JP2003300742A - In-furnace roll of sheet glass heat treatment furnace and method for manufacturing the same - Google Patents
In-furnace roll of sheet glass heat treatment furnace and method for manufacturing the sameInfo
- Publication number
- JP2003300742A JP2003300742A JP2002102391A JP2002102391A JP2003300742A JP 2003300742 A JP2003300742 A JP 2003300742A JP 2002102391 A JP2002102391 A JP 2002102391A JP 2002102391 A JP2002102391 A JP 2002102391A JP 2003300742 A JP2003300742 A JP 2003300742A
- Authority
- JP
- Japan
- Prior art keywords
- roll
- heat treatment
- glass
- furnace
- chromium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005357 flat glass Substances 0.000 title claims abstract description 39
- 238000010438 heat treatment Methods 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 title description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 36
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 32
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000010304 firing Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 38
- 239000005350 fused silica glass Substances 0.000 claims description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 239000005388 borosilicate glass Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000005365 phosphate glass Substances 0.000 claims description 4
- 239000005368 silicate glass Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 229910021487 silica fume Inorganic materials 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 11
- 238000011282 treatment Methods 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B35/00—Transporting of glass products during their manufacture, e.g. hot glass lenses, prisms
- C03B35/14—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands
- C03B35/16—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands by roller conveyors
- C03B35/18—Construction of the conveyor rollers ; Materials, coatings or coverings thereof
- C03B35/181—Materials, coatings, loose coverings or sleeves thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
- Tunnel Furnaces (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、板ガラスを熱処理
する炉に用いる炉内ロールとその製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a furnace roll used in a furnace for heat treatment of sheet glass and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来、自動車等の窓ガラスに用いられ
る、湾曲したガラス板は、平板状のガラス板を加熱して
湾曲させる成形にて製造するのが一般的である。この加
熱成形は、平板状のガラス板をローラコンベア上で搬送
しながらヒータで加熱する形式の加熱炉内で行われてい
る。すなわち、加熱炉にて約650〜780 ℃の曲げ成形温
度まで加熱された平板状のガラス板は、例えば１つのモ
ールドでプレス成形されたのち、2つの湾曲ローラーに
よる成形を経て、所望の曲率の湾曲ガラス板に成形され
る。このような加熱炉内において、ローラコンベアを構
成する各ローラは、加熱炉の高温にも耐え得る必要があ
るため、シリカ等のセラミックスから製造されている。2. Description of the Related Art Conventionally, a curved glass plate used for a window glass of an automobile or the like is generally manufactured by heating a flat glass plate to bend it. This heat molding is performed in a heating furnace of a type in which a flat glass plate is conveyed by a roller conveyor and heated by a heater. That is, a flat glass plate heated to a bending temperature of about 650 to 780 ° C. in a heating furnace is press-molded by, for example, one mold and then molded by two curving rollers to obtain a desired curvature. It is formed into a curved glass plate. In such a heating furnace, each roller constituting the roller conveyor needs to be able to withstand the high temperature of the heating furnace, and thus is manufactured from ceramics such as silica.
【０００３】ところで、加熱炉内および加熱炉の搬出口
付近を搬送されるガラス板には、ローラに付着している
異物が付着したり、またガラス板が高温に加熱されて軟
化しているため、その搬送時にローラ表面の凹凸がガラ
ス板に転写されることがある。特に、ローラ表面が剥離
して生じたダストは、ガラス板の品質を著しく低下する
ため、その発生を確実に抑制する必要があり、従来は定
期的にローラを洗浄または研磨して、その表面を清浄に
することによってダストの発生を抑制し、またローラの
表面を平滑化することによって転写の発生を抑制してい
た。By the way, foreign substances adhering to the rollers adhere to the glass plate conveyed in the heating furnace and in the vicinity of the outlet of the heating furnace, and the glass plate is softened by being heated to a high temperature. During the transportation, irregularities on the roller surface may be transferred to the glass plate. In particular, dust generated by peeling off the roller surface significantly deteriorates the quality of the glass plate, so it is necessary to reliably suppress the generation of the dust. Conventionally, the roller is regularly cleaned or polished to clean the surface. Generation of dust was suppressed by cleaning, and transfer was suppressed by smoothing the surface of the roller.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ローラ
を洗浄または研磨するためには、製造工程を中断してロ
ーラをラインから取り外し、取り外したローラを人手で
研磨する必要があり、このメンテナンスは負担が大きい
ことが問題になっていた。However, in order to clean or polish the roller, it is necessary to interrupt the manufacturing process, remove the roller from the line, and manually polish the removed roller, which is a burden for maintenance. The big thing was a problem.
【０００５】そこで、本発明は、このような課題を解決
するためのものであり、従来に比べてダストの発生並び
に異物の付着の少ない、メンテナンスフリーの炉内ロー
ラを、その製造方法とともに提供することを目的とす
る。Therefore, the present invention is to solve such a problem, and provides a maintenance-free in-furnace roller with less generation of dust and adhesion of foreign matter as compared with the conventional method, together with its manufacturing method. The purpose is to
【０００６】[0006]
【課題を解決するための手段】本発明者らは、表面が清
浄で高品質な板ガラスを得るための方法について鋭意究
明したところ、加熱炉内において板ガラスを搬送、保持
する、炉内ロールの板ガラスとの接触面において、高温
のガラスと反応しにくく、かつガラスとの接触、擦過に
対してロール基材構成成分の離脱およびそれの製品ガラ
ス表面への付着が少ない、溶融シリカ材の形成技術を確
立するのが有効であることを見出した。すなわち、板ガ
ラスを搬送、保持する、溶融シリカ材製のロールにおい
て、その表層の板ガラスと接触する部分に対して、酸化
クロム単独あるいは、これと焼結助剤とからなる複合酸
化物皮膜を形成して、表層のシリカ粒子間の結合を高め
ることが、所期した特性の向上に極めて有効であるのを
知見し、本発明を完成するに到った。DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies on a method for obtaining a sheet glass having a clean surface and high quality. As a result, the sheet glass of a roll in a furnace that conveys and holds the sheet glass in a heating furnace. A technique for forming fused silica material that does not easily react with high temperature glass on the contact surface with the glass, and has little detachment of the constituent components of the roll base material and its adhesion to the surface of the product glass due to contact with the glass and abrasion. It has been found to be effective to establish. That is, in a roll made of fused silica material that conveys and holds plate glass, chromium oxide alone or a composite oxide film consisting of this and a sintering aid is formed on the surface layer contacting plate glass. As a result, they have found that increasing the bonding between the silica particles in the surface layer is extremely effective in improving the desired properties, and have completed the present invention.
【０００７】本発明の構成は、次のとおりである。
（１）板ガラスの熱処理炉において、該板ガラスの搬送
ラインを構成する、溶融シリカ材製のロールであって、
該ロールの表面に、酸化クロム単独あるいは、酸化クロ
ムおよび焼結助剤からなる複合酸化物による改質層を有
することを特徴とする板ガラス熱処理炉の炉内ロール。The structure of the present invention is as follows. (1) A roll made of a fused silica material, which constitutes a sheet glass conveying line in a plate glass heat treatment furnace,
An in-furnace roll for a plate glass heat treatment furnace, characterized in that it has a modified layer of chromium oxide alone or a complex oxide of chromium oxide and a sintering aid on the surface of the roll.
【０００８】（２）改質層は、溶融シリカ材の表面に対
して、酸化クロムを含む水溶液あるいは、酸化クロムお
よび焼結助剤を含む水溶液を、付着させた後、加熱、焼
成してなるものであることを特徴とする上記（１）に記
載の板ガラス熱処理炉の炉内ロール。(2) The modified layer is formed by depositing an aqueous solution containing chromium oxide or an aqueous solution containing chromium oxide and a sintering aid on the surface of the fused silica material, followed by heating and firing. The in-furnace roll of the flat glass heat treatment furnace according to (1) above, which is characterized in that
【０００９】（３）改質層は、SiＯ２粒子間にクロム酸
化物が介在してなることを特徴とする上記（１）に記載
の板ガラス熱処理炉の炉内ロール。(3) The furnace roll of the plate glass heat treatment furnace as described in (1) above, wherein the modified layer is formed by interposing chromium oxide between SiO 2 particles.
【００１０】（４）焼結助剤は、焼成することによって
非晶質無機物質を生成する材料を含む水溶液を塗布、噴
霧もしくはこの水溶液中に浸漬した後、加熱、焼成する
ことによって生成させたものであり、珪酸塩ガラス、ほ
う珪酸塩ガラスあるいはりん酸塩ガラスを主として含む
ものであることを特徴とする請求項１または２に記載の
板ガラス熱処理炉の炉内ロール。(4) The sintering aid is produced by applying, spraying or dipping an aqueous solution containing a material which produces an amorphous inorganic substance by firing, and then heating and firing it. The in-furnace roll of the flat glass heat treatment furnace according to claim 1 or 2, which mainly contains silicate glass, borosilicate glass or phosphate glass.
【００１１】（５）溶融シリカ材は、骨材であるSiＯ2
粒子の構成比率が、平均粒径7〜8μm：70〜90 mass％、
平均粒径0.3〜0.5μｍ：5〜15 mass％および平均粒径0.
1〜0.2μm：５〜15 mass％であり、かつ気孔率が２〜15
％であることを特徴とする請求項１ないし３のいずれか
１項に記載の板ガラス熱処理炉の炉内ロール。(5) The fused silica material is SiO 2 which is an aggregate.
The composition ratio of the particles is such that the average particle size is 7 to 8 μm: 70 to 90 mass%,
Average particle size 0.3-0.5 μm: 5-15 mass% and average particle size 0.
1 to 0.2 μm: 5 to 15 mass% and porosity of 2 to 15
%, The in-furnace roll of the plate glass heat treatment furnace according to any one of claims 1 to 3.
【００１２】（６）板ガラスの熱処理炉において、該板
ガラスの搬送ラインを構成する、溶融シリカ材製のロー
ルについて、該溶融シリカ材の表面に対して、酸化クロ
ムを含む水溶液または、酸化クロムおよび焼結助剤を含
む水溶液を塗布または噴霧するか、あるいは該水溶液中
に浸漬した後、250〜750 ℃で加熱、焼成することを特
徴とする板ガラス熱処理炉の炉内ロールの製造方法。(6) In a plate glass heat treatment furnace, regarding a roll made of a fused silica material that constitutes a conveyance line for the glass sheet, an aqueous solution containing chromium oxide or a mixture of chromium oxide and calcined on the surface of the fused silica material. A method for producing a furnace roll in a plate glass heat treatment furnace, which comprises coating or spraying an aqueous solution containing a binder, or immersing in an aqueous solution and then heating and firing at 250 to 750 ° C.
【００１３】（７）焼結助剤は、焼成することによって
非晶質無機物質を生成する材料を含む水溶液を塗布、噴
霧もしくはこの水溶液中に浸漬した後、加熱、焼成する
ことによって生成させたものであり、珪酸塩ガラス、ほ
う珪酸塩ガラスあるいはりん酸塩ガラスを主として含む
ものであることを特徴とする請求項５に記載の板ガラス
熱処理炉の炉内ロールの製造方法。(7) The sintering aid is produced by applying, spraying or dipping an aqueous solution containing a material which produces an amorphous inorganic substance by firing, and then heating and firing. The method for manufacturing an inner roll of a plate glass heat treatment furnace according to claim 5, characterized in that it mainly contains silicate glass, borosilicate glass or phosphate glass.
【００１４】[0014]
【発明の実施の形態】さて、炉内ロールの基材となる溶
融シリカは、セラミックマトリックス複合材の一種とし
て知られており、工業材料としては、珪砂を溶融したも
のを粉砕したのち、プレス成形し焼成することによって
得られる。BEST MODE FOR CARRYING OUT THE INVENTION Fused silica, which is a base material for furnace rolls, is known as a type of ceramic matrix composite material. As an industrial material, fused silica sand is crushed and then press-molded. It is obtained by firing.
【００１５】発明者らは、このような焼結材である溶融
シリカの表面特性について種々の実験、検討を重ねたと
ころ、これまで工業的に得られているものは、平均粒子
径７〜８μmのSiＯ2粒子を、さらに細かいSiＯ2の粒子
層が結合していて、これらを圧子押し込み法で硬さ測定
すると、それぞれHV 500および同250級の値が得られる
こと、そして表面をSiＣサンドペーパーで擦過すると、
かなり容易に微細なシリカ粒子が脱落することが判明し
た。すなわち、この微細なシリカ粒子が、前記したダス
トの原因になっていたものと考えられ、この微細シリカ
粒子の脱落を防止することが、ダストの発生並びに異物
の付着の少ないロールの実現に有効であることを見出
し、本発明を完成するに到った。なお、前記の溶融シリ
カの表面特性は、市販品溶融シリカの焼結度に起因する
と考えられる。The inventors of the present invention have conducted various experiments and studies on the surface characteristics of fused silica which is such a sintered material. As a result, those obtained so far industrially have an average particle diameter of 7 to 8 μm. of SiO 2 particles, are bound finer SiO 2 layers of particles, when these are measured hardness by indentation method, the value of HV 500 and the 250 grade, respectively are obtained, and SiC surface sandpaper When rubbed with
It was found that the fine silica particles fell off fairly easily. That is, it is considered that the fine silica particles were the cause of the dust described above, and preventing the fine silica particles from falling off is effective in realizing a roll with less dust generation and foreign matter adhesion. It was found that there is something, and the present invention has been completed. The surface characteristics of the fused silica are considered to be due to the degree of sintering of the commercially available fused silica.
【００１６】そこで、本発明では、ロールの表面に、酸
化クロム単独あるいは、酸化クロムおよび焼結助剤から
なる複合酸化物による改質層を形成することによって、
前記の現象を抑制することとした。すなわち、酸化クロ
ム単独あるいはさらに焼結助剤を含む水溶液を、ロール
の溶融シリカ基材の表面に付着させてから焼成すること
によって、SiＯ2粒子間をクロム酸化物が介在した強固
な改質層が形成される結果、微細シリカ粒子の脱落は防
止されるのである。Therefore, in the present invention, by forming a modified layer of chromium oxide alone or a complex oxide of chromium oxide and a sintering aid on the surface of the roll,
It was decided to suppress the above phenomenon. That is, an aqueous solution containing chromium oxide alone or a sintering aid is attached to the surface of the fused silica base material of the roll and then baked to give a strong modified layer in which chromium oxide is present between the SiO 2 particles. As a result, the fine silica particles are prevented from falling off.
【００１７】これらのクロム酸化物あるいは無機焼結助
剤の作用機構について、以下に具体的に説明する。な
お、この改質層は、化学的緻密化法により、基材表面清
浄化→含浸液作用→焼成の工程を繰り返すことによって
得られる。The action mechanism of these chromium oxides or inorganic sintering aids will be specifically described below. The modified layer can be obtained by repeating the steps of cleaning the surface of the base material → action of the impregnating liquid → baking by a chemical densification method.
【００１８】本発明で用いる酸化クロムの水溶液は、間
隙に対する浸透性に優れるとともに、加熱履歴を受ける
ことによって、種々の中間体を経た後、クロム酸化物Cr
2Ｏ3を生成する。そして、浸透した焼結体の微細間隙で
Cr2Ｏ3を生成する結果、焼結体の緻密度を高めるととも
に、SiＯ2粒子間の密着強度を高める作用がある。The aqueous solution of chromium oxide used in the present invention is excellent in the permeability into the gap and, after undergoing various heating intermediates by undergoing a heating history, the chromium oxide Cr.
2 O 3 is produced. And in the fine gap of the infiltrated sintered body
As a result of producing Cr 2 O 3 , it has the effects of increasing the compactness of the sintered body and increasing the adhesion strength between the SiO 2 particles.
【００１９】ここで、含酸化クロム水溶液のロール表面
への含浸そして焼成による、溶融シリカ材表面の強度特
性の向上は、表面ショア硬さの上昇として捉えることが
できる。すなわち、85 mmφ×2800 mmのロールについ
て、含浸、焼成処理しないもの、含浸、焼成処理をそれ
ぞれ１、２、３、６および９回実施したもの、の6本の
ロールを作製し、ロールの同一母線上の複数点において
ショア硬さを測定した。表１に、その結果を示すよう
に、無処理に比べ１回以上の処理実行では、硬さの上昇
が優位に認められる。なお、図２は、含浸回数：なし、
２、３、６および９回のときの改質層の厚みの変化を示
すロール断面図である。Here, the improvement of the strength characteristics of the surface of the fused silica material by impregnating the surface of the roll with the chromium oxide aqueous solution and firing, can be regarded as an increase in the surface Shore hardness. That is, with respect to a roll of 85 mmφ × 2800 mm, six rolls were prepared, one not impregnated and fired, and one impregnated and fired 1, 2, 3, 6 and 9 times, respectively. Shore hardness was measured at a plurality of points on the bus bar. As shown in the results in Table 1, an increase in hardness is recognized predominantly when the treatment is performed one or more times as compared with the case where no treatment is performed. 2 shows the number of impregnations: none,
It is roll sectional drawing which shows the change of the thickness of a modified layer at the time of 2, 3, 6 and 9 times.
【００２０】なお、ショア硬さは、たとえば80程度だと
基材の耐塑性変形能が不十分で、改質層が座屈破壊する
ことがあるから、85以上もあれば十分である。一方、上
限は、シリカ基材の耐塑性変形能を過度に高める必要が
ないから、100以下に調整することが好ましい。If the Shore hardness is, for example, about 80, the plastic deformation resistance of the base material is insufficient and the modified layer may be buckled, so that a hardness of 85 or more is sufficient. On the other hand, the upper limit is preferably adjusted to 100 or less because it is not necessary to excessively increase the plastic deformation resistance of the silica base material.
【００２１】[0021]
【表１】 [Table 1]
【００２２】また、前記改質層の厚みは、ロールの断面
を現出させたうえクロム酸化物Cr2Ｏ3の生成、含浸深さ
を測定することによって求めた。The thickness of the modified layer was obtained by exposing the cross section of the roll and measuring the formation and impregnation depth of chromium oxide Cr 2 O 3 .
【００２３】一方、酸化クロム水溶液などで含浸される
溶融シリカロールの３次元積層構造は、シリカをほとん
どの構成成分とすることが重要であるため、他の焼結助
剤などを積極的に用いることはできない。なぜなら、こ
れらが不純物となる危険性があるからである。したがっ
て、本発明の溶融シリカ材において、骨材であるSiＯ 2
粒子の構成比率は、平均粒径７〜８μmが70〜90 mass％
を占め、平均粒径0.3〜0.5μmが５〜15 mass％および平
均粒径0.1〜0.2μmが５〜15 mass％で粒子間隙を埋め
る、充填構造をとるように配合することが好ましい。On the other hand, it is impregnated with a chromium oxide aqueous solution or the like.
The three-dimensional laminated structure of fused silica roll is
Since it is important which component is used, other sintering aids
Agents and the like cannot be used aggressively. Because this
This is because they have a risk of becoming impurities. According to
In the fused silica material of the present invention, 2
The composition ratio of the particles is such that the average particle size of 7 to 8 μm is 70 to 90 mass%.
The average particle size of 0.3 to 0.5 μm is 5 to 15 mass% and the average particle size is 0.3 to 0.5 μm.
The average particle size of 0.1 to 0.2 μm is 5 to 15 mass% to fill the particle gap.
It is preferable to mix them so as to have a filling structure.
【００２４】ここで、平均粒径とは、中心粒径、すなわ
ち粉末の粒径ごとの頻度重量％を示すヒストグラムを求
め、これから粒子径と累積重量％の関係を得たとき、累
積重量％が50％になるときの粒子径である。Here, the average particle diameter is a central particle diameter, that is, a histogram showing the frequency weight% for each particle diameter of the powder is obtained, and when the relation between the particle diameter and the cumulative weight% is obtained, the cumulative weight% is It is the particle size when it reaches 50%.
【００２５】まず、平均粒径：７〜８μmのものの配合
下限を70 mass％としたのは、この径の粒子が70 mass％
未満になると、細微粉の量が多くなり、成形、焼成の効
率が低下し、ロールのような大型品の作製が困難になる
からである。一方、90 mass％を超えると、積層体の十
分な充填構造が得られ難いことから、90 mass％を上限
とすることが望ましい。First, the lower limit of the compounding of particles having an average particle diameter of 7 to 8 μm is set to 70 mass% because particles having this diameter are 70 mass%.
If it is less than the above range, the amount of fine powder increases, the efficiency of molding and firing decreases, and it becomes difficult to produce a large product such as a roll. On the other hand, when it exceeds 90 mass%, it is difficult to obtain a sufficient filling structure of the laminate, so that it is desirable to set 90 mass% to the upper limit.
【００２６】また、含浸、充填効果が十分でないと、ク
ロム酸化物が存在しない粒界が生じることから、平均粒
径：0.1 〜0.2μmのものの配合を、５〜10 mass％とす
ることが好ましい。この範囲とすることによって、焼結
体の曲げ強度が極大域に達するとともに、本発明の含
浸、充填によるクロム酸化物が粒子間に明瞭に存在する
ことになる。If the effect of impregnation and filling is not sufficient, grain boundaries in which chromium oxide does not exist occur. Therefore, it is preferable to mix 5 to 10 mass% of particles having an average particle diameter of 0.1 to 0.2 μm. . By setting the content in this range, the bending strength of the sintered body reaches the maximum range, and the chromium oxide by the impregnation and filling of the present invention clearly exists between the particles.
【００２７】平均粒径が0.3〜0.5μmのものは、５mass
未満だと、７〜８μｍ粒の粒界を充填する効果が減殺さ
れ焼結体の強度が阻害される。また、15 massを超える
と７〜８μｍ粒子間の間隙が著しく小さくなり、クロム
酸水溶液の含浸が抑制される結果Cr2Ｃ3の生成量が減少
するから、５〜15 mass％とすることが好ましい。If the average particle size is 0.3 to 0.5 μm, it is 5 mass.
If it is less than the above range, the effect of filling the grain boundaries of 7 to 8 μm is diminished and the strength of the sintered body is hindered. Further, when it exceeds 15 mass, the gap between the particles of 7 to 8 μm becomes remarkably small, and the amount of Cr 2 C 3 produced decreases as a result of suppressing the impregnation of the aqueous chromic acid solution. preferable.
【００２８】さらに、溶融シリカ基材の気孔率を２〜15
％とすることが好ましい。すなわち、気孔率が2％より
小さくなると、本発明の含浸効率が著しく低下し、一方
気孔率が15％を超えると、含浸・焼成処理を繰り返して
も、ショア硬さやビッカース硬さであらわされる、表面
硬化および緻密化効果が顕著に得られないため、溶融シ
リカ基材の気孔率を２〜15％、より好ましくは３〜10％
とすることが推奨される。Further, the porosity of the fused silica base material is 2 to 15
% Is preferable. That is, when the porosity is less than 2%, the impregnation efficiency of the present invention is significantly reduced, while when the porosity is more than 15%, it is represented by Shore hardness and Vickers hardness even after repeated impregnation and firing treatments. Since the effect of surface hardening and densification cannot be remarkably obtained, the porosity of the fused silica base material is 2 to 15%, more preferably 3 to 10%.
Is recommended.
【００２９】ちなみに、図１は、本発明に係る改質層を
有する溶融シリカ基材表層部分の断面を示す、走査電子
顕微鏡反射電子線像である。この電子像において、１は
溶融シリカ基材、白い色調の観察されるところが、酸化
クロムの含浸、生成による改質層２である。By the way, FIG. 1 is a scanning electron microscope backscattered electron image showing a cross section of the surface layer of the fused silica substrate having the modified layer according to the present invention. In this electron image, 1 is a fused silica base material, and the observed white color tone is a modified layer 2 due to impregnation and formation of chromium oxide.
【００３０】次に、溶融シリカ基材１そのものおよび、
含酸化クロム水溶液による含浸、焼成回数を変化させた
試料を作製し、これらの表面をＪＩＳ Ｈ 8665に基づく
平面摩耗試験法にて、SiＣサンドペーパーによる摩耗減
量を調べた。その結果を表２に示す。なお、この摩耗試
験は一種の引っかき磨耗であって、引っかき後の試料の
摩耗減量を定量化するものであり、改質面を構成する個
々の粒子間結合力の大きさを表しているものと考えるこ
とができる。Next, the fused silica base material 1 itself and
Samples were prepared by impregnation with an aqueous chromium oxide solution and the number of firings was changed, and the wear loss of these surfaces with a SiC sandpaper was examined by a plane wear test method based on JIS H 8665. The results are shown in Table 2. Incidentally, this abrasion test is a kind of scratch abrasion, which is intended to quantify the amount of abrasion loss of the sample after scratching, and represents the magnitude of the individual interparticle bonding force constituting the modified surface. I can think.
【００３１】[0031]
【表２】 [Table 2]
【００３２】表２から、本発明の含浸改質処理を実施す
ると、改質回数とともに摩耗減量が少なくなり、その量
は比較例である含浸改質処理しないものに比べて78〜60
％にとどまることがわかる。From Table 2, when the impregnation reforming treatment of the present invention is carried out, the amount of wear reduction decreases with the number of reforming, and the amount thereof is 78 to 60 as compared with the non-impregnation reforming treatment which is a comparative example.
It turns out that it stays in%.
【００３３】[0033]
【実施例】実施例１
この実施例１では、本発明にかかる改質処理を施して得
られた溶融シリカ基材とガラスに見立てた引っかき針に
よる改質層表面の引っかき摩耗特性を調査した。すなわ
ち、50×50×６mmの溶融シリカ基材の表面に、比重1.60
の酸化クロム水溶液を50 cm3／ｍ2で塗布してから７分
保持後に、不繊布で表面を拭いとり、550℃で1時間焼成
した。この処理を、１、３および７回行って、それぞれ
試料を作製した。引っかきによる条痕深さの測定結果を
表３に示す。表３から、本発明の溶融シリカ表面改質材
は、非改質材に比べて引っかき摩耗減が有意に減少して
いることが明らかである。EXAMPLES Example 1 In this Example 1, the scratch wear characteristics of the surface of the modified layer by a scratching needle that was likened to the fused silica substrate and glass obtained by performing the modification treatment according to the present invention were investigated. That is, a specific gravity of 1.60 is applied to the surface of a 50 × 50 × 6 mm fused silica substrate.
After applying the chromium oxide aqueous solution of 50 cm 3 / m 2 for 7 minutes, the surface was wiped with a non-woven cloth and baked at 550 ° C. for 1 hour. This treatment was performed 1, 3 and 7 times to prepare samples. Table 3 shows the measurement results of the scratch depth due to scratching. From Table 3, it is clear that the fused silica surface modified material of the present invention has a significantly reduced scratch wear reduction as compared to the unmodified material.
【００３４】[0034]
【表３】 [Table 3]
【００３５】実施例２
この実施例２では、自動車用板ガラス用の熱処理炉内に
おいて、板ガラスの搬送に用いられる炉内ロールの表面
を含酸化クロム水溶液で改質したものを装着し、その効
果を調べた。すなわち、ロール基材に、Al2Ｏ3：2000 p
pm 、Fe2Ｏ3 ：200 ppm および残部SiＯ2の溶融シリカ
を適用して、φ55 mm×2800 mmの寸法のロールを作製し
た。該ロールの周面を、円周方向二等分位置を通る母線
で二分し、その一方の周面部分を一部および他方を二部
とし、一部に対しては、本発明の改質処理を３回実施
し、二部は溶融シリカ基材のままとした。Example 2 In this Example 2, in a heat treatment furnace for sheet glass for automobiles, a furnace roll used for conveying sheet glass, the surface of which was modified with an aqueous solution of chromium oxide, was mounted, and its effect was obtained. Examined. That is, Al 2 O 3 : 2000 p
Fused silica of pm, Fe 2 O 3 : 200 ppm and the balance SiO 2 was applied to make rolls with dimensions of φ55 mm × 2800 mm. The peripheral surface of the roll is bisected by a generatrix passing through the bisecting position in the circumferential direction, one peripheral surface part of which is part and the other part is part of which is partly modified. Was carried out 3 times, and 2 parts were left as the fused silica base material.
【００３６】次いで、炉内にこれらのロールを、50本配
置して、板ガラスを通過させた後、そのガラス表面の異
種材料による汚染について詳細に調査した。すなわち、
製品ガラス表面を詳細に目視観察して、ビルドアップ物
を採取して化学成分分析を行った。その結果を表４に示
す。Next, 50 rolls of these rolls were placed in the furnace, and after passing the glass sheet, the contamination of the glass surface by different materials was investigated in detail. That is,
The surface of the product glass was visually inspected in detail, the build-up product was collected, and the chemical composition was analyzed. The results are shown in Table 4.
【００３７】[0037]
【表４】 [Table 4]
【００３８】表４に示す結果から明らかなように、本発
明による表面改質を行ったロール部分を通過して生産さ
れた板ガラス表面の異種材付着によるビルドアップはほ
とんど認められなかった。これに対して、比較例である
溶融シリカ基材単独の条件では、板ガラス表面に、ほぼ
SiＯ2 100％の付着物が検出された。製品ガラスは、Si
Ｏ2 70％を含有するソーダガラスであることから、この
付着物はロール表面からの汚染と考えられる。As is clear from the results shown in Table 4, almost no build-up was observed due to the adhesion of different materials on the surface of the sheet glass produced by passing through the surface-modified roll portion according to the present invention. On the other hand, under the conditions of the fused silica base material alone, which is a comparative example, the surface of the plate glass is
A 100% SiO 2 deposit was detected. Product glass is Si
Since it is soda glass containing 70% of O 2 , this deposit is considered to be contamination from the roll surface.
【００３９】[0039]
【発明の効果】以上説明したように本発明によれば、表
面の清浄さが要求される板ガラス搬送用溶融シリカ製ロ
ールにおいて、このロール基材の表層を酸化クロム水溶
液あるいはこれと焼結助剤を含む混合水溶液で含浸、焼
成して改質することによって、溶融シリカ基材を構成す
る微細シリカ粒子の離脱、脱落を防ぐことができるた
め、ロールを通過またはロールと接触する板ガラスの表
面汚染を防止するのに有効である。As described above, according to the present invention, in a fused silica roll for conveying flat glass, which requires a clean surface, the surface layer of the roll base material is an aqueous solution of chromium oxide or a sintering aid thereof. By impregnating with a mixed aqueous solution containing, and firing to modify, it is possible to prevent the fine silica particles constituting the fused silica substrate from coming off and falling off, so that surface contamination of the plate glass that passes through or comes into contact with the roll is prevented. It is effective in preventing.
【図１】 本発明の改質層の断面構造を示す模式図であ
る。FIG. 1 is a schematic view showing a cross-sectional structure of a modified layer of the present invention.
【図２】 改質層の厚みの変化を示すロール断面のマク
ロ観察結果の写真である。FIG. 2 is a photograph of a macro observation result of a roll cross section showing a change in thickness of a modified layer.
１ 溶融シリカ基材 ２ 改質層 1 fused silica base material 2 Modified layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 見上 泰治 兵庫県豊中市上新田四丁目８番Ｂ−503 (72)発明者 戸越 健一郎 兵庫県神戸市垂水区小束山本町二丁目21− １−602 (72)発明者 前田 健治 神奈川県愛甲郡愛川町角田字小沢上原426 番１ 旭硝子株式会社内 (72)発明者 三橋 道男 愛知県知多郡武豊町字旭１番地 旭硝子株 式会社内 (72)発明者 野村 謙 愛知県知多郡武豊町字旭１番地 旭硝子株 式会社内 Ｆターム(参考） 4G015 GA00 4K050 AA01 BA07 CG05 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Taiji apparently 4-8 Kaminita B-503, Toyonaka City, Hyogo Prefecture (72) Inventor Kenichiro Togoshi 2-21-, Kozukayama Honcho, Tarumi-ku, Kobe City, Hyogo Prefecture 1-602 (72) Inventor Kenji Maeda 426 Ozawa Uehara, Kakuda, Aikawa-cho, Aiko-gun, Kanagawa Prefecture No. 1 Asahi Glass Co., Ltd. (72) Inventor Michio Mitsuhashi Asahi Glass Co., Ltd. 1 Asahi, Taketoyo-cho, Chita-gun, Aichi Inside the company (72) Inventor Ken Nomura Asahi Glass Co., Ltd. 1 Asahi, Taketoyo-cho, Chita-gun, Aichi Inside the company F-term (reference) 4G015 GA00 4K050 AA01 BA07 CG05
Claims (7)
スの搬送ラインを構成する、溶融シリカ材製のロールで
あって、該ロールの表面に、酸化クロム単独あるいは、
酸化クロムおよび焼結助剤からなる複合酸化物による改
質層を有することを特徴とする板ガラス熱処理炉の炉内
ロール。1. A roll made of a fused silica material, which constitutes a transport line for the flat glass in a flat glass heat treatment furnace, wherein chromium oxide alone or on the surface of the roll.
An in-furnace roll for a plate glass heat-treating furnace, which has a modified layer of a complex oxide composed of chromium oxide and a sintering aid.
て、酸化クロムを含む水溶液あるいは、酸化クロムおよ
び焼結助剤を含む水溶液を、付着させた後、加熱、焼成
してなるものであることを特徴とする請求項１に記載の
板ガラス熱処理炉の炉内ロール。2. The modified layer is formed by depositing an aqueous solution containing chromium oxide or an aqueous solution containing chromium oxide and a sintering aid on the surface of a fused silica material, and then heating and firing the same. The inner roll of the flat glass heat treatment furnace according to claim 1, wherein
が介在してなることを特徴とする請求項１に記載の板ガ
ラス熱処理炉の炉内ロール。3. The in-furnace roll for a plate glass heat treatment furnace according to claim 1, wherein the modified layer is formed by interposing chromium oxide between SiO 2 particles.
質無機物質を生成する材料を含む水溶液を塗布、噴霧も
しくはこの水溶液中に浸漬した後、加熱、焼成すること
によって生成させたものであり、珪酸塩ガラス、ほう珪
酸塩ガラスあるいはりん酸塩ガラスを主として含むもの
であることを特徴とする請求項１または２に記載の板ガ
ラス熱処理炉の炉内ロール。4. The sintering aid is produced by applying, spraying or dipping an aqueous solution containing a material that produces an amorphous inorganic substance by firing, and then heating and firing it. 3. The inner roll of the flat glass heat treatment furnace according to claim 1 or 2, which mainly contains silicate glass, borosilicate glass or phosphate glass.
の構成比率が、平均粒径７〜８μm：70〜90 mass％、平
均粒径0.3〜0.5μm：５〜15 mass％および平均粒径0.1
〜0.2μm：５〜15 mass％であり、かつ気孔率が２〜15
％であることを特徴とする請求項１ないし３のいずれか
１項に記載の板ガラス熱処理炉の炉内ロール。5. The fused silica material has a composition ratio of SiO 2 particles, which is an aggregate, with an average particle size of 7 to 8 μm: 70 to 90 mass%, an average particle size of 0.3 to 0.5 μm: 5 to 15 mass%, and an average particle size. Particle size 0.1
~ 0.2μm: 5 ~ 15mass% and porosity is 2 ~ 15
%, The in-furnace roll of the plate glass heat treatment furnace according to any one of claims 1 to 3.
スの搬送ラインを構成する、溶融シリカ材製のロールに
ついて、該溶融シリカ材の表面に対して、酸化クロムを
含む水溶液または、酸化クロムおよび焼結助剤を含む水
溶液を塗布または噴霧するか、あるいは該水溶液中に浸
漬した後、250〜750 ℃で加熱、焼成することを特徴と
する板ガラス熱処理炉の炉内ロールの製造方法。6. In a heat treatment furnace for plate glass, regarding a roll made of a fused silica material that constitutes a conveying line for the plate glass, an aqueous solution containing chromium oxide or chromium oxide and sintering are applied to the surface of the fused silica material. A method for producing a furnace roll in a plate glass heat treatment furnace, which comprises coating or spraying an aqueous solution containing an auxiliary agent, or immersing the solution in the aqueous solution and then heating and firing at 250 to 750 ° C.
質無機物質を生成する材料を含む水溶液を塗布、噴霧も
しくはこの水溶液中に浸漬した後、加熱、焼成すること
によって生成させたものであり、珪酸塩ガラス、ほう珪
酸塩ガラスあるいはりん酸塩ガラスを主として含むもの
であることを特徴とする請求項５に記載の板ガラス熱処
理炉の炉内ロールの製造方法。7. The sintering aid is produced by applying, spraying or dipping an aqueous solution containing a material that produces an amorphous inorganic substance by firing, and then heating and firing it. The method for producing a furnace roll of a plate glass heat treatment furnace according to claim 5, characterized in that it mainly contains silicate glass, borosilicate glass or phosphate glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002102391A JP4183961B2 (en) | 2002-04-04 | 2002-04-04 | In-furnace roll of plate glass heat treatment furnace and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002102391A JP4183961B2 (en) | 2002-04-04 | 2002-04-04 | In-furnace roll of plate glass heat treatment furnace and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2003300742A true JP2003300742A (en) | 2003-10-21 |
| JP2003300742A5 JP2003300742A5 (en) | 2005-08-25 |
| JP4183961B2 JP4183961B2 (en) | 2008-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002102391A Expired - Fee Related JP4183961B2 (en) | 2002-04-04 | 2002-04-04 | In-furnace roll of plate glass heat treatment furnace and method for producing the same |
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| JP (1) | JP4183961B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009537431A (en) * | 2006-05-16 | 2009-10-29 | ベスビウス クルーシブル カンパニー | Refractory and manufacturing method thereof |
| WO2012157439A1 (en) * | 2011-05-16 | 2012-11-22 | 旭硝子株式会社 | Method for detecting defect of glass ribbon conveying roll and device for conveying glass ribbon |
-
2002
- 2002-04-04 JP JP2002102391A patent/JP4183961B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009537431A (en) * | 2006-05-16 | 2009-10-29 | ベスビウス クルーシブル カンパニー | Refractory and manufacturing method thereof |
| US9388081B2 (en) | 2006-05-16 | 2016-07-12 | Vesuvius Crucible Company | Refractory article and production process thereof |
| WO2012157439A1 (en) * | 2011-05-16 | 2012-11-22 | 旭硝子株式会社 | Method for detecting defect of glass ribbon conveying roll and device for conveying glass ribbon |
| JP5900492B2 (en) * | 2011-05-16 | 2016-04-06 | 旭硝子株式会社 | Defect identification method for glass ribbon conveying roll and glass ribbon conveying apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4183961B2 (en) | 2008-11-19 |
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