the temperature range of 500 to 750 ° C. The expansion coefficient α _c was determined. The linear thermal expansion coefficient α _s can be measured using the above-described push rod dilatometer.
Since the linear thermal expansion coefficient α _c of the ceramic sprayed coating in one embodiment of the present invention is 8 × 10 ⁻⁶ / ° C. ≦ α _c ≦ 14 × 10 ⁻⁶ / ° C., the linear thermal expansion coefficient α _{s of the} roll base material. Is preferably 10 × 10 ⁻⁶ / ° C. ≦ α _s ≦ 16 × 10 ⁻⁶ / ° C.
Examples of the metal material having a linear thermal expansion coefficient α _s satisfying the above range include SUS430 of ferritic stainless steel, SUS410 of martensitic stainless steel, Inconel 625 of Ni-based alloy, SKH of high-speed steel, SKD of tool steel, and the like. Illustrated.
Although the outer diameter of a roll base material is not specifically limited, The outer diameter of the roll base material in the roll for general glass conveyance is 200-500 mm.

<Ceramic spray coating>
In the glass transport roll of the present invention, the surface of the metal roll base material is coated with a ceramic spray coating.
The ceramic forming the thermal spray coating has a linear thermal expansion coefficient α _s of the roll base material and a linear thermal expansion coefficient α _{c of the} ceramic thermal spray coating, and the difference between the linear thermal expansion coefficients α _s −α _c ≦ 2 × It is required to satisfy 10 ⁻⁶ / ° C.
As a coating for a roll for transporting glass, since it has an advantage that glass, tin, tin oxide or the like hardly adheres even at a high temperature, zirconia ceramics mainly composed of zirconium oxide (ZrO ₂ ), or aluminum oxide ( Alumina-based ceramics whose main component is Al ₂ O ₃ ) are preferred. Here, “main component” means that it is contained in an amount of 50% by mass or more, preferably 80% by mass or more, based on the entire ceramic phase. The zirconia-based ceramics are particularly stabilized zirconia or partially stabilized containing about 3 to 20% by mass of Y ₂ O ₃ , CaO, MgO, CeO ₂ or other oxides as additives. Zirconia is preferred. Hereinafter, in the present specification, the term “stabilized zirconia” refers to both stabilized zirconia and partially stabilized zirconia.

In the present invention, since the linear thermal expansion coefficient difference α _s -α _c is required to satisfy the above range, yttrium fluoride is further added to the stabilized zirconia containing about 3 to 20% by mass of the above additive. Or a metal oxide having a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. or less, and a linear thermal expansion coefficient of 11 × 10 ⁻ It is preferable to use a metal oxide containing at least one metal oxide greater than ⁶ / ° C.
Yttrium fluoride has the effect of increasing the coefficient of linear thermal expansion of stabilized zirconia, and is 7 to 23 wt. % Linear thermal expansion coefficient difference α _s −α _c falls within the above range.
The content of yttrium fluoride is 7 wt. If it is less than%, the effect of increasing the linear thermal expansion coefficient of stabilized zirconia is insufficient, and the linear thermal expansion coefficient difference α _s -α _c may be higher than 2 × 10 ⁻⁶ / ° C.
On the other hand, the content of yttrium fluoride is 23 wt. If it exceeds%, the hardness of the ceramic sprayed coating will decrease, making it unusable as a coating for a glass transport roll. The hardness of the ceramic sprayed coating was determined from the average value obtained by measuring the micro Vickers hardness 10 times with a load of 300 g in the cross section of the ceramic sprayed coating.
As the metal oxide having a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. or less, zirconia (ZrO ₂ ) or alumina (Al ₂ O ₃ ) is preferably used, and the linear thermal expansion coefficient is 11 × 10 ⁻⁶ / It is preferable to use magnesia (MgO) or calcia (CaO) as the metal oxide higher than ° C. Further, silica (SiO ₂ ) may be included. By adding silica (SiO ₂ ), it becomes easy to sinter the thermal spray material mixed with oxide.
In addition, the hardness of the ceramic spray coating in one embodiment of the present invention is preferably 600 or more, more preferably 650 or more, and further preferably 700 or more in terms of Vickers hardness (Hv).

Since the roll for conveying a glass of the present invention has a very small difference in linear thermal expansion coefficient α _s −α _c ≦ 2 × 10 ⁻⁶ / ° C., peeling of the ceramic sprayed coating due to the difference in linear thermal expansion coefficient between the two is marked. Can be suppressed. Thereby, the drop-off of particles from the ceramic spray coating and the peeling of the ceramic spray coating itself can be remarkably suppressed.
Here, the reason why the linear thermal expansion coefficient difference α _s −α _c in the temperature range of 500 to 750 ° C. is defined is the temperature range assumed when the glass transport roll is used.
In one embodiment of the present invention, the linear thermal expansion coefficient difference α _s −α _c ≦ 2 × 10 ⁻⁶ / ° C. is preferably satisfied, and the linear thermal expansion coefficient difference α _s −α _c ≦ 1 × 10 ⁻⁶ / ° C. is satisfied. It is more preferable to satisfy.

In the present invention, the linear thermal expansion coefficient α _c of the ceramic sprayed coating is 8 × 10 ⁻⁶ / ° C. ≦ α _c ≦ 14 × 10 ⁻⁶ / ° C. because the linear thermal expansion coefficient difference α _s −α _c Elongation due to thermal expansion of the ceramic spray coating, specifically, elongation due to thermal expansion from room temperature to a temperature range assumed when the roll for glass conveyance is used is also suitable for the above range. This is because it affects the peeling of the thermal spray coating. If the linear thermal expansion coefficient alpha _c is the range of the ceramic sprayed coating, be in the range of elongation due to thermal expansion from room temperature to a temperature range that is assumed when using the glass conveying rolls will be described later, the peeling of the ceramic sprayed coating is suppressed Because it is done.
When the linear thermal expansion coefficient α _c is less than 8 × 10 ⁻⁶ / ° C., cracks occur in the coating after thermal spraying, and fine cracks occur as the temperature rises. In some cases, the coating expands the base material. There is a problem in that it cannot follow and causes peeling.
On the other hand, if it exceeds 14 × 10 ⁻⁶ / ° C., there is a problem in that the mechanical properties of the film deteriorate.
In one embodiment of the present invention, the linear thermal expansion coefficient α _c is preferably 8 × 10 ⁻⁶ / ° C. ≦ α _c ≦ 14 × 10 ⁻⁶ / ° C., and 11 × 10 ⁻⁶ / ° C. ≦ α _c ≦. More preferably, it is 13 × 10 ⁻⁶ / ° C.

The ceramic sprayed coating in the present invention has an elongation of 0.6 to 1.05% due to thermal expansion from room temperature to 750 ° C. The elongation due to linear expansion can be obtained by multiplying the linear thermal expansion coefficient by temperature. The elongation due to the thermal expansion from room temperature to 750 ° C. corresponds to the elongation due to the thermal expansion of the ceramic spray coating when the glass conveying roll is heated up. Since the ceramic sprayed coating has the largest elongation due to thermal expansion when the glass conveying roll is heated, peeling of the coating tends to occur at this point.
When the elongation due to thermal expansion from room temperature to 750 ° C. is in the above range, the elongation due to thermal expansion is appropriate when the glass conveying roll is heated up, and peeling of the ceramic spray coating is suppressed.

The thickness of the ceramic sprayed coating in the present invention is 100 to 500 μm.
When the thickness of the ceramic sprayed coating is 100 μm or more, the effect as a thermal shock buffer layer is sufficiently obtained, and the ceramic sprayed coating is hardly peeled off due to thermal cycling.
On the other hand, when the thickness of the ceramic sprayed coating is 500 μm or less, cracks due to mechanical force during maintenance or the like hardly occur.
The thickness of the ceramic sprayed coating in one embodiment of the present invention is preferably 100 to 500 μm, and more preferably 150 to 300 μm.

The ceramic sprayed coating in the present invention has a porosity of 2% or less by a cross-sectional image analysis method. When the porosity of the ceramic spray coating is within the above range, it is possible to suppress peeling due to a difference in coefficient of linear thermal expansion between the roll base material and the ceramic spray coating. In addition, even when glass transport rolls are used in an atmosphere where oxygen or sulfur oxides are present, these metal corrosive gases pass through the ceramic spray coating and prevent contact with the roll base material over a long period of time. it can.
When the porosity of the ceramic sprayed coating exceeds 2%, peeling of the ceramic sprayed coating cannot be suppressed. Further, erosion of the roll base material by oxygen or sulfur oxide present in the atmosphere in which the glass transport roll is installed becomes a problem. The porosity was calculated by an image analysis method in the field of view of an optical microscope (200 times) after polishing a cross-section of the ceramic sprayed coating with a diamond paste having a particle size of 1 μm.

The ceramic sprayed coating in one embodiment of the present invention can be formed by a known spraying method such as plasma spraying, high-speed flame spraying, and powder flame spraying. However, it is preferably formed by plasma spraying in that a high melting temperature can be realized and the sprayed particles can be in a semi-molten state.
The raw material used for forming the ceramic sprayed coating is preferably a powder raw material. The powder raw material is previously mixed, granulated, sintered, pulverized, classified and used as a granulated sintered powder or sintered pulverized powder for thermal spraying. preferable.
However, the ceramic coating formed by the thermal spraying method generally has pores because the droplet particles in which the raw material is melted collide with the base material (roll base material surface) and rapidly solidify.
As described above, the ceramic sprayed coating in the present invention is required to have a porosity of 2% or less.
Therefore, the ceramic film formed by thermal spraying, preferably by plasma spraying, needs to have a porosity of 2% or less by performing a sealing treatment.

  One aspect of the sealing treatment performed for the above purpose is performed by impregnation with a silica precursor solution.

<Silica precursor solution>
The silica precursor refers to a compound that generates silica (SiO ₂ ) by physical and chemical changes. Examples of the silica precursor include alkoxysilane and oligomers thereof, polysilazane, alkali silicate, and polysilicic acid. Here, the alkoxysilane oligomer refers to a partially hydrolyzed condensate of alkoxysilane. As an oligomer of alkoxysilane, for example, there is a 2-20 mer obtained by partially hydrolytic condensation of alkoxysilane. As the polysilazane, perhydropolysilazane is preferable. Specific examples of alkoxysilanes include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane (ethyl silicate), tetraisopropoxysilane, and oligomers thereof; organoalkoxysilanes such as methyltriethoxysilane, ethyltriethoxysilane, and oligomers thereof. Etc. These alkoxysilanes are preferably used in a hydrolyzed form in the precursor solution. As a specific example of polysilazane, perhydropolysilazane is preferable.

  As the silica precursor solution, a known coating solution containing a silica precursor can be appropriately used. Specific examples include an alcoholic solution of alkoxysilane and its oligomer, an organic solvent solution of polysilazane, an aqueous alkali silicate solution (water glass), an aqueous polysilicic acid solution, and the like. The silica precursor solution may appropriately contain other components such as a catalyst, a surfactant, and a shrinkage inhibitor as necessary.

  Precursor solution consisting of alkali silicate aqueous solution (water glass) is applied to the surface of ceramic sprayed coating and kept at an appropriate temperature in the atmosphere, silicon dioxide is deposited, and macroscopically becomes a surface coating. Some penetrate into the particle boundary of the thermal spray coating. This infiltration effect can be increased by adjusting the concentration of the aqueous solution. However, these silicon dioxide materials may have a slightly weak effect of improving the bonding force between the ceramic spray particles. In addition, a coating formed on the surface of the sprayed coating inevitably generates a tortoiseshell-like crack by holding at a high temperature, and a liquid phase easily appears in the structure.

  Alkoxysilane (typically, tetramethoxysilane, tetraethoxysilane) turns into silica depending on the heating history but forms a fine powder gel. They are poorly cohesive and often detach into the environment when an external force is applied. However, these problems can be solved by using an alkoxysilane oligomer or using a shrinkage inhibitor such as silica sol.

  On the other hand, compared with silicon oxide formed from alkoxysilanes, silicon oxide formed from polysilazanes has a dense structure, high mechanical durability and gas barrier properties, and sealing of ceramic spray coating When used as an agent, it enhances the bonding force of ceramic particles and has a great effect on preventing the particles from falling off.

  The silica precursor used in one embodiment of the present invention is not limited to alkoxysilane, its oligomer, polysilazane, or alkali silicate, and other silica precursors can be used.

  The impregnation conditions are preferably set so that the silica precursor solution penetrates into all pores existing on the surface of the formed ceramic film by thermal spraying, preferably by plasma spraying. The penetration depth at which the silica precursor solution penetrates into the pores is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 50 μm or more in order to satisfactorily prevent permeation of oxygen and corrosive gas. It may penetrate through the entire thickness of the ceramic spray coating. The penetration depth of the silica precursor solution can be adjusted by the viscosity of the silica precursor solution, the impregnation time, the atmospheric temperature, and the like.

After impregnating the silica precursor solution, preferably, the silica precursor solution adhered on the ceramic spray coating is wiped off, and the silica precursor solution layer remaining on the surface of the ceramic spray coating is cured and formed It is preferable that the thickness (residue film thickness) of the silica film is 5 μm or less. The area where the residual film thickness is zero on the surface of the ceramic sprayed coating, that is, the area where the silica precursor solution penetrates into the pores and the silica precursor solution does not adhere to the surface before curing. May be.
Although the wiping off of the silica precursor solution described above is not essential, the occurrence of cracks in the silica precursor cured on the surface at the time of heating can be suppressed by wiping before the curing of the silica precursor solution described later.

In addition, it is preferable to grind the surface of this ceramic sprayed coating after forming the ceramic sprayed coating and before carrying out the sealing treatment by impregnation with the silica precursor solution described above. By performing polishing before impregnation with the silica precursor solution, generation of cracks in the coating after curing of the silica precursor can be suppressed.
The surface roughness (Ra) of the ceramic spray coating after polishing is preferably 0.2 to 0.8 μm. It is only necessary to remove the fragile outermost layer of the sprayed coating and obtain a smooth surface.
The surface roughness (Ra) of the ceramic sprayed coating after impregnation with the silica precursor solution is determined by wiping away the polysilazane on the surface after impregnation, so that the surface roughness of the ceramic sprayed coating before impregnation with the silica precursor solution is reduced. Is substantially equal to (Ra).
The polishing method is not particularly limited, and for example, hand polishing using water-resistant polishing paper, mechanical polishing with a diamond tool, or the like can be used.

Another embodiment of the treatment for reducing the porosity of the ceramic sprayed coating to 2% or less is performed by explosive spraying.
In explosive spraying, oxygen and flammable gas such as acetylene are mixed and explode inside the spray gun, and a fine powder spray material is mixed in the combustion flame, spraying the spray material onto the surface of the base material and coating it. Since the combustion energy can be obtained at high temperature and high speed by the explosion energy, the porosity of the film becomes very small.

In the roll for glass conveyance of one embodiment of the present invention, the linear thermal expansion coefficient is α _b in a temperature range of 500 to 750 ° C. made of cermet or metal between the roll base material and the ceramic sprayed coating. In some cases, a base film satisfying α _c ≦ α _b ≦ α _s may be formed.
When such a base film is formed, when the transport roll is used in the presence of a corrosive gas such as sulfur oxide, corrosion of the roll base material due to the corrosive gas that has passed through the ceramic spray coating can be suppressed. .
Incidentally, the linear thermal expansion coefficient alpha _b of the base film, and linear thermal expansion coefficient alpha _c of the ceramic sprayed coating, the linear thermal expansion coefficient alpha _s of the roll base material, in order to position the intermediate, and the roll base material described above Further, it is possible to further improve the action of suppressing the peeling of the ceramic sprayed coating resulting from the difference in the coefficient of linear thermal expansion between the ceramic sprayed coating and the ceramic sprayed coating. The linear thermal expansion coefficient α _b can be measured using a push rod dilatometer in the same manner as described above.

(cermet)
The cermet forming the base film is not particularly limited as long as the linear thermal expansion coefficient α _b satisfies the above range, and a known cermet can be appropriately used as the base film in the glass transport roll.
For example, chromium carbide cermet, boride cermet, oxide dispersion cermet and the like are preferably used.

The chromium carbide cermet is composed of a ceramic phase mainly composed of chromium carbide and a metal phase serving as a binder. The ceramic phase is mainly composed of Cr ₃ C ₂ , but may contain Cr ₂₃ C ₆ , Cr ₇ C _3, etc. as inevitable impurities. In addition, the main body in this invention refers to the compound used as the center in comprising a ceramic sprayed coating or a ceramic layer, and the compound is the compound whose content rate is 50% or more.
Further, “consisting mainly of Cr ₃ C ₂ ” means that the ceramic phase contains the largest amount of Cr ₃ C ₂ , and specifically, 50% by mass or more with respect to the entire ceramic phase, preferably Means 80% by weight or more. Here, the metal phase is made of a heat resistant alloy containing two or more metals selected from Co, Ni, and Cr.
The ceramic phase content in the chromium carbide cermet is preferably 45 to 95% by mass, and the metal phase content is preferably 5 to 55% by mass. The ratio of the ceramic phase and the metal phase can be obtained by obtaining the area ratio of each phase based on the cross-sectional photograph and converting it to the mass ratio (the same applies hereinafter).
As a raw material for forming a chromium carbide-based cermet sprayed coating, a powder prepared by sintering a mixture of chromium carbide ceramics and a heat-resistant alloy serving as a binder, pulverizing and adjusting the particle size to about 30 to 150 μm is used. It is preferable to use it. A commercially available chromium carbide cermet sprayed material may be used.

The boride-based cermet is composed of a ceramic phase mainly composed of a composite boride containing at least one of Mo and W, Co, Cr and B, and a metal phase mainly composed of Co and Cr. Here, the “ceramic phase mainly composed of composite boride” means that the ceramic phase contains the largest amount of composite boride, and specifically, 50% by mass or more based on the entire ceramic phase. , Preferably, it means that 80% by weight or more is contained.
Preferable content of each element constituting the ceramic phase is Mo: 60% by mass or less, W: 74% by mass or less, Co: 15-36% by mass, Cr: 3-16% by mass, B: 4-7% by mass The total of Mo and W is 65% by mass or more. In addition to these elements, the ceramic phase may contain Nb, Ta, V, etc. as inevitable impurities.
The total content of Co and Cr in the metal phase is preferably 75% by mass or more. Moreover, it is preferable that mass ratio (Cr: Co) of Cr content and Co content in the metal phase is 1: 0.15 to 1: 0.40. In addition to Co and Cr, the metal phase may contain Ti, Al, Ta, Nb, etc. as inevitable impurities.
A preferable content of the ceramic phase in the boride-based cermet is 40 to 80% by mass, and more preferably 50 to 75% by mass. The preferable content rate of a metal phase is 20-60 mass%, and 25-50 mass% is more preferable.

The oxide-dispersed cermet is composed of a ceramic phase mainly composed of oxide and a metal phase serving as a binder. The ceramic phase is mainly composed of Al ₂ O ₃ , but may contain ZrO ₂ , Cr ₂ O ₃ or the like which does not melt even at high temperatures. Here, “consisting mainly of Al ₂ O ₃ ” means containing the most Al ₂ O ₃ in the ceramic phase, specifically, 50% by mass or more based on the entire ceramic phase, Preferably, it means that 80% by weight or more is contained. The metal phase is made of a heat-resistant alloy containing two or more metals selected from Co, Ni, and Cr. For example, a Ni-based alloy, a Co-based alloy, or the like is preferably used. Examples of the Ni-based alloy include a Cr—Ni alloy containing about 20 to 70% by mass of Cr. Examples of the Co-based alloy include a Co alloy containing 15 to 30% by mass of Cr, 5 to 16% Al, and 0.1 to 1% by mass of Y. Moreover, a well-known MCrAlY alloy (M is at least 1 type of Ni and Co) etc. can also be used.
The ceramic phase content in the oxide dispersion cermet is preferably 5 to 20% by mass, and the metal phase content is preferably 80 to 95% by mass.
As a raw material for forming an oxide-dispersed cermet sprayed coating, it is preferable to use a mixture of an oxide whose particle diameter is adjusted to about 10 to 100 μm and a heat-resistant alloy as a binder.

(metal)
The metal forming the base film is not particularly limited as long as the linear thermal expansion coefficient α _b satisfies the above range, and a known metal material can be appropriately used as the base film in the glass transport roll.

  For example, a Ni-based alloy, a Co-based alloy, or the like is preferably used as the metal material for the base film. Examples of the Ni-based alloy include a Cr—Ni alloy containing about 20 to 70% by mass of Cr. Examples of the Co-based alloy include a Co alloy containing 15 to 30% by mass of Cr, 5 to 16% by mass of Al, and 0.1 to 1% by mass of Y. Also, a known cobalt-based alloy such as a stellite alloy or a trivalloy alloy can be used.

  As a constituent material of the base film, cermet is more preferable in terms of high adhesion to the roll base material.

The base film can be formed by a known spraying method such as plasma spraying or high-speed flame spraying. However, it is preferably formed by plasma spraying in that a high melting temperature can be realized and the sprayed particles can be in a semi-molten state.
The raw material used for forming the base film is preferably a powder raw material, and the powder raw material is preferably used for thermal spraying as a granulated sintered powder or sintered pulverized powder by mixing, granulating, sintering, pulverizing, classification, etc. in advance. .

The thickness of the base film is preferably 30 to 150 μm, and more preferably 50 to 80 μm. When the thickness of the base film is in the above range, the adhesion of the ceramic sprayed coating is easily obtained.
Moreover, when forming a base film between a roll base material and a ceramic sprayed coating, it is preferable that the sum total of the thickness of a base film and a ceramic sprayed coating is 100-500 micrometers.

  The base film in one embodiment of the present invention preferably has a porosity of 0.5 to 5% according to a cross-sectional image analysis method. If the porosity of the underlying film is in the above range, the roll base metal is corroded by the corrosive gas that has passed through the ceramic spray coating when the transport roll is used in the presence of a corrosive gas such as sulfur oxide. Can be suppressed over a relatively long period of time.

  When forming the roll base material, the ceramic sprayed coating, and the base film, it is preferable to perform a blasting process for roughening the surface of the roll base material before forming the base film. The surface roughness (arithmetic average height Ra defined in JIS B0601: 2001, the same shall apply hereinafter) of the roll base material after the blast treatment is preferably 2.0 to 5.0 μm.

<Method for producing plate glass>
The manufacturing method of the plate glass of 1 aspect of this invention can be utilized regardless of well-known various manufacturing methods, such as plate glass for construction, automobile glass, and plate glass for displays, and a glass composition. For example, a sheet glass manufacturing method generally includes a melting step in which raw materials are melted to obtain molten glass, a molding step in which molten glass is molded, and slow cooling in which the glass after molding is gradually cooled to remove stress. And a cutting step of cutting the glass. There are various molding processes such as a float process, a roll-out process, a down draw process, and a fusion process. The conveyance roll of the present invention can be used anywhere as long as it is in the process intended for conveyance in the above process, and is mainly at a high temperature in each process after the molding process and between each process, preferably 550 to 750. It is used to transport glass ribbons in the atmosphere at 0 ° C and flat glass after cutting.

Furthermore, when a physical strengthening process is included after the above-described cutting process, the sheet glass after the above cutting is moved using a transport roll, heated to a temperature higher than the softening point in a tempering furnace, then rapidly cooled with cooling air, or softened as necessary. The plate glass formed after heating to a point or higher is quenched with cooling air. The rapid cooling is usually performed by blowing cooling air from a plurality of nozzles opposed to the glass surface. As a result, compressive residual stress is applied to the surface of the glass, and a tempered glass sheet is obtained by a so-called physical strengthening method or air cooling strengthening method. The said physical reinforcement | strengthening process may be continued with the said cutting process, may take out plate glass after storing plate glass, and may perform it after cutting | disconnection as needed. The conveyance roll of the present invention can be used anywhere as long as it is intended for conveyance during the above process.
In addition to the physical strengthening step in the plate glass manufacturing method, there is a so-called chemical strengthening step in which compressive stress is chemically applied to the glass surface by ion exchange. The conveyance roll of one embodiment of the present invention can be used even for the purpose of conveyance during the chemical strengthening step.
A high-quality plate glass can be provided by the above-described method for producing a plate glass using the glass transport roll of the present invention.

The production roll and the production method of the conveyance roll in one embodiment of the present invention will be described in more detail below using examples, but the present invention is not limited to these examples.
Example 1
First, a roll base material made of stainless steel (SUS430 equivalent, for high temperature) containing about 18% by mass of Cr was prepared. The linear thermal expansion coefficient α _s in the temperature range of 500 to 750 ° C. of this roll base material is 12 × 10 ⁻⁶ / ° C. The shape of the roll base material is a disk shape with an outer diameter of 150 mm × thickness of 20 mm for convenience in use in the test described later, the radial cross section of the outer peripheral surface of the roll is an outwardly convex curved surface, and the curvature radius of the curved surface Was 50 mm.
The linear thermal expansion coefficient of the roll base material was measured using the aforementioned push rod dilatometer.
Next, the outer peripheral surface of the roll base material was blasted using alumina particles having an average particle diameter of about 300 μm, and the surface roughness (Ra) was set to 3.0 μm. The surface roughness was measured with a surface roughness / contour shape measuring instrument (SURFCOM130A manufactured by Tokyo Seimitsu Co., Ltd.).
After the blast treatment, a base film made of Al ₂ O ₃ —CoNiCrAlY was formed by plasma spraying. A powder having a particle size of 50 to 150 μm was used as the thermal spray material. The film thickness of the obtained base film was 80 μm.

The linear thermal expansion coefficient α _b of the base film in the temperature range of 500 to 750 ° C. is measured by the following procedure.
After a thermal spray coating having a thickness of 1 mm is formed on the surface of a carbon flat plate, only the coating is mechanically peeled off and measured in an argon atmosphere using a push rod dilatometer.
The linear thermal expansion coefficient α _b of the base film is 12 × 10 ⁻⁶ / ° C.

Next, a ceramic sprayed coating was formed on the base film by plasma spraying. As a thermal spraying raw material, yttria stabilized zirconia (3YSZ) and yttrium fluoride at 7 wt. % Added, powder having a particle size of 10 to 60 μm was used. The obtained ceramic sprayed coating had a film thickness of 400 μm, a surface roughness (Ra) of 2.0 μm, and a porosity of 8%.
Subsequently, the surface of the ceramic sprayed coating was polished by hand polishing. The film thickness of the ceramic sprayed coating after polishing was 300 μm, the surface roughness (Ra) was 0.5 μm, and the porosity was 8%.

Next, the silica precursor solution was applied onto the polished ceramic spray coating, and the pores of the ceramic spray coating were impregnated with the silica precursor solution. The silica precursor solution is a polysilazane-based perhydropolysilazane xylene solution (perhydropolysilazane containing) that easily impregnates the pores of the sprayed coating and easily reacts with atmospheric oxygen and moisture to form amorphous silica. Amount: 10% by mass). The coating method was performed by painting with a brush. The same results can be obtained even if the application method is a method such as spraying, roll coating, or liquid immersion. The coating was performed until the solution was sufficiently infiltrated into the ceramic spray coating, and the remaining of the solution on the ceramic spray coating was visually confirmed, and the coating amount was controlled by this visual observation.
After the application, the silica precursor solution on the surface of the ceramic sprayed coating was wiped off using a wiping cloth, and the residual film thickness of the silica precursor solution on the surface of the ceramic sprayed coating was set to 1 μm or less. These operations were performed in an air environment having a temperature of 5 to 35 ° C. and a relative humidity of 35 to 60%. Thereafter, the silica precursor solution was cured by holding in room temperature atmosphere for 24 hours to obtain a sprayed coating in which pores of the ceramic sprayed coating were sealed. The porosity after the sealing treatment was 1% or less.
In addition, the same result as the case where it hold | maintains at room temperature air | atmosphere for 24 hours is obtained also by hold | maintaining in the air | atmosphere of 100 degreeC temperature.

The linear thermal expansion coefficient α _c of the ceramic spray coating in the temperature range of 500 to 750 ° C. and the elongation due to thermal expansion from room temperature to 750 ° C. were evaluated by the following procedure.
Yttrium fluoride was mixed with yttria-stabilized zirconia (3YSZ) at a specified ratio, and a sintered body having a diameter of 20 mm and a length of 20 mm was produced by using a spark plasma sintering (SPS) method. The linear thermal expansion coefficient in the temperature range of 20 to 750 ° C. of the sintered body was measured with a Rigaku thermomechanical analyzer (TMA) to determine the linear thermal expansion coefficient α _c in the temperature range of 500 to 750 ° C. Further, the elongation due to thermal expansion at the time of measuring the linear thermal expansion coefficient was defined as elongation due to thermal expansion from room temperature to 750 ° C.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 12 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.9%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic sprayed coating and the roll base material is 0 × 10 ⁻⁶ / ° C.

(Example 2)
The same procedure as in Example 1 was performed except that yttria-stabilized zirconia (8YSZ) powder having a particle size of 10 to 60 μm was used as a raw material for the ceramic spray coating.
The porosity of the ceramic sprayed coating after the sealing treatment was 1%.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s of the ceramic spray coating and the roll base material was 2 × 10 ⁻⁶ / ° C.
(Example 3)
As a thermal spraying raw material, magnesia (MgO) and zirconia (ZrO ₂ ) at 12.5 wt. %, Silica (SiO ₂ ) 6.5 wt. The same procedure as in Example 1 was performed, except that sintered and pulverized powder having a particle diameter of 10 to 60 μm was mixed and sintered without clogging.
The porosity of the ceramic sprayed coating not subjected to the sealing treatment was 8%.
Further, the linear thermal expansion coefficient α _c of the ceramic spray coating was 12 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.9%.
There was no difference (α _s −α _c ) between the coefficient of linear thermal expansion α _c and α _s between the ceramic sprayed coating and the roll base material (0 × 10 ⁻⁶ / ° C.).
Example 4
As a thermal spraying raw material, magnesia (MgO) and zirconia (ZrO ₂ ) 7 wt. %, The same procedure as in Example 1 was carried out except that sintered and pulverized powders having a particle diameter of 10 to 60 μm were mixed in a ratio of silica (SiO ₂ ).
The porosity of the ceramic sprayed coating after the sealing treatment was 1%.
Further, the linear thermal expansion coefficient α _c of the ceramic spray coating was 12 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.9%.
There was no difference (α _s −α _c ) between the coefficient of linear thermal expansion α _c and α _s between the ceramic sprayed coating and the roll base material (0 × 10 ⁻⁶ / ° C.).

(Comparative Example 1)
In all of the comparative examples, a roll base material made of stainless steel (SUS310 equivalent, for high temperature) containing about 25% by mass of Cr was used. The linear thermal expansion coefficient α _s in the temperature range of 500 to 750 ° C. of this roll base material is 17 × 10 ⁻⁶ / ° C.
Moreover, all the comparative examples used the powder of the yttria stabilized zirconia (8YSZ) with the particle diameter of 10-60 micrometers which does not add the yttrium fluoride to the raw material of a ceramic sprayed coating.
The porosity of the ceramic sprayed coating after polishing was 8%, and the porosity of the ceramic sprayed coating after sealing treatment was 1%.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic spray coating and the roll base material was 7 × 10 ⁻⁶ / ° C.

(Comparative Example 2)
It is the same as Comparative Example 1 except that the porosity of the ceramic sprayed coating after polishing is 2% and the porosity of the ceramic sprayed coating after sealing treatment is 1%.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic spray coating and the roll base material was 7 × 10 ⁻⁶ / ° C.

(Comparative Example 3)
The same as Comparative Example 1 except that the ceramic sprayed coating after polishing was not sealed.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic spray coating and the roll base material was 7 × 10 ⁻⁶ / ° C.

(Comparative Example 4)
The same as Comparative Example 2 except that the ceramic sprayed coating after polishing was not sealed.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic spray coating and the roll base material was 7 × 10 ⁻⁶ / ° C.

(Comparative Example 5)
The same as Comparative Example 1 except that the surface of the ceramic sprayed coating after the sealing treatment was polished by 20 μm by manual polishing. The surface sprayed ceramic spray coating had a surface roughness (Ra) of 0.5 μm and a porosity of 1%.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic spray coating and the roll base material was 7 × 10 ⁻⁶ / ° C.

(Comparative Example 6)
The same as Comparative Example 1 except that the surface of the ceramic sprayed coating after the sealing treatment was polished by 200 μm by hand polishing. The surface sprayed ceramic spray coating had a surface roughness (Ra) of 0.5 μm and a porosity of 1%.
The linear thermal expansion coefficient α _c of the ceramic sprayed coating was 10 × 10 ⁻⁶ / ° C., and the elongation due to thermal expansion from room temperature to 750 ° C. was 0.75%.
The difference (α _s −α _c ) between the linear thermal expansion coefficients α _c and α _s between the ceramic spray coating and the roll base material was 7 × 10 ⁻⁶ / ° C.

(Evaluation of particle adhesion)
In order to evaluate the performance of the roll for glass conveyance based on the above samples, the adhesion of particles to the glass plate at a high temperature was evaluated by the following method.
FIG. 1 is a schematic diagram for explaining a test apparatus used for the evaluation. This test apparatus is configured by combining a roll-on-disk type rolling friction tester (hereinafter sometimes simply referred to as a tester) 1 (manufactured by Takachiho Seiki Co., Ltd.) and an electric furnace (not shown).
In the roll-on-disk type rolling friction tester 1, the peripheral surface of a glass transport roll (hereinafter sometimes simply referred to as a roll) 3 is in contact with the upper surface of a disk-shaped glass plate 2 that rotates in the circumferential direction. It is provided to do. The roll 3 is rotatable in the circumferential direction, the rotation axis direction is the same as the radial direction of the glass plate 2, and is provided so as to be able to advance and retreat in the rotation axis direction.
In the testing machine 1, the upper surface of the glass plate 2 and the peripheral surface of the roll 3 are brought into contact with each other, and a constant load is applied to the roll 3 in the direction from the center of the roll 3 toward the glass plate 2. When the plate 2 is rotated, the roll 3 rotates so as to roll on the glass plate 2 along with the rotation. And while rotating the glass plate 2, the roll 3 rolls forward while drawing a spiral friction mark on the upper surface of the glass plate 2 by advancing the roll 3 toward the center of the glass plate 2 in the rotation axis direction. Moreover, in the said Example and comparative example, since the outer peripheral surface of the roll was made into the outward convex curved surface, the contact with the upper surface of the glass plate 2 and the peripheral surface of the roll 3 becomes a point contact, and a friction trace becomes linear. .
The testing machine 1 is accommodated in an electric furnace, and the atmospheric temperature of the testing machine 1 is controlled to a predetermined temperature.

The test conditions were an atmospheric temperature of 600 ° C., a load of 500 gf on the roll 3, a radius of the glass plate 2 of 90 mm, a rotation speed of the glass plate 2 of 0.5 rps, and a width of the friction trace (corresponding to a point contact diameter between the glass plate 2 and the roll 3. The distance between the friction marks in the radial direction of the glass plate 2 (the distance between the centers in the width direction of the friction marks) was 0.125 mm.
First, the glass plate 2 and the roll 3 were set in the testing machine 1. The temperature in the electric furnace was raised to 600 ° C. so that the glass plate 2 and the roll 3 were not in contact with each other. After holding at 600 ° C. for 30 minutes, when the temperature of the glass plate 2 and the roll 3 becomes sufficiently uniform, the peripheral surface of the roll 3 is brought into contact with the edge of the upper surface of the glass plate 2 and a predetermined load is applied to the roll 3. In the applied state, the rotation of the glass plate 2 and the advance of the roll 3 in the axial direction (axial feed) were started simultaneously. The axial feed speed of the roll 3 is set so that the distance between the friction marks becomes a predetermined value. When the roll 3 reached the center of the glass plate 2, the contact between the two was released, and the rotation of the glass plate 2 was stopped. And the temperature in an electric furnace was dropped gradually so that the glass plate 2 might not be broken, and after lowering to room temperature, the glass plate 2 was taken out.

The following method evaluated how much ZrO ₂ particles adhered to the upper surface of the glass plate 2 thus obtained.
On the upper surface of the obtained glass plate 2, observation points were determined at intervals of 10 mm along the radial direction from the edge toward the center. A glass plate piece of an appropriate size including all of the observation points was cut out from the glass plate 2, and the upper surface thereof was carbon coated. Thereafter, a backscattered electron image centered on each observation point was photographed at a constant magnification by an electron microscope, and based on the area of ZrO ₂ particles present in each photographed image (observation region) and the total area of the photographed image, The particle adhesion rate in each observation region was calculated according to equation (1).
Particle adhesion rate (%) = (total area of ZrO ₂ particles / total area of photographed image) × 100 (1)

In this way, the glass conveying rolls obtained in Examples 1 to 4 and Comparative Examples 1 to 6, shows the result of measuring the deposition rate of ZrO ₂ particles to the glass plate in FIG.
In FIG. 2, the horizontal axis indicates the distance from the edge (outer periphery) of the glass plate 2 to each observation point, and the vertical axis indicates the particle adhesion rate (unit:%) to the glass plate.

As shown in the graph of FIG. 2, the glass conveyance rolls of Comparative Examples 1 to 6 caused much adhesion of ZrO ₂ particles from the roll to the glass plate, whereas the glass conveyance rolls of Examples 1 and 2 The roll for use had an adhesion rate of such particles of almost 0%, and Examples 3 and 4 also had an adhesion rate of 0.05% or less, and the adhesion was well suppressed. Since Comparative Examples 5 and 6 were polished after the sealing treatment, foreign matter adhered due to polishing scraps on the surface of the film or cracks in the film due to processing stress.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2013-127591 filed on Jun. 18, 2013, the contents of which are incorporated herein by reference.

ADVANTAGE OF THE INVENTION According to this invention, in the roll for glass conveyance by which the metal roll base material surface was coat | covered with the ceramic sprayed coating, particle | grain omission from this ceramic sprayed coating and peeling of this ceramic sprayed coating itself can be suppressed significantly. .
Further, in the glass transport roll of the present invention, when a base film made of cermet or metal is formed between the roll base material and the ceramic spray coating, in the presence of corrosive gas such as sulfur oxide. When the transport roll is used, corrosion of the roll base material due to the corrosive gas that has passed through the ceramic spray coating can be suppressed.
High quality plate glass can be provided by the manufacturing method of plate glass and tempered plate glass using the roll for glass conveyance of the present invention.

1 Roll-on-disk type rolling friction tester (tester)
2 Glass plate 3 Glass transport roll (roll)

Claims (24)

The roll base material made of metal is a roll for glass conveyance coated with a ceramic spray coating,
Α _s −α _c ≦ 2 × 10 ⁻⁶ when α _s is the linear thermal expansion coefficient of the roll base material and α _c is the linear thermal expansion coefficient of the ceramic sprayed coating in the temperature range of 500 to 750 ° C. / ° C., 8 × 10 ⁻⁶ / ° C. ≦ α _c ≦ 14 × 10 ⁻⁶ / ° C.
The elongation due to thermal expansion of the ceramic sprayed coating from room temperature to 750 ° C. is 0.6 to 1.05%,
The ceramic sprayed coating has a thickness of 100 to 500 μm,
A glass conveying roll, wherein the ceramic sprayed coating has a porosity of 2% or less by a cross-sectional image analysis method. The roll for glass conveyance according to claim 1, wherein 10 × 10 ⁻⁶ / ° C. ≦ α _s ≦ 16 × 10 ⁻⁶ / ° C.   The glass conveying roll according to claim 1 or 2, wherein the ceramic sprayed coating is formed by plasma spraying, and the formed coating is sealed.   The roll for glass conveyance of Claim 3 in which the said sealing process is made | formed by the impregnation of a silica precursor solution.   The glass conveying roll according to claim 3, wherein the sealing treatment is performed by explosion spraying. When the linear thermal expansion coefficient is α _b in the temperature range of 500 to 750 ° C., between the roll base material and the ceramic spray coating, and α _c ≦ α _b ≦ α _s. The roll for glass conveyance of any one of Claims 1-5 in which the base film which satisfy | fills is formed.   The said base film is a roll for glass conveyance of Claim 6 currently formed by plasma spraying.   The glass transport roll according to claim 6 or 7, wherein the base film is made of cermet, and the cermet is any one of oxide dispersion cermet, chromium carbide cermet, and boride cermet. The base film is made of cermet, the ceramic phase of the cermet is mainly made of Al ₂ O ₃ , and the metal phase of the cermet is made of MCrAlY alloy (M is at least one of Ni and Co). The roll for glass conveyance of 7.   The roll for glass conveyance of any one of Claims 6-9 whose thickness of the said base film is 30-150 micrometers, and the sum total of the thickness of the said base film and the said ceramic sprayed coating is 100-500 micrometers.   The ceramic sprayed coating contains 7 to 23 wt. The roll for glass conveyance of any one of Claims 1-10 which consists of stabilized zirconia containing%. The ceramic sprayed coating includes a plurality of metal oxides, and the metal oxide has a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. or less and a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. The roll for glass conveyance of any one of Claims 1-10 containing 1 or more each larger metal oxide. The metal oxide having a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. or less contains ZrO _2, and the metal oxide having a linear thermal expansion coefficient greater than 11 × 10 ⁻⁶ / ° C. is at least one of MgO and CaO. The roll for glass conveyance of Claim 12 containing these.   The roll for glass conveyance of any one of Claims 1-13 whose hardness of the said ceramic sprayed coating is Hv600 or more. Formation of a ceramic sprayed coating on the surface of a roll base material having a linear thermal expansion coefficient α _s in the temperature range of 500 to 750 ° C. of 10 × 10 ⁻⁶ / ° C. ≦ α _s ≦ 16 × 10 ⁻⁶ / ° C. A membrane process;
An impregnation step of impregnating the ceramic sprayed coating with a silica precursor solution;
The manufacturing method of the roll for glass conveyance which has a hardening process which hardens this silica precursor solution and seals a ceramic sprayed coating. The surface of a roll base material having a linear thermal expansion coefficient α _s in a temperature range of 500 to 750 ° C. of 10 × 10 ⁻⁶ / ° C. ≦ α _s ≦ 16 × 10 ⁻⁶ / ° C. is subjected to thermal spraying consisting of metal or cermet. A first film forming step for forming a base film;
A second film forming step of forming a ceramic sprayed coating on the sprayed undercoat;
An impregnation step of impregnating the ceramic sprayed coating with a silica precursor solution;
The manufacturing method of the roll for glass conveyance which has a hardening process which hardens this silica precursor solution and seals a ceramic sprayed coating.   The method for producing a roll for conveying a glass according to claim 16, wherein the cermet of the thermal spray base film is any one of an oxide dispersion cermet, a chromium carbide cermet, and a boride cermet.   The roll for glass conveyance of any one of Claims 15-17 which has a grinding | polishing process which grind | polishes the surface of the said ceramic sprayed coating between the film-forming process of the said ceramic sprayed coating, and the said impregnation process. Production method.   The method for producing a glass transport roll according to any one of claims 15 to 18, wherein the ceramic sprayed coating has a porosity of 2% or less as measured by a cross-sectional image analysis method.   The ceramic sprayed coating contains 7 to 23 wt. The manufacturing method of the roll for glass conveyance of any one of Claims 15-19 which consists of stabilized zirconia containing%. The ceramic sprayed coating includes a plurality of metal oxides, and the metal oxide has a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. or less and a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. The manufacturing method of the roll for glass conveyance of any one of Claims 15-19 containing 1 or more each larger metal oxide. The metal oxide having a linear thermal expansion coefficient of 11 × 10 ⁻⁶ / ° C. or less contains ZrO _2, and the metal oxide having a linear thermal expansion coefficient greater than 11 × 10 ⁻⁶ / ° C. is at least one of MgO and CaO. The manufacturing method of the roll for glass conveyance of Claim 21 containing these.   The manufacturing method of plate glass which has the process of conveying glass using the roll for glass conveyance of any one of Claims 1-14.   The manufacturing method of the plate glass of Claim 23 which uses the said roll for glass conveyance under the atmospheric temperature of 550-750 degreeC.

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