CN102539207A - Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components - Google Patents

Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components Download PDF

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CN102539207A
CN102539207A CN2011104434379A CN201110443437A CN102539207A CN 102539207 A CN102539207 A CN 102539207A CN 2011104434379 A CN2011104434379 A CN 2011104434379A CN 201110443437 A CN201110443437 A CN 201110443437A CN 102539207 A CN102539207 A CN 102539207A
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single oxide
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oxide glass
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CN102539207B (en
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彭慧仙
成勇
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Abstract

本发明公开了用于X射线荧光光谱测定硬质合金成分的标准样品的制备方法和测定方法,标准样品制备方法包括以下步骤:先通过与制备待测样品玻璃熔片一样的条件制备多种高纯单一氧化物玻璃熔片;再将多种单一氧化物玻璃熔片磨粉并分别装瓶;称取包含待测样品中多种待测元素的多种单一氧化物玻璃熔片粉配制标准样品,并使标准样品各元素的含量范围覆盖待测样品中各元素的含量;最后按照上述方式制备得到标准样品玻璃熔片。利用标准样品玻璃熔片制取工作曲线,再用X射线荧光光谱测定硬质合金待测样品各元素含量。采用本发明制备的标准样品,可解除因标准样品造成的对硬质合金检测手段的限制、提高结果的准确度并扩展X射线荧光光谱检测的适用范围。The invention discloses a preparation method and a measurement method of a standard sample for determining the composition of cemented carbide by X-ray fluorescence spectrometry. The standard sample preparation method includes the following steps: firstly, a variety of high Pure single oxide glass frit; then grind multiple single oxide glass frits and bottle them separately; weigh a variety of single oxide glass frit powders containing multiple analyte elements in the sample to be tested to prepare standard samples , and make the content range of each element in the standard sample cover the content of each element in the sample to be tested; finally prepare the standard sample glass frit according to the above method. The working curve is prepared by using the standard sample glass frit, and then the content of each element of the cemented carbide sample to be tested is determined by X-ray fluorescence spectroscopy. By adopting the standard sample prepared by the invention, the restriction on the cemented carbide detection means caused by the standard sample can be removed, the accuracy of the result can be improved and the application range of the X-ray fluorescence spectrum detection can be extended.

Description

用于测定硬质合金成分的标准样品的制备方法和测定方法Preparation method and determination method of standard sample for determination of cemented carbide composition

技术领域 technical field

本发明属于X射线荧光光谱分析技术领域,具体地讲,涉及一种X射线荧光光谱测定样品的方法及其所使用的标准样品的制备方法,更具体地说,涉及一种X射线荧光光谱测定硬质合金成分的方法及其所使用的标准样品的制备方法。  The invention belongs to the technical field of X-ray fluorescence spectrometry analysis, in particular, it relates to a method for measuring samples by X-ray fluorescence spectrometry and a method for preparing standard samples used therein, and more specifically, relates to a method for measuring X-ray fluorescence spectrometry Methods of cemented carbide compositions and the preparation of standard samples for their use. the

背景技术 Background technique

硬质合金的牌号众多,各种产品牌号的元素含量范围差异较大,而各成分的含量直接影响到硬质合金成品的使用性能,因此,快速、准确地测定如钨基硬质合金等硬质合金的烧结前混合料和硬质合金产品中各金属元素的含量尤为重要。X射线荧光光谱法因分析速度快、精密度高、制样简单、可多元素同时检测,能够避免硬质合金湿法分析,试样消解可使用氢氟酸等强腐蚀酸而得到广泛应用。然而,由于X射线荧光光谱分析为相对方法,即通过比较待测样品和标准样品中待测元素的强度进行分析,因此标准样品的制备直接影响分析结果的准确度。目前,钨基硬质合金的标准样品缺乏,使X射线荧光光谱法的应用受到限制。  There are many grades of cemented carbide, and the range of element content of various product grades varies greatly, and the content of each component directly affects the performance of the finished cemented carbide. Therefore, it is necessary to quickly and accurately determine The content of each metal element in the pre-sintering mixture of cemented carbide and cemented carbide products is particularly important. X-ray fluorescence spectrometry is widely used because of its fast analysis speed, high precision, simple sample preparation, simultaneous detection of multiple elements, avoiding wet analysis of cemented carbide, and strong corrosive acids such as hydrofluoric acid for sample digestion. However, since X-ray fluorescence spectroscopic analysis is a relative method, that is, the analysis is performed by comparing the intensity of the analyte elements in the analyte sample and the standard sample, so the preparation of the standard sample directly affects the accuracy of the analysis results. At present, the lack of standard samples of tungsten-based cemented carbide limits the application of X-ray fluorescence spectroscopy. the

现有技术中使用X射线荧光光谱法测定硬质合金预烧混合料及硬质合金产品成分并涉及X射线荧光光谱法测定用标准样品的配制,如文献《X射线荧光光谱测定高密度钨合金中铁和镍》、《硬质合金-X射线荧光光谱法测定金属元素含量-熔融法》、《X射线荧光光谱分析铁合金样品的制备方法进展》、《熔融制样X射线荧光光谱法测定铌铁合金中的铌、铝、钛》等,而目前最新实施的《GB/T 26050-2010硬质合金X射线荧光测定金属元属含量-熔融法》在无标准样品情况下采用的是用生产方法一致的流程制取人工标准样品,然后进行化学定值。  In the prior art, X-ray fluorescence spectrometry is used to measure the composition of cemented carbide calcined mixtures and cemented carbide products, and it involves the preparation of standard samples for X-ray fluorescence spectrometry, such as the document "X-ray fluorescence spectrometry determination of iron in high-density tungsten alloys". and Nickel", "Cemented Carbide-X-ray Fluorescence Spectrometry Determination of Metal Element Content-Melting Method", "Progress in the Preparation of Ferroalloy Samples for X-ray Fluorescence Spectrometry Analysis", "Melt Sample Preparation X-ray Fluorescence Spectrometry Determination of Ferro-Niobium Niobium, aluminum, titanium", etc., and the latest implementation of "GB/T 26050-2010 X-ray fluorescence determination of metal element content of cemented carbide-melting method" adopts the same production method in the absence of standard samples The process prepares artificial standard samples, and then carries out chemical determination. the

总之,目前X射线荧光光谱测定用工作曲线标准样品的配制主要采用以下几种方法:a、有标准样品,且待测样品数量多时采用称取各标准样品交叉配制所需标准样品;b、无标准样品,一般采用生产方法一致的流程制取人工 标准样品,然后进行化学定值;c、主量元素选用相应的高纯氧化物加入,微量元素选用相应的标准溶液加入。  In a word, at present, the following methods are mainly used for the preparation of standard samples of working curves for X-ray fluorescence spectrometry: a. There are standard samples, and when the number of samples to be tested is large, each standard sample is weighed to cross-preparate the required standard samples; b. For standard samples, artificial standard samples are generally prepared by the same process as the production method, and then chemically determined; c. The major elements are added with corresponding high-purity oxides, and the trace elements are added with corresponding standard solutions. the

然而,上述方法对于硬质合金尤其是钨基硬质合金的检测而言,仍存在以下不足: However, the above method still has the following deficiencies for the detection of cemented carbide, especially tungsten-based cemented carbide:

①由于钨基硬质合金的大部分元素极难溶解,需使用腐蚀性极强的氢氟酸且在常温下极难消解,而加入标准溶液会引入不必要的杂质元素,还必须烘干试样,操作要求高。  ① Since most elements of tungsten-based cemented carbide are extremely difficult to dissolve, it is necessary to use highly corrosive hydrofluoric acid and it is extremely difficult to digest at room temperature, and adding unnecessary impurity elements to the standard solution will introduce unnecessary impurity elements, and it must be dried to test As such, the operation requirements are high. the

②按生产方法一致的流程制取人工标准样品后必须采用化学方法定值,工作量较大。当产品含量范围变化后,必须再次按生产方法一致的流程制取人工标准样品,之后仍然必须进行化学方法定值,成本高、耗时长。  ②Chemical methods must be used to determine the value after the artificial standard samples are prepared according to the same process as the production method, and the workload is relatively large. When the content range of the product changes, artificial standard samples must be prepared again according to the same process as the production method, and then the chemical method must still be used to determine the value, which is costly and time-consuming. the

③直接称取高纯氧化物配制标准样品的方法,其称样量太小,导致误差较大;但若增大称样量进行配制,就需要将高纯氧化物研磨至均匀,而高纯氧化物不易均匀,研磨耗时太长且容易玷污。  ③The method of directly weighing high-purity oxides to prepare standard samples, the sample size is too small, resulting in large errors; but if the sample size is increased for preparation, it is necessary to grind the high-purity oxides to uniformity, and the high-purity The oxide is not uniform, takes too long to grind and stains easily. the

目前为止,现有的标准样品配制技术仍不能解决以上问题。  So far, the existing standard sample preparation technology still cannot solve the above problems. the

发明内容 Contents of the invention

本发明的目的在于提供一种操作简便、可自由组合配制的X射线荧光光谱测定硬质合金成分用标准样品的制备方法以及使用所配制的标准样品对硬质合金成分进行X射线荧光光谱测定的方法。  The object of the present invention is to provide a method for preparing a standard sample for determination of cemented carbide components by X-ray fluorescence spectrometry that is easy to operate and can be freely combined and prepared, and a method for using the prepared standard sample to carry out X-ray fluorescence spectrometry for cemented carbide components. method. the

为了实现上述目的,本发明的一方面提供了一种X射线荧光光谱测定硬质合金成分用标准样品的制备方法,所述制备方法包括如下步骤:a)称取一定质量的单一氧化物,按照1∶10~1∶100的稀释比加入熔剂,同时加入质量为熔剂质量的0.1~1倍的助熔剂以及0.1~2g的脱模剂,混合均匀后放入马弗炉或高频自动熔样机内,加热至700℃~1200℃熔融5~40min,之后放置冷却自动脱模得到单一氧化物玻璃熔片,根据需要制备多种单一氧化物玻璃熔片,其中,控制所述单一氧化物玻璃熔片的制备条件与待测样品玻璃熔片的制备条件相同;b)对各种单一氧化物玻璃熔片进行称重,计算单位质量单一氧化物玻璃熔片中所包含的单一氧化物的质量,同时用碳化钨振动研钵将单一氧化物玻璃熔片磨粉,按照单一氧化物的品种将单一氧化物玻璃熔片粉分别装瓶;c)称取包含待测样品中多种待测元素的多种单一氧化物玻璃熔片粉以配制标准样品,称取时需满足待测样品的称取质量=每种单一氧化物的称取质量 =多种单一氧化物玻璃熔片粉中的单一氧化物的质量加和,并使标准样品各元素的含量范围覆盖待测样品中各元素的含量;d)在上述称取好的包含待测样品各元素的多种单一氧化物玻璃熔片粉中混入0.1~2g脱模剂,混合均匀后按照上述制备单一氧化物玻璃熔片的加热条件制备得到标准样品玻璃熔片。  In order to achieve the above object, one aspect of the present invention provides a method for preparing a standard sample for determining the composition of cemented carbide by X-ray fluorescence spectroscopy. Add flux at a dilution ratio of 1:10 to 1:100, and at the same time add flux with a mass of 0.1 to 1 times the mass of the flux and 0.1 to 2g of release agent, mix well and put it into a muffle furnace or a high-frequency automatic melting machine Inside, heat to 700°C-1200°C to melt for 5-40 minutes, then place it to cool and automatically release the mold to obtain a single oxide glass frit, and prepare a variety of single oxide glass frits as required, wherein the single oxide glass frit is controlled The preparation conditions of the sheet are the same as the preparation conditions of the sample glass frit to be tested; b) weighing various single oxide glass frits, calculating the mass of the single oxide contained in the single oxide glass frit per unit mass, Simultaneously use the tungsten carbide vibrating mortar to grind the single oxide glass frit into powder, and bottle the single oxide glass frit powder respectively according to the type of single oxide; A variety of single oxide glass fusing powders are used to prepare standard samples. When weighing, the weighing quality of the sample to be tested must be satisfied = the weighing quality of each single oxide = the single oxide in multiple single oxide glass fusing powders Add the mass of the substance, and make the content range of each element of the standard sample cover the content of each element in the sample to be tested; d) in the above-mentioned weighed multiple single oxide glass frit powders containing each element of the sample to be tested Mix in 0.1-2 g of release agent, mix evenly, and prepare a standard sample glass frit according to the above heating conditions for preparing a single oxide glass frit. the

根据本发明的X射线荧光光谱测定硬质合金成分用标准样品的制备方法,所述硬质合金为钨基硬质合金。  According to the preparation method of a standard sample for determining the composition of cemented carbide by X-ray fluorescence spectrometry of the present invention, the cemented carbide is tungsten-based cemented carbide. the

根据本发明的X射线荧光光谱测定硬质合金成分用标准样品的制备方法,所述单一氧化物为钴、镍、铁、铬、钽、铌和钨的高纯氧化物中的至少一种。  According to the preparation method of standard samples for determination of cemented carbide components by X-ray fluorescence spectrometry of the present invention, the single oxide is at least one of high-purity oxides of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten. the

根据本发明的X射线荧光光谱测定硬质合金成分用标准样品的制备方法,每种单一氧化物的纯度达到4N或3N。  According to the preparation method of the standard sample for determination of cemented carbide composition by X-ray fluorescence spectrometry of the present invention, the purity of each single oxide can reach 4N or 3N. the

根据本发明的X射线荧光光谱测定硬质合金成分用标准样品的制备方法,所述熔剂为四硼酸锂,所述助熔剂为碳酸锂,所述脱模剂为碘化铵。  According to the preparation method of standard samples for determination of cemented carbide components by X-ray fluorescence spectrometry of the present invention, the flux is lithium tetraborate, the flux is lithium carbonate, and the release agent is ammonium iodide. the

根据本发明的X射线荧光光谱测定硬质合金成分用标准样品的制备方法,在对每种单一氧化物玻璃熔片磨粉前,先用事先制备的同种单一氧化物玻璃熔片清洗所述碳化钨振动研钵并用酒精擦拭,再放入待磨的单一氧化物玻璃熔片,每次磨粉控制相同的研磨时间,研磨时间为5~60s,将装瓶后的单一氧化物玻璃熔片粉放入干燥器内保存。  According to the preparation method of the standard sample used for determining the cemented carbide composition by X-ray fluorescence spectrometry of the present invention, before grinding each single oxide glass frit, the same single oxide glass frit prepared in advance is used to clean the Vibrate the tungsten carbide mortar and wipe it with alcohol, then put the single oxide glass frit to be ground, control the same grinding time for each grinding, the grinding time is 5-60s, put the single oxide glass frit after bottling Store the powder in a desiccator. the

本发明的另一方面提供了一种X射线荧光光谱测定硬质合金成分的方法,包括以下步骤:a)按照根据前述制备方法制备标准样品,用X射线荧光光谱仪制作、定量分析工作曲线;b)称取一定质量的待测样品,按照1∶10~1∶100的稀释比加入熔剂,同时加入质量为熔剂质量的0.1~1倍的助熔剂以及0.1~2g的脱模剂,混合均匀后放入马弗炉或高频自动熔样机内,加热至700℃~1200℃熔融5~40min,之后放置冷却自动脱模得到待测样品玻璃熔片;c)结合标准样品得到的工作曲线,用X射线荧光光谱仪对上述待测样品玻璃熔片进行测定。  Another aspect of the present invention provides a method for X-ray fluorescence spectrometry determination of cemented carbide components, comprising the following steps: a) preparing a standard sample according to the aforementioned preparation method, making and quantitatively analyzing the work curve with an X-ray fluorescence spectrometer; b ) Weigh a certain mass of the sample to be tested, add the flux according to the dilution ratio of 1:10 to 1:100, and at the same time add the flux with a mass of 0.1 to 1 times the mass of the flux and 0.1 to 2g of the release agent, after mixing evenly Put it into a muffle furnace or a high-frequency automatic melting machine, heat it to 700 ° C ~ 1200 ° C for 5 ~ 40 minutes, and then place it to cool and automatically demould to obtain a glass fusion sheet of the sample to be tested; c) combine the working curve obtained by the standard sample, use The X-ray fluorescence spectrometer measures the glass frit of the sample to be tested. the

根据本发明的X射线荧光光谱测定硬质合金成分的方法,所述硬质合金为钨基硬质合金,所述熔剂为四硼酸锂,所述助熔剂为碳酸锂,所述脱模剂为碘化铵。  According to the method for determining the composition of cemented carbide by X-ray fluorescence spectroscopy of the present invention, the cemented carbide is tungsten-based cemented carbide, the flux is lithium tetraborate, the flux is lithium carbonate, and the release agent is ammonium iodide. the

本发明采用全新思路提出了一种基于高纯氧化物熔盐细粉,经二次熔融制备X射线荧光光谱测定硬质合金成分用标准样品的方法。本发明与现有技 术相比,方法操作简便,大大缩短了制取标准样品的流程和时间,同时避免了已有标准样品配制方法定值繁琐、引入不必要的杂质元素以及用于配制的氧化物称取量太小而带来误差等缺陷。由于高纯氧化物熔盐细粉便于制取并可长期保存,制备后续所需标准样品时可任意变换配比得到适应分析检测产品含量范围要求的标准样品,这使标准样品的制备简便快捷。采用本发明最终制备的标准样品,可解除因无法获得X射线荧光光谱分析用标准样品而造成的对硬质合金检测手段的限制,提高分析结果的准确度并可极大地扩展X射线荧光光谱分析检测的适用范围。  The present invention adopts a brand-new idea and proposes a method based on high-purity oxide molten salt fine powder, which is prepared by secondary melting for standard samples used for determining cemented carbide components by X-ray fluorescence spectroscopy. Compared with the prior art, the method of the present invention is simple and convenient to operate, greatly shortens the process and time for preparing standard samples, and avoids the cumbersome value determination of existing standard sample preparation methods, the introduction of unnecessary impurity elements, and the preparation of The amount of oxide weighed is too small to bring defects such as errors. Since the high-purity oxide molten salt fine powder is easy to prepare and can be stored for a long time, when preparing subsequent standard samples, the ratio can be changed arbitrarily to obtain standard samples that meet the requirements of the analysis and detection product content range, which makes the preparation of standard samples simple and fast. Using the standard sample finally prepared by the present invention can remove the limitation on the detection means of cemented carbide caused by the inability to obtain the standard sample for X-ray fluorescence spectrum analysis, improve the accuracy of the analysis results and greatly expand the X-ray fluorescence spectrum analysis The scope of application of the test. the

具体实施方式 Detailed ways

下面对本发明的X射线荧光光谱测定硬质合金成分的方法和其所用标准样品的制备方法进行详细的描述。  The method for determining the composition of cemented carbide by X-ray fluorescence spectrometry of the present invention and the preparation method of the standard sample used therein will be described in detail below. the

本发明的思路在于采用多种高纯单一氧化物的玻璃熔片粉,按照待测样品的各元素含量配制后再经二次熔融制备X射线荧光光谱测定硬质合金用的标准样品。然后,利用该制备方法制得的标准样品,通过X射线荧光光谱法测定硬质合金预烧结料和硬质合金产品中各金属元素如Co、Ni、Fe、Cr、Ta、Nb、W等的含量,并使测定可追溯到基准物质的量值传递思路,实现波长色散X射线荧光光谱法准确测定硬质合金中主次量元素含量的目的。  The idea of the present invention is to use a variety of high-purity single oxide glass fusing powder, prepare according to the content of each element of the sample to be tested, and then undergo secondary melting to prepare a standard sample for X-ray fluorescence spectrum determination of cemented carbide. Then, use the standard sample prepared by this preparation method to measure the content of each metal element such as Co, Ni, Fe, Cr, Ta, Nb, W, etc. in cemented carbide pre-sintered materials and cemented carbide products by X-ray fluorescence spectrometry. content, and make the measurement traceable to the value transfer idea of the reference material, to achieve the purpose of accurately determining the content of primary and secondary elements in cemented carbide by wavelength dispersive X-ray fluorescence spectrometry. the

根据本发明的一方面,X射线荧光光谱测定硬质合金成分用标准样品的制备方法包括以下几个步骤。  According to one aspect of the present invention, the preparation method of the standard sample for determining the composition of cemented carbide by X-ray fluorescence spectrometry includes the following steps. the

第一步:称取一定质量的单一氧化物,按照1∶10~1∶100的稀释比加入熔剂,同时加入为熔剂质量0.1~1倍的助熔剂以及0.1~2g的脱模剂,混合均匀后放入马弗炉或高频自动熔样机内,加热至700℃~1200℃熔融5~40min,之后放置冷却自动脱模得到单一氧化物玻璃熔片,根据需要制备多种单一氧化物玻璃熔片。优选地,将单一氧化物与熔剂、助溶剂、脱模剂的混合物在温度1150℃熔融25min。若放入马弗炉中加热,则期间需要取出摇动一次;若放入高频自动熔样机中加热,则无须取出,机器可以自动完成摇动。其中,需要注意的是,需要控制单一氧化物玻璃熔片的制备条件与待测样品玻璃熔片的制备条件相同,例如制备待测样品玻璃熔片时的稀释比为20,则制备单一氧化物玻璃熔片时的稀释比也应为20,加热时间、加热温度等参数也应一 致,但不限于此。  Step 1: Weigh a certain mass of single oxide, add flux according to the dilution ratio of 1:10~1:100, add flux 0.1~1 times the mass of flux and 0.1~2g release agent at the same time, mix well Then put it into a muffle furnace or a high-frequency automatic melting machine, heat it to 700 ° C ~ 1200 ° C for 5 ~ 40 minutes, and then place it to cool and automatically demould to obtain a single oxide glass fusion sheet, and prepare a variety of single oxide glass fusion sheets as required. piece. Preferably, the mixture of a single oxide, a flux, a co-solvent, and a release agent is melted at a temperature of 1150° C. for 25 minutes. If it is heated in a muffle furnace, it needs to be taken out and shaken once during the period; if it is heated in a high-frequency automatic fusion machine, it does not need to be taken out, and the machine can complete the shaking automatically. Among them, it should be noted that it is necessary to control the preparation conditions of the single oxide glass frit to be the same as the preparation conditions of the sample glass frit to be tested. The dilution ratio of the glass fusing sheet should also be 20, and parameters such as heating time and heating temperature should also be consistent, but not limited thereto. the

稀释比是待熔融样品与熔剂的质量比。加入助熔剂是为了增加待熔融样品的流动性并降低熔融温度,助熔剂一般为碳酸盐且加入量小,在高温时大部分分解,一般不算入稀释比中。助熔剂的加入量一般为助熔剂:熔剂=0.1~1,加入方式为直接在熔融样品之前称取后加入坩埚内并与待熔融样品混合均匀。加入脱模剂是为了便于玻璃样品的脱模。具体地,熔剂可以是三氧化二硼与氧化锂按任意比混合的混合物熔剂、偏硼酸盐(如偏硼酸钠、偏硼酸锂)、四硼酸盐(如四硼酸钠、四硼酸锂)、偏磷酸盐(如偏磷酸钠、偏磷酸锂)等;助熔剂可以是不影响分析待测元素测定的任意碳酸盐,例如碳酸锂;脱模剂可以是任意卤化物(如溴化物、碘化物、氯化物等),例如碘化铵。  The dilution ratio is the mass ratio of the sample to be melted to the flux. The purpose of adding flux is to increase the fluidity of the sample to be melted and reduce the melting temperature. The flux is generally carbonate and the amount added is small. Most of the flux is decomposed at high temperature and is generally not included in the dilution ratio. The amount of flux added is generally flux: flux = 0.1 to 1, and the addition method is to weigh it directly before melting the sample and then add it to the crucible and mix it evenly with the sample to be melted. The release agent was added to facilitate the release of the glass samples. Specifically, the flux can be a mixture of boron trioxide and lithium oxide in any ratio. Flux, metaborate (such as sodium metaborate, lithium metaborate), tetraborate (such as sodium tetraborate, lithium tetraborate) , metaphosphate (such as sodium metaphosphate, lithium metaphosphate), etc.; the flux can be any carbonate that does not affect the determination of the element to be analyzed, such as lithium carbonate; the release agent can be any halide (such as bromide, iodide, chloride, etc.), such as ammonium iodide. the

根据本发明,单一氧化物可以为钴、镍、铁、铬、钽、铌和钨的高纯氧化物如三氧化二钴、三氧化二镍、三氧化二铁、三氧化二铬、五氧化二钽、五氧化二铌和三氧化钨中的一种,并且单一氧化物的纯度需达到4N或3N。  According to the present invention, the single oxide can be high-purity oxides of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten such as dicobalt oxide, nickel oxide, iron oxide, chromium oxide, pentoxide One of ditantalum, niobium pentoxide and tungsten trioxide, and the purity of the single oxide must reach 4N or 3N. the

第二步:对各种单一氧化物玻璃熔片进行称重,计算单位质量单一氧化物玻璃熔片中所包含的单一氧化物的质量,同时用碳化钨振动研钵将单一氧化物玻璃熔片磨粉,按照单一氧化物的品种将单一氧化物玻璃熔片粉分别装瓶。  Step 2: Weigh various single oxide glass frits, calculate the mass of single oxide contained in the single oxide glass frit per unit mass, and use a tungsten carbide vibrating mortar to shake the single oxide glass frit Grinding, bottling the single oxide glass frit powder according to the type of single oxide. the

在第二步中,对每一块单一氧化物玻璃熔片进行准确称量,称量精度为±0.0001g。根据单一氧化物的称量质量/单一氧化物玻璃熔片的称量质量计算单位质量单一氧化物玻璃熔片中所包含的单一氧化物的质量。优选地,在对每种单一氧化物玻璃熔片磨粉前,先用事先制备的同种单一氧化物玻璃熔片清洗碳化钨振动研钵并用酒精擦拭后,再放入待磨的单一氧化物玻璃熔片,每次磨粉控制相同的研磨时间,研磨时间为5~60s,之后按照单一氧化物的品种将单一氧化物玻璃熔片粉分别装瓶,再将装瓶后的单一氧化物玻璃熔片粉放入干燥器内保存。  In the second step, each single oxide glass frit is accurately weighed with a weighing accuracy of ±0.0001g. The mass of the single oxide contained in the single oxide glass frit per unit mass is calculated according to the weighed mass of the single oxide/the weighed mass of the single oxide glass frit. Preferably, before grinding each single oxide glass frit, clean the tungsten carbide vibrating mortar with the same single oxide frit prepared in advance and wipe it with alcohol, then put the single oxide to be ground For glass frits, control the same grinding time each time, the grinding time is 5-60s, and then bottle the single oxide glass fusing powders separately according to the type of single oxide, and then bottle the single oxide glass The melt powder is stored in a desiccator. the

第三步:称取包含待测样品中多种待测元素的多种单一氧化物玻璃熔片粉以配制标准样品,称取时需满足待测样品的称取质量=每种单一氧化物的称取质量=多种单一氧化物玻璃熔片粉中的单一氧化物的质量加和,并使标准样品各元素的含量范围覆盖待测样品中各元素的含量。  Step 3: Weigh a variety of single oxide glass fusing powders containing multiple elements to be tested in the sample to be tested to prepare a standard sample. Weighing mass = the sum of the mass of single oxides in multiple single oxide glass frit powders, and make the content range of each element in the standard sample cover the content of each element in the sample to be tested. the

本步骤的目的在于配制标准样品的混合粉并且保证配制的标准样品与待测样品有相同的烧损和片重,本方法的片重差占片重的比例约为 0.01~0.3%。  The purpose of this step is to prepare the mixed powder of the standard sample and ensure that the prepared standard sample has the same burning loss and tablet weight as the sample to be tested. The weight difference of this method accounts for about 0.01-0.3% of the tablet weight. the

第四步:在称取好的包含待测样品各元素的多种单一氧化物玻璃熔片粉中加入0.1~2g脱模剂,混合均匀后按照上述制备单一氧化物玻璃熔片的加热条件制备得到标准样品玻璃熔片。  Step 4: Add 0.1 to 2 g of release agent to the weighed various single oxide glass fusing powders containing each element of the sample to be tested, mix well and prepare according to the above heating conditions for preparing single oxide glass fusing Obtain the standard sample glass frit. the

至此,即完成了X射线荧光光谱测定硬质合金成分用标准样品的制备。具体地,所述硬质合金可以为钨基硬质合金,其包括钨基硬质合金预烧料和钨基硬质合金产品。本发明中所制备得到的标准样品可用于上述产品的金属元素的测定,但不局限于此。  So far, the preparation of the standard sample for determining the cemented carbide composition by X-ray fluorescence spectrometry has been completed. Specifically, the cemented carbide may be tungsten-based cemented carbide, which includes tungsten-based cemented carbide pre-sintered material and tungsten-based cemented carbide product. The standard sample prepared in the present invention can be used for the determination of the metal elements of the above-mentioned products, but is not limited thereto. the

根据本发明另一方面的X射线荧光光谱测定硬质合金成分的方法包括以下几个步骤。  According to another aspect of the present invention, the method for determining the composition of cemented carbide by X-ray fluorescence spectrometry includes the following steps. the

首先,按照上述X射线荧光光谱测定硬质合金成分用标准样品的制备方法制备标准样品,并用X射线荧光光谱仪制作、定量分析工作曲线。  Firstly, prepare a standard sample according to the method for preparing a standard sample for determination of cemented carbide composition by X-ray fluorescence spectrometry, and use an X-ray fluorescence spectrometer to make and quantitatively analyze the working curve. the

然后,称取一定质量的待测样品,按照1∶10~1∶100的稀释比加入熔剂,同时加入为熔剂质量0.1~1倍的助熔剂以及0.1~2g的脱模剂,混合均匀后放入马弗炉或高频自动熔样机内,加热至700℃~1200℃熔融5~40min,之后放置冷却自动脱模得到待测样品玻璃熔片。同样的,若放入马弗炉中加热,则期间需要取出摇动一次;若放入高频自动熔样机中加热,则无须取出,机器可以自动完成摇动。并且,需要控制单一氧化物玻璃熔片的制备条件与待测样品玻璃熔片的制备条件相同,具体地在此不再赘述。  Then, weigh a certain mass of the sample to be tested, add flux according to the dilution ratio of 1:10 to 1:100, and add flux 0.1 to 1 times the mass of flux and 0.1 to 2 g of release agent at the same time, mix well and put Put it into a muffle furnace or a high-frequency automatic melting machine, heat it to 700 ° C ~ 1200 ° C for 5 ~ 40 minutes, and then leave it to cool and automatically demould to obtain a glass fusion piece of the sample to be tested. Similarly, if it is heated in a muffle furnace, it needs to be taken out and shaken once during the period; if it is heated in a high-frequency automatic fusion machine, it does not need to be taken out, and the machine can automatically complete the shaking. Moreover, it is necessary to control the preparation conditions of the single oxide glass frit to be the same as the preparation conditions of the sample glass frit to be tested, and details will not be repeated here. the

最后,结合标准样品得到的工作曲线,用X射线荧光光谱仪对上述待测样品玻璃熔片进行测定,可获得其中主次量元素Co、Ni、Fe、Cr、Nb、Ta、W等的含量。  Finally, combined with the working curve obtained from the standard sample, the X-ray fluorescence spectrometer is used to measure the glass frit of the sample to be tested, and the content of the primary and secondary elements Co, Ni, Fe, Cr, Nb, Ta, W, etc. can be obtained. the

下面结合实施例对本发明的具体实施方式做进一步的描述。  The specific implementation of the present invention will be further described below in conjunction with the examples. the

在本发明的实施例中使用光谱纯的高纯氧化物:三氧化二钴、三氧化二镍、三氧化二铁、三氧化二铬、五氧化二钽、五氧化二铌、三氧化钨,纯度为3N。而且,在本发明的实施例中使用:分析纯四硼酸锂、分析纯碳酸锂、分析纯碘化铵;20mL Pt-Au坩埚、碳化钨研钵。此外,还使用日本理学公司ZSX100e波长色散X射线荧光光谱仪、日本理学公司振动磨样机、日本理学可控温马弗炉。  Spectrally pure high-purity oxides are used in the embodiments of the present invention: dicobalt oxide, nickel oxide, iron oxide, chromium oxide, tantalum pentoxide, niobium pentoxide, tungsten trioxide, The purity is 3N. And, used in the embodiment of the present invention: analytically pure lithium tetraborate, analytically pure lithium carbonate, analytically pure ammonium iodide; 20mL Pt-Au crucible, tungsten carbide mortar. In addition, the ZSX100e wavelength dispersive X-ray fluorescence spectrometer from Rigaku Corporation, the vibration mill prototype from Rigaku Corporation, and the temperature-controllable muffle furnace from Rigaku Corporation were also used. the

实施例1  Example 1

单一氧化物三氧化二钽玻璃熔片粉的制备 Preparation of single oxide tantalum trioxide glass fusing powder

以单一氧化物三氧化二钽为例来说明本发明的标准样品制备方法中单一氧化物玻璃熔片粉的制备过程和优点。  Taking the single oxide tantalum trioxide as an example to illustrate the preparation process and advantages of the single oxide glass frit powder in the standard sample preparation method of the present invention. the

A、称取0.2000g的高纯三氧化二钽,按照1∶20的稀释比加入4.000g的四硼酸锂,同时加入为四硼酸锂熔剂质量0.1倍的0.400g碳酸锂作为助熔剂以及0.5g的碘化铵作为脱模剂,混合均匀后放入马弗炉中,加热至1150℃熔融25min,期间取出摇动一次,之后放置冷却自动脱模得到三氧化二钽玻璃熔片。称重该三氧化二钽玻璃熔片,计算单位质量三氧化二钽玻璃熔片中所包含的三氧化二钽的质量,同时用碳化钨振动研钵将三氧化二钽玻璃熔片研磨15s,将三氧化二钽玻璃熔片粉装瓶后密封待用,将该三氧化二钽玻璃熔片粉称作1号样品。  A. Weigh 0.2000g of high-purity tantalum trioxide, add 4.000g of lithium tetraborate at a dilution ratio of 1:20, and add 0.400g of lithium carbonate 0.1 times the mass of lithium tetraborate flux as a flux and 0.5g of lithium tetraborate at the same time. Ammonium iodide was used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C and melted for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the tantalum trioxide glass frit per unit mass, and grind the tantalum trioxide glass frit for 15 seconds with a tungsten carbide vibrating mortar. The tantalum trioxide glass fusing powder was bottled and sealed for use, and the tantalum trioxide glass fusing powder was called No. 1 sample. the

B、称取0.4000g的高纯三氧化二钽,按照1∶20的稀释比加入8.000g的四硼酸锂,同时加入为四硼酸锂熔剂质量0.1倍的0.800g碳酸锂作为助熔剂以及0.5g的碘化铵作为脱模剂,混合均匀后放入马弗炉中,加热至1150℃熔融25min,期间取出摇动一次,之后放置冷却自动脱模得到三氧化二钽玻璃熔片。称重该三氧化二钽玻璃熔片,计算单位质量三氧化二钽玻璃熔片中所包含的三氧化二钽的质量,同时用碳化钨振动研钵将三氧化二钽玻璃熔片研磨15s,将三氧化二钽玻璃熔片粉装瓶后密封待用,将该三氧化二钽玻璃熔片粉称作2号样品。  B. Weigh 0.4000g of high-purity tantalum trioxide, add 8.000g of lithium tetraborate at a dilution ratio of 1:20, and simultaneously add 0.800g of lithium carbonate 0.1 times the quality of lithium tetraborate flux as flux and 0.5g Ammonium iodide was used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C and melted for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the tantalum trioxide glass frit per unit mass, and grind the tantalum trioxide glass frit for 15 seconds with a tungsten carbide vibrating mortar. The tantalum trioxide glass fusing powder was bottled and sealed for use, and the tantalum trioxide glass fusing powder was called sample No. 2. the

C、称取0.4000g的高纯三氧化二钽,按照1∶10的稀释比加入4.000g的四硼酸锂,同时加入为四硼酸锂熔剂质量0.1倍的0.400g碳酸锂作为助熔剂以及2g的碘化铵作为脱模剂,混合均匀后放入马弗炉中,加热至1150℃熔融25min,期间取出摇动一次,之后放置冷却自动脱模得到三氧化二钽玻璃熔片。称重该三氧化二钽玻璃熔片,计算单位质量三氧化二钽玻璃熔片中所包含的三氧化二钽的质量,同时用碳化钨振动研钵将三氧化二钽玻璃熔片研磨15s,将三氧化二钽玻璃熔片粉装瓶后密封待用,将该三氧化二钽玻璃熔片粉称作3号样品。  C. Weigh 0.4000g of high-purity tantalum trioxide, add 4.000g of lithium tetraborate at a dilution ratio of 1:10, and simultaneously add 0.400g of lithium carbonate that is 0.1 times the quality of lithium tetraborate flux as a flux and 2g of lithium tetraborate. Ammonium iodide is used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the tantalum trioxide glass frit per unit mass, and grind the tantalum trioxide glass frit for 15 seconds with a tungsten carbide vibrating mortar. The tantalum trioxide glass fusing powder was bottled and sealed for use, and the tantalum trioxide glass fusing powder was called No. 3 sample. the

D、称取0.1000g的高纯三氧化二钽,按照1∶100的稀释比加入10.000g的四硼酸锂,同时加入为四硼酸锂熔剂质量0.1倍的1.000g碳酸锂作为助熔剂以及0.1g的碘化铵作为脱模剂,混合均匀后放入马弗炉中,加热至1150℃熔融25min,期间取出摇动一次,之后放置冷却自动脱模得到三氧化二钽玻璃熔片。称重该三氧化二钽玻璃熔片,计算单位质量三氧化二钽玻璃熔片 中所包含的三氧化二钽的质量,同时用碳化钨振动研钵将三氧化二钽玻璃熔片研磨60s,将三氧化二钽玻璃熔片粉装瓶后密封待用,将该三氧化二钽玻璃熔片粉称作4号样品。  D. Weigh 0.1000g of high-purity tantalum trioxide, add 10.000g of lithium tetraborate at a dilution ratio of 1:100, and simultaneously add 1.000g of lithium carbonate which is 0.1 times the mass of lithium tetraborate flux as a flux and 0.1g Ammonium iodide was used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C and melted for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the unit mass tantalum trioxide glass frit, and grind the tantalum trioxide glass frit with a tungsten carbide vibrating mortar for 60 seconds at the same time, The tantalum trioxide glass fusing powder is bottled and sealed for use, and the tantalum trioxide glass fusing powder is called sample No. 4. the

上述1-4号样品的试验结果均得到符合要求的易于脱模,透明的玻璃熔片,具体如表1所示。  The test results of the above-mentioned samples No. 1-4 all obtained easy-to-release and transparent glass frits that meet the requirements, as shown in Table 1. the

表1三氧化二钽玻璃熔片粉制备的试验结果  Table 1 Test results of preparation of tantalum trioxide glass frit powder

Figure BDA0000125358730000081
Figure BDA0000125358730000081

由实施例1和表1中的试验结果可知,本发明的标准样品的制备方法简单易行,并可改变稀释比,按稀释比成比例的扩大玻璃熔片质量以制备单一氧化物玻璃熔片粉。从表中的后四项可知,本发明标准样品的二次熔融配制含同一含量待测元素浓度的称样量为原纯氧化物称样量的25倍,这使低浓度配制成为可能,并可以减小称量误差。  From the test results in Example 1 and Table 1, it can be seen that the preparation method of the standard sample of the present invention is simple and easy, and the dilution ratio can be changed, and the mass of the glass frit is enlarged in proportion to the dilution ratio to prepare a single oxide glass frit pink. As can be seen from the last four items in the table, the secondary melting preparation of the standard sample of the present invention contains 25 times of the original pure oxide sample weight, which makes the preparation of low concentration possible, and Weighing errors can be reduced. the

实施例2  Example 2

标准样品的配制 Preparation of standard samples

制取两个牌号的钨基硬质合金标准样品以说明本发明标准样品制备方法中的配制步骤。  Prepare two grades of tungsten-based cemented carbide standard samples to illustrate the preparation steps in the standard sample preparation method of the present invention. the

称取0.2000g的单一氧化物,按照1∶20的稀释比加入4.000g的四硼酸锂,同时加入为四硼酸锂熔剂质量0.1倍的0.400g碳酸锂作为助熔剂以及0.5g的碘化铵作为脱模剂,混合均匀后放入马弗炉中,加热至1150℃熔融25min,期间取出摇动一次,之后放置冷却自动脱模得到单一氧化物玻璃熔片。在本实施例中,制备了三氧化二钴玻璃熔片、三氧化二镍玻璃熔片、三氧化二铁玻璃熔片、三氧化二铬玻璃熔片、五氧化二钽玻璃熔片、五氧化二铌玻璃熔片、三氧化钨玻璃熔片。  Weigh 0.2000g of a single oxide, add 4.000g of lithium tetraborate at a dilution ratio of 1:20, and simultaneously add 0.400g of lithium carbonate that is 0.1 times the mass of lithium tetraborate flux as a flux and 0.5g of ammonium iodide as a flux. Release agent, mixed evenly, put into muffle furnace, heated to 1150°C and melted for 25 minutes, took out and shaked once during the period, then left to cool and automatically released from the mold to obtain a single oxide glass frit. In this example, cobalt trioxide glass frits, nickel sesquioxide glass frits, ferric oxide glass frits, chromium oxide glass frits, tantalum pentoxide glass frits, pentoxide glass frits, Niobium glass frit, tungsten trioxide glass frit. the

称重上述每种单一氧化物玻璃熔片,计算单位质量单一氧化物玻璃熔片中所包含的单一氧化物的质量,同时用碳化钨振动研钵将单一氧化物玻璃熔片磨粉,按照单一氧化物的品种将单一氧化物玻璃熔片粉分别装瓶,其中,经计算,单位质量的每种氧化物玻璃熔片中所包含的氧化物的质量为 0.04590mg/mg。  Weigh each of the above-mentioned single oxide glass fusion pieces, calculate the mass of the single oxide contained in the unit mass single oxide glass fusion piece, and simultaneously use a tungsten carbide vibrating mortar to grind the single oxide glass fusion piece, according to the unit Varieties of oxides Bottle the single oxide glass fusing powder separately, and, after calculation, the mass of oxide contained in each oxide glass fusing per unit mass is 0.04590mg/mg. the

根据待测样品的元素含量称取各种氧化物玻璃熔片粉。需满足的是待测样品的称取质量=每种单一氧化物的称取质量=多种单一氧化物玻璃熔片粉中的单一氧化物的质量加和=0.2000g=200mg。以Co元素为例,若待测样品中Co含量为8wt%,则可根据式m三氧化二钴的玻璃熔片粉质量×0.04590×MCo的原子百分比=200mg×8%计算得到所需的三氧化二钴玻璃熔片粉的质量,以此类推,可分别计算得到所需的三氧化二镍玻璃熔片粉、三氧化二铁玻璃熔片粉、三氧化二铬玻璃熔片粉、五氧化二钽玻璃熔片粉、五氧化二铌玻璃熔片粉、三氧化钨玻璃熔片粉的质量。  Weigh various oxide glass frit powders according to the element content of the sample to be tested. What needs to be satisfied is that the weighed mass of the sample to be tested = the weighed mass of each single oxide = the sum of the mass of the single oxides in the multiple single oxide glass frit powders = 0.2000 g = 200 mg. Taking Co element as an example, if the Co content in the sample to be tested is 8wt%, then the required formula can be calculated according to the mass of glass frit powder of dicobalt trioxide × 0.04590 × M Co atomic percentage = 200mg × 8%. The quality of cobalt trioxide glass fusing powder, by analogy, can calculate respectively required nickel sesquioxide glass fusing powder, ferric oxide glass fusing powder, dichromium trioxide glass fusing powder, five The quality of tantalum oxide glass fusing powder, niobium pentoxide glass fusing powder and tungsten trioxide glass fusing powder.

最后,在上述称取好的包含待测样品各元素的多种单一氧化物玻璃熔片粉中混入0.5g碘化铵,混合均匀后按照上述制备单一氧化物玻璃熔片的条件制备得到两组标准样品玻璃熔片。  Finally, mix 0.5 g of ammonium iodide into the above-mentioned weighed various single oxide glass frit powders containing each element of the sample to be tested, and after mixing evenly, prepare two groups according to the above conditions for preparing single oxide glass frit Standard sample glass frit. the

具体地,两个牌号的待测硬质合金为WC-Co和WC-Ni,其各元素含量和各氧化物玻璃熔片粉的相应用量如表2所示,并且分别将相应的两个标准样品称作5号样品和6号样品。  Specifically, the two grades of cemented carbide to be tested are WC-Co and WC-Ni, the content of each element and the corresponding amount of each oxide glass fusing powder are shown in Table 2, and the corresponding two standard The samples are referred to as sample No. 5 and sample No. 6. the

表2标准样品的配制用量  The preparation dosage of table 2 standard sample

由实施例2和表2中的试验结果表明,每一标准玻璃熔片的烧失量可人为地将其控制为一致,而且各元素的含量范围可以任意变化以符合待测样品中各元素的含量范围,本发明的标准样品的配制简便可行。  The test results in Example 2 and Table 2 show that the loss on ignition of each standard glass frit can be artificially controlled to be consistent, and the content range of each element can be changed arbitrarily to meet the requirements of each element in the sample to be tested. content range, the preparation of the standard sample of the present invention is simple and feasible. the

实施例3  Example 3

下面通过完整的实施例来描述本发明的X射线荧光光谱测定硬质合金成 分的方法和其所用标准样品的制备方法。  Describe the method for X-ray fluorescence spectrometry of the present invention to measure cemented carbide composition and the preparation method of its used standard sample by complete embodiment below. the

称取0.2000g的高纯单一氧化物于铂金坩埚中,按照稀释比1∶20加入4.000g±0.001g的熔剂四硼酸锂,0.400g±0.001g的助熔剂碳酸锂以及0.5g的脱模剂碘化铵,混合均匀后放入马弗炉内,在温度1150℃熔融25min,期间取出摇动一次,之后放置冷却自动脱模得到单一氧化物玻璃熔片。分别制备三氧化二钴、三氧化二镍、三氧化二铁、三氧化二铬、五氧化二钽玻璃熔片各6片,以及三氧化钨玻璃熔片10片。分别称量每一氧化物玻璃熔片,计算单位质量单一氧化物玻璃熔片中所包含的单一氧化物的质量。  Weigh 0.2000g of high-purity single oxide into a platinum crucible, add 4.000g±0.001g of flux lithium tetraborate, 0.400g±0.001g of flux lithium carbonate and 0.5g of release agent according to the dilution ratio of 1:20 Ammonium iodide, mixed evenly, put into the muffle furnace, melted at a temperature of 1150°C for 25 minutes, took it out and shook it once during the period, and then left it to cool and automatically demolded to obtain a single oxide glass frit. Prepare 6 pieces of cobalt oxide, nickel oxide, iron oxide, chromium oxide, and tantalum pentoxide glass frits, and 10 tungsten trioxide glass frits. Each oxide glass frit is weighed separately, and the mass of the single oxide contained in the single oxide glass frit per unit mass is calculated. the

将各氧化物玻璃熔片分别用振动磨样机研磨15s,然后按照不同的氧化物玻璃熔片粉的品种将其立即装瓶并放入干燥器内保存。在每一种氧化物玻璃熔片磨粉前必须清洗研钵,即先用预先制备的同一种待磨粉氧化物玻璃熔片研磨清洗研钵后再用酒精擦拭,弃去粉末,再进行该种氧化物玻璃熔片粉的研磨,按以上流程依次制备每毫克氧化物玻璃熔片粉中含有0.04590毫克氧化物的氧化物玻璃熔片粉。称取各氧化物玻璃熔片粉,按氧化物玻璃熔片粉中各氧化物合量为0.2000g的原则,配制出14个标准样品,各标准样品中的各元素含量范围为Co(1-30wt%)、Ni(0.2-15wt%)、Fe(0.2-1wt%)、Cr(0.25-1wt%)、Nb(0.2-1wt%)、Ta(0.2-1wt%)、W(36-79wt%),对均匀度要求高的样品,可分别独立配制11次。之后将粉末状的标准样品与0.5g脱模剂碘化铵混合均匀后放入马弗炉中,以与之前相同的条件加热熔融并待其冷却后,制得标准样品玻璃熔片。选定其中一个含有所配制的7种氧化物玻璃熔片粉的标准样品玻璃熔片进行具体试验,测定其X射线强度并统计标准偏差,将该样品称作7号样品,其试验结果如表3所示。  Grind each oxide glass frit with a vibrating mill for 15 s, and then immediately bottle them according to different types of oxide glass frit powder and store them in a desiccator. The mortar must be cleaned before grinding each oxide glass frit, i.e. first use the same pre-prepared oxide glass frit to be ground to grind and clean the mortar, then wipe it with alcohol, discard the powder, and then carry out the For the grinding of the oxide glass fusing powder, the oxide glass fusing powder containing 0.04590 mg of oxide is prepared sequentially according to the above process. Take each oxide glass fusing powder, and prepare 14 standard samples according to the principle that the total amount of each oxide in the oxide glass fusing powder is 0.2000g, and the content range of each element in each standard sample is Co(1- 30wt%), Ni (0.2-15wt%), Fe (0.2-1wt%), Cr (0.25-1wt%), Nb (0.2-1wt%), Ta (0.2-1wt%), W (36-79wt%) ), samples with high uniformity requirements can be independently prepared 11 times. Afterwards, the powdered standard sample was mixed evenly with 0.5 g of release agent ammonium iodide and placed in a muffle furnace, heated and melted under the same conditions as before and cooled to obtain a standard sample glass frit. Select one of the standard sample glass frits containing 7 kinds of prepared oxide glass frit powders to carry out specific tests, measure its X-ray intensity and count the standard deviation, this sample is called No. 7 sample, and its test results are shown in the table 3 shown. the

表3标准样品的精密度  Table 3 Precision of Standard Samples

Figure BDA0000125358730000101
Figure BDA0000125358730000101

由表3可见,该标准样品的制备精密度良好,完全可满足用于制备工作曲线;用X射线荧光光谱仪自带软件进行基体校正,各元素工作曲线校正因 子大于0.9999,准确度<0.01,完全满足试样的测定要求。  It can be seen from Table 3 that the preparation precision of the standard sample is good, which can fully meet the requirements for preparing the working curve; the X-ray fluorescence spectrometer comes with the software for matrix calibration, and the calibration factor of the working curve of each element is greater than 0.9999, and the accuracy is less than 0.01. Fully meet the determination requirements of the sample. the

然后,选定四种WC-Co硬质合金牌号:四川科力特硬质合金公司生产的CMS032,四川自贡硬质合金厂生产的11YG15、11YG6A、YT5。将上述四种硬质合金待测样品进行预氧化(预氧化按照GB/T 26050-2010操作,800℃氧化1h),然后称取0.2000g预氧化后的待测样品置于铂金坩埚中,加入4.000g±0.001g的熔剂四硼酸锂,以及0.400g±0.001g的助熔剂碳酸锂和0.5g脱模剂碘化铵,混合均匀后放入马弗炉内,加热至1150℃温度下熔融25min,期间取出摇动一次,放置冷却后自动脱模得到待测样品玻璃熔片。按照上述制备条件将每种牌号的硬质合金各制备2块待测样品玻璃熔片。然后用本发明制备的标准样品得到的工作曲线对待测样品进行测定,试验结果如表4所示。  Then, four WC-Co cemented carbide grades were selected: CMS032 produced by Sichuan Keliite Cemented Carbide Company, and 11YG15, 11YG6A, YT5 produced by Sichuan Zigong Cemented Carbide Factory. Pre-oxidize the above four kinds of cemented carbide samples to be tested (pre-oxidize according to GB/T 26050-2010, oxidize at 800°C for 1h), then weigh 0.2000g of the pre-oxidized samples to be tested and place them in a platinum crucible, add 4.000g±0.001g of lithium tetraborate as a flux, 0.400g±0.001g of lithium carbonate as a flux and 0.5g of ammonium iodide as a release agent, mix well and put them in a muffle furnace, heat to 1150°C and melt for 25 minutes , take it out and shake it once during the period, and automatically release the mold after cooling to obtain the sample glass frit to be tested. According to the above preparation conditions, two pieces of glass frits to be tested were prepared for each grade of cemented carbide. Then the working curve obtained by the standard sample prepared by the present invention is measured for the sample to be tested, and the test results are as shown in table 4. the

表4实测的待测样品成分与给定值的数据对照(wt%)  Table 4 actual measured sample composition to be measured and the data contrast (wt%) of given value

Figure BDA0000125358730000111
Figure BDA0000125358730000111

由表4可知,根据本发明所制备的标准样品而制备的工作曲线对待测硬质合金样品的测定结果与对照结果的误差在GB/T 26050-2010《硬质合金X射线荧光测定金属元属含量-熔融法》的允许差范围内,表明本发明所制备的标准样品的分析结果具有较高的准确性和可靠性。  As can be seen from Table 4, the working curve prepared according to the standard sample prepared by the present invention has an error between the measurement result and the contrast result of the hard alloy sample to be tested in GB/T 26050-2010 "Carbide X-ray Fluorescence Determination of Metal Elements". Content-melting method "in the allowable error scope, show that the analysis result of the standard sample prepared by the present invention has higher accuracy and reliability. the

综上所述,本发明的X射线荧光光谱测定硬质合金成分标准样品的制备方法通过使用多种高纯单一氧化物玻璃熔片粉来配制标准样品,不仅标准样品的制样重现性好,而且氧化物玻璃熔片粉易于保存,可灵活配置各种标准样品。将根据本发明配制完成的标准样品玻璃熔片用于各种波长色散X射线荧光光谱仪测定硬质合金制作定量分析工作曲线,可实现对钨基硬质合金如硬质合金预烧料和硬质合金产品中金属元素含量的高效可靠的测定。  In summary, the method for preparing the standard sample of cemented carbide composition by X-ray fluorescence spectrometry of the present invention prepares the standard sample by using a variety of high-purity single oxide glass fusing powders, not only the sample preparation of the standard sample has good reproducibility , and the oxide glass frit powder is easy to store, and various standard samples can be flexibly configured. The standard sample glass frit prepared according to the present invention is used in various wavelength dispersive X-ray fluorescence spectrometers to measure hard alloys to make quantitative analysis work curves, which can realize the analysis of tungsten-based hard alloys such as hard alloy pre-sintered materials and hard alloys. Efficient and reliable determination of metal element content in alloy products. the

本发明不限于上述实施例,在不脱离本发明权利要求保护范围的情况下,可以进行各种变形和修改。  The present invention is not limited to the above-mentioned embodiments, and various variations and modifications can be made without departing from the protection scope of the claims of the present invention. the

Claims (8)

1. an X-ray fluorescence spectra is measured the preparation method of wimet composition with standard model, it is characterized in that said preparation method comprises the steps:
A) take by weighing the single oxide of certain mass; Select 1: 10~1: 100 dilution ratio to add flux; Adding quality simultaneously is 0.1~1 times flux of flux quality and the release agent of 0.1~2g, puts into the molten automatically model machine of muffle furnace or high frequency after mixing, and is heated to 700 ℃~1200 ℃ fusion 5~40min; Place the cooling automatic demoulding afterwards and obtain single oxide glass fuse piece; Prepare multiple single oxide glass fuse piece as required, wherein, the preparation condition of controlling said single oxide glass fuse piece is identical with the preparation condition of testing sample glass fuse piece;
B) various single oxide glass fuse pieces are weighed; The quality of the single oxide that is comprised in the unit of account quality single oxide glass fuse piece; Vibrate mortar with single oxide glass fuse piece abrasive dust with tungsten carbide simultaneously, single oxide glass fuse piece powder is bottled respectively according to the kind of single oxide;
C) take by weighing the multiple single oxide glass fuse piece powder that comprises multiple element to be measured in the testing sample with the preparation standard model; The quality that takes by weighing the single oxide in quality=multiple single oxide glass fuse piece powder that takes by weighing quality=every kind of single oxide that satisfies testing sample when taking by weighing add with, and make the content range of each element of standard model cover the content of each element in the testing sample;
D) in the above-mentioned multiple single oxide glass fuse piece powder that comprises each element of testing sample that takes by weighing, sneak into 0.1~2g release agent, the heating condition according to above-mentioned preparation single oxide glass fuse piece after mixing prepares standard model glass fuse piece.
2. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that said wimet is the tungsten base cemented carbide.
3. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that, single oxide is at least a in the high pure oxide of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten.
4. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that the purity of every kind of single oxide reaches 4N or 3N.
5. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that said flux is lithium tetraborate, and said flux is a lithium carbonate, and said release agent is an ammonium iodide.
6. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model; It is characterized in that; Before to every kind of single oxide glass fuse piece abrasive dust; Single oxide glass fuse piece of the same race with prepared beforehand cleans said tungsten carbide vibration mortar and uses alcohol wipe earlier, puts into single oxide glass fuse piece to be ground again, the identical milling time of each abrasive dust control; Milling time is 5~60s, the single oxide glass fuse piece powder after the bottling is put into exsiccator preserve.
7. an X-ray fluorescence spectra is measured the method for wimet composition, it is characterized in that may further comprise the steps:
A) according to according to any described preparation method's preparation standard of claim sample in claim 1 to the claim 6, with Xray fluorescence spectrometer make, the quantitative test working curve;
B) take by weighing the testing sample of certain mass; Add flux according to 1: 10~1: 100 dilution ratio; Adding quality simultaneously is 0.1~1 times flux of flux quality and the release agent of 0.1~2g; Put into the molten automatically model machine of muffle furnace or high frequency after mixing, be heated to 700 ℃~1200 ℃ fusion 5~40min, place the cooling automatic demoulding afterwards and obtain testing sample glass fuse piece;
C) working curve that obtains of combined standard sample is measured said testing sample glass fuse piece with Xray fluorescence spectrometer.
8. X-ray fluorescence spectra according to claim 7 is measured the method for wimet composition, it is characterized in that said wimet is the tungsten base cemented carbide, and said flux is lithium tetraborate, and said flux is a lithium carbonate, and said release agent is an ammonium iodide.
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