氟化钆 | 13765-26-9

• 物质功能分类: 无机化工 - 无机盐 - 金属卤化物及卤酸盐
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 镧系盐
• 中文名称: 氟化钆
• 中文别名: 氟化钆(III)；无水氟化钆；氟化钆无水；无水氯化钆
• 英文名称: gadolinium(III) fluoride
• 英文别名: gadolinium fluoride；gadolinium(3+);trifluoride
• CAS: 13765-26-9
• 化学式: F₃Gd
• 分子量: 214.245
• InChiKey: TYIZUJNEZNBXRS-UHFFFAOYSA-K

物化性质

• 熔点：
  1231°C
• 密度：
  7.1
• 暴露限值：
  a/nm
• 稳定性/保质期：
  在常温常压下，该物质是稳定的。应避免与酸接触。它不易溶于冷水，但在热水中的氢氟酸中会轻微溶解。

计算性质

• 辛醇/水分配系数(LogP)：
  1.26
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

ADMET

毒理性

• 副作用

纤维原性 - 引发组织损伤和纤维化（疤痕形成）。

Fibrogenic - Inducing tissue injury and fibrosis (scarring).

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

安全信息

• TSCA：
  Yes
• 危险等级：
  6.1
• 危险品标志：
  Xi
• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  28469000
• 危险品运输编号：
  UN 3288 6.1/PG 3
• 包装等级：
  III
• 危险类别：
  6.1
• 储存条件：
  常温下应保持密闭、存放在阴凉、通风和干燥处。

SDS

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Section 1: Product Identification
Chemical Name: Gadolinium (III) fluoride, anhydrous (99.9%-Gd) (REO)
CAS Registry Number: 13765-26-9
Formula: GdF3
EINECS Number: 237-369-4
Chemical Family: metal halide
Synonym: Gadolinium trifluoride

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 13765-26-9 100% 2.5mg/m3 (as F) 2.5mg/m3 (as F)

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Section 3: Hazards Identification
Emergency Overview: Irritating to the respiratory tract, skin and eyes. May be harmful if swallowed.
Primary Routes of Exposure: Contact with skin and eyes. Inhalation of dust.
Eye Contact: Causes irritation of the eyes.
Skin Contact: Causes slight to mild irritation of the skin.
Inhalation: Irritating to skin, eyes and respiratory tract.
Toxicity reduced to the extent that this compound is relatively insoluble. In large amounts may cause vomiting,
Ingestion:
abdominal pain and diarrhea.
Irritating to skin, eyes and respiratory tract. Fluoride poisoning may cause nausea, vomiting, diarrhea,
Acute Health Affects:
weakness, coma, and respiratory paralysis.
Chronic Health Affects: Prolonged exposure to hydrolysable fluorine compounds can cause deterioration of bone and tooth structure.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area with water. Remove contaminated clothes if necessary. Apply calcium gluconate jelly
Skin Exposure:
or water soluble calcium salts as antidote. Seek medical assistance.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: not applicable
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: None. Material is non-flammable.
Special Fire Fighting Procedures: No special fire fighting procedures required.
Hazardous Combustion and none
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Spill and Leak Procedures: Small spills can be mixed with powdered sodium bicarbonate, lime, or calcium carbonate and swept up.

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SECTION 7: Handling and Storage
Handling and Storage: Store solid in a tightly sealed container.

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SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves. Consult with glove manufacturer to determine the proper type of glove.
Ventilation: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
If in form of fine dust and ventilation is not available a respirator should be worn. The use of respirators
Respirator:
requires a Respirator Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: white pwdr.
Molecular Weight: 214.25
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air and moisture stable
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: none
Incompatibility: none
Decomposition Products: none

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: no data
Mutagenic Effects: no data
Tetratogenic Effects: no data

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SECTION 12: Ecological Information
Ecological Information: No information available

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SECTION 13: Disposal Considerations
Disposal: Dispose of according to local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Non-hazardous
Hazard Class (CFR): NA
Additional Hazard Class (CFR): NA
Packaging Group (CFR): NA
UN ID Number (CFR): NA
Shipping Name (IATA): Non-hazardous
Hazard Class (IATA): NA
Additional Hazard Class (IATA): NA
Packaging Group (IATA): NA
UN ID Number (IATA): NA

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SECTION 15: Regulatory Information
TSCA: Listed in the TSCA inventory.
SARA (Title 313): Title compound not listed.
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用途

该物质用于制备金属钆等，并可用于合成非氧化物玻璃。

生产方法

主要采用氢氟酸沉淀-真空脱水法。具体步骤如下：

1. 将40%～48%的氢氟酸加入到硫酸钆溶液中，析出水合氟化钆。
2. 在真空中加热以去除结晶水。
3. 氢氟酸消耗量约为理论量的110%～120%。从水溶液中析出的氟化物沉淀体积较大，并吸附有一定数量的硫酸根离子，需用充分洗涤除去，采用倾泻法进行水洗。
4. 过滤后的沉淀在100～150℃下干燥，以去除吸附水并确保只含有结晶水的氟化物。为避免高温水解生成氟氧化物GdOF，在真空度高于0.133 Pa的情况下于不低于300℃的温度进行脱水。

另一种脱水方法是将水合氟化钆置于干燥的氟化氢气流中加热至600～650℃，在氟化氢气氛保护下进一步氟化，以确保产品质量。由于生产过程中使用了水溶液，通常采用塑料容器，并选用耐高温腐蚀材料作为脱水设备，如镍基合金或纯镍内衬。

注意事项：整个过程需严格控制温度和真空度，以避免副反应的发生。

反应信息

• 作为反应物：
  描述：

  氟化钆 以 solid matrix 为溶剂， 以5-10的产率得到
  参考文献：
  名称：

  Gamma‐Induced Divalent Dysprosium in Calcium Fluoride

  摘要：

  Experiments dealing with photochemical and thermal reactions of dysprosium in calcium fluoride are described. Trivalent dysprosium ions doped in calcium fluoride have been reduced by gamma irradiation at room temperature. The efficiency of reduction of Dy3+ in CaF2 is described in terms of the dosage of gamma irradiation and concentration of the dopant ions. The optimum conditions for the photoreduction are given. The absorption band responsible for the reoxidation of the gamma-reduced dysprosium has been determined. It has been established that high densities of gamma-induced defect sites are necessary for the conversion of the majority of divalent ions to the trivalent state, which may be indicative of the tunneling of Dy2+ electrons to hole centers via the gamma-induced defect centers. The tunneling process is also believed to be responsible for the saturation of local and macroscopic concentrations of Dy2+ ions. The thermal reoxidation of Dy2+ ions is accompanied by bright luminescence, the spectrum of which resembles that of the photoluminescence of Dy3+ ions. The decay of the thermoluminescent emission bands is nonexponential, and the reaction kinetics fit the description of a second-order reaction. The evaluated activation energy (0.33 eV) is indistinguishable from the energy required for the thermal ionization of holes from V1 centers in alkali halides.

  DOI：

  10.1063/1.1725628
• 作为产物：
  描述：

  gadolinium(III) oxide 在 HF 作用下， 生成 氟化钆
  参考文献：
  名称：

  稀土三氟化物的热化学 I. 氟弹量热法测定 LaF3、PrF3、NdF3、GdF3、DyF3、HoF3 和 ErF3 的形成焓

  摘要：

  摘要 用弹量热计测量了镧、镨、钕、钆、镝、钬和铒的高纯度样品在氟中燃烧形成各自的三氟化物的能量。获得的标准生成焓ΔH fo (298.15 K)/kJ mol -1 的结果如下： LaF 3 ，-(1699.5 ± 2.0)；PrF 3 ，-(1689.1 ± 2.6)；NdF 3 , -(1679.4 ± 1.9); GdF 3 , -(1699.3 ± 2.3); DyF 3 , -(1692.0 ± 1.9); HoF 3 , -(1697.8 ± 2.3); 和 ErF 3 , -(1693.6 ± 1.9)。

  DOI：

  10.1016/0021-9614(80)90123-8
• 作为试剂：
  描述：

  氟光气 、 fluorine 在 氟化钆 作用下， 以95%的产率得到双(三氟甲基)过氧化物
  参考文献：
  名称：

  Kennedy, R. C.; Cady, G. H., Journal of Fluorine Chemistry, 1973, vol. 3, p. 41 - 54

  摘要：

  DOI：

文献信息

• Preparation of REFeAsO1−F (RE=Sm and Gd) superconductors at a relatively low temperature
  作者：Y.J. Cui、Y.L. Chen、C.H. Cheng、Y. Yang、Y.Z. Wang、Y.C Li、Y. Zhao

  DOI：10.1016/j.jpcs.2010.10.041

  日期：2011.5

  relatively low temperature. The samples have been sintered at 1100 and 1120 °C for SmFeAsO 1− x F x and GdFeAsO 1− x F x , respectively. These temperatures are at least 50–60° lower than other previous reports. All of the so-prepared samples possess a tetragonal ZrCuSiAs-type structure. Dramatically supression of the lattice parameters and increase in T c proved that this low temperature process was

  摘要 以纳米级 ReF 3 作为氟资源，在相对较低的温度下制备了一系列 SmFeAsO 1− x F x 和 GdFeAsO 1− x F x ( x =0.05, 0.1, 0.15, 0.2, 0.25) 样品. SmFeAsO 1− x F x 和 GdFeAsO 1− x F x 分别在 1100 和 1120 °C 下烧结样品。这些温度至少比之前的其他报告低 50–60°。所有如此制备的样品都具有四方 ZrCuSiAs 型结构。晶格参数的显着抑制和 T c 的增加证明这种低温过程更有效地将氟引入稀土 FeAsO 中。SmFeAsO 1− x F x 的超导转变出现在 39.5 K 处，x =0.05，而 GdFeAsO 1− x F x 出现在 22 K 处，x =0.1。检测到的最高 T c 在 SmFeAsO 0.8 F 0.2 中为 54 K，在 GdFeAsO 0.75 F
• Polymorphism of high-purity rare earth trifluorides
  作者：O. Greis、M.S.R. Cader

  DOI：10.1016/0040-6031(85)85329-6

  日期：1985.5

  Abstract Polymorphism and melting behavior of high-purity rare earth trifluorides have been studied by differential thermal analysis. Modified sample holders were used to increase the sensitivity of temperature measurements. Melting points and solid—solid transitions are reported as well as the stability fields of the different modifications with space groups P 3 c1, P63/mmc, Pnma, and P 3 m1. For

  摘要 采用差热分析方法研究了高纯三氟化稀土的多晶型和熔融行为。改进的样品架用于提高温度测量的灵敏度。报告了熔点和固-固转变以及空间群 P 3 c1、P63/mmc、Pnma 和 P 3 m1 的不同变体的稳定性场。首次通过差热分析检测到了泰森石型稀土三氟化物的有序-无序转变P 3 c1α P63/mmc。
• Synthesis, structure and VUV luminescent properties of rubidium rare-earth fluorides
  作者：Fangtian You、Shihua Huang、Shuman Liu、Ye Tao

  DOI：10.1016/j.jssc.2004.04.040

  日期：2004.8

  rare-earth elements form LnF3 (Ln=La–Nd), while the heavy ones form RbLn2F7 (Ln=Y, Er, Yb and Lu) with the RbEr2F7 structure type. RbLn3F10 compounds were found for the in-between rare-earth cations (Ln=Eu–Tm and Y), which crystallize exclusively in the cubic γ-KYb3F10-type structure. The luminescent properties under vacuum ultraviolet light were studied for the Eu3+-doped RbLn3F10 (Ln=Y, Gd) and a

  RbF– Ln F 3（Ln =稀土）系统是通过水热技术合成的。在水热条件下，轻稀土元素形成Ln F 3（Ln = La–Nd），重稀土元素形成Rb Ln 2 F 7（Ln = Y，Er，Yb和Lu），RbEr 2 F 7结构类型。在稀土阳离子之间发现了Rb Ln 3 F 10化合物（Ln = Eu–Tm和Y），它们仅在立方γ- KYb 3 F 10中结晶。型结构。研究了掺Eu 3+的Rb Ln 3 F 10（Ln = Y，Gd）在真空紫外光下的发光特性，观察到RbGd 3 F 10：Eu 3+的高量子效率约为150％。
• The determination of fluorine in rare earth fluorides by high temperature hydrolysis
  作者：Charles V. Banks、Keith E. Burke、Jerome W. O'Laughlin

  DOI：10.1016/s0003-2670(00)88149-0

  日期：——

  determination of fluorine in the fluorides of scandium, yttrium, and the lanthanons. These fluorides have been divided into two classes according to their rate of hydrolysls. Lutetium, ytterbium, cerium (III), scandium. gadolinium, terbium, dysprosium, holmium, erbium, and thulium auorides can be hydrolyzed in 30 min or less. Yttrium. lanthanum, praseodymium. neodymlum, samarium, and europium fluorides

  热水解技术已用于测定钪、钇和镧系元素的氟化物中的氟。这些氟化物根据它们的水解速率分为两类。镥、镱、铈 (III)、钪。钆、铽、镝、钬、铒和氧化铥可以在 30 分钟或更短的时间内水解。钇。镧、镨。钕、钐和铕氟化物需要 45 到 150 分钟才能完全水解。加速剂，如氧化铀（U/sub 3/C/sub 8/）、氧化铬（UI）。这些氧化物的混合物已成功地用于减少后一组氟化物定量水解所需的时间。对于除镧、镨和钕之外的所有这些氟化物，使用正确的促进剂可将水解时间缩短至 30 分钟或更短。（授权）
• Thermochemical studies on the lanthanoid complexes of trifluoroacetic acid
  作者：Y. Yoshimura、K. Ohara

  DOI：10.1016/j.jallcom.2004.12.082

  日期：2006.2

  decomposition of the lanthanoid complexes of trifluoroacetic acid (Ln(CF 3 COO) 3 ·3H 2 O; Ln=La-Lu) was studied by TG and DTA methods. The Ln(CF 3 COO) 3 ·3H 2 O complexes decompose in several stages; first dehydrate to the anhydrous state, then followed by decomposition of the anhydrous salt to a stable product of LnF 3 . From the endothermic and exothermic data of Ln(CF 3 COO) 3 ·3H 2 O complexes, pyrolysis

  用TG和DTA方法研究了三氟乙酸镧系元素络合物(Ln(CF 3 COO) 3 ·3H 2 O；Ln=La-Lu)的热分解。Ln(CF 3 COO) 3 ·3H 2 O配合物分几个阶段分解；首先脱水至无水状态，然后将无水盐分解为稳定的 LnF 3 产物。从Ln(CF 3 COO) 3 ·3H 2 O配合物的吸热放热数据来看，配合物的热解行为可分为三类：(1)La-Pr盐类；(2) Nd-Gd盐类；(3) Tb-Lu盐。已经表明，发现所有最终分解产物都导致形成LnF 3 。