熔融制样X射线荧光光谱法测定碳化钨及其废料中的钨

叶淑爱; 王伟; 普旭力; 蔡继杰

doi:10.15898/j.cnki.11-2131/td.2015.01.013

熔融制样X射线荧光光谱法测定碳化钨及其废料中的钨

厦门出入境检验检疫局检验检疫技术中心, 福建厦门 361026

基金项目: 国家质检总局科技计划项目——特殊稀土产品的成分和放射性检测研究项目(2013IK020)

详细信息

作者简介: 叶淑爱, 硕士, 工程师, 从事进出口矿产品及金属材料检验工作.E-mail:jszx-gks-yesa@xmciq.gov.cn

通讯作者: 普旭力, 博士, 高级工程师, 从事进出口矿产品及金属材料检验工作.E-mail:puxuli@126.com

中图分类号: O614.613;O657.31

收稿日期: 2014-05-26

修回日期: 2014-12-10

录用日期: 2015-01-05

刊出日期: 2015-01-25

Determination of Tungsten Content in Tungsten Carbide and Waste Product by X-ray Fluorescence Spectrometry with Fusion Sample Preparation

Xiamen Technology Center, Entry-Exit Inspection and Quarantine Bureau, Xiamen 361012, China

More Information

Corresponding author: PU Xu-li, puxuli@126.com

Received Date: 26 May 2014

Revised Date: 10 December 2014

Accepted Date: 05 January 2015

Publish Date: 25 January 2015

摘要

摘要:
碳化钨被广泛应用于硬质合金生产材料, 其钨的含量关系碳化钨的性能及货物结算, 生产过程中因配比错误、打磨等原因还会产生大量的含钨废料, 从废料中回收钨能弥补钨资源的不足, 因此测定碳化钨及其废料中的钨具有重要意义.目前碳化钨中钨含量的测定通常参照国家标准采用辛可宁重量法, 准确度较高, 但只适用于检测三氧化钨含量大于50%的样品, 且过程繁琐, 工作量大.本文根据碳化钨在高温下易氧化的特点, 借鉴国际标准ASTM B890-07, 提出将碳化钨转化为三氧化钨, 采用熔融制样-X射线荧光光谱(XRF)测定钨含量的方法.即碳化钨先在马弗炉中灼烧至钨完全转化为三氧化钨, 再加入五氧化二钽作内标, 四硼酸钠-四硼酸锂为混合熔剂, 在1150℃下熔融制成试样片, 用XRF法测定钨的含量.结果表明, 最佳的灼烧温度为800℃, 在此温度下碳化钨完全转化成三氧化钨, 有效地解决了碳化钨熔融制样的难点; 方法精密度(RSD)为0.2%, 实际样品的测定值与国家标准方法(辛可宁重量法)一致, 可测量三氧化钨含量的范围为30%~100%, 且分析时间大大缩短, 可满足大量实际样品检测的需要.
- 碳化钨 /
- 废料 /
- 三氧化钨 /
- 钨 /
- 熔融制样 /
- X射线荧光光谱法
Abstract:
Tungsten carbide is widely used in the production of cemented carbide materials and the content of tungsten in tungsten carbide has a significant impact on its performance and cargo accounts settlement. The ratio error and grinding in the production process produces generous tungsten-containing waste, and the recovery of tungsten from waste material can make up for the shortage of tungsten resources, so it is important to determine tungsten in tungsten carbide and its waste. At present, the determination of tungsten in tungsten carbide is usually estimated by the national standard and is analyzed by using the cinchonine gravimetric method. The method has high accuracy, but, only for the detection of tungsten trioxide content greater than 50% of the sample and the process is tedious and work intensive. According to the characteristics of tungsten carbide, such as easy oxidation at high temperature, reference to the international standard ASTM B890-07, it can be converted into tungsten trioxide, and the tungsten content can then be detected by melting the sample preparation for X-ray Fluorescence Spectrometry (XRF). To achieve this, the tungsten carbide was first placed in a muffle furnace to make convert the tungsten completely into tungsten trioxide, then tantalum pentoxide was added as the internal standard, with sodium borate-lithium tetraborate as mixed solvent, to a temperature of 1150℃ to make a sample piece, and then the tungsten was determined by XRF. Experiments show that the optimum temperature of ignition is 800℃, and at this temperature tungsten carbide is completely converted into tungsten trioxide, so the tungsten carbide fusion sample preparation, which is normally considered difficult is effectively solved; the precision of the method (RSD) is 0.2; the actual sample determination value is consistent with the national standard method (cinchonine gravimetric method); tungsten trioxide content range is 30%-100% through measure. The analysis time is greatly shortened and it meets the need of a large number of actual sample detection.
- tungsten carbide /
- waste product /
- tungsten trioxide /
- tungsten /
- fusion sampling /
- X-ray Fluorescence Spectrometry

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图 1 不同温度下的GOI值变化

Figure 1.

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图 2 不同温度下灼烧前后样品XRD衍射图谱

Figure 2.

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表 1 分析元素的XRF测量条件

Table 1. Measurement conditions of the elements by XRF

元素	分析线	晶体	实际2θ (°)	准直器 (μm)	探测器	电压 (kV)	电流 (mA)	测量时间 (s)
W	Lα	LiF200	43.003	0.15	SC	60	50	20
Ta	Lα	LiF200	44.399	0.15	SC	60	50	20

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表 2 碳化钨和碳化钨废料在不同温度下灼烧的样品外观

Table 2. The appearance of different samples at different temperature

灼烧温度	碳化钨	碳化钨废料
常温	黑色粉末	黑色粉末
400℃	黑色粉末	黑色粉末
500℃	黄色带有少量墨绿色粉末	灰色带有黄色粉末
600℃	黄色粉末，体积变大明显	灰色带有黄色粉末，体积变大明显
800℃	黄色粉末，体积变大较明显	灰色粉末，体积变大较明显
1000℃	黄色粉末，带部分结块	灰色粉末，带部分结块

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表 3 校准样片中钨的含量

Table 3. Concentration of elements in calibration samples

校准样片编号	称样量(g)		WO₃含量 (%)
校准样片编号	WO₃	Ta₂O₅	WO₃含量 (%)
STD0	0	0.2500	0
STD1	0.0625	0.2500	25.0
STD2	0.1250	0.2500	50.0
STD3	0.1875	0.2500	75.0
STD4	0.2500	0.2500	100.0

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表 4 方法准确度和精密度

Table 4. Accuracy and precision tests of the method

样品	XRF法测定值(%)				RSD (%)	化学法测定值 (%)
样品	分次测定值	最大值	最小值	平均值	RSD (%)	化学法测定值 (%)
碳化钨	93.18 93.26 92.92 93.49 93.41 93.22 93.28 93.19 93.22 93.19 93.23	93.49	92.92	93.23	0.2	93.46
碳化钨废料	33.12 33.19 33.20 33.08 33.11 33.19 33.02 33.06 33.28 32.95 33.00	33.28	32.95	33.11	0.2	33.14

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表 5 样品中钨的分析结果

Table 5. Analytical results of W in samples

样品	钨含量的测定值(%)
样品	本法	辛可宁重量法
碳化钨样品1	93.37	93.46
碳化钨样品2	93.32	93.47
废钨料1	52.33	52.30
废钨料2	50.42	50.53
废钨料3	33.11	33.14
废钨料4	68.95	69.06

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