JP2012254920A - Glass - Google Patents
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- JP2012254920A JP2012254920A JP2012112994A JP2012112994A JP2012254920A JP 2012254920 A JP2012254920 A JP 2012254920A JP 2012112994 A JP2012112994 A JP 2012112994A JP 2012112994 A JP2012112994 A JP 2012112994A JP 2012254920 A JP2012254920 A JP 2012254920A
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- 239000011521 glass Substances 0.000 title claims abstract description 119
- 230000005855 radiation Effects 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 33
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 26
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 21
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 238000006124 Pilkington process Methods 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 description 23
- 238000004031 devitrification Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000005340 laminated glass Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
- 239000006066 glass batch Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007088 Archimedes method Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- -1 for example Polymers 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Abstract
Description
本発明は、ガラスに関し、具体的には、放射線遮蔽性能が高いガラスに関する。 The present invention relates to glass, and specifically relates to glass having high radiation shielding performance.
Ｘ線画像撮像装置等の放射線装置を取り扱う施設では、技師等が当該装置を操作する際、放射線被曝しないように、高い放射線遮蔽性能を有する特殊ガラスが用いられている。従来まで、このような特殊ガラスの主要成分として、放射線吸収係数が高い鉛が使用されてきた。 In facilities that handle radiation devices such as X-ray imaging devices, special glass having high radiation shielding performance is used so that technicians and the like operate the device so as not to be exposed to radiation. Conventionally, lead having a high radiation absorption coefficient has been used as a main component of such special glass.
しかし、鉛は、人体や環境に対する負荷が高いとされている。よって、鉛を含むガラスを製造、或いは廃棄する際には、鉛を外部に流出させないような対策が必要になり、結果として、ガラスの処理コストが高騰するという問題があった。 However, lead is said to have a high load on the human body and the environment. Therefore, when manufacturing or discarding glass containing lead, it is necessary to take measures to prevent lead from flowing out to the outside. As a result, there has been a problem that the processing cost of the glass increases.
このような問題に鑑み、近年、鉛を含まないガラス、所謂、無鉛ガラスが開発されるに至っている。例えば、特許文献１には、ＢａＯやＳｒＯを含むケイ酸塩ガラスが開示されている。特許文献２には、ビスマスを含むガラスが開示されている。特許文献３には、酸化ガドリニウム等の希土類金属酸化物を含むガラスが開示されている。 In view of such problems, in recent years, glass containing no lead, so-called lead-free glass has been developed. For example, Patent Document 1 discloses a silicate glass containing BaO or SrO. Patent Document 2 discloses a glass containing bismuth. Patent Document 3 discloses a glass containing a rare earth metal oxide such as gadolinium oxide.
ところが、従来の無鉛ガラスには、未だ改良の余地が残されていた。 However, conventional lead-free glass still has room for improvement.
例えば、特許文献１に記載の無鉛ガラスは、上記の通り、ＢａＯとＳｒＯを含むものの、その含有量が少ないため、放射線遮蔽性能が十分であるとは言えない。 For example, although the lead-free glass described in Patent Document 1 contains BaO and SrO as described above, it cannot be said that the radiation shielding performance is sufficient because the content thereof is small.
また、特許文献２に記載の無鉛ガラスは、Ｂｉ２Ｏ３とＳｉＯ２を各々１０モル％以上含むが、Ｂｉ２Ｏ３とＳｉＯ２の含有量が共に多くなると、分相や失透が生じて、ガラスの可視光透過性が低下し易くなる。また、ビスマスは、周期律表上で鉛の隣に位置するため、鉛の化学的特性と類似しており、人体や環境に対する負荷が懸念される。 Furthermore, lead-free glass described in Patent Document 2 include Bi 2 O 3 and of SiO 2 respectively 10 mol% or more, when the content of Bi 2 O 3 and SiO 2 increases both phase separation and devitrification occur As a result, the visible light transmittance of the glass tends to be lowered. Moreover, since bismuth is located next to lead on the periodic table, it is similar to the chemical characteristics of lead, and there are concerns about the burden on the human body and the environment.
また、特許文献３に記載の無鉛ガラスは、高価な希土類酸化物（Ｇｄ２Ｏ３等）を多量に含むため、原料コストが高騰するという問題がある。 Moreover, since the lead-free glass described in Patent Document 3 contains a large amount of expensive rare earth oxides (Gd 2 O 3 or the like), there is a problem that the raw material cost increases.
本発明は、上記問題に鑑み成されたものであり、その技術的課題は、ガラス組成中に鉛を含まなくても、放射線遮蔽性能が高いガラスを創案することである。 This invention is made | formed in view of the said problem, The technical subject is creating the glass with high radiation shielding performance, even if lead is not included in a glass composition.
本発明者等は、鋭意検討を行なった結果、ガラス組成を所定範囲に規制することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明のガラスは、ガラス組成として、質量％で、ＳｉＯ２ １５〜５５％、Ｂ２Ｏ３ ０〜１０％、ＳｒＯ ０．００１〜３５％、ＺｒＯ２＋ＴｉＯ２ ０．００１〜３０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜１０％を含有し、質量比ＢａＯ／ＳｒＯが０〜４０、質量比ＳｉＯ２／ＳｒＯが０．５〜４０であることを特徴とする。ここで、「ＺｒＯ２＋ＴｉＯ２」は、ＺｒＯ２とＴｉＯ２の合量を指す。「Ｌａ２Ｏ３＋Ｎｂ２Ｏ５」は、Ｌａ２Ｏ３とＮｂ２Ｏ５の合量を指す。 As a result of intensive studies, the present inventors have found that the above technical problem can be solved by regulating the glass composition within a predetermined range, and propose the present invention. That is, the glass of the present invention has a glass composition in terms of mass%, SiO 2 15 to 55%, B 2 O 3 0 to 10%, SrO 0.001 to 35%, ZrO 2 + TiO 2 0.001 to 30%. La 2 O 3 + Nb 2 O 5 0 to 10%, the mass ratio BaO / SrO is 0 to 40, and the mass ratio SiO 2 / SrO is 0.5 to 40. Here, “ZrO 2 + TiO 2 ” refers to the total amount of ZrO 2 and TiO 2 . “La 2 O 3 + Nb 2 O 5 ” refers to the total amount of La 2 O 3 and Nb 2 O 5 .
第二に、本発明のガラスは、ガラス組成として、質量％で、ＳｉＯ２ ２０〜５０％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜１０％、ＭｇＯ ０〜５％、ＣａＯ ０〜１０％、ＳｒＯ １〜３０％、ＢａＯ ０〜４０％、ＺｎＯ ０〜１２％、ＺｒＯ２＋ＴｉＯ２ ０．００１〜３０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜１０％、Ｇｄ２Ｏ３ ０〜１％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０〜１５％、ＳｎＯ２ ０〜３％、Ｓｂ２Ｏ３ ０〜３％を含有し、実質的にＰｂＯ、Ｂｉ２Ｏ３を含有せず、質量比ＢａＯ／ＳｒＯが０〜４０、質量比ＳｉＯ２／ＳｒＯが１〜４０であることが好ましい。ここで、「Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、Ｌｉ２Ｏ、Ｎａ２Ｏ、及びＫ２Ｏの合量を指す。 Second, the glass of the present invention has a glass composition, in mass%, SiO 2 20~50%, Al 2 O 3 0~10%, B 2 O 3 0~10%, 0~5% MgO, CaO 0~10%, SrO 1~30%, BaO 0~40%, 0~12% ZnO, ZrO 2 + TiO 2 0.001~30%, La 2 O 3 + Nb 2 O 5 0~10%, Gd 2 O 3 0~1%, Li 2 O + Na 2 O + K 2 O 0~15%, SnO 2 0~3%, contain Sb 2 O 3 0~3%, contains substantially no PbO, Bi 2 O 3 The mass ratio BaO / SrO is preferably 0 to 40 and the mass ratio SiO 2 / SrO is preferably 1 to 40. Here, “Li 2 O + Na 2 O + K 2 O” refers to the total amount of Li 2 O, Na 2 O, and K 2 O.
第三に、本発明のガラスは、液相粘度が１０３．０ｄＰａ・ｓ以上であることが好ましい。ここで、「液相粘度」は、液相温度におけるガラスの粘度を白金球引き上げ法で測定した値を指す。「液相温度」は、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）に残るガラス粉末を白金ボートに入れ、温度勾配炉中に２４時間保持した後、結晶の析出する温度を測定した値を指す。 Thirdly, the glass of the present invention preferably has a liquidus viscosity of 10 3.0 dPa · s or more. Here, “liquid phase viscosity” refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method. “Liquid phase temperature” refers to the temperature at which crystals precipitate after passing through a standard sieve 30 mesh (500 μm), putting the glass powder remaining on 50 mesh (300 μm) into a platinum boat and holding it in a temperature gradient furnace for 24 hours. Refers to the measured value.
第四に、本発明のガラスは、１５０ｋｅＶのエネルギーにおける線吸収係数が０．９／ｃｍ以上であることが好ましい。ここで、「１５０ｋｅＶのエネルギーにおける線吸収係数」は、例えば、ＰＨＯＴＸのデータを用いて、ガラス組成と密度から算出することができる。 Fourth, the glass of the present invention preferably has a linear absorption coefficient of 0.9 / cm or more at an energy of 150 keV. Here, the “linear absorption coefficient at an energy of 150 keV” can be calculated from the glass composition and density using, for example, PHOTX data.
第五に、本発明のガラスは、屈折率ｎｄが１．５５〜２．３であることが好ましい。ここで、「屈折率ｎｄ」は、市販の屈折率測定器（例えば、島津製作所製の屈折率測定器ＫＰＲ−２０００）で測定可能である。 Fifth, the glass of the present invention preferably has a refractive index nd of 1.55 to 2.3. Here, “refractive index nd” can be measured with a commercially available refractive index measuring instrument (for example, a refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation).
第六に、本発明のガラスは、板状であることが好ましい。 Sixth, the glass of the present invention is preferably plate-shaped.
第七に、本発明のガラスは、フロート法で成形されてなることが好ましい。 Seventh, the glass of the present invention is preferably formed by a float process.
第八に、本発明のガラスは、１０４．０ｄＰａ・ｓにおける温度が１２５０℃以下であることが好ましい。ここで、「１０４．０ｄＰａ・ｓにおける温度」は、白金球引き上げ法で測定した値を指す。 Eighth, the glass of the present invention preferably has a temperature at 10 4.0 dPa · s of 1250 ° C. or lower. Here, “temperature at 10 4.0 dPa · s” refers to a value measured by a platinum ball pulling method.
第九に、本発明のガラスは、歪点が６５０℃以上であることが好ましい。ここで、「歪点」は、ＡＳＴＭ Ｃ３３６−７１に基づいて測定した値である。 Ninth, the glass of the present invention preferably has a strain point of 650 ° C. or higher. Here, the “strain point” is a value measured based on ASTM C336-71.
第十に、本発明のガラスは、放射線遮蔽窓又は放射線遮蔽衝立に用いることが好ましい。 Tenth, the glass of the present invention is preferably used for a radiation shielding window or a radiation shielding screen.
本発明のガラスは、ガラス組成として、質量％で、ＳｉＯ２ １５〜５５％、Ｂ２Ｏ３ ０〜１０％、ＳｒＯ ０．００１〜３５％、ＺｒＯ２＋ＴｉＯ２ ０．００１〜３０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜１０％を含有し、質量比ＢａＯ／ＳｒＯが０〜４０、質量比ＳｉＯ２／ＳｒＯが０．５〜４０である。上記のように各成分の含有範囲を限定した理由を以下に説明する。なお、以下の含有範囲の説明において、％表示は、特に断りがある場合を除き、質量％を表す。 The glass of the present invention has a glass composition of mass%, SiO 2 15 to 55%, B 2 O 3 0 to 10%, SrO 0.001 to 35%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10% is contained, the mass ratio BaO / SrO is 0 to 40, and the mass ratio SiO 2 / SrO is 0.5 to 40. The reason for limiting the content range of each component as described above will be described below. In addition, in description of the following content ranges,% display represents the mass% except the case where there is particular notice.
ＳｉＯ２は、ガラスのネットワークを形成する成分である。ＳｉＯ２の含有量は１５〜５５％である。ＳｉＯ２の含有量が多くなると、溶融性、成形性が低下し易くなり、また放射線遮蔽性能が低下し易くなる。よって、ＳｉＯ２の含有量は５３％以下、５２％以下、５０％以下、４９％以下、４８％以下、特に４５％以下が好ましい。一方、ＳｉＯ２の含有量が少なくなると、ガラスの網目構造を形成し難くなり、ガラス化が困難になる。またガラスの粘性が低下し過ぎて、高い液相粘度を確保し難くなる。よって、ＳｉＯ２の含有量は２０％以上、２５％以上、３０％以上、３５％以上、特に４０％以上が好ましい。 SiO 2 is a component that forms a network of glass. The content of SiO 2 is 15 to 55%. When the content of SiO 2 increases, the meltability and moldability tend to be lowered, and the radiation shielding performance tends to be lowered. Therefore, the content of SiO 2 is preferably 53% or less, 52% or less, 50% or less, 49% or less, 48% or less, particularly 45% or less. On the other hand, when the content of SiO 2 decreases, it becomes difficult to form a glass network structure, and vitrification becomes difficult. Further, the viscosity of the glass is excessively lowered, and it becomes difficult to ensure a high liquid phase viscosity. Therefore, the content of SiO 2 is preferably 20% or more, 25% or more, 30% or more, 35% or more, and particularly preferably 40% or more.
Ｂ２Ｏ３は、ガラスのネットワークを形成する成分である。Ｂ２Ｏ３の含有量は０〜１０％である。Ｂ２Ｏ３の含有量が多くなると、温度変化に対して粘度変化が急激になって、ガラス板を成形し難くなると共に、ヤング率が低下し易くなる。よって、Ｂ２Ｏ３の好適な上限範囲は８％以下、７％以下、５％以下、４％以下、３％以下、２％未満、１％以下、特に１％未満である。 B 2 O 3 is a component that forms a glass network. The content of B 2 O 3 is 0 to 10%. When the content of B 2 O 3 is increased, the viscosity change is abrupt with respect to the temperature change, and it becomes difficult to form the glass plate, and the Young's modulus is easily lowered. Therefore, the preferable upper limit range of B 2 O 3 is 8% or less, 7% or less, 5% or less, 4% or less, 3% or less, less than 2%, 1% or less, particularly less than 1%.
ＳｒＯは、放射線遮蔽性能を高める成分である。ＳｒＯの含有量は０．００１〜３５％である。ＳｒＯは、アルカリ土類金属酸化物の中では、失透性を抑制しつつ、放射線遮蔽性能を高める効果が大きい成分である。しかし、ＳｒＯの含有量が多くなると、密度、熱膨張係数が高くなったり、ガラス組成の成分バランスを欠いて、耐失透性が低下し易くなる。よって、ＳｒＯの好適な上限範囲は３０％以下、２５％以下、２０％以下、１５％以下、１２％以下、１０％以下、特に８％以下である。ＳｒＯの好適な下限範囲は０．０１％以上、０．１％以上、１％以上、２％以上、３％以上、３．５％以上、特に４％以上である。 SrO is a component that enhances radiation shielding performance. The content of SrO is 0.001 to 35%. Among alkaline earth metal oxides, SrO is a component that has a large effect of improving radiation shielding performance while suppressing devitrification. However, when the SrO content is increased, the density and thermal expansion coefficient are increased, and the component balance of the glass composition is lacking, and the devitrification resistance is likely to be lowered. Therefore, the preferable upper limit range of SrO is 30% or less, 25% or less, 20% or less, 15% or less, 12% or less, 10% or less, and particularly 8% or less. A preferable lower limit range of SrO is 0.01% or more, 0.1% or more, 1% or more, 2% or more, 3% or more, 3.5% or more, particularly 4% or more.
質量比ＳｉＯ２／ＳｒＯは０．５〜４０である。質量比ＳｉＯ２／ＳｒＯが大き過ぎると、放射線遮蔽性能が低下し易くなる。一方、質量比ＳｉＯ２／ＳｒＯが小さ過ぎると、耐失透性が低下し易くなったり、密度や熱膨張係数が高くなり過ぎる虞がある。よって、質量比ＳｉＯ２／ＳｒＯの好適な上限範囲は３０以下、２０以下、１５以下、１０以下、９以下、特に８以下である。質量比ＳｉＯ２／ＳｒＯの好適な下限範囲は１以上、２以上、２．５以上、特に３以上である。 Weight ratio SiO 2 / SrO is 0.5 to 40. When the mass ratio SiO 2 / SrO is too large, the radiation shielding performance tends to be lowered. On the other hand, if the mass ratio SiO 2 / SrO is too small, the devitrification resistance tends to decrease, and the density and the thermal expansion coefficient may become too high. Therefore, a preferable upper limit range of the mass ratio SiO 2 / SrO is 30 or less, 20 or less, 15 or less, 10 or less, 9 or less, and particularly 8 or less. A preferable lower limit range of the mass ratio SiO 2 / SrO is 1 or more, 2 or more, 2.5 or more, particularly 3 or more.
ＺｒＯ２＋ＴｉＯ２は、放射線遮蔽性能を高める成分である。ＺｒＯ２＋ＴｉＯ２の含有量は０．００１〜３０％である。ＺｒＯ２＋ＴｉＯ２の含有量が多くなると、耐失透性が低下し易くなったり、密度や熱膨張係数が高くなり過ぎる虞がある。一方、ＺｒＯ２＋ＴｉＯ２の含有量が少なくなると、上記効果を得難くなる。よって、ＺｒＯ２＋ＴｉＯ２の好適な上限範囲は２５％以下、２０％以下、１８％以下、１５％以下、１４％以下、特に１３％以下である。ＺｒＯ２＋ＴｉＯ２の好適な下限範囲は０．０１％以上、０．５％以上、１％以上、３％以上、５％以上、６％以上、特に７％以上である。 ZrO 2 + TiO 2 is a component that enhances radiation shielding performance. The content of ZrO 2 + TiO 2 is 0.001 to 30%. When the content of ZrO 2 + TiO 2 increases, the devitrification resistance tends to decrease, and the density and thermal expansion coefficient may become too high. On the other hand, when the content of ZrO 2 + TiO 2 decreases, it is difficult to obtain the above effect. Therefore, the preferable upper limit range of ZrO 2 + TiO 2 is 25% or less, 20% or less, 18% or less, 15% or less, 14% or less, particularly 13% or less. A suitable lower limit range of ZrO 2 + TiO 2 is 0.01% or more, 0.5% or more, 1% or more, 3% or more, 5% or more, 6% or more, particularly 7% or more.
ＺｒＯ２は、放射線遮蔽性能を高める成分である。ＺｒＯ２の含有量は０〜３０％が好ましい。ＺｒＯ２は、放射線遮蔽性能を高めつつ、液相温度付近の粘性を高める効果が大きい成分である。しかし、ＺｒＯ２の含有量が多くなると、密度が高くなり過ぎたり、耐失透性が低下し易くなる。よって、ＺｒＯ２の好適な上限範囲は２０％以下、１８％以下、１５％以下、１０％以下、７％以下、特に６％以下である。ＺｒＯ２の好適な下限範囲は０．００１％以上、０．０１％以上、０．５％以上、１％以上、２％以上、特に３％以上である。 ZrO 2 is a component that enhances radiation shielding performance. The content of ZrO 2 is preferably 0 to 30%. ZrO 2 is a component that has a large effect of increasing the viscosity near the liquidus temperature while enhancing the radiation shielding performance. However, when the content of ZrO 2 increases, the density becomes too high, and the devitrification resistance tends to decrease. Therefore, the preferable upper limit range of ZrO 2 is 20% or less, 18% or less, 15% or less, 10% or less, 7% or less, particularly 6% or less. A suitable lower limit range of ZrO 2 is 0.001% or more, 0.01% or more, 0.5% or more, 1% or more, 2% or more, particularly 3% or more.
ＴｉＯ２の含有量は０〜３０％が好ましい。ＴｉＯ２は、放射線遮蔽性能を高める成分であるが、ＴｉＯ２の含有量が多くなると、密度や熱膨張係数が高くなり過ぎたり、耐失透性が低下し易くなったり、透過率が低下する傾向にある。よって、ＴｉＯ２の好適な上限範囲は２５％以下、１５％以下、１２％以下、特に８％以下である。ＴｉＯ２の好適な下限範囲は０．００１％以上、０．０１％以上、０．５％以上、１％以上、特に３％以上である。 The content of TiO 2 is preferably 0 to 30%. TiO 2 is a component that enhances radiation shielding performance. However, if the content of TiO 2 increases, the density and thermal expansion coefficient become too high, the devitrification resistance tends to decrease, or the transmittance decreases. There is a tendency. Therefore, the preferable upper limit range of TiO 2 is 25% or less, 15% or less, 12% or less, and particularly 8% or less. A preferable lower limit range of TiO 2 is 0.001% or more, 0.01% or more, 0.5% or more, 1% or more, and particularly 3% or more.
Ｌａ２Ｏ３＋Ｎｂ２Ｏ５の含有量は０〜１０％である。Ｌａ２Ｏ３＋Ｎｂ２Ｏ５の含有量が多くなると、放射線遮蔽性能が高くなり易いが、その含有量が１０％より多くなると、ガラス組成の成分バランスを欠いて、耐失透性が低下したり、原料コストが上昇して、ガラスの製造コストが高騰する虞がある。よって、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５の好適な下限範囲は８％以下、５％以下、３％以下、２％以下、１％以下、０．５％以下、特に０．１％以下である。 The content of La 2 O 3 + Nb 2 O 5 is 0 to 10%. When the content of La 2 O 3 + Nb 2 O 5 increases, radiation shielding performance tends to increase. However, when the content exceeds 10%, the component balance of the glass composition is lacking, and devitrification resistance decreases. There is a risk that the raw material cost will rise and the glass manufacturing cost will rise. Therefore, a suitable lower limit range of La 2 O 3 + Nb 2 O 5 is 8% or less, 5% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, particularly 0.1% or less. .
Ｌａ２Ｏ３は、放射線遮蔽性能を高める成分である。Ｌａ２Ｏ３の含有量が多くなると、耐失透性が低下し易くなり、また密度、熱膨張係数が高くなり過ぎる虞がある。よって、Ｌａ２Ｏ３の含有量は１０％以下、８％以下、５％以下、２％以下、１％以下、０．５％以下、特に０．１％以下が好ましい。 La 2 O 3 is a component that enhances radiation shielding performance. When the content of La 2 O 3 increases, the devitrification resistance tends to decrease, and the density and thermal expansion coefficient may become too high. Therefore, the content of La 2 O 3 is preferably 10% or less, 8% or less, 5% or less, 2% or less, 1% or less, 0.5% or less, particularly preferably 0.1% or less.
Ｎｂ２Ｏ５は、放射線遮蔽性能を高める成分である。Ｎｂ２Ｏ５の含有量が多くなると、耐失透性が低下し易くなり、また密度、熱膨張係数が高くなり過ぎる虞がある。よって、Ｎｂ２Ｏ５の含有量は１０％以下、８％以下、５％以下、２％以下、１％以下、０．５％以下、特に０．１％以下が好ましい。 Nb 2 O 5 is a component that enhances radiation shielding performance. When the content of Nb 2 O 5 increases, the devitrification resistance tends to decrease, and the density and thermal expansion coefficient may become too high. Therefore, the content of Nb 2 O 5 is preferably 10% or less, 8% or less, 5% or less, 2% or less, 1% or less, 0.5% or less, particularly preferably 0.1% or less.
質量比（Ｌａ２Ｏ３＋Ｎｂ２Ｏ５）／（ＺｒＯ２＋ＴｉＯ２）は０〜３０が好ましい。質量比（Ｌａ２Ｏ３＋Ｎｂ２Ｏ５）／（ＺｒＯ２＋ＴｉＯ２）が大きい程、耐失透性の低下を抑制しつつ、放射線遮蔽性能を高めることが可能になるが、この値が大き過ぎると、ガラス組成の成分バランスを欠いて、耐失透性が低下したり、原料コストが高くなり過ぎる。よって、質量比（Ｌａ２Ｏ３＋Ｎｂ２Ｏ５）／（ＺｒＯ２＋ＴｉＯ２）の好適な上限範囲は２０以下、１０以下、５以下、２以下、１以下、０．１以下、特に０．０１以下である。 Mass ratio (La 2 O 3 + Nb 2 O 5) / (ZrO 2 + TiO 2) 0 to 30 is preferred. As the mass ratio (La 2 O 3 + Nb 2 O 5 ) / (ZrO 2 + TiO 2 ) is larger, it is possible to improve radiation shielding performance while suppressing a decrease in devitrification resistance, but this value is larger. If too much, the balance of the components of the glass composition is lost, devitrification resistance is lowered, and the raw material cost is too high. Therefore, the preferable upper limit range of the mass ratio (La 2 O 3 + Nb 2 O 5 ) / (ZrO 2 + TiO 2 ) is 20 or less, 10 or less, 5 or less, 2 or less, 1 or less, 0.1 or less, especially 0. 01 or less.
ＢａＯは、アルカリ土類金属酸化物の中では、ガラスの粘性を極端に低下させずに、放射線遮蔽性能を高める成分であり、その含有量は０〜４０％が好ましい。ＢａＯの含有量が多くなると、放射線遮蔽性能、密度、熱膨張係数が高くなり易い。しかし、ＢａＯの含有量が４０％を超えると、ガラス組成の成分バランスを欠いて、耐失透性が低下し易くなる。よって、ＢａＯの好適な上限範囲は３５％以下、３２％以下、３０％以下、２９．５％以下、２９％以下、特に２８％以下が好ましい。但し、ＢａＯの含有量が少なくなると、所望の放射線遮蔽性能を得難くなる上、高い液相粘度を確保し難くなる。よって、ＢａＯの好適な下限範囲は０．５％以上、１％以上、２％以上、５％以上、１０％以上、１５％以上、２３％以上、特に２５％以上が好ましい。 BaO is a component that enhances radiation shielding performance without excessively reducing the viscosity of glass among alkaline earth metal oxides, and its content is preferably 0 to 40%. When the content of BaO increases, radiation shielding performance, density, and thermal expansion coefficient tend to increase. However, when the content of BaO exceeds 40%, the component balance of the glass composition is lacking, and the devitrification resistance tends to decrease. Therefore, the preferable upper limit range of BaO is 35% or less, 32% or less, 30% or less, 29.5% or less, 29% or less, and particularly preferably 28% or less. However, when the content of BaO decreases, it becomes difficult to obtain a desired radiation shielding performance and it is difficult to ensure a high liquid phase viscosity. Therefore, a preferable lower limit range of BaO is preferably 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, 15% or more, 23% or more, particularly 25% or more.
質量比ＢａＯ／ＳｒＯは０〜４０である。質量比ＢａＯ／ＳｒＯが大き過ぎると、耐失透性が低下したり、密度や熱膨張係数が高くなり過ぎる虞がある。一方、質量比ＢａＯ／ＳｒＯが小さ過ぎると、放射線遮蔽性能が低下したり、ガラス組成の成分バランスを欠いて、耐失透性が低下する虞がある。よって、質量比ＢａＯ／ＳｒＯの好適な上限範囲は３０以下、２０以下、１０以下、８以下、特に５以下である。質量比ＢａＯ／ＳｒＯの好適な下限範囲は０．１以上、０．５以上、１以上、２．５以上、特に３以上である。 The mass ratio BaO / SrO is 0-40. If the mass ratio BaO / SrO is too large, the devitrification resistance may decrease, or the density and the thermal expansion coefficient may become too high. On the other hand, if the mass ratio BaO / SrO is too small, the radiation shielding performance may be deteriorated, or the component balance of the glass composition may be lost, and the devitrification resistance may be deteriorated. Therefore, a preferable upper limit range of the mass ratio BaO / SrO is 30 or less, 20 or less, 10 or less, 8 or less, and particularly 5 or less. A preferable lower limit range of the mass ratio BaO / SrO is 0.1 or more, 0.5 or more, 1 or more, 2.5 or more, particularly 3 or more.
上記成分以外にも、任意成分として、例えば以下の成分を添加してもよい。 In addition to the above components, for example, the following components may be added as optional components.
Ａｌ２Ｏ３は、ガラスのネットワークを形成する成分である。Ａｌ２Ｏ３の含有量は０〜２０％が好ましい。Ａｌ２Ｏ３の含有量が多くなると、ガラスの粘度が上昇したり、ガラスに失透結晶が析出し易くなって、液相粘度が低下し易くなる。よって、Ａｌ２Ｏ３の好適な上限範囲は１５％以下、１０％以下、８％以下、７％以下、特に６％以下である。なお、Ａｌ２Ｏ３の含有量が少なくなると、ガラス組成の成分バランスを欠いて、逆にガラスが失透し易くなる。よって、Ａｌ２Ｏ３の好適な下限範囲は０．１％以上、０．５％以上、１％以上、特に３％以上である。 Al 2 O 3 is a component that forms a glass network. The content of Al 2 O 3 is preferably 0 to 20%. When the content of Al 2 O 3 increases, the viscosity of the glass increases, or devitrified crystals tend to precipitate on the glass, and the liquidus viscosity tends to decrease. Therefore, the preferable upper limit range of Al 2 O 3 is 15% or less, 10% or less, 8% or less, 7% or less, particularly 6% or less. Incidentally, the content of Al 2 O 3 is reduced, lacks component balance of the glass composition, the glass is liable to devitrify reversed. Therefore, a preferable lower limit range of Al 2 O 3 is 0.1% or more, 0.5% or more, 1% or more, particularly 3% or more.
ＭｇＯの含有量は０〜１０％が好ましい。ＭｇＯは、ヤング率、歪点を高める成分であると共に、高温粘度を低下させる成分であるが、ＭｇＯを多量に添加すると、液相温度が上昇して、耐失透性が低下したり、密度や熱膨張係数が高くなり過ぎる虞がある。よって、ＭｇＯの好適な上限範囲は５％以下、３％以下、２％以下、１．５％以下、１％以下、特に０．５％以下である。 The content of MgO is preferably 0 to 10%. MgO is a component that raises the Young's modulus and strain point and lowers the high-temperature viscosity. However, when MgO is added in a large amount, the liquidus temperature rises, devitrification resistance decreases, and density increases. And the thermal expansion coefficient may be too high. Therefore, a suitable upper limit range of MgO is 5% or less, 3% or less, 2% or less, 1.5% or less, 1% or less, particularly 0.5% or less.
ＣａＯは、高温粘度を低下させる成分である。ＣａＯの含有量は０〜１５％が好ましい。ＣａＯの含有量が多くなると、密度、熱膨張係数が高くなり易く、更にＣａＯの含有量が多過ぎると、ガラス組成の成分バランスを欠いて、耐失透性が低下し易くなる。よって、ＣａＯの好適な上限範囲は１２％以下、１０％以下、９％以下、８．５％以下、８％以下、特に７％以下である。なお、ＣａＯの含有量が少なくなると、溶融性が低下したり、ヤング率が低下し易くなる。よって、ＣａＯの好適な下限範囲は０．５％以上、１％以上、２％以上、３％以上、特に４％以上である。 CaO is a component that lowers the high temperature viscosity. The content of CaO is preferably 0 to 15%. When the content of CaO increases, the density and the thermal expansion coefficient tend to be high, and when the content of CaO is too large, the component balance of the glass composition is lacking and the devitrification resistance tends to decrease. Therefore, the preferable upper limit range of CaO is 12% or less, 10% or less, 9% or less, 8.5% or less, 8% or less, particularly 7% or less. In addition, when content of CaO decreases, a meltability will fall or a Young's modulus will fall easily. Therefore, the preferable lower limit range of CaO is 0.5% or more, 1% or more, 2% or more, 3% or more, particularly 4% or more.
質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯは０〜２０が好ましい。質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯが大きくなると、放射線遮蔽性能を維持しつつ、ガラスを低密度化したり、高温粘度を低下させることが可能になるが、液相温度も高くなり易く、高い液相粘度を維持し難くなる。よって、質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯの好適な上限範囲は１０以下、８以下、５以下、３以下、２以下、特に１以下である。 The mass ratio (MgO + CaO) / SrO is preferably 0-20. When the mass ratio (MgO + CaO) / SrO increases, it is possible to reduce the density of the glass and reduce the high-temperature viscosity while maintaining the radiation shielding performance, but the liquidus temperature tends to increase, and the high liquidus viscosity. It becomes difficult to maintain. Therefore, a suitable upper limit range of the mass ratio (MgO + CaO) / SrO is 10 or less, 8 or less, 5 or less, 3 or less, 2 or less, particularly 1 or less.
ＺｎＯは、放射線遮蔽性能の向上に有効な成分である。ＺｎＯの含有量は０〜１２％が好ましい。ＺｎＯの含有量が多くなると、密度や熱膨張係数が高くなり過ぎたり、ガラス組成の成分バランスを欠いて、耐失透性が低下したり、高温粘性が低下し過ぎて、高い液相粘度を確保し難くなる。よって、ＺｎＯの好適な上限範囲は１０％以下、８％以下、４％以下、２％以下、１％以下、０．５％以下、０．１％以下、特に０．０１％以下である。 ZnO is an effective component for improving radiation shielding performance. The content of ZnO is preferably 0 to 12%. When the content of ZnO increases, the density and thermal expansion coefficient become too high, the balance of the composition of the glass composition is lacking, the devitrification resistance is lowered, the high temperature viscosity is lowered too much, and the high liquidus viscosity is increased. It becomes difficult to secure. Therefore, the preferable upper limit range of ZnO is 10% or less, 8% or less, 4% or less, 2% or less, 1% or less, 0.5% or less, 0.1% or less, particularly 0.01% or less.
Ｇｄ２Ｏ３の含有量は０〜１２％が好ましい。Ｇｄ２Ｏ３は放射線遮蔽性能を高める成分であるが、Ｇｄ２Ｏ３の含有量が多くなると、密度や熱膨張係数が高くなり過ぎたり、ガラス組成の成分バランスを欠いて、耐失透性が低下したり、高温粘性が低下し過ぎて、高い液相粘度を確保し難くなる。よって、Ｇｄ２Ｏ３の好適な上限範囲は８％以下、４％以下、２％以下、１％以下、０．５％以下、０．１％以下、特に０．０１％以下である。 The content of Gd 2 O 3 is preferably 0 to 12%. Gd 2 O 3 is a component that enhances radiation shielding performance. However, if the content of Gd 2 O 3 increases, the density and thermal expansion coefficient become too high, and the glass composition component balance is lacking, resulting in resistance to devitrification. Or the high-temperature viscosity decreases too much, making it difficult to ensure a high liquid phase viscosity. Therefore, the preferable upper limit range of Gd 2 O 3 is 8% or less, 4% or less, 2% or less, 1% or less, 0.5% or less, 0.1% or less, particularly 0.01% or less.
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量は０〜１５％が好ましい。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏは、ガラスの粘性を低下させる成分であり、また熱膨張係数を調整する成分であるが、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏを多量に添加すると、ガラスの粘性が低下し過ぎて、高い液相粘度を確保し難くなることに加えて、アルカリ成分の溶出量が増加して、白やけとなって、ガラス表面に析出する虞がある。よって、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの好適な上限範囲は１０％以下、８％以下、５％以下、２％以下、１％以下、０．５％以下、特に０．１％以下である。なお、Ｌｉ２Ｏ、Ｎａ２Ｏ、及びＫ２Ｏの各々の含有量は、好ましくは１０％以下、８％以下、５％以下、２％以下、１％以下、０．５％以下、特に０．１％以下である。 The content of Li 2 O + Na 2 O + K 2 O is preferably 0 to 15%. Li 2 O + Na 2 O + K 2 O is a component that lowers the viscosity of the glass and adjusts the thermal expansion coefficient. However, if a large amount of Li 2 O + Na 2 O + K 2 O is added, the viscosity of the glass decreases. In addition, it is difficult to ensure a high liquid phase viscosity, and in addition, the elution amount of the alkali component increases, and there is a possibility that it becomes whitish and precipitates on the glass surface. Therefore, a suitable upper limit range of Li 2 O + Na 2 O + K 2 O is 10% or less, 8% or less, 5% or less, 2% or less, 1% or less, 0.5% or less, particularly 0.1% or less. The content of each of Li 2 O, Na 2 O, and K 2 O is preferably 10% or less, 8% or less, 5% or less, 2% or less, 1% or less, particularly 0.5% or less. 0.1% or less.
清澄剤として、Ａｓ２Ｏ３、Ｓｂ２Ｏ３、ＣｅＯ２、ＳｎＯ２、Ｆ、Ｃｌ、ＳＯ３の群から選択された一種又は二種以上を添加することができる。但し、Ａｓ２Ｏ３、及びＦ、特にＡｓ２Ｏ３は、環境的観点から、その使用を極力控えることが好ましく、各々の含有量は０．１％未満が好ましい。 As a fining agent, one or more selected from the group of As 2 O 3 , Sb 2 O 3 , CeO 2 , SnO 2 , F, Cl, and SO 3 can be added. However, As 2 O 3 and F, particularly As 2 O 3 , it is preferable to refrain from using them as much as possible from the environmental viewpoint, and the content of each is preferably less than 0.1%.
ＳｎＯ２、及びＳｂ２Ｏ３は、放射線遮蔽性能を高める効果もあり、放射線遮蔽性能を高めつつ、清澄効果を確保したい場合は、その含有量を各々０〜５％、０〜３％、０〜１％、０．０１〜０．５％、特に０．０５〜０．４％とすることが好ましい。 SnO 2 and Sb 2 O 3 also have an effect of increasing the radiation shielding performance, and when it is desired to ensure the clarification effect while enhancing the radiation shielding performance, the contents thereof are 0 to 5%, 0 to 3%, 0, respectively. -1%, 0.01-0.5%, particularly preferably 0.05-0.4%.
ＰｂＯは、高温粘性を低下させる成分であるが、環境的観点から、その使用を極力控えることが好ましく、その含有量は０．５％以下が好ましく、実質的に含有しないこと、即ち１０００ｐｐｍ（質量）未満がより好ましい。 PbO is a component that lowers the high temperature viscosity, but it is preferable to refrain from using it as much as possible from an environmental point of view, and its content is preferably 0.5% or less, that is, substantially not contained, that is, 1000 ppm (mass) ) Is more preferable.
Ｂｉ２Ｏ３は、高温粘性を低下させる成分であるが、環境的観点から、その使用を極力控えることが好ましく、その含有量は０．５％以下が好ましく、実質的に含有しないこと、即ち１０００ｐｐｍ（質量）未満がより好ましい。 Bi 2 O 3 is a component that lowers the high temperature viscosity, but it is preferable to refrain from using it as much as possible from an environmental point of view, and its content is preferably 0.5% or less, that is, it does not substantially contain, More preferably less than 1000 ppm (mass).
上記の成分以外にも、本発明の効果を大幅に損なわない限り、他の成分、例えばＷＯ３等を添加してもよい。 In addition to the above components, other components such as WO 3 may be added as long as the effects of the present invention are not significantly impaired.
各成分の好適な含有範囲を組み合わせて、好適なガラス組成範囲を構築することは当然に可能であるが、その中でも、放射線遮蔽性能、耐失透性、製造コスト等の観点から、特に好適なガラス組成範囲は以下の通りである。 Of course, it is possible to construct a suitable glass composition range by combining preferred ranges of each component, but among them, particularly preferred from the viewpoint of radiation shielding performance, devitrification resistance, production cost, etc. The glass composition range is as follows.
（１）ガラス組成として、質量％で、ＳｉＯ２ ２０〜５０％、Ａｌ２Ｏ３ ０〜１０％、Ｂ２Ｏ３ ０〜１０％、ＭｇＯ ０〜５％、ＣａＯ ０〜１０％、ＳｒＯ １〜３０％、ＢａＯ ０〜４０％、ＺｎＯ ０〜１２％、ＺｒＯ２＋ＴｉＯ２ ０．００１〜３０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜１０％、Ｇｄ２Ｏ３ ０〜１％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０〜１５％、ＳｎＯ２ ０〜３％、Ｓｂ２Ｏ３ ０〜３％を含有し、実質的にＰｂＯ、Ｂｉ２Ｏ３を含有せず、質量比ＢａＯ／ＳｒＯが０〜４０、質量比ＳｉＯ２／ＳｒＯが１〜４０。 (1) as a glass composition, in mass%, SiO 2 20~50%, Al 2 O 3 0~10%, B 2 O 3 0~10%, 0~5% MgO, CaO 0~10%, SrO 1 ~30%, BaO 0~40%, 0~12 % ZnO, ZrO 2 + TiO 2 0.001~30%, La 2 O 3 + Nb 2 O 5 0~10%, Gd 2 O 3 0~1%, Li 2 O + Na 2 O + K 2 O 0-15%, SnO 2 0-3%, Sb 2 O 3 0-3%, substantially no PbO, Bi 2 O 3 , and the mass ratio BaO / SrO is 0-40, the weight ratio SiO 2 / SrO is 1 to 40.
（２）ガラス組成として、質量％で、ＳｉＯ２ ２０〜５０％、Ｂ２Ｏ３ ０〜８％、ＣａＯ ０〜１０％、ＳｒＯ ０．０１〜３５％、ＢａＯ ０〜３０％、ＺｎＯ ０〜４％、ＺｒＯ２＋ＴｉＯ２ ０．００１〜２０％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜３％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０〜１％を含有し、質量比ＢａＯ／ＳｒＯが０〜２０、質量比ＳｉＯ２／ＳｒＯが１〜１５、質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯが０〜１０。 (2) as a glass composition, in mass%, SiO 2 20~50%, B 2 O 3 0~8%, CaO 0~10%, SrO 0.01~35%, BaO 0~30%, ZnO 0~ 4%, ZrO 2 + TiO 2 0.001~20%, La 2 O 3 + Nb 2 O 5 0~3%, Li 2 O + Na 2 O + K 2 contain O 0 to 1%, weight ratio BaO / SrO is 0 20, the weight ratio SiO 2 / SrO is 1 to 15, the mass ratio (MgO + CaO) / SrO 0 to 10.
（３）ガラス組成として、質量％で、ＳｉＯ２ ３５〜５０％、Ｂ２Ｏ３ ０〜５％、ＣａＯ ０〜９％、ＳｒＯ １〜３５％、ＢａＯ ０〜２９％、ＺｎＯ ０〜３％、ＺｒＯ２＋ＴｉＯ２ １〜１５％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜０．１％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０〜０．１％を含有し、質量比ＢａＯ／ＳｒＯが０〜１０、質量比ＳｉＯ２／ＳｒＯが１〜１０、質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯが０〜５。 (3) as a glass composition, in mass%, SiO 2 35~50%, B 2 O 3 0~5%, CaO 0~9%, SrO 1~35%, BaO 0~29%, ZnO 0~3% , ZrO 2 + TiO 2 1-15%, La 2 O 3 + Nb 2 O 5 0-0.1%, Li 2 O + Na 2 O + K 2 O 0-0.1%, and the mass ratio BaO / SrO is 0 10. Mass ratio SiO 2 / SrO is 1 to 10, and mass ratio (MgO + CaO) / SrO is 0 to 5.
（４）ガラス組成として、質量％で、ＳｉＯ２ ３５〜５０％、Ｂ２Ｏ３ ０〜３％、ＣａＯ ０〜９％、ＳｒＯ ２〜２０％、ＢａＯ ０〜２８％、ＺｎＯ ０〜１％、ＺｒＯ２＋ＴｉＯ２ ３〜１５％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜０．１％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０〜０．１％を含有し、質量比ＢａＯ／ＳｒＯが０〜８、質量比ＳｉＯ２／ＳｒＯが２〜１０、質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯが０〜３。 (4) as a glass composition, in mass%, SiO 2 35~50%, B 2 O 3 0~3%, CaO 0~9%, SrO 2~20%, BaO 0~28%, ZnO 0~1% ZrO 2 + TiO 2 3 to 15%, La 2 O 3 + Nb 2 O 5 0 to 0.1%, Li 2 O + Na 2 O + K 2 O 0 to 0.1%, and the mass ratio BaO / SrO is 0 to 0%. 8. The mass ratio SiO 2 / SrO is 2 to 10, and the mass ratio (MgO + CaO) / SrO is 0 to 3.
（５）ガラス組成として、質量％で、ＳｉＯ２ ３５〜５０％、Ｂ２Ｏ３ ０〜１％、ＣａＯ ０〜８．５％、ＳｒＯ ４〜１５％、ＢａＯ ０〜２８％、ＺｎＯ ０〜０．１％、ＺｒＯ２＋ＴｉＯ２ ６〜１５％、Ｌａ２Ｏ３＋Ｎｂ２Ｏ５ ０〜０．１％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０〜０．１％を含有し、質量比ＢａＯ／ＳｒＯが０〜８、質量比ＳｉＯ２／ＳｒＯが２．５〜１０、質量比（ＭｇＯ＋ＣａＯ）／ＳｒＯが０〜３。 (5) as a glass composition, in mass%, SiO 2 35~50%, B 2 O 3 0~1%, CaO 0~8.5%, SrO 4~15%, BaO 0~28%, ZnO 0~ 0.1%, ZrO 2 + TiO 2 6~15%, La 2 O 3 + Nb 2 O 5 0~0.1%, Li 2 O + Na 2 O + K 2 contain O 0 to 0.1%, the mass ratio BaO / SrO is 0 to 8, mass ratio SiO 2 / SrO is 2.5 to 10, and mass ratio (MgO + CaO) / SrO is 0 to 3.
本発明のガラスにおいて、１５０ｋｅＶのエネルギーにおける線吸収係数は、好ましくは０．９／ｃｍ以上、０．９３／ｃｍ以上、特に０．９５／ｃｍ以上である。１５０ｋｅＶのエネルギーにおける線吸収係数が低下すると、放射線遮蔽性能が低下して、放射線遮蔽窓又は放射線遮蔽衝立に適用し難くなる。 In the glass of the present invention, the linear absorption coefficient at an energy of 150 keV is preferably 0.9 / cm or more, 0.93 / cm or more, particularly 0.95 / cm or more. When the linear absorption coefficient at an energy of 150 keV is lowered, the radiation shielding performance is lowered and it becomes difficult to apply the radiation shielding window or the radiation shielding screen.
本発明のガラスにおいて、屈折率ｎｄは、好ましくは１．５５以上、１．５８以上、１．６以上、１．６３以上、１．６５以上、特に１．６６以上である。屈折率ｎｄが低くなると、放射線遮蔽性能が低下する傾向がある。一方、屈折率ｎｄが２．３超になると、空気−ガラス界面で光の反射率が高くなる。よって、屈折率ｎｄは２．３以下、２．２以下、２．１以下、２．０以下、１．９以下、特に１．７５以下が好ましい。 In the glass of the present invention, the refractive index nd is preferably 1.55 or more, 1.58 or more, 1.6 or more, 1.63 or more, 1.65 or more, particularly 1.66 or more. When the refractive index nd decreases, the radiation shielding performance tends to decrease. On the other hand, when the refractive index nd exceeds 2.3, the reflectance of light increases at the air-glass interface. Therefore, the refractive index nd is preferably 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, 1.9 or less, particularly 1.75 or less.
本発明のガラスにおいて、液相温度は１２００℃以下、１１５０℃以下、１１３０℃以下、１１１０℃以下、１０９０℃以下、１０７０℃以下、特に１０５０℃以下が好ましい。また、液相粘度は１０３．０ｄＰａ・ｓ以上、１０３．５ｄＰａ・ｓ以上、１０３．８ｄＰａ・ｓ以上、１０４．０ｄＰａ・ｓ以上、１０４．１ｄＰａ・ｓ以上、１０４．２ｄＰａ・ｓ以上、特に１０４．３ｄＰａ・ｓ以上が好ましい。このようにすれば、成形時にガラスが失透し難くなり、フロート法でガラス板を成形し易くなる。 In the glass of the present invention, the liquidus temperature is preferably 1200 ° C. or lower, 1150 ° C. or lower, 1130 ° C. or lower, 1110 ° C. or lower, 1090 ° C. or lower, 1070 ° C. or lower, particularly 1050 ° C. or lower. Further, the liquid phase viscosity is 10 3.0 dPa · s or more, 10 3.5 dPa · s or more, 10 3.8 dPa · s or more, 10 4.0 dPa · s or more, 10 4.1 dPa · s or more. It is preferably 10 4.2 dPa · s or more, particularly preferably 10 4.3 dPa · s or more. If it does in this way, it will become difficult to devitrify glass at the time of shaping | molding, and will become easy to shape | mold a glass plate by the float glass process.
本発明のガラスは、板状であることが好ましい。このようにすれば、放射線遮蔽窓や放射線遮蔽衝立に適用し易くなる。 The glass of the present invention is preferably plate-shaped. If it does in this way, it will become easy to apply to a radiation shielding window or a radiation shielding partition.
本発明のガラスは、フロート法で成形されてなることが好ましい。このようにすれば、未研磨で表面品位が良好なガラス板を安価、且つ大量に製造することができる。 The glass of the present invention is preferably formed by a float process. In this way, it is possible to manufacture a glass plate that is unpolished and has good surface quality at a low cost and in large quantities.
フロート法以外にも、ガラス板の成形方法として、例えば、ダウンドロー法（オーバーフローダウンドロー法、スロットダウン法、リドロー法等）、キャスト法、プレス法、ロールアウト法等を採用することもできる。 In addition to the float method, for example, a down draw method (overflow down draw method, slot down method, redraw method, etc.), a cast method, a press method, a roll out method, or the like can be employed as a glass plate forming method.
本発明のガラスにおいて、密度は５．０ｇ／ｃｍ３以下、４．８ｇ／ｃｍ３以下、４．５ｇ／ｃｍ３以下、４．３ｇ／ｃｍ３以下、３．７ｇ／ｃｍ３以下、特に３．５ｇ／ｃｍ３以下が好ましい。このようにすれば、ガラスが軽量化する。なお、「密度」は、周知のアルキメデス法で測定可能である。 In the glass of the present invention, the density is 5.0 g / cm 3 or less, 4.8 g / cm 3 or less, 4.5 g / cm 3 or less, 4.3 g / cm 3 or less, 3.7 g / cm 3 or less, particularly 3 0.5 g / cm 3 or less is preferable. This reduces the weight of the glass. The “density” can be measured by a known Archimedes method.
本発明のガラスにおいて、１０２．５ｄＰａ・ｓにおける温度は１４００℃以下、１３５０℃以下、１３００℃以下、１２５０℃以下、特に１２００℃以下が好ましい。このようにすれば、溶融性が向上するため、泡品位に優れたガラスが得られ易く、ガラスの製造効率が向上する。 In the glass of the present invention, the temperature at 10 2.5 dPa · s is preferably 1400 ° C. or lower, 1350 ° C. or lower, 1300 ° C. or lower, 1250 ° C. or lower, particularly 1200 ° C. or lower. If it does in this way, since a meltability will improve, the glass excellent in foam quality will be easy to be obtained, and the manufacturing efficiency of glass will improve.
本発明のガラスにおいて、１０４．０ｄＰａ・ｓにおける温度は１２５０℃以下、１２００℃以下、１１５０℃以下、１１１０℃以下、特に１０６０℃以下である。このようにすれば、フロート法による成形において、成形温度を低下させることが可能になる。結果として、低温操業が可能になり、成形部に使用されている耐火物が長寿命化して、ガラス板の製造コストが低下し易くなる。 In the glass of the present invention, the temperature at 10 4.0 dPa · s is 1250 ° C. or lower, 1200 ° C. or lower, 1150 ° C. or lower, 1110 ° C. or lower, particularly 1060 ° C. or lower. In this way, the molding temperature can be lowered in the molding by the float method. As a result, low-temperature operation becomes possible, and the refractory used in the molded part has a long life, and the manufacturing cost of the glass plate is likely to decrease.
本発明のガラスの製造方法を例示すると、まず所望のガラス組成になるように、ガラス原料を調合して、ガラスバッチを作製する。次いで、このガラスバッチを１０００〜１６００℃で溶融した上で、清澄した後、得られた溶融ガラスを板厚５〜３０ｍｍ程度の板状に成形する。 To illustrate the glass manufacturing method of the present invention, first, glass raw materials are prepared so as to have a desired glass composition, and a glass batch is prepared. Next, the glass batch is melted at 1000 to 1600 ° C. and clarified, and then the obtained molten glass is formed into a plate shape having a thickness of about 5 to 30 mm.
その後、必要に応じて、アニール（徐冷）、切断、研磨等の加工処理を施し、表面に機能性膜を形成する。なお、機能性膜として、防曇性膜、反射防止膜等を例示できる。機能性膜の形成には、スパッタ法、ＣＶＤ法、ＰＶＤ法等の蒸着法を用いることが好ましい。これらの方法によれば、膜厚の制御を容易に行うことができる。 Thereafter, if necessary, processing such as annealing (slow cooling), cutting, and polishing is performed to form a functional film on the surface. Examples of the functional film include an antifogging film and an antireflection film. For forming the functional film, it is preferable to use a vapor deposition method such as a sputtering method, a CVD method, or a PVD method. According to these methods, the film thickness can be easily controlled.
上記のようにして作製されたガラス板は、例えば、樹脂シート等と積層して、合わせガラスとしてもよい。合わせガラスは、例えば、二枚のガラス板で樹脂シートを挟み込むようにして接着することで作製することができる。ガラス板と樹脂シートを接着する方法として、例えば、樹脂シートとガラス板とを熱圧着する方法、液状樹脂をガラス板に塗布して挟み込んだ後に、熱や紫外線等の外部刺激によって当該液状樹脂を硬化させる方法等を採用することができる。樹脂として、例えば、ポリビニルブチラール、エチレン−酢酸ビニル、フッ素樹脂等を用いることができる。なお、合わせガラスであれば、放射線遮蔽窓や放射線遮蔽衝立の厚みを大きくすることができる。 The glass plate produced as described above may be laminated with a resin sheet or the like, for example, to make a laminated glass. Laminated glass can be produced, for example, by adhering a resin sheet between two glass plates. As a method for bonding the glass plate and the resin sheet, for example, a method in which the resin sheet and the glass plate are thermocompression bonded, a liquid resin is applied to the glass plate and sandwiched, and then the liquid resin is applied by an external stimulus such as heat or ultraviolet rays. A curing method or the like can be employed. As the resin, for example, polyvinyl butyral, ethylene-vinyl acetate, fluorine resin, or the like can be used. In addition, if it is a laminated glass, the thickness of a radiation shielding window or a radiation shielding partition can be enlarged.
なお、上記の合わせガラスの作製方法は一例であり、その態様は任意に変更してもよい。例えば、二枚以上のガラス板を樹脂シートと交互に積層してもよい。また、合わせガラスの表面に更に樹脂シートを積層してもよい。最表面に樹脂層を形成すれば、合わせガラスの耐候性を高めることができる。 Note that the above method for producing a laminated glass is an example, and the mode may be arbitrarily changed. For example, two or more glass plates may be alternately laminated with a resin sheet. Further, a resin sheet may be further laminated on the surface of the laminated glass. If the resin layer is formed on the outermost surface, the weather resistance of the laminated glass can be improved.
次に、放射線遮蔽窓の作製方法を例示する。各種形状（例えば、板状、ブロック状、合わせガラス等）のガラスを金枠に固定した上で、この金枠をコンクリートや鉄の壁に設けられた開口部に嵌め込んだ後、金枠と開口部との間に目地剤等を充填する。なお、金枠に固定するガラスは、単数だけでなく、複数でもよい。 Next, a method for producing a radiation shielding window is illustrated. After fixing glass of various shapes (for example, plate shape, block shape, laminated glass, etc.) to a metal frame, and fitting this metal frame into an opening provided in a concrete or iron wall, Fill with a joint preparation between the opening. In addition, the glass fixed to a metal frame may be not only single but plural.
以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative. The present invention is not limited to the following examples.
表１〜３は、本発明の実施例（試料Ｎｏ．１〜２８）及び比較例（試料Ｎｏ．２９）を示している。 Tables 1 to 3 show examples (sample Nos. 1 to 28) and comparative examples (sample No. 29) of the present invention.
まず表１〜３に記載のガラス組成になるように、ガラス原料を調合した後、得られたガラスバッチをガラス溶融炉に供給して１５００〜１６００℃で４時間溶融した。次に、得られた溶融ガラスをカーボン板の上に流し出して板状に成形した後、所定のアニール処理（４５０℃に設定した電気炉内で炉冷）を行った。最後に、得られたガラス板について、種々の特性を評価した。 First, after preparing a glass raw material so that it might become a glass composition of Tables 1-3, the obtained glass batch was supplied to the glass melting furnace, and it fuse | melted at 1500-1600 degreeC for 4 hours. Next, the obtained molten glass was poured onto a carbon plate and formed into a plate shape, and then subjected to a predetermined annealing treatment (furnace cooling in an electric furnace set at 450 ° C.). Finally, various characteristics of the obtained glass plate were evaluated.
密度は、アルキメデス法を用いて測定した。 The density was measured using the Archimedes method.
１５０ｋｅＶにおける放射線の線吸収係数は、ガラス組成と密度から算出した。なお、各元素の質量吸収係数としてＰＨＯＴＸのデータを用いた。 The linear absorption coefficient of radiation at 150 keV was calculated from the glass composition and density. PHOTX data was used as the mass absorption coefficient of each element.
耐失透性は、溶融ガラスを流し出した際、得られたガラスが失透せずに透明であったものを○、部分的に乳白していたものを△、全体的に不透明であったものを×として評価した。 Regarding the devitrification resistance, when the molten glass was poured out, the obtained glass was transparent without devitrification, ◯ when it was partially milky, and totally opaque. Things were evaluated as x.
表１〜３に示すように、試料Ｎｏ．１〜２８は、何れも１５０ｋｅＶにおける線吸収係数が０．９／ｃｍ以上であり、放射線遮蔽性能が良好であった。一方、試料Ｎｏ．２９は、ガラス組成が所定範囲外であるため、放射線遮蔽性能が劣っていた。 As shown in Tables 1-3, Sample No. Nos. 1 to 28 each had a linear absorption coefficient at 150 keV of 0.9 / cm or more and good radiation shielding performance. On the other hand, Sample No. No. 29 was inferior in radiation shielding performance because the glass composition was outside the predetermined range.
本発明のガラスは、例えば、放射線遮蔽窓又は放射線遮蔽衝立に利用可能であり、特に放射線施設における観察窓、Ｘ線を発する分析機器の観察窓等に利用可能である。 The glass of the present invention can be used for, for example, a radiation shielding window or a radiation shielding screen, and in particular, can be used for an observation window in a radiation facility, an observation window of an analytical instrument that emits X-rays, and the like.
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| DE112014002123T5 (en) * | 2013-04-25 | 2016-01-21 | Nippon Electric Glass Co., Ltd. | Glass with high refractive index |
| JP6268805B2 (en) * | 2013-08-13 | 2018-01-31 | 日本電気硝子株式会社 | Manufacturing method of glass plate |
| JP2015227272A (en) * | 2014-06-02 | 2015-12-17 | 日本電気硝子株式会社 | Phase-split glass and composite substrate using the same |
| JP6792807B2 (en) * | 2015-09-02 | 2020-12-02 | 日本電気硝子株式会社 | Low photoelastic glass plate |
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