CN102263004B - Inductively coupled plasma ion source gas protection device - Google Patents
Inductively coupled plasma ion source gas protection device Download PDFInfo
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- CN102263004B CN102263004B CN201010183193.0A CN201010183193A CN102263004B CN 102263004 B CN102263004 B CN 102263004B CN 201010183193 A CN201010183193 A CN 201010183193A CN 102263004 B CN102263004 B CN 102263004B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/105—Ion sources; Ion guns using high-frequency excitation, e.g. microwave excitation, Inductively Coupled Plasma [ICP]
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Abstract
The invention relates to an inductively coupled plasma ion source gas protection method and an inductively coupled plasma ion source gas protection device. The inductively coupled plasma ion source gas protection device provided by the invention comprises a hollow gas shielding case body, wherein one end of the gas shielding case body is provided with a torch tube hole corresponding to a plasma torch tube and a gas inlet, and the other end of the gas shielding case body is provided with an opening communicated with the outside; the opening is against an inductively coupled plasma interface device; a water cooling device is arranged at the opening, and is in fit with the inductively coupled plasma interface device to form the gas outlet end of the gas shielding case body; and the gas outlet end of the gas shielding case body is communicated with the outside. By the inductively coupled plasma ion source gas protection method and the inductively coupled plasma ion source gas protection device provided by the invention, inductively coupled plasmas (ICP) are positioned in an inert gas atmosphere to radically eliminate or reduce interference formed by O, N, H, C and the like, reduce background equivalent concentration and improve a linear correlation coefficient and a detection limit.
Description
Technical field
The present invention relates to inductance coupled plasma device, relate in particular to a kind of ion source of the inductively coupled plasma for inductivity coupled plasma mass spectrometry gas shield device.
Background technology
Inductivity coupled plasma mass spectrometry (ICP-MS) is that grow up the eighties in last century a kind of usingd inductively coupled plasma (ICP) as ion source, generally using the Element and isotope analytical technology of quadrupole rod as mass analyzer.ICP-MS can carry out qualitative analysis, semi-quantitative analysis, quantitative analysis, isotope ratio analysis, with the Elemental Speciation Analysis of isolation technics coupling.
Inductance coupled plasma device is comprised of plasma torch pipe, the induction coil that is connected in radio-frequency generator.The plasma torch pipe be comprised of three concentric quartz tubes is placed in induction coil.When introducing argon gas, if make to manage interior part gas ionization with a high tension spark, produce a small amount of electronics and ion, electronics and ion are because of the effect of managed interior axial magnetic field, and in pipe, the motion of closed-loop path, space high speed, collide neutral atom and molecule, more gas is ionized, form very soon the ICP torch, the ICP torch is a kind of electrodless discharge, rather than chemical flame.
In ICP-MS analyzes, the mass spectrum interference problem of low quality number is main restraining factors always, causes the detection limit variation of many elements, and because the fluctuation of background signal degenerates precision.During the mass spectrum of low quality number disturbs, the most serious is N, the O in air atmosphere, plasma and sample itself, acid or the solvent etc. from plasma, the Polyatomic ion that H, C etc. form.Inductively coupled plasma forms in atmospheric air, thereby airborne N, O, H etc. inevitably can penetrate into ICP, N, O, H isoconcentration in increase ICP, the formation Polyatomic ions such as aggravation O, N, H, C, Ar.
The research that mass spectrum is disturbed and reduction or elimination can improve accuracy, precision and the detection limit of most elements.The method that reduction or elimination ICP-MS mass spectrum disturb has multiple: the one, by the instrument condition optimization, reduced, as the parameters such as the sampling depth that can optimize plasma, flow rate of carrier gas are realized, yet best instrument condition can make to disturb in reduced levels, but can not eliminate fully, the 2nd, the mass spectrometer of use high resolution, but high-resolution mass spectrometer is expensive, complicated operation, and to reach high mass resolution, and will reduce ion transmission efficiency, cause sensitivity to descend, detection limit is impaired, the 3rd, adopt the cold plasma technology, the cold plasma technology is mainly by revising the ICP operating parameter, reduce ICP power, increase flow rate of carrier gas, lengthen sampling depth, be used for reducing the Polyatomic ion that Ar produces, its background signal significantly reduces than analyzing signal, thereby make the Fe of ultra trace in semicon industry, Ca, the detectability of K can reach the ng/L level, because the temperature of cold plasma central passage is lower, matrix decomposes not exclusively, the matrix tolerance is poor, oxide interference is larger, thereby be only applicable to sample that matrix is very low as water and diluted acid, simultaneously, low ionization energy, make cold plasma be difficult to analyze some difficult ionizing elements as B, Zn, Cd etc., the 4th, adopt collision/reaction tank technology, what in the body of collision/reaction tank pond, occur is ion-molecule reaction, comprise that electric charge transfer, hydrogen atom transfer, proton translocation, associated reaction, condensation reaction, collision induced dissociation reaction etc. are several, this technology has the potentiality that sensitivity does not reduce when reducing the interference of many elements existence, but its maximum limitation is the formation of potential new interference, the 5th, the interference correction method, although can proofread and correct the impact that mass spectrum disturbs, fundamentally do not eliminate and disturb, the 6th, sample is introduced technology, but the sample adopted is introduced the degree that technology can greatly affect some mass spectrums interference.Adopt above traditional method, shortcomings and limitations are more or less arranged.
Chinese patent CN201411486Y discloses the protective device of a kind of plasma gun with plasma arc and powder particle flow, by device body, formed, described device body comprises protection tube, described protection tube is by setting gradually as contraction flow region, trunnion section and enlarged portion integrative-structure form, described protection tube periphery is provided with gas access, be provided with the water-cooled cavity between described protection tube and outer tube, described outer tube periphery is provided with water inlet and delivery port, one end of protection tube is connected with spray gun, because protection tube is one first to shrink the pipe with special shape of expanding afterwards, can to prevent atmosphere, be involved in plasma arc by the isolated atmosphere of machinery.But this plasma gun is with the protective device of plasma arc and powder particle flow and be not suitable for inductivity coupled plasma mass spectrometry and use in analyzing; it can not be hedged off from the outer world plasma fully on the one hand; on the other hand; even be filled with inert gas in its gas access, also very easily cause inductively coupled plasma to maintain; cause the ICP torch to extinguish; and due to ICP torch extreme temperatures; and this plasma gun causes its heat radiation good not by structure and the inflation angle of the protective device of plasma arc and powder particle flow, be easy to cause the damage of instrument.
Summary of the invention
The present invention be mainly solve prior art existing in ICP-MS analyzes the mass spectrum of low quality number disturb and cause the detection limit variation of element, the fluctuation of background signal to make the technical problems such as precision degenerates; a kind of inductively coupled plasma ion source gas shield device is provided; ICP is in atmosphere of inert gases; fundamentally eliminate or reduce the interference of the formation such as O, N, H and C; reduce the background equipotent concentration, improve linearly dependent coefficient and detection limit.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: inductively coupled plasma ion source gas shield device of the present invention, it comprises the shroud of gas cover body of hollow, described shroud of gas cover body one end has torch pore and the air inlet corresponding with the plasma torch pipe, the other end is arranged to the opening be connected with outside, described opening is relative with the inductively coupled plasma interface arrangement, described opening part is provided with cooling device, described water cooling plant and inductively coupled plasma interface arrangement match and form the gas outlet side of shroud of gas cover body, the gas outlet side of this shroud of gas cover body communicates with the external world.Gas shield device is used in the inductivity coupled plasma mass spectrometry analysis; be difficult to solve airtight problem; thereby atmosphere and plasma torch effectively can't be isolated; because gas shield device and inductively coupled plasma interface arrangement interval are gapped; be difficult to eliminate fully; in test, between gas shield device and inductively coupled plasma interface arrangement, need before use to adjust, so both can not be connected to one.Further, on gas shield device, plasma torch will become intense radiation, high-temperature area on every side, if shut fully in gap; radiating effect is bad; the temperature straight line rises, and while surpassing 300 °, can cause devices such as burning out the torch pipe, or even the sampling spiroid on the inductively coupled plasma interface arrangement etc.The present invention uses inert gas as argon gas; or other protective gas carry out the gas sealing; the shroud of gas cover body is arranged to an end opening state; and the gap of giving vent to anger is arranged to in this device and the gap at inductively coupled plasma interface arrangement interval, use mobile inert gas to carry out dynamic gas sealing.Like this; gas continues to flow into from the air admission hole of shroud of gas cover body; flow in the shroud of gas cover body, and flow out from gap, plasma torch is enclosed in the atmosphere of protective gas; thereby prevented that air from entering; got rid of O, N, H and C and sneaked into plasma torch formation interference, further, protective gas can also be taken away the heat of this device together with cooling device; the heat around plasma torch particularly, thus this device maintained in temperature range normally.In sum, this inductively coupled plasma ion source gas shield device is simple in structure, and cost is extremely low, efficiently solves the airtight difficult problem of gas shield device, and the heat dissipation problem of the device such as torch pipe.
As preferably, described cooling device is water cooling plant, and described water cooling plant is the heat-conducting metal piece that is shaped with cooling water hole, and described heat-conducting metal piece middle part is shaped with the cooling torch hole matched with plasma torch, and described torch hole communicates with ambient atmosphere.Water cooling plant to Cooling Water in cooling water hole, can reduce the temperature around plasma torch by outside circulating cooling water pipe; Be separated with certain gap between between water cooling plant and inductively coupled plasma interface arrangement, protective gas is given vent to anger by this gap, also takes away the part heat.In igniting experiments after 2 hours; the basic still normal temperature of the temperature of heat-conducting metal piece; temperature in the polytetrafluoroethylene device only has 90 ℃ of left and right; therefore use this inductively coupled plasma ion source gas shield device as fine as the protection effect of torch pipe etc. for mass spectrometer, the useful life of greatly having improved mass spectrometer.
As preferably, described heat-conducting metal piece is threaded in the opening part of shroud of gas cover body.Like this, can adjust flexibly the gap between this inductively coupled plasma ion source gas shield device and inductively coupled plasma interface arrangement according to different plasma torchs, make this gas shield device scope of application wider.
As preferably, described shroud of gas cover body is cylindric, and described air inlet is arranged on the end face of shroud of gas cover body, and its inlet channel is elbow-shaped.
As preferably, the internal orifice of described air inlet is towards the tangential direction of described torch pore.The collar extension of air inlet can outreach air inlet pipe, and gas can pass through the passage break-in of air inlet or directly enter, then enters in the shroud of gas cover body from the internal orifice of air inlet.Like this, from the air inlet internal orifice of the tangential direction towards described torch pore, enter the air-flow in the shroud of gas cover body, gas can flow along plasma torch pipe tangential direction, and the air-flow of formation can not push plasma torch and cause plasma torch to extinguish.The internal orifice axis direction of air inlet can be arranged to parallel with torch pore axis direction.
As preferably, described air inlet has two at least, and is oppositely arranged along shroud of gas cover body axle center, and the material of described shroud of gas cover body is polytetrafluoroethylene.Adopt relative equidirectional two-way air-flow, guarantee gas-cooled better effects if, the shroud of gas cover body adopts chemical stability, corrosion resistance and resistant to elevated temperatures polytetrafluoroethylmaterial material, can be more suitable in the environment for use of mass spectral analysis, and can not bring extra interference to the ion source of mass spectral analysis.
The method of inductively coupled plasma ion source of the present invention Buchholz protection; the coil of plasma torch pipe and radio-frequency generator is placed in a shroud of gas cover body of can air inlet and giving vent to anger; continue to pass into inert gas to this shroud of gas cover body; inert gas enters from inlet end; in the shroud of gas cover body, flow through the plasma torch pipe in edge; from outlet side, flow out, inert gas surrounds the plasma torch of the coil of radio-frequency generator and the generation of plasma torch pipe and be enclosed in atmosphere of inert gases.
In order can better to dispel the heat, as preferably, the water cooling plant of cooling plasma torch radiation can be set in the outlet side of described shroud of gas cover body.The water-cooled assembling device is set in outlet side, can takes away heat, particularly plasma torch heat on every side, to prevent causing the devices such as sampling spiroid on torch pipe and inductively coupled plasma interface arrangement to burn out due to overheated.
The beneficial effect that the present invention brings is; efficiently solve the airtight difficult problem of gas shield device, and the heat dissipation problem of the device such as torch pipe, ICP is in atmosphere of inert gases; fundamentally eliminate or reduce the interference of the formation such as O, N, H and C; reduce the background equipotent concentration, improve linearly dependent coefficient and detection limit, and cost of manufacture is low; convenient disassembly; operating cost is low, does not substantially change the structure of instrument, reaches practical purpose.
The accompanying drawing explanation
Accompanying drawing 1 is a kind of structural representation of the present invention;
Accompanying drawing 2 is a kind of structural representations of the water cooling plant in the present invention;
Accompanying drawing 3 is the present invention's a kind of structural representations while using;
Accompanying drawing 4 is another kind of structural representations of the present invention;
Accompanying drawing 5 is another kind of structural representations of the water cooling plant in the present invention;
Accompanying drawing 6 is the comparative result tables that use and do not use the analytical performance of inductively coupled plasma ion source gas shield device of the present invention;
Accompanying drawing 7 is continueds of accompanying drawing 6.
Accompanying drawing explanation: 1, shroud of gas cover body; 1-1, torch pore; 1-2, air inlet; 1-3, opening; 1-4, internal thread hole; 2, water cooling plant; 2-1, cooling torch hole; The 2-2 cooling water hole; 3, plasma torch pipe; 3-1, plasma torch; 4, the coil of radio-frequency generator; 5, inductively coupled plasma interface arrangement; 6, gap.
Embodiment
Below by embodiment, and by reference to the accompanying drawings, the technical scheme of inventing is described in further detail.
Embodiment 1: the inductively coupled plasma ion source gas shield device of the present embodiment, as shown in Figure 1, the shroud of gas cover body 1 that comprises hollow, its material is polytetrafluoroethylene, this shroud of gas cover body 1 is cylindric, the end face of shroud of gas cover body 1 one ends has for the torch pore 1-1 of plasma torch pipe 3 is installed, the size of torch pore 1-1 is suitable mutually with plasma torch pipe 3 sizes, as shown in Figure 3, this shroud of gas cover body 1 is by the coil of part plasma torch pipe 3 and radio-frequency generator 4 parcels, also be shaped with two air inlet 1-2 along the shroud of gas cover body 1 symmetrical layout in axle center on the end face of this shroud of gas cover body 1, inlet channel is bending road shape, the internal orifice of air inlet 1-2 is towards the direction of torch pore 1-1 tangent line.
Make the opening 1-3 be connected with outside at shroud of gas cover body 1 other end, this opening 1-3 is relative with inductively coupled plasma interface arrangement 5, at this opening 1-3 place, water cooling plant 2 is installed, as shown in Figure 2, water cooling plant 2 is made by square red copper piece, at red copper piece middle part, be shaped with for wrapping up the cooling torch hole 2-1 of plasma torch 3-1, between this water cooling plant 2 and inductively coupled plasma interface arrangement 5, certain interval 6 is arranged, these gap 6 surroundings are exposed in outside atmosphere, in use, plasma torch 3-1 is connected inductively coupled plasma interface arrangement 5 by cooling torch hole 2-1, inert gas surrounds plasma torch 3-1, and flow out from the gap 6 of surrounding, be outlet side herein, on the red copper piece, 2-1 upper and lower, cooling torch hole is shaped with respectively the cooling water hole 2-2 be connected with the outer loop feed pipe.
The method of this inductively coupled plasma ion source Buchholz protection of the present embodiment, the coil of plasma torch pipe 3 and radio-frequency generator 4 is placed in to shroud of gas cover body 1, these shroud of gas cover body 1 one end openings, the openend of shroud of gas cover body 1 is towards inductively coupled plasma interface arrangement 5, around the corresponding plasma torch pipe 3 generation plasma torch 3-1 of this openend, also used water cooling plant 2 cooling, leave space between this water cooling plant 2 and inductively coupled plasma interface arrangement 5, plasma torch 3-1 is connected inductively coupled plasma interface arrangement 5 by water cooling plant 2, like this, continue to pass into inert gas in air inlet 1-2, inert gas enters from air inlet 1-2, interior mobile along torch pore 1-1 tangential direction at shroud of gas cover body 1, from opening 1-3, through gap 6, flow out, make plasma torch pipe 3, coil 4 and the plasma torch 3-1 of radio-frequency generator are enclosed in inert gas, isolated with ambient atmos, and inert gas and water cooling plant 2 form dual-cooled, cooling effect improves greatly.
Embodiment 2: the inductively coupled plasma ion source gas shield device of the present embodiment; as shown in Figure 4,5; the red copper piece of water cooling plant 2 is made circle; on the red copper piece, an end is shaped with the protruding rank of protrusion; to facilitate rotation, be shaped with external screw thread around the red copper piece, be shaped with corresponding internal thread hole 1-4 in shroud of gas cover body 1 relevant position, opening 1-3 place; make the red copper piece be threaded with shroud of gas cover body 1, housing can be for the size of different plasma torch 3-1 adjusting plays 6 like this.The other technologies feature is consistent with embodiment 1.
When this device is used, adjust the clearance distance of device and inductively coupled plasma interface arrangement 5, then to shroud of gas cover body 1, with the speed of 0.3 L/min, pass into argon gas, and cold the anhydrating in outside of connection water cooling plant 2 can be carried out mass spectral analysis.
Before and after feeder apparatus, solution sample introduction analytical performance is relatively:
Under selected instrument condition of work; in the situation that add this inductively coupled plasma ion source gas shield device of forming the ICP argon atmosphere and feeder apparatus not; gather respectively the signal of two cover standard liquids; after linear fit, carry out linearly dependent coefficient, detection limit and background equipotent concentration relatively.The comparative result of analytical performance is listed in Fig. 6,7 tables.
In order to find out at a glance which analytical performance is better in both cases, the molecular ion or the more serious mass number of Polyatomic ion that particularly for O, N, H, C, Ar etc., form, we have introduced two and have estimated the factor.One is background equipotent concentration ratio R
bEC, another is the detection limit ratio R
dL.
R
bECduring=feeder apparatus background Deng effect Nong Du ∕ background equipotent concentration during feeder apparatus not
Work as R
bEC<1 o'clock, after feeder apparatus is described or sensitivity improves or background reduces (Polyatomic ion that is mainly composition such as material introduced in O, N, H, C, Ar or solution diminishes) or they comprehensively causes the analytical performance improvement.
Work as R
bEC>1 o'clock, after feeder apparatus is described or sensitivity descends or background increases (the Polyatomic ion increase that is mainly composition such as material introduced in O, N, H, C, Ar or solution) or they comprehensively causes the analytical performance variation.
Work as R
bEC=1 o'clock, after feeder apparatus is described or sensitivity is substantially constant or background substantially constant (Polyatomic ion that is mainly the compositions such as material introduced in O, N, H, C, Ar or solution is substantially constant) or their synchronous variation causes analytical performance substantially constant.
When the background equipotent concentration occurs when negative, noiseless, sensitiveer mass number often, R
bECinapplicable.
Owing to being the solution sample introduction, there are a large amount of O, H etc. in ICP, thereby can embody the effect of feeder apparatus, can only look at that the interference of the former molecular molecular ion such as N, C or multi-atomic ion reduces situation.As can be seen from the table,
24mg(exists
12c
12c disturbs),
28si(exists
14n
14n,
13c
15the interference such as N),
42ca(exists
14n
14n
14n,
12c
15n
15n,
13c
14n
15the interference such as N),
53cr(exists
13c
40ar,
15n
38the interference such as Ar),
55mn(exists
15n
40ar disturbs),
60ni(exists
12c
12c
36ar disturbs),
65cu(exists
12c
13c
40ar,
12c
15n
38ar,
13c
14n
38ar,
14n
15n
36the interference such as Ar) etc. R
bECall be less than 0.6, illustrate that the background equipotent concentration of these mass numbers descends obviously, from the R of high-quality number
bECduring known feeder apparatus, sensitivity does not increase, thus the background equipotent concentration of these mass numbers to descend be mainly that N, C isoconcentration descend and make and due to background descends, the protective device energy air-isolation that adds formation ICP argon atmosphere be described.
The detection limit ratio R
dLdetect not detection limit during feeder apparatus of Xian ∕ during=feeder apparatus
Work as R
dL, illustrate that detection limit improves after feeder apparatus at<1 o'clock.As can be seen from the table, the R of most of mass number
dLbe less than 1, particularly
24mg(exists
12c
12c disturbs),
28si(exists
14n
14n,
13c
15the interference such as N),
42ca(exists
14n
14n
14n,
12c
15n
15n,
13c
14n
15the interference such as N),
53cr(exists
13c
40ar,
15n
38the interference such as Ar),
55mn(exists
15n
40ar disturbs),
60ni(exists
12c
12c
36ar disturbs),
65cu(exists
12c
13c
40ar,
12c
15n
38ar,
13c
14n
38ar,
14n
15n
36the interference such as Ar) etc. R
dLall be less than 1, illustrate that adding the protective device rear stability that forms the ICP argon atmosphere also improves.
Claims (7)
1. an inductively coupled plasma ion source gas shield device; it is characterized in that; the shroud of gas cover body that comprises hollow; described shroud of gas cover body one end has torch pore and the air inlet corresponding with the plasma torch pipe; the other end is arranged to the opening be connected with outside; described opening is relative with the inductively coupled plasma interface arrangement; described opening part is provided with cooling device; described cooling device and inductively coupled plasma interface arrangement match and form the gas outlet side of shroud of gas cover body, and the gas outlet side of this shroud of gas cover body communicates with the external world.
2. inductively coupled plasma ion source gas shield device according to claim 1; it is characterized in that; described cooling device is water cooling plant; described water cooling plant is the heat-conducting metal piece that is shaped with cooling water hole; described heat-conducting metal piece middle part is shaped with the cooling torch hole matched with plasma torch, and described torch hole communicates with ambient atmosphere.
3. inductively coupled plasma ion source gas shield device according to claim 2, is characterized in that, described heat-conducting metal piece is threaded in the opening part of shroud of gas cover body.
4. inductively coupled plasma ion source gas shield device according to claim 1, is characterized in that, described shroud of gas cover body is cylindric, and described air inlet is arranged on the end face of shroud of gas cover body, and its inlet channel is elbow-shaped.
5. according to claim 1 or 2 or 3 or 4 described inductively coupled plasma ion source gas shield devices, it is characterized in that, the internal orifice of described air inlet is towards the tangential direction of described torch pore.
6. inductively coupled plasma ion source gas shield device according to claim 5, is characterized in that, described air inlet has two at least, and be oppositely arranged along shroud of gas cover body axle center.
7. according to claim 1 or 2 or 3 or 4 described inductively coupled plasma ion source gas shield devices, the material of described shroud of gas cover body is polytetrafluoroethylene.
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| CN106290155A (en) * | 2016-08-02 | 2017-01-04 | 钢研纳克检测技术有限公司 | One is applied to ICP spectrogrph light source shield structure |
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| CN105355534B (en) * | 2015-11-23 | 2017-01-25 | 中国科学院地质与地球物理研究所 | A method and device for realizing an inductively coupled plasma ion source working in an inert gas environment |
| CN109192646B (en) * | 2018-09-11 | 2020-12-08 | 德淮半导体有限公司 | Ion implanter |
| GB2585327B (en) * | 2018-12-12 | 2023-02-15 | Thermo Fisher Scient Bremen Gmbh | Cooling plate for ICP-MS |
| EP3712923A1 (en) | 2019-03-18 | 2020-09-23 | ETH Zurich | Ion source for inductively coupled plasma mass spectrometry |
| CN114203508B (en) * | 2021-11-01 | 2022-09-06 | 中国地质大学（武汉） | Oxygen reduction device for inductively coupled plasma ion source region |
| CN116321655B (en) * | 2023-03-15 | 2024-01-30 | 瑞莱谱(杭州)医疗科技有限公司 | Closed ion source and debugging method thereof |
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| JP2004327243A (en) * | 2003-04-24 | 2004-11-18 | Tdk Corp | Inductively coupled plasma mass spectrometer and mass spectrometry method |
| CN201830540U (en) * | 2010-05-26 | 2011-05-11 | 宁波检验检疫科学技术研究院 | Ion source gas protector of inductively coupled plasma |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004327243A (en) * | 2003-04-24 | 2004-11-18 | Tdk Corp | Inductively coupled plasma mass spectrometer and mass spectrometry method |
| CN201830540U (en) * | 2010-05-26 | 2011-05-11 | 宁波检验检疫科学技术研究院 | Ion source gas protector of inductively coupled plasma |
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| CN106290155A (en) * | 2016-08-02 | 2017-01-04 | 钢研纳克检测技术有限公司 | One is applied to ICP spectrogrph light source shield structure |
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