络合滴定法快速测定激光光纤用镱螯合物中镱含量

刘荣丽; 张思进; 罗勉; 朱其鹏; 王承远; 石雪峰

doi:10.11884/HPLPB202638.250419

络合滴定法快速测定激光光纤用镱螯合物中镱含量

doi: 10.11884/HPLPB202638.250419

湖南稀土金属材料研究院有限责任公司，长沙 410126

详细信息

作者简介:
刘荣丽，8971711264@qq.com

中图分类号: O614.33
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出版历程
- 收稿日期: 2025-11-25
- 修回日期: 2026-01-13
- 录用日期: 2026-01-07
- 网络出版日期: 2026-01-28

Rapid complexometric determination of ytterbium in laser-fiber grade ytterbium chelate

Hunan Rare-Earth Metal Materials Research Institute Co, Ltd, Changsha 410126, China

摘要

摘要: Yb(TMHD)₃是高增益掺镱石英光纤不可替代的气相掺杂前驱体，其Yb含量直接决定光纤性能。传统重量检测法周期长达6 h，无法满足光纤预制棒在线工艺调整的时效需求。为了提高生产效率，建立了一种“硝酸-双氧水敞口消解-EDTA络合滴定”的方法在六次甲基四胺缓冲体系（pH=5～6）中，以二甲酚橙（XO）为指示剂，用EDTA标准液与Yb³⁺按1∶1摩尔比络合滴定，终点由玫瑰红突变为亮黄色，变色敏锐、重现性好。系统研究了Yb(TMHD)₃消解方法、缓冲液六次甲基四胺pH对镱测定的影响因素，确定了最优条件。方法平均回收率在98.2%～100.2%之间，精密度RSD(n=11)≤0.5%。Yb(TMHD)₃实际样品测定结果与重量法对照偏差＜0.3%，单样检测时间由6 h缩短至15 min。该方法准确、精密、简便、成本低，可直接部署于生产现场，实现Yb(TMHD)₃中Yb含量的快速检测，为掺镱光纤预制棒的工艺实时优化与质量稳定提供了可靠的技术支撑。
- Yb(TMHD)₃ /
- Yb /
- EDTA /
- 快速滴定
Abstract: Background
Yb(TMHD)₃ (ytterbium tris (2,2,6,6-tetramethyl-3,5-heptanedionate)) is the irreplaceable vapor-phase dopant for fabricating high-gain Yb-doped silica laser fibers, and its exact Yb content dictates final fiber performance. The conventional oxalate gravimetric method requires 6 h per sample, incompatible with the real-time feedback demanded by modern preform manufacture.
Purpose
In order to enhance the production efficiency,
Methods
we report a “nitric acid-hydrogen peroxide open-vessel digestion/EDTA complexometric titration” protocol. After 3 min oxidative decomposition of the organic matrix, the solution is buffered with hexamethylenetetramine (pH=5-6) and titrated with standard EDTA using xylenol orange (XO) as indicator.
Results
The stoichiometric Yb³⁺ : EDTA ratio is 1∶1; the sharp colour change from rose-red to bright yellow with a relative standard deviation (RSD, n=11) of ≤ 0.5%. Mean recoveries for spiked Yb(TMHD)₃ ranged 98.2%-100.2%. Results for ten commercial lots deviated <0.3% from the gravimetric reference, while the total analysis time was reduced from 6 h to 15 min.
Conclusions
The procedure is accurate, precise, inexpensive and field-robust, enabling on-site monitoring of Yb loading and immediate optimisation of preform deposition parameters.
- Yb(TMHD)₃ /
- ytterbium /
- EDTA /
- rapid titration

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图 1 沉淀物的XRD检测结果

Figure 1. XRD pattern of the precipitate

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图 2 美国Yb(TMHD)₃差热分析图

Figure 2. DTA curve of the Yb(TMHD)₃ from USA

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图 3 国产Yb(TMHD)₃析出沉淀物的差热分析图

Figure 3. DTA trace of the precipitate formed from domestically produced Yb(TMHD)₃

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表 1 不同样品量的回收率

Table 1. Recovery rates of different sample mass

sample mass/g	Yb original mass/mg	Yb addition mass/mg	Yb determination mss/mg	Yb recovery rate/%
0.10	23.91	10.00	33.87	99.88
0.15	35.86	15.00	50.94	100.16
0.20	47.82	20.00	47.02	98.33

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表 2 消解方法对Yb测定的影响因素

Table 2. Comparison of digestion methods and their influence on Yb determination

digestion methods	digestion of completeness	Yb loss risk	organic residue	operational safety	subsequent compatibility
HCl	poor	low	obvious	high	poor
HNO₃ + H₂O₂	well	extremely low	non	intermediate	well
Ethanol	non	non	non	high	non

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表 3 共存元素干扰及掩蔽实验

Table 3. Interference and masking experiments of coexisting elements

intervention element addition mass/μg				ascorbic acid/g	sulfosalicylic acid/mL	Yb recovery rate/%
Al³⁺	Fe³⁺	Ca²⁺	Mg²⁺	ascorbic acid/g	sulfosalicylic acid/mL	Yb recovery rate/%
0.50	0.50	0.50	0.50	0.10	2.00	100.02
1.00	1.00	1.00	1.00	0.10	2.00	100.36
1.50	1.50	1.50	1.50	0.10	2.00	100.42

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表 4 精密度实验（n=11）

Table 4. Precision experiments（n=11）

number	Yb mass fraction/%
number	sample 1#	sample 2#	sample 3#
1	23.85	23.95	23.97
2	23.80	24.00	23.92
3	23.95	23.79	24.01
4	23.80	23.84	23.92
5	23.79	23.93	23.91
6	23.97	24.01	23.91
7	23.75	23.68	23.76
8	23.81	23.73	23.72
9	23.92	23.74	23.82
10	23.98	23.68	23.98
11	23.74	23.77	23.65
average	23.85	23.83	23.87
RSD	0.075	0.45	0.40

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表 5 不同方法测定结果比较（单位）

Table 5. Comparison of analytical results obtained by different methods

number	Yb mass fraction/%		absolute deviation/%
number	this work	oxalate gravimetric method	absolute deviation/%
1	23.87	23.75	0.12
2	23.80	24.02	0.22
3	23.95	23.71	0.24
average	23.87	23.83	0.19

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