JPS5950048A - Optical glass - Google Patents
Optical glassInfo
- Publication number
- JPS5950048A JPS5950048A JP15967682A JP15967682A JPS5950048A JP S5950048 A JPS5950048 A JP S5950048A JP 15967682 A JP15967682 A JP 15967682A JP 15967682 A JP15967682 A JP 15967682A JP S5950048 A JPS5950048 A JP S5950048A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- sio2
- component
- amount
- present
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、屈折率(nd)約1.70−’1.95、ア
ツベ数(νd)約25〜50の範囲の光学恒数を有する
5i02 B2O3La2O3Nb205−ZrO2
Ti02−RO(Rはアルカリ土類金属元素)系の光学
ガラスに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 5i02 B2O3La2O3Nb205-ZrO2 having a refractive index (nd) of about 1.70-'1.95 and an Abbe number (vd) of about 25-50.
The present invention relates to a Ti02-RO (R is an alkaline earth metal element) optical glass.
従来、上記本発明のガラスと同等の光学恒数を有するガ
ラスは、特公昭lう−712)1号公報、特開昭)↓8
−3キ91ろ号公報および特開昭119−2140g号
公報等において知られている。これらのガラスは、それ
ぞれB2O3−La2o3Z r02 Nb205
Zn O系、B2O3−La203−(BaOおよび
/またけZnO)−Pb0−Li2o系およびB2O3
5i02 La2O3BaO系等のガラスであるが、
化学的耐久性、溶融性および光線透過性のいずれかの点
で十分良好であるとはいえない。また、特公昭う5−1
87う0号公報および特開昭48−23809号公報等
においても同様のガラスが知られているが、これらに示
されたガラスはいずれもG e 02、Gd2O3、Y
2O3およびTa205等の高価な原料を一種または二
種以上を組合わせて比較的多量に使用しなければならな
い。Conventionally, glasses having optical constants equivalent to those of the glass of the present invention have been disclosed in Japanese Patent Publication No. 712) No. 1 and Japanese Patent Application Laid-open No. Sho) ↓8.
It is known from Japanese Patent Laid-Open No. 119-2140g and the like. These glasses are respectively B2O3-La2o3Z r02 Nb205
ZnO system, B2O3-La203-(BaO and/over ZnO)-Pb0-Li2o system and B2O3
5i02 La2O3BaO type glass etc.
It cannot be said that it is sufficiently good in terms of chemical durability, meltability, and light transmittance. In addition, Tokuko Showa 5-1
Similar glasses are also known in JP-A No. 87-0 and JP-A-48-23809, but all of the glasses shown in these documents contain G e 02, Gd2O3, Y
Expensive raw materials such as 2O3 and Ta205 must be used alone or in combination in relatively large amounts.
本発明の目的は、前記所定の光学恒数を有し、かつ、従
来のガラスにみられる上記の諸欠点を解消したガラスを
提供することにある。An object of the present invention is to provide a glass that has the above-mentioned predetermined optical constants and eliminates the above-mentioned drawbacks found in conventional glasses.
本発明者は、この目的を達成するため鋭意試験研究を重
ねた結果、特定組成範囲の8+02B203−La2O
3Nb205−Zr02−Ti02−RO(Rは、アル
カリ土類金属元素)系ガラスにおいては、優れた化学的
耐久性と溶融性とを示すガラスが存在することをみいだ
し、本発明をなすに至った。As a result of extensive testing and research to achieve this objective, the present inventor discovered that 8+02B203-La2O with a specific composition range.
We have discovered that there is a glass that exhibits excellent chemical durability and meltability among 3Nb205-Zr02-Ti02-RO (R is an alkaline earth metal element) type glass, leading to the present invention. .
上記の目的を達成するための本発明にかかる光学ガラス
の組成範囲は、重量%で、5i028〜う0%、B20
32〜17%、A12030〜5%、ただしく S i
02 +B203+A1203≦う5%、かつ、B2
O3/SiO2≦1.0)、La2O31〜l+0%、
Nb2o51−22%、ZrO21〜10%、Ti02
1〜20%、ただしく La203 +Nb205+Z
rO2≧17.5%、かつ、ZrO2+TlO2>5%
)、Mg0O〜5%、cao o〜6.5%、SrO0
−20%、BaO0〜30%、ただしくMgO+CaO
+SrO+BaO15−う5%未満→、ZnO0−15
%、 I、+20 0〜う%、 Na 2 QO
−10%、 K2O03’%、 ただしくLizO+
Na2O+Kz0 0〜10%)、 Al12030〜
1%、5b2030〜1%、ただし上記各成分の合計9
5〜100%であることを要する。The composition range of the optical glass according to the present invention to achieve the above object is 5i028 to 0% by weight, B20
32-17%, A12030-5%, however Si
02 +B203+A1203≦5% and B2
O3/SiO2≦1.0), La2O31~l+0%,
Nb2o51-22%, ZrO21-10%, Ti02
1-20%, just La203 +Nb205+Z
rO2≧17.5% and ZrO2+TlO2>5%
), Mg0O~5%, cao~6.5%, SrO0
-20%, BaO0-30%, MgO+CaO
+SrO+BaO15-less than 5%→, ZnO0-15
%, I, +20 0~%, Na 2 QO
-10%, K2O03'%, however LizO+
Na2O+Kz0 0~10%), Al12030~
1%, 5b2030~1%, but the total of each component above is 9
It needs to be 5-100%.
本発明のガラスにおいては、溶融条件によってガラス中
のTiO2成分が還元されるためと考えられる着色性強
化傾向がみられるが、ガラス中にアルカリ金属酸化物成
分を含有させると意外にもこの欠点を改善することがで
きるので有用である。In the glass of the present invention, there is a tendency to strengthen the coloring property, which is thought to be due to the reduction of the TiO2 component in the glass depending on the melting conditions, but the inclusion of an alkali metal oxide component in the glass surprisingly alleviates this drawback. It is useful because it can be improved.
つぎに、本発明にかかる光学ガラスの各成分の組成範囲
を上記のとおり限定した理由について述べる。Next, the reason for limiting the composition range of each component of the optical glass according to the present invention as described above will be described.
すなわち、本発明のガラスの主要なガラス形成酸化物成
分である5i02とB2O3のうち、S r 02成分
の量がg%未満であるとガラスは失透しやすくなり、安
定なガラスを製造することが困難となり、またその量が
う0%を超えると目標の光学恒数を満足することが困難
になる。また、B2O3成分の量が2%未満であるとガ
ラスの粘性が大きくなり、均質なガラスを得がたくなり
、またその量が17%を超えるとガラスの化学的耐久性
が劣化しやすくなる。That is, if the amount of Sr02 component is less than g% among 5i02 and B2O3, which are the main glass-forming oxide components of the glass of the present invention, the glass tends to devitrify, and it is difficult to produce a stable glass. If the amount exceeds 0%, it becomes difficult to satisfy the target optical constants. Furthermore, if the amount of the B2O3 component is less than 2%, the viscosity of the glass increases, making it difficult to obtain a homogeneous glass, and if the amount exceeds 17%, the chemical durability of the glass tends to deteriorate.
へ1203成分け、ガラス原料の溶融を促進し、化学的
耐、久性の向上等の効果があるので任意に添加し得るが
、その量が5%を超えるとガラスの失透性が増大する。The 1203 component promotes the melting of glass raw materials and has the effect of improving chemical resistance and durability, so it can be added arbitrarily, but if its amount exceeds 5%, the devitrification of the glass will increase. .
ただし、上記のS i 02、B2O3およびA120
3の主成分の合計が35%を超えると目標の光学恒数を
得ることが困難となる。さらに、5i02成分に対する
B2O3成分の重量比は、優れた化学的耐久性を維持す
るため、1.0以下である必要がある。However, the above S i 02, B2O3 and A120
If the sum of the three principal components exceeds 35%, it will be difficult to obtain the target optical constants. Furthermore, the weight ratio of the B2O3 component to the 5i02 component needs to be 1.0 or less in order to maintain excellent chemical durability.
La2O3成分は、ガラスの屈折率を高めるので、本発
明のガラスに必要であり、またアツベ数を大きくする効
果があるが、その量が1%未満では所望の屈折率が得ら
れず、またその量が40%を超えるとガラスの失透性が
増大する。The La2O3 component is necessary for the glass of the present invention because it increases the refractive index of the glass, and has the effect of increasing the Atsube number, but if its amount is less than 1%, the desired refractive index cannot be obtained, and the La2O3 component increases the refractive index of the glass. When the amount exceeds 40%, the devitrification of the glass increases.
Nb2O5成分は、ガラスの屈折率を高め、アツベ数を
小さくし、また化ノ奮久性を増大しさらに失透傾向を抑
制する効果を有するが、その量が1%未満ではこれらの
効果が十分でなく、またその量が22%を超えるとかえ
ってガラスの失透性を増大させるので好ましくない。The Nb2O5 component has the effect of increasing the refractive index of the glass, reducing the Atsube number, increasing the durability of the chemical reaction, and suppressing the tendency to devitrify, but if the amount is less than 1%, these effects are insufficient. However, if the amount exceeds 22%, it is not preferable because it will actually increase the devitrification of the glass.
ZrO2成分は、ガラスの屈折率を高め、化学的耐久性
を向上させ、また失透傾向を抑制する効果があるが、そ
の量が1%未満であるとこれらの効果が十分得られず、
またその量が10%を超えるとガラスは、溶融の際、未
溶融物を生じたり、かえって失透しゃすくなったりする
。The ZrO2 component has the effect of increasing the refractive index of the glass, improving the chemical durability, and suppressing the tendency to devitrify, but if the amount is less than 1%, these effects cannot be sufficiently obtained.
Moreover, if the amount exceeds 10%, the glass may produce unmelted substances during melting or become more likely to devitrify.
T ! 02成分は、ガラスの屈折率を高め、アツベ数
を小さくし、化学的耐久性と失透に対する安定性とを増
大する効果があるが、その量が1%未満ではこれらの効
果が顕著でなく、またその量が20%を超えるとガラス
の着色が強くなる。T! Component 02 has the effect of increasing the refractive index of glass, decreasing the Atsube number, and increasing chemical durability and stability against devitrification, but if the amount is less than 1%, these effects are not noticeable. , and when the amount exceeds 20%, the glass becomes strongly colored.
上記のL& 203、Nb2O5およびZ r O2の
三成分の合計、およびZrO2とTiO□の二成分の合
計は、ガラスに所定の光学恒数を維持させつつ優れた化
学的耐久性を与えるため、それぞれ17.5%以上およ
び5%を超える量でなければならない。The sum of the three components of L&203, Nb2O5 and ZrO2, and the sum of the two components of ZrO2 and TiO□ are each The amount must be at least 17.5% and more than 5%.
MgO1Cab、 SrOおよびBaQ のアルカリ土
類金属酸化物の各成分は、いずれもガラスを溶融する際
、5I02原料の溶融を促進し、ガラスの失透傾向を抑
制する効果がある。しかし、MgOおよびCaOの量は
、それぞれ5 %および6.5%を超えると失透性が増
大し、SrOの量は20%を超えると失透性の増大と化
学的耐久性の劣化を生じ、またBaOの量は30%を超
えると化学的耐久性の劣化を生ずるので好ましくない。Each of the alkaline earth metal oxide components MgO1Cab, SrO, and BaQ has the effect of promoting melting of the 5I02 raw material and suppressing the tendency of glass to devitrify when melting glass. However, when the amount of MgO and CaO exceeds 5% and 6.5%, respectively, devitrification increases, and when the amount of SrO exceeds 20%, devitrification increases and chemical durability deteriorates. Moreover, if the amount of BaO exceeds 30%, it is not preferable because chemical durability deteriorates.
さらに、これらMgO1CaO1SrOおよびBaOの
一成分または二成分以上の合計量は15%未満である七
ガラスの失透傾向が極めて増大し、また′55%以上で
あると化学的耐久性が劣化する。Furthermore, if the total amount of one or more of these MgO1CaO1SrO and BaO components is less than 15%, the tendency of glass to devitrify increases significantly, and if it is more than 55%, the chemical durability deteriorates.
ZnO成分は、ガラスの屈折率を高め、溶融の際、5i
02原料のガラス中への溶融を促進する効果を有するの
で添加し得るが、その量が】5%を超えるとガラスの化
学的耐久性が劣化しやすくなる。The ZnO component increases the refractive index of the glass and increases the 5i during melting.
It can be added because it has the effect of promoting the melting of the 02 raw material into the glass, but if its amount exceeds 5%, the chemical durability of the glass tends to deteriorate.
本発明のガラスにおいて、Li2O、Na2OおよびK
Oのアルカリ金属酸化物成分は、いずれも前述のとおり
のガラス着色化傾向を低減させる効果があるので使用す
ることが好ましい。しかし、ガラスの化学的耐久性や防
火透性を良好に維持するためL i 20、Na20お
よびに20の各成分の量は、それぞれ5%、10%およ
び10%を超えないことが望ましく、またこれらの二成
分以上の合計量は同様の理由で10%以内とすることが
好ましい。In the glass of the present invention, Li2O, Na2O and K
It is preferable to use any of the alkali metal oxide components of O since they have the effect of reducing the glass coloring tendency as described above. However, in order to maintain good chemical durability and fire permeability of the glass, it is desirable that the amounts of each of Li20, Na20 and Ni20 do not exceed 5%, 10% and 10%, respectively. For the same reason, the total amount of these two or more components is preferably within 10%.
A8□03および5b203の各成分は、ガラス溶融の
際の脱泡清澄剤として、それぞれ1%迄添加し得る。Each component of A8□03 and 5b203 can be added up to 1% each as a defoaming and clarifying agent during glass melting.
なお、本発明のガラスにおいて、上記以外のpboSy
b2o3、Y2O3、Gd2O3、Ta2 osG e
O2およびWO2等の成分の使用は、ガラスの着色性
、失透性または原料跡W性等の点で不利となるので好ま
しくないが、とくにそれらの点で差し支えない場合は、
これらの一種以上の成分を合計で5%まで添加すること
ができる。In addition, in the glass of the present invention, pboSy other than the above
b2o3, Y2O3, Gd2O3, Ta2 osG e
The use of components such as O2 and WO2 is disadvantageous in terms of glass coloring, devitrification, raw material trace W property, etc., and is therefore undesirable, but especially when there is no problem in these respects,
One or more of these components can be added up to a total of 5%.
つぎに、本発明の光学ガラスの実施組成例とこれから得
られたガラスの光学恒数(nd、νd)と化学的耐久性
試験の測定結果を表−1に示す。化学的耐久性試験は、
耐水性(RW(P))と耐酸性(RA (p) )につ
いて、日本光学硝子工業会規格JOGIS−OGの測定
法に準じて行なった。すなわち、標準ふるい420〜5
90μm内にとどまる粉末ガラス試料を99°C以上の
試薬(耐水性試験では純水、耐酸性試験では0 、01
.N硝酸水溶液)中に60分間処理して、処理前後の試
料の減量率(4)を求め、減量率により6階級に区分す
る方法による。耐水性試験について、級−1は0.05
wt%未満、級−2は0.05〜0110wt%未満
であり、耐酸性試験について、級−1は0.20wt%
未満、級−2は0.20−0.う5wt%未満である。Next, Table 1 shows an example of the composition of the optical glass of the present invention, the optical constants (nd, vd) of the glass obtained from the composition, and the measurement results of the chemical durability test. Chemical durability test
Water resistance (RW (P)) and acid resistance (RA (p)) were measured according to the measurement method of Japan Optical Glass Industry Association standard JOGIS-OG. That is, standard sieve 420-5
Powdered glass samples that remain within 90 μm are heated to 99°C or above with reagents (pure water for water resistance tests, 0, 01 for acid resistance tests)
.. The weight loss rate (4) of the sample before and after the treatment was determined by treating the sample in a N nitric acid aqueous solution for 60 minutes, and classifying the sample into 6 classes based on the weight loss rate. Regarding water resistance test, class-1 is 0.05
Less than wt%, class-2 is less than 0.05 to 0110 wt%, and for acid resistance test, class-1 is 0.20 wt%.
less than, class-2 is 0.20-0. It is less than 5wt%.
また、本発明において、新たにみいだされたアルカリ金
属酸化物成分の添加によるガラスの着色性低減化効果を
示す分光透過率比較図を図−1(本発明の実施組成例A
1 (無アルカリガラス)と問屋2〜lI(アルカリ
含有ガラス)との比較)および図−2(本発明の実施組
成例扁5(無アルカリガラス)と同A6〜g(アルカリ
含有ガラス)との比較)に示した。ガラス試料はいずれ
も一定溶融条件で溶融されたもので、厚さは10mmで
ある。In addition, in the present invention, Figure 1 (composition example
1 (alkali-free glass) and Wholesaler 2-lI (alkali-containing glass)) and Figure 2 (Comparison of practical composition example of the present invention, Flat 5 (alkali-free glass) and A6-g (alkali-containing glass)) Comparison). All glass samples were melted under constant melting conditions and have a thickness of 10 mm.
表−1に示したきおり、本発明の実施組成例の光学ガラ
スはいずれも所定の光学恒数を有しており、しかも耐水
性および耐酸性がともに優れている。また、図−1およ
び図−2に示したアルカリ金属酸化物成分を含有する本
発明の実施組成例のガラスはこれを含有しないガラスに
比べいずれも一段と光線透過性が向上し着色性低減化効
果を示している。As shown in Table 1, the optical glasses of the composition examples of the present invention all have predetermined optical constants and are excellent in both water resistance and acid resistance. In addition, the glasses of the composition examples of the present invention containing the alkali metal oxide components shown in Figures 1 and 2 have a much higher light transmittance than glasses that do not contain this component, and have the effect of reducing coloration. It shows.
なお、図示していないが、本発明のアルカリ成分を含有
する他の実施組成例のガラスも同様に光線透過性に一段
と優れたものである。Although not shown, other composition examples of glasses containing an alkali component according to the present invention also have superior light transmittance.
(以下余白)
以上に述べたとおり、本発明にかかる光学ガラスは、(
nd)約1.70〜1.95、(νd)約25〜50の
範囲の光学恒数を有し、従来のガラスに比べて化学的耐
久性と原料経済性にともに優れており、またアルカリ金
属酸化物成分を添加する場合は、溶融条件の変化による
光線透過性の悪化を防止することができ、そのうえガラ
スの溶融性も向上できるので有用である。(Hereinafter, blank space) As stated above, the optical glass according to the present invention is (
nd) approximately 1.70 to 1.95, (νd) approximately 25 to 50, and has superior chemical durability and raw material economy compared to conventional glasses. Adding a metal oxide component is useful because it can prevent deterioration of light transmittance due to changes in melting conditions and can also improve the meltability of the glass.
なお、本発明の光学ガラスは、原料バッチを白金ルツボ
等に投入し、約1200〜1ヰ00°Cで溶融して攪拌
と泡切りを行ない、ついで約1000〜1150°Cま
で降温した後、金型等に鋳込んで徐冷することにより容
易に製造することができる。The optical glass of the present invention is produced by putting a raw material batch into a platinum crucible or the like, melting it at about 1200 to 100°C, stirring and removing bubbles, and then cooling it to about 1000 to 1150°C. It can be easily manufactured by casting it into a mold or the like and slowly cooling it.
図−1および図−2は、いずれも本発明の光学ガラスの
実施組成例におけるアルカリ成分添加による分光透過率
向上効果を示す比較曲線図である。
叫有許世願人 ネ木六シ發才を小ぷりし匂硝子型丘F
、71イ15−
手続補正書(方式)
%式%
()
()
1、事件の表示
昭和57年特許願159676号
2、発明の名称
光学ガラス
3、補正をする者
事件との関係 特許出願人
4、補正命令の日付
昭和58年1月5日(発送日昭和58年1月25日5、
補正の対象
(1)明細書の3、発明の詳細な説明の欄6、補正の内
容
明細書の浄書(内容に変更なし)
(1)明細書第12頁〜第14頁に記載の表−1を別紙
表−1のとおり訂正する。FIG. 1 and FIG. 2 are comparative curve diagrams showing the effect of improving spectral transmittance due to addition of an alkali component in composition examples of optical glasses of the present invention. Shouting to the Lord, Negi Rokushi is a small size glass-shaped hill F.
, 71-15- Written amendment (method) % formula % () () 1. Indication of the case 1982 Patent Application No. 159676 2. Name of the invention Optical glass 3. Person making the amendment Relationship to the case Patent applicant 4. Date of amendment order: January 5, 1982 (Shipping date: January 25, 1982)
Subject of amendment (1) Description 3, Detailed Description of the Invention Column 6, Contents of the amendment The engraving of the specification (no change in content) (1) Tables described on pages 12 to 14 of the specification - 1 shall be corrected as shown in Attached Table-1.
Claims (1)
A12030〜5%、 ただしくS i 02 +B2
03 +A7203≦35%、かつ、B203/540
2≦1.0)、 La2031〜ヰ0%、Nb2051
−22%、ZrO21−10%、T IO21−20%
、 ただしく L a203 +N b 205 +Z
r 02≧17.5%、かつ、Z r 02 +T
i 02ン5%)、Mg0O〜5%、Ca00−6.5
%、5r00〜20%、Ba0O〜30%、ただしくM
gO+CaO+SrO+BaO15−ろ5%未満→ Z
nO0−15%、Li2o o−ろ%、Na2O0−
10%、 K2O0〜10%、ただしくLis+O十N
a20 +K 20 o〜x 0%)、A s 20
30〜1%、5b2030〜1%、ただし上記各成分の
合計 95〜100%であることを特徴とする光学ガラ
ス。In weight%, 5iO38-60%, B2032-17%,
A12030~5%, where S i 02 +B2
03 +A7203≦35% and B203/540
2≦1.0), La2031~0%, Nb2051
-22%, ZrO21-10%, TIO21-20%
, However, L a203 +N b 205 +Z
r 02 ≧ 17.5%, and Z r 02 +T
i02-5%), Mg0O~5%, Ca00-6.5
%, 5r00~20%, Ba0O~30%, just M
gO+CaO+SrO+BaO15-ro less than 5% → Z
nO0-15%, Li2o o-ro%, Na2O0-
10%, K2O0~10%, just Lis+O1N
a20 +K 20 o~x 0%), A s 20
30 to 1%, 5b2030 to 1%, provided that the total of each of the above components is 95 to 100%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15967682A JPS5950048A (en) | 1982-09-16 | 1982-09-16 | Optical glass |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15967682A JPS5950048A (en) | 1982-09-16 | 1982-09-16 | Optical glass |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5950048A true JPS5950048A (en) | 1984-03-22 |
Family
ID=15698893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15967682A Pending JPS5950048A (en) | 1982-09-16 | 1982-09-16 | Optical glass |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5950048A (en) |
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