The present invention relates generally to inductively coupled plasma mass spectrometer (ICP-MS) and particularly to a cooling system for an interface used in ICP-MS.
Mass spectrometers (MS) are used to determine the constituents of a sample and its chemical composition by measuring the mass-to-charge ratio of ions. Molecular compounds or elements within a sample of interest are detected by first ionizing the molecules and atoms within the sample and then detecting them in a vacuum according to their mass-to-charge (m/z) values using electric and magnetic fields. In order to achieve this, a sample that is to be characterized is ionized and then injected into the mass spectrometer.
One method of sample ionization is by using inductively coupled plasma. A plasma is generated by inducing a radio-frequency current within a flow of gas, (for example, argon, helium, nitrogen, air, etc.). Ionization and atomization occur as a result of the discharge, resulting in an intense heat typically in range of 5,000 to 10,000K.
Another method of sample ionization is by a microwave induced plasma. In this case the plasma is formed by inducing a microwave current into the plasma support gas (for example, argon, helium, nitrogen, air, etc.), resulting is very high temperatures in the range of 5,000 to 10,000K.
The sample can also be ionized by using glow discharge, a flame, an arc, or a spark.
A sample to be analyzed is injected into the plasma, typically using a carrier gas (for example, argon, helium, nitrogen, oxygen, air, etc.). The injected sample is ionized at the extremely high temperatures of the plasma.
The plasma is formed in the ICP torch, usually at atmospheric pressures. Since the mass spectrometer works under vacuum, a sampling interface is usually used to gradually decrease the pressure from atmospheric level to vacuum (i.e., microTorr) in successive stages. The sampling interface operates at reduced pressure, typically a few mbar. The flow of plasma into the interface is thereby driven by the pressure difference between the plasma and the expansion chamber within the interface. To form an ion beam from the sample ions in the plasma, the plasma is sampled through an aperture in the sampling interface operating under vacuum. This is done by implementing a sampler in the interface in the form of a sampler plate or cone that has a narrow aperture, usually about 0.1 to 2 mm in diameter. Downstream of the sampler plate or cone, the plasma expands within the sampling interface as it passes through an evacuated expansion chamber within the interface. A central portion of the expanding plasma passes through a second aperture provided by a skimmer cone into a second evacuation chamber that has a higher degree of vacuum. Downstream of the skimmer cone, there may be additional orifices as well as electrostatic lenses that extract ions from the plasma, thereby forming an ion beam. The resulting ion beam is then deflected and/or guided towards a mass spectrometer by one or more ion deflectors, ion lenses and/or ion guides.
The sampling interface is sensitive to deposits forming on the sampler cone, which deteriorates the performance of the mass spectrometer and results in signal drift, or artefacts in the obtained mass spectrum. Deposits can form on the sampler plate or cone, in particular close to its tip and aperture, resulting in these issues. Clogging can originate in the sampler itself, or it can originate in components of the sampling interface.
Conditions at the sampling interface in ICP-MS are harsh. Due to the extremely high temperature at the plasma source (up to 10,000 K), the sampler, which is in front of the plasma, needs to be cooled. Preventing heat dissipation to the other components of the mass spectrometer is highly necessary in order to protect them from thermal damage. In other words, functionality of the ICP-MS system highly depends on controlling the spread of heat to the temperature-sensitive parts and devices.
Traditionally, the sampling interface is cooled with water (or a water-based coolant or other liquids) to prevent the heat from reaching other parts of the ICP-MS system. Water-cooling is troublesome and adds enormous expenses and complexity. In most cases, bulky chillers are employed to further assist the cooling process by keeping the temperature of the coolant (e.g., water) from rising during operation. A typical chiller requires up to 3 kW power, 5 liters/min water containing a corrosion inhibitor to protect the interface and the aluminum components. Corrosion is, nevertheless, a problem with these chillers. The size and weight of the chiller could be around up to 70×50×65 cm3 and 45 kg, respectively This further adds to the size, footprint, complexity, and cost of the instrumentation. Water-cooling also reduces the temperature of the path where the ions travel through, causing ion recombination and clustering which in turn reduces the sensitivity of the ICP-MS system. Recombination and clustering limit the employment of other desirable devices which can otherwise lead to reducing the limits of detection and improving sensitivity of the instrument.
In order to reduce cost, complexity, and size of ICP-MS systems, elimination of the water cooling and its associated devices is desirable. An air-cooled interface for ICP-MS is highly cost effective, simple, and reduces the size of the system significantly. However, since the thermal conductivity and specific heat capacity of air are significantly lower than those of water, using air as an agent for cooling the ICP-MS interface instead of water or other liquids is extremely difficult. Consequently, designing an air-cooled interface is a challenging task as it needs a deep knowledge of plasma, mass spectrometry, heat transfer, fluid flow, material science, etc. Therefore, several attempts to design an air-cooled interface by others have failed up until now.
Currently, cooling of the interface and its components in conventional ICP-MS systems is typically achieved by mounting the sampler and other components of the sampling interface on a water-cooled plate (i.e., cooling plate, or cooling jacket) on the front end of the interface, facing the ICP source.
The present invention addresses the above described deficiencies by providing an improved interface for inductively coupled plasma mass spectrometers (ICP-MS). The invention provides an air-cooling system for use at the sampling interfaces, thereby totally removing the need for using water or any other cooling liquids in ICP-MS systems. This invention significantly reduces the size, cost, and complexity of the system, in addition to increasing the cooling efficiency, as compared to the currently available water/liquid cooling systems.
The present system has an air-cooled interface with a sampling orifice mounted on its front surface facing the ICP. The interface may have one or more sampling cones in succession, each working at different vacuum pressures. The air-cooled interface is cooled either naturally (free convention) or by using fans or other devices to circulate air or any other suitable cooling gas. It may also be cooled by a combination of air-cooling and radiation. Depending on the plasma power, the airflow may be adjusted to a range of 20-2000 CFM, preferably between 50-200 CFM. The air-cooled interface may be coupled with one or a combination of an open cell foam heat exchanger, finned heat exchanger, compact heat exchanger, a heat exchanger with a honey-comb structure, or heat pipes to enhance air-cooling of the sampling interface. The open cell foam may be made of metals or alloys of metals such as aluminum, copper, nickel, iron, or non-metals such as carbon, silicon carbide, or ceramics. The porosity of the foam may be up to 98%. The pore density of the foam may be in the range of 1-100 pores per inch (PPI), preferably between 5-20 PPI. The relative mass density of the foam may be in the range of 1-30%. Various thermal resistance are implemented in various locations of the sampling interface to prevent the heat from reaching heat sensitive components of the interface. The material, thickness and length of these thermal resistors are adjusted to control the flux of heat through various components of the interface. The thermal resistors are used in a way to direct and confine the heat close to the path of ions to prevent recombination and clustering.
Embodiments herein will hereinafter be described in conjunction with the appended drawings provided to illustrate and not to limit the scope of the claims, wherein like designations denote like elements, and in which:
Exemplary embodiments of the present invention are described in the followings with referring to the figures and without limiting the scope of the invention.
The invention here describes a method and design of interface for ICP-MS based on air circulating through a set of fins, a metal foam structure, a compact heat exchanger, or a combination of these methods in order to control heat dissipation to surrounding devices. The presently disclosed air-cooled system enhances the convective heat transfer to the coolant air, using fins, open-cell metal foams, honey-comb structures, compact heat exchangers, or other air cooling systems, or a combination of these methods, as provided here. In some embodiment of the present system, the adjustment of thermal resistance is also used in appropriate locations of the interface to control the spread of heat. This is another novel aspect of the present invention. One or a combination of any of these technologies with the aid of a simple air fan or other air circulation systems provides enough cooling in order to control heat dissipation to surrounding devices while directing the heat toward specific regions of the interface and localizing the necessary high temperatures in the ion beam path to avoid recombination and clustering and improve the sensitivity and lower the detection limits of the ICP-MS instrument.
In particular, a large number of sealing systems, such as sealing gaskets 218, and O-rings 219 are used to keep the sampling interface and MS at vacuum conditions. High temperatures will damage these seals. Therefore, either special and very costly seals have to be used or the seals have to be located far from the high temperature zone, adding complexity, cost and footprint to the device. In the present system, a set of thermal resistors 303 are used to prevent heat from reaching the components of the device that are prone to damage by heat. Thermal resistors 303 may also be used to prevent the spread of heat toward other sections of the MS which contains heat sensitive electronics, turbopumps, heat sensitive components, detectors, ion guides, mass analyzers, flow control and sensing components, etc. The thermal resistors are any of a set of thin walls, long walls, insulators, materials with medium to low thermal conductivity, or a combination thereof.
The front surface 201 of the interface 200 that faces ICP torch 101 is in close proximity to the ICP source (1-20 mm from the outer coil), and therefore, it is exposed to high plasma temperatures, and needs to be cooled. Prior ICP-MS systems use water/liquid cooling systems to cool the front side of the interface that is exposed to plasma as well as the other components that may be mounted on the various stages and locations of the interface such as sampler cones, skimmer cones, apertures, ion guides and lenses, sensors, ion deflectors, electronic components, etc. This is because liquids (especially water) typically have much higher thermal conductivity, density, and specific heat capacity compared to gases, making them the first, obvious choice for cooling purposes. Water cooling used in conventional ICP-MS systems increases complexity, expense, and system size. It also causes temperature drop in the path of the ion beam 260, increasing probability of recombination and cluster forming. To avoid recombination and cluster forming, MS designers are normally forced to reduce the length of ion trajectory path and hence limiting the other and more effective ion transfer devices and methods that can otherwise be used along the path of the ion beam. The present invention discloses an air cooled interface with targeted cooling to only cool the interface surfaces, and not the ions.
Open-cell foams are a new type of highly porous and permeable structures, with random cavities and a high ratio of surface area to volume, made from different materials (e.g., Al, Cu, Ni, carbon, ceramics, etc.). The cooling agent (e.g., air) can easily circulate through the cavities, providing a very large surface area for convective heat transfer. Heat transfer from the foam fins/struts to the cooling agent provides substantial enhancement in cooling capabilities of metal foams which results in a high rate of convective heat transfer from the cooling target to the cooling agent. Also the random positioning of the pores/cavities induces circulation and mixing of the fluid, which again improves heat transfer from the struts to the fluid.
Depending on the size of the system, a free (natural) convention may be sufficient to cool the system, without any need for a fan to force the air through the system.
In operation, an inductively coupled plasma is generated by winding a load coil around the torch and supplying an alternating current through a radio-frequency generator; injecting one or various plasma gases to the ICP torch, and generating an electrical spark to ignite the plasma. The frequency of the plasma may be in the range of 400 kHz to 100 MHz, preferably between 27 to 40 MHz. The plasma power can be between 300 W to 2000 W, more typically between 700 W-1600 W, preferably between 700 W-1000 W. One or more types and flows of gases may be introduced to the plasma torch for the purpose of generating the plasma, carrying the sample, or cooling the torch walls. The plasma gas may be one or a combination of various gases such as argon, helium, air, nitrogen, oxygen, hydrogen or any other suitable atomic or molecular gases. The plasma gas flow rate may be in the range of 0.5-20 L/min, preferably 1-10 L/min, also 5-8 L/min.
Once the plasma is generated, it is set in front of a sampling orifice. The orifice diameter may be in the range of 0.1-5 mm, preferably 0.3-1 mm, more precisely 0.3-0.7 mm. The distance between the sampling orifice and the end of the load coil around the ICP torch may be adjusted to optimize signal intensity, sensitivity, plasma signal stability, matrix effects, etc. The distance may be in the range of 1-20 mm, preferable 5-10 mm.
The sampling orifice may be made of a high-temperature material, for example, nickel, copper, aluminum, platinum, molybdenum, stainless-steel, alloys of various metals or ceramics. The sampling orifice may be coated with on or multiple layers of a thermal barrier coating to protect the orifice from thermal damage and corrosion. The thickness of the coating may be in the range of 50 nm to 2 mm, preferably between 1 μm to 0.5 mm. The coating material may be one or a combination of yttria-stabilized zirconia (YSZ), alumina, yttria, ceria, zirconia, rare-earth oxides, rare-earth zirconates.
The sampling orifice is mounted on an air-cooled sampling interface. The interface typically houses one or more sampling cones in succession, each working at different vacuum pressures. The range of vacuum may be between 10-10 Torr to 500 Torr, preferably between 10-7 Torr to 10 Torr. The air-cooled interface may be cooled using fans or other devices to circulate air or any other suitable cooling gas. Depending on the plasma power, the airflow may be adjusted to a range of 20-2000 CFM, preferably between 50-200 CFM.
The air-cooled interface may be coupled with one or a combination of an open cell foam heat exchanger, finned heat exchanger, compact heat exchanger, a heat exchanger with a honey-comb structure, or heat pipes to enhance air-cooling of the sampling interface. The open cell foam may be made of metals or alloys of metals such as aluminum, copper, nickel, iron, or non-metals such as carbon, silicon carbide, or ceramics. The porosity of the foam may be up to 98%. The pore density of the foam may be in the range of 1-100 pores per inch (PPI), preferably between 5-20 PPI. The relative mass density of the foam may be in the range of 1-30%.
Various thermal resistance may be implemented in various locations of the sampling interface to prevent the heat from reaching heat sensitive components of the interface. The type, material, thickness and length of these thermal resistors may be adjusted to control the flux of heat through various components of the interface. The thermal resistors may be adjusted in a way to direct and confine the heat close to the path of ions to prevent recombination and clustering.
The sampling interface may include sealing components at various locations to keep the vacuum inside the mass spectrometer and the sampling interface. These sealing components may be one or a combination of O-rings, gaskets, or washers made from various suitable materials such as rubber, plastic, metal, ceramic, alloys, composite materials, or graphite. The thermal resistors mentioned above, may be adjusted in a way to prevent the heat from reaching and damaging these sealing components.
The method further includes a mass spectrometer coupled with the sampling interface to filter and analyze the sampled ions through the sampling orifice. The mass spectrometer may have various architectures including a single-quadrupole, triple-quadrupole, magnetic sector, ion trap, time-of-flight, ion mobility, or any other type. The mass spectrometer typically works under vacuum. One or more vacuum pumps may be connected to the mass spectrometer to provide the vacuum inside the mass spectrometer.
The method further comprising of a sample introduction system to introduce the sample of interest into the ICP torch to be atomized and ionized by the plasma and analyzed by the mass spectrometer. The sample introduction system may introduce the sample to the plasma in the form of aerosol, atomized solution, evaporated suspension, single particles, powder, ablated material, gas, or any other suitable forms. Usually, a flow of carrier gas transport the sample into the plasma. This gas may be one or a combination of various atomic or molecular gases such as argon, helium, air, nitrogen, oxygen, hydrogen, water, etc. The flow rate of the carrier gas should be adjusted to optimize signal intensity, sensitivity, plasma robustness, signal stability, etc. The carrier gas flow rate may be in the range of 0.05-2 L/min, preferably 0.1-1 L/min, also 0.2-0.6 L/min.
The method further includes the following steps for analyzing a sample of interest: Pumping down the mass spectrometer and sampling interface to reach vacuum conditions, generating a plasma inside the ICP torch, preparing a sample of interest and injecting it into the plasma using the sample introduction system. The plasma atomizes and ionizes the sample to generate an abundance of sample ions. The generated ions being sampled by the sampler orifice. The plasma usually works under atmospheric conditions, while pressure behind the sampler orifice is kept below atmosphere to suck in the ions. The sampling interface being totally air-cooled without any need for water-cooling or a water chiller, to dissipate the heat generated by the ICP torch. Transferring and filtering the ions of interest through various stages, ion guides, ion lenses, interface cones, collision cells, or mass filters inside the mass spectrometer until they reach the ion detector to be detected and analyzed. Connecting the mass spectrometer to a computer for data collection and analysis.
Number | Date | Country | |
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63115394 | Nov 2020 | US |