• 专利附录
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    • 专利摘要:
    A probe, which makes it possible to use two or more spectroscopic or photometric techniques simultaneously, consisting of a viewing window perpendicular to the central radiation channel and a mechanical optical assembly to guide the radiations from various connected radiation sources to the product to be analyzed and to filter the return signal from all interferences and negative influences of the other techniques used before sending it to the analysis instruments.
    公开号:BE1027312B1
    申请号:E20205393
    申请日:2020-06-03
    公开日:2021-07-13
    发明作者:Tomas Vermeire
    申请人:Measure Analyse Control Bvba；
    IPC主号:
    专利说明:

    IMPROVED PROBE FOR COMBINED ELECTROMAGNETIC SPECTRA OR OPTICAL ANALYSIS AND ITS USE/ METHOD
    TECHNICAL FIELD The present invention relates to a probe for the electromagnetic spectrum or optical analysis of a material to be analyzed contained in a processing volume, transport volume or storage volume, such as a feeding station, mixing station, container or tube. More specifically, the invention relates to the spectroscopic, photometric or image analysis of pure or mixed powder, bulk material, granulated material, cream, viscous liquid or the like, by a measuring probe comprising; at least one element that receives radiation or light; at least one viewing window positioned in the probe tip and in the path of the radiation, and at least two outputs for connecting analysis instruments.
    BACKGROUND ART D1 describes an existing optical probe wherein the probe includes an observation window oriented toward a sample to be analyzed in US patent 6873409B1 ("optical probe includes a probe body having a window with a Surface oriented toward a Sample under investigation"). The patent describes the method in which a liquid is used to prevent contact between the sample and the observation window. This method, according to the patent, is applicable to all forms of optical measurements, including Raman, fluorescence and so on. “The approach is applicable to any form of optical Sampling, including Raman detection, fluorescence, and So forth.” Also known is the probe described in D2 (US2014/0340683A1) in which a viewing window is directed to the sample to be analyzed. The patent further describes that via the viewing window, different optical techniques can be used and must therefore have certain properties, and that it has a device that can rinse the window: “According to the invention, a window is intended to mean a component of the measuring apparatus which is at least partially transparent for electromagnetic radiation. Preferably, the window is at least partially transparent for electromagnetic radiation in the wavelength range of from 200 to 700 nm (UV/Vis) and/or in the wave number range of from 400 to 4000 cm (IR) and/or from 4000 to 14000 cm (NIR).” Yet another example can be found in D3 (US8730467B2) which describes a probe that can perform different spectroscopic measurements at different locations. The patent also describes a method to detect impurities in a sample with this type of probe. This method can be used with different spectroscopic methods: “This analysis device also includes means for emitting monochromatic or polychromatic light, in particular within a range of ultraviolet, visible, infrared, near infrared or also mid infrared wavelengths. This emitted light will be used for illuminating the sample to be analyzed in particular by means of the above-mentioned probe.' Likewise, the probe described in D4 (US20080212087A1) can use various spectroscopic or photometric techniques in reflection to measure a sample in a given volume. can be analyzed thanks to a separate viewing window placed tangentially in the wall perimeter of the probe for each technique.
    Finally, D5 shows another example of existing technique in US00611852A where two spectroscopic techniques by means of two independent optical paths can be used in a specially designed probe tip. The patent states: “The types of Spectrometric analyzes that may be performed with the present probe include, for example, attenuated total reflectance (ATR), light Scatter analysis, image analysis, and refractive index (RI) determination. Light Scatter analysis may include backScatter analysis, Raman, Rayleigh Scattering, and fluorescence, for example.” D6 (US 2016/299060) describes an immersion probe, suitable for simultaneously performing a first analysis of a part of light from liquids and/or particles in a liquid and a second analysis of a part of light from liquids and/or particles in a liquid. The system describes an optical axis and includes an analyzer, a window, a first optical path extending between the window and the first analyzer, the system also includes a second analyzer and a second optical path extending between the window and the second analyzer. The immersion probe further includes a spectral selector positioned in the first optical axis and in the second optical axis to pass the first portion of the light from the liquids and/or particles to a second analyzer. In addition, the immersion probe includes an illumination path that delivers the light onto a base, which is inclined at an oblique angle to the optical axis. The first component and the second component share a common optical path between the window and the spectral selector.
    D7 (US 2015/377787) describes examples of a spectroscopy probe for performing measurements of Raman spectra, reflectance spectra and fluorescence spectra. The integrated spectral probe may include one or more light sources for producing white light to generate the reflectance spectra, an excitation light to generate a UV visible fluorescence spectra, and a narrow band NIR excitation to generate Raman spectra.
    The various modalities of spectral measurements can be performed in two seconds or less.
    Furthermore, the document describes examples of methods for operating the disclosed integrated spectroscopy probe. The embodiments in D1 and D2 mention having specific elements to protect the observation window from adhesion by the sample.
    Although several spectroscopic methods are mentioned, it is obvious to anyone knowledgeable in the matter that the probe can only be used alternately by the different methods and not by the different methods simultaneously.
    The observation window design is too small to allow the transmission of several methods at the same time.
    Increasing the observation windows would result in such an increase in the volume of liquid needed to avoid adhesion that it would interfere with the sample and thus make the measurements unreliable.
    D3 has options to connect several spectroscopic analysis devices but is unsuitable to run them simultaneously as the design shows no provisions to avoid interference from one light source on the signal from the other method.
    This can cause a distortion of the signal which would lead to unreliable results.
    The design in D4 could potentially overcome the interference of the light sources from one spectroscopic method on the detection of the other by using different tangentially oriented observation windows for each method, but the signal will consequently also be from a completely different volume of the object to be measured. analyze sample come.
    In addition, in a linearly moving product flow, the insertion of the probe will affect the movement of the product so that some of it may get stuck on one side of the probe while on the other side may create turbulence and even a vacuum causing the product may even separate.
    This will cause non-representative measurements if the probe is not oriented correctly.
    Although the design in D5 allows to use different spectroscopic techniques at the same time, the proper functioning of the probe relies on the probe being immersed in the product and in this way the probe influences the advancement of the product and there is a strong possibility of segregation or turbulence that can lead to erroneous measurement results.
    D6 and D7 each describe a probe coming into contact with a sample, where the sample could stick to the window of the probe or crystallize on it due to temperature difference with the environment. The analysis of the sample can be negatively influenced during the analysis of the sample.
    The present invention aims to find at least a solution to some of the above-mentioned problems or drawbacks. Indeed, the invention will make it possible to allow different spectroscopic or photometric techniques at the same time through 1 or more observation windows without disturbing the medium and without the techniques used being able to influence each other's results. The present invention, without limiting its use thereto, is well suited to analyze continuous processes such as mixing, filling or tabletting of powder mixtures, granulated material or combinations of both in pharmaceutical processes without any risk of segregation or other adverse effect which could cause be achieved by introducing a probe into such a system. In addition, with the present invention, it is also possible to apply a method which improves the accuracy of the results or part of the results of a spectroscopic or photometric method by combining with the results or part of the results of a second.
    SUMMARY OF THE INVENTION The present invention and its embodiments provide a solution to one or more of the drawbacks mentioned above. In a first aspect, the invention relates to a spectroscopic probe which offers the possibility to use several spectroscopic instruments simultaneously. The invention, thanks to the use of optical filters, allows these instruments to be used simultaneously to analyze the same volume of a sample without these methods interfering with each other. For clarification, we cite an embodiment in which the Raman and NIR spectrum of a sample can be determined simultaneously by installing a filter in the optical source channel of the NIR light source, which blocks the light from the NIR light source below 1100nm because the Raman spectrometer wavelengths below 950 nm. In this way the light from the NIR light source, which normally extends well below 950 nm and has an intensity many times higher than the Raman signal to be measured, can be kept away from the detector of the Raman spectrometer so that both instruments can be used simultaneously. to measure.
    The use of these optical filters allows to use both spectroscopic methods simultaneously through the same viewing window mounted in the tip of the probe. Preferred embodiments of the invention are described in claims 1 to 9. The use of a single viewing window mounted flush in the tip of the probe ensures that the sample studied is not disturbed during possible operations in the volume where it is located. while the two or more spectroscopic or optical techniques can analyze the same volume of the sample. In a second aspect, the present invention also concerns the use of a parabolic concentrator in the source channel of the spectroscopic or photometric technique so as to minimize the specular reflection on the surface of the viewing window and thus obtain a significant improvement of the signal such as described in claims 2 to 9. Finally, the present invention also concerns a method of combining at least two spectroscopic or photometric methods and by merging the results or parts of the results of the individual methods into a new overarching method on achieve better results in this way than was possible with the individual methods. In the particular embodiment of the Raman NIR probe mentioned above, the Raman signal is less sensitive to adhesion of product to the viewing window than the NIR signal and thus the results of this could be used to correct the NIR signal if appropriate. The NIR signal is more intensive, making measurements faster and allowing smaller volumes of product to be analysed, so that it can determine the variation in composition of a moving sample to a much smaller scale. However, the NIR signal is disrupted much faster by material adhesion to the viewing window. Combining both methods in 1 overarching method will therefore result in a much more efficient analysis method. This example is by no means limiting of the patent as many more synergies are expected, also when using other spectroscopic or photometric methods.
    DESCRIPTION OF THE DRAWINGS The following are descriptions of some specific embodiments of the invention which have been chosen to provide as much clarity as possible about the details of the invention without wishing to limit the invention or its application to the embodiments shown. The numbering chosen in the drawings to name details is used for all drawings so that the same number always means the same part.
    Figure 1 shows a longitudinal section of an embodiment of the probe showing the basic provisions for the simultaneous use of two different spectroscopic or photometric techniques. The probe is provided with two sets of radiation conductors at one end to which, for each spectroscopic or photometric technique, on the one hand a radiation source can be connected to conduct the radiation specific for that technique to the sample, and on the other hand the obtained signal via the connection to the analysis device can be brought. The embodiment is further described in Example 1.
    Figure 2 shows the back of the same embodiment with the radiation guides replaced by connectors making the probe easier to handle. This embodiment is not further described.
    Figure 3 shows a specific embodiment of the invention where the probe was installed in front of a second window. By using the second window, the elements guiding the radiation in the probe will have to be adapted to the additional distance from the sample to be analyzed and the additional reflections caused by the refraction at the additional material surface. This embodiment will not be discussed further.
    Figure 4 shows yet another possible specific application of the invention in which the probe tip is adapted to the internal curvature of the volume containing the sample. Again, the internal components directing the various radiations to and from the sample will have to be adjusted to compensate for the extra lens action of the curved viewing window.
    We will also not describe this embodiment in further detail.
    Figure 5 shows a sectional view of the optical details showing the preferred embodiment of a combined Raman NIR probe. The figure is further explained in detail in Example 2.
    Figure 6 shows a cross-section of another embodiment described in Example 2, where two observation windows are used instead of a single one.
    DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a probe for spectroscopic or photometric measurements of substances or substance mixtures in a liquid or solid form or a combination of both, in a static or dynamic state.
    The design of the probe allows different spectroscopic or photometric techniques to be used simultaneously on the same sample with the volumes analyzed by the techniques being identical, overlapping or adjacent, without the techniques interfering with each other. The probe has no influence whatsoever on the dynamics of the sample to be analyzed other than the change in surface properties of the observation window compared to the wall of the volume containing the sample.
    Unless otherwise defined, all terms used in the description of the invention, including technical and scientific terms, have the meaning as generally understood by those skilled in the art of the invention. For a better assessment of the description of the invention, the following terms are explicitly explained.
    When used in this text, the following expressions have the following meanings: “A”, “the” and “the” in this document refer to both the singular and the plural unless the context clearly dictates otherwise. For example, "a segment" means one or more than one segment.
    When "about" or "around" in this document is used with a measurable quantity, a parameter, a duration or moment, etc., then variations of +/-20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-1% or less, and even more preferably +/-0.1% or less than and of the quoted value, to the extent that such variations apply in the disclosed invention. However, this should be understood to mean that the value of the quantity using the term “approximately” or “around” is itself specifically disclosed.
    The terms “comprise”, “comprising”, “consist of”, “consisting of”, “includes”, “contain”, “containing”, “contents”, “includes” are synonyms and are inclusive or open terms that indicate the presence of the following, and which do not exclude or preclude the presence of other components, features, elements, members, steps known from or described in the art. In addition, terms such as “first”, “second”, “third” and the like are used in the description and in the claims to distinguish between similar elements and not necessarily to indicate a sequential or chronological order. The terms in question are interchangeable in appropriate circumstances, and the embodiments of the invention may operate in orders other than those described or illustrated herein.
    In addition, the terms "above", "below", "front", "behind", and the like in the description and the claims are used for descriptive purposes only and not necessarily to describe relative positions. It should be understood that the terms used in this manner are interchangeable in appropriate circumstances, and that the embodiments of the invention described herein may also operate in sequences other than those described or illustrated herein.
    When presenting an enumeration by using the start and end number, it is assumed that all numbers and, if applicable, also fractions between the start and end number, as well as the start number and end number of the series are included.
    When reference is made to another document, reference is made to the entire document, in particular the claims of these references are intended.
    Where reference is made in this specification to "one embodiment" or to "an embodiment" it means that a particular feature, structure, or characteristic described in the context of the embodiments is incorporated into at least one embodiment of the embodiment. present invention. Thus, the occurrence of the terms "in one embodiment" or "in an embodiment" in different places in this specification does not necessarily refer to the same embodiment, although it may. In addition, the particular features, structures, or characteristics may be combined in any suitable manner, as will be apparent to those skilled in the art to which this disclosure belongs, in one or more embodiments.
    Similarly, it should be noted that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together into a single embodiment, a single figure, or a description thereof, for the purpose of streamlining the description and to assist in the understanding of one or more of the various aspects of the invention. However, this manner in which the description is given should not be interpreted as implying that the claimed invention requires more features than are expressly stated in any claim. As the following claim shows, inventive aspects are reflected in less than all the features of a single previously described embodiment.
    Accordingly, the claims which follow the detailed description are expressly incorporated into this detailed description, each claim being independently to be regarded as a separate embodiment of the present invention.
    In addition, while some embodiments described herein include some features while others are not present but are incorporated into other embodiments, combinations of features from different embodiments will be understood to be within the scope of the invention and constitute different embodiments, as is apparent. are for those skilled in the art. In the following claims, any of the claimed embodiments may be used in any combination.
    The terms “viewing window” and “observing window” as used in this document both refer to a physical barrier between the “product”, “process” or “sample” being analyzed and the internal space and components of the probe and being made. from a material transparent to the radiation that spectroscopic or photometric techniques that the embodiment can handle, thus protecting the internal parts of the probe from the material to be analyzed. The material chosen for this barrier is also chemically resistant to the product to be analyzed. For example, a viewing window could be made of sapphire, cubic zirconium or diamond, without being limited to.
    “Spectroscopic or photometric technique”, as used throughout this document, can refer to any technique where electromagnetic radiation is analyzed such as Ultra Violet spectroscopy, Laser Induced Fluorescense spectroscopy, Near Infrared spectroscopy, Raman spectroscopy, Mid Infrared spectroscopy, image analysis, … With “source radiation ” refers to any form of light or radiation that aims to generate a particular spectroscopic or photometric signal from the product or sample to be analysed. Some non-limiting examples are a halogen lamp, UV light source, a laser beam, … A “radiation guide”, “radiation channel”, “optical channel” or “light guide” in this text refers to a part that is capable of transporting certain electromagnetic radiation with minimum losses. This transport can be in the direction of the sample to be analyzed as well as in the direction of the analysis instrument or even bi-directional. Typical examples in spectroscopy are optical fibers, light tunnels, ... This enumeration is by no means limiting for the embodiments of this invention.
    In a first aspect, the invention relates to a probe to enable simultaneous use of two or more spectroscopic or photometric techniques. Preferably, the probe comprises a minimum of two spectroscopic or photometric assemblies. Preferably, the probe comprises a first spectroscopic or photometric assembly and a second spectroscopic or photometric assembly. Preferably, the probe has a viewing window. Preferably, the viewing window is arranged perpendicular to the path of the radiation and a mechanical-optical assembly which directs the various radiations from the connected radiation sources to the sample to be analyzed and back to the analysis devices, meanwhile ensuring that no unwanted are interferences or unwanted parts of the signals go to the analysis instruments. Preferably, the viewing window is made of a material that transmits electromagnetic radiation, more specifically the selected material is transparent to visible light,
    UV light, infrared light and near infrared light, without this list being limiting to the radiations that could be used for the probe. The viewing window allows to use at least two spectroscopic or photometric techniques at the same time, which allows to analyze the composition of substances with a higher accuracy. As a result, the quality control of the composition and in particular the chemical composition and even more in particular the chemical composition in pharmaceutical applications can be improved. In addition, the viewing window ensures that the optical parts and optical components in the probe do not come into physical contact with a sample or product under test, which is beneficial to the operation of the probe and does not contaminate or disrupt the product or sample. More specifically, in this way the quality control can be improved with a non-destructive method.
    The dimensions of the probe can be optimized by the combination of different assemblies in a single probe, in particular this is an advantage allowing the probe structures such as portable instruments, which can determine the composition of products with high accuracy on remote, smaller product volumes or hard-to-reach places.
    A preferred embodiment of the probe consists of at least one source radiation channel and at least one signal radiation channel. Preferably, each spectroscopic or photometric assembly consists of at least one source-radiation channel and at least one signal-radiation channel. Preferably, the source radiation channel directs the radiation from the radiation source to the viewing window and ultimately to the sample to be analyzed. Preferably, the signal-radiation channel conducts the signal returning from the sample towards the analysis instrument. Preferably, the radiation channel is a fiber, in particular an optical fiber.
    A preferred embodiment of the probe comprises at least one lens to convert the monochromatic radiation from the light source into a collimated beam at the end of the first source radiation channel of the probe. Preferably, the probe includes at least one mirror. Preferably, the mirror has the property of bringing a collimated radiation into a central radiation path.
    Preferably, the mirror reflects only the wavelength of the collimated radiation and is transparent to other wavelengths. Preferably, the central radiation path consists of a space created by the widening of a beam of radiation conductors guiding the radiation from a second radiation source before these conductors terminate in an annular formation. Preferably, the probe also has at least one parabolic concentrator. Preferably, the radiation from the second radiation source, after leaving the annular formation of radiation guides, is focused through the viewing window by means of the parabolic concentrator. Preferably, the radiations from all radiation sources converge at the same point after the viewing window to irradiate the same volume of the sample to be analyzed so that the resulting radiation is guided back into the probe via the same radiation path, through the mirror which is reflective only for the wavelength of the first radiation source. Preferably, the probe after the mirror has a device that splits the resulting radiation into parts needed for the specific coupled analysis instruments and a means that those parts of radiation are directed with maximum efficiency in the radiation guides to those coupled instruments. Preferably, this device also has additional components that filter interfering wavelengths from the signal before forwarding it to the analysis instruments. In a preferred embodiment of the invention, the source radiations of the different spectroscopic or photometric techniques, after having been cleaned of all possible interfering elements for the other techniques, by means of preferably optical filters, are combined in a common radiation channel which transmits the radiations on direct the volume of product to be analyzed through the viewing window. The electromagnetic design will minimize all possible sources of internal and specular reflection in the radiation guide channel by preferably using anti-reflective coatings or specific lenses. The resulting electromagnetic or photometric signal, which after interaction of the source signal with the product to be analysed, returns in the same radiation guide channel is divided into fractions suitable for each connected technique by means of preferably dichroic mirrors and forwarded via radiation guides to the instruments.
    In a preferred embodiment of the invention, each connected spectroscopic or photometric technique has its own source signal conductor where the radiation, after all parts possibly interfering with the other connected techniques have been removed, is sent through its own or common viewing window to the product or process to be analyzed is going to be. In the event that each technique has its own viewing window, different coatings and lenses may be used per radiation channel and viewing window as stated in the description of the preferred embodiment of the invention above. The resulting electromagnetic or photometric signal can be sent back to the analysis instruments via the same radiation channel, with or without additional dichroic filters that keep out additional interferences, for example but not limited to the wavelength of a laser source.
    A preferred embodiment consists of at least two radiation guides. Preferably, the radiation guide is split into individual radiation guides for each spectroscopic or photometric technique.
    A preferred embodiment consists of at least two viewing windows. Preferably, each viewing window is transparent to the particular spectroscopic or photometric technique using the viewing window. More specifically, this is advantageous to avoid interferences between two or more optical assemblies leading to more accurate results.
    In a preferred embodiment, the probe includes an element to control the temperature of the probe tip. Preferably, the element is integrated into the probe near the viewing window and the radiation guides. Preferably, the element can cool and heat the probe tip. Preferably, the element is electrically energized by a control element arranged outside the probe. Preferably, the element has a temperature sensor to accurately control the temperature.
    In a preferred embodiment of the probe, the surface of the viewing window and the tip of the probe is adapted to the curvature of the volume containing the product to be analyzed. Preferably, the optical elements in the probe tip are adjusted to compensate for the changed geometry.
    A preferred embodiment includes one or more light sources.
    A preferred embodiment can be connected to at least one analysis instrument.
    A preferred embodiment has at least one filter at one or more radiation sources and/or at one or more analysis instruments. Preferably, all these filters are located at the sources or the analysis instruments.
    A preferred embodiment has a mechanical or optical system for making a calibration measurement. Preferably, this system can be used to calibrate or zero the attached spectroscopic or photometric techniques without removing the probe and without disrupting the process or product.
    In an advantageous refinement of these embodiments, by adding a mechanical, optical or electronic device, or a combination of these three, to the probe, the radiation or part of the radiation can be deflected so that the coupled instruments can perform a baseline value or calibration against a built-in standard incorporating the full path of radiation from source to detector. In a further refinement, the probe can also be equipped with an electrical heating element to heat or cool the tip of the probe so that the viewing window of the probe is kept free from condensation and/or adherence by the product to be analyzed. In a further refinement of the embodiments as described above, the viewing window and/or the tip of the probe can be adapted to maintain the curvature of a vessel or pipe where the probe will be mounted. If necessary, additional optical elements may be installed to compensate for the influence on the signal caused by the curvature. In a second aspect, the invention also relates to a method of combining the two or more spectroscopic or photometric signals taken simultaneously from the same volume of the product to be analyzed in front of the tip of the probe and thus enabling an analysis of the properties of that product, which is more accurate than would be possible with any of the individual spectroscopic or photometric signals alone.
    In a preferred embodiment, the method consists of a first step in which the product to be analyzed is viewed by various spectroscopic or photometric techniques to determine the best combination of techniques which will then be integrated into the probe. Preferably, the method also consists of an analysis of the process and the device in which the product is located in order to find the best location for the probe where the most representative measurement of the product can take place without monitoring the course of the process within the device. influence. Preferably, the method has a further step in which the device is adapted to allow the probe to be installed with the viewing window flush with the inner wall or to be mounted slightly more inward to prevent adhesion of product to the tip of the probe. Preferably, the method also includes a further step in which spectroscopic or photometric models are developed for each of the techniques employed as anyone familiar with the art would do and more preferably would share or combine results from these spectroscopic or photometric models in a single or multiple meta-models.
    A preferred embodiment of the method involves the analysis of a chemical, biological or biochemical composition. Preferably, the chemical, biological or biochemical composition is a pure or mixed powder, bulk material, granulated material, slurry, paste or the like in a batch or continuous mixer, tabletting machine, transfer channel or reactor.
    A preferred embodiment sends the data obtained from the analysis tools and preferably also the data from the device parameters to a machine learning system before it is analyzed.
    A preferred embodiment has as end result a feed-forward process control system that adjusts the parameters of processing equipment further in the production line to the measured properties of the product in the current equipment in order to guarantee a constant quality of the end product of the production line.
    A preferred embodiment has as end result a feed-back process control system that adapts the parameters of the processing device where the probe is located to the measured properties of the product in order to guarantee a certain and constant quality of the end product of the device.
    A preferred embodiment has at least a partial Raman spectroscopic system as the first spectroscopic or photometric assembly. Preferably, the second spectroscopic or photometric assembly consists of at least a partial near infrared spectroscopic system. In particular, the combination of the Raman and near infrared optical system is advantageous for accurately determining the chemical composition of a sample.
    In a third aspect, the invention comprises a system comprising at least two spectroscopic or photometric assemblies and a viewing window, at least two radiation sources and at least one, preferably two or more analytical instruments.
    Preferably, this probe has a diameter of a maximum of 5 cm, more preferably a maximum of 4.5 cm, even more preferably a maximum of 3.5 cm, even more preferably a maximum of 3 cm, even more preferably a maximum of 2.5 cm and even even more preferably 2 cm.
    The invention is further described by the following non-limiting embodiments which illustrate the invention and are not intended or should be construed as limiting the scope of the invention.
    EXAMPLES The present invention will be explained hereinafter with reference to the following examples without being otherwise limited thereto.
    It will be apparent to one of ordinary skill in the art that the various embodiments of the examples may be combined into any embodiment described in the detailed description.
    Example 1: Drawing of the general principles. For explanation, reference is made to FIG.1 where a longitudinal section of the general principle of an embodiment using two spectroscopic or photometric techniques is depicted.
    The drawing shows the probe housing (9) mounted in the volume (10) containing the product, with the probe tip and viewing window (1) mounted flush with the inner wall of the container and the probe sealed against the volume by means of a gasket (12) which may be specific to each application.
    The probe in this embodiment has two connections for connecting spectroscopic or photometric techniques (13a and 13b). Each technique has its radiation source that introduces the generated radiation into the probe via one of the radiation guides (5 and 5'). Depending on the chosen spectroscopic or photometric technique, the source radiation will have to be convergent, divergent or collimated using lenses (3) to get the correct radiation diameter on the product. This will result in a radiation having a certain depth of focus in the product as represented by 7 or collimated in the product as in figure 8. To generate this converging, diverging or collimating radiation in other embodiments such as the probes in FIG 3 and FIG. 4 other types of lenses will have to be used. Nearly all commercially available spectroscopic or photometric systems have their own radiation source that was not designed to be used in combination with other spectroscopic or photometric techniques and may require the installation of additional filters (4) to separate portions of the radiation from one method. blocks that could negatively affect the other method without compromising the operation of the original method. In the embodiment shown here, these filters are located after the lenses, but there is no reason why the filters could not be mounted in front of them or even between the radiation source and the radiation guide. The filter could also be part of or mounted on the lens.
    For example, in a probe where NIR (near infrared) and Raman spectroscopy are combined, a cut-off filter can be installed in the NIR light source, which are known to produce a very broad spectrum of radiation, to block light that would interfere with the Raman spectrometer ( wavelengths shorter than about 1000 nm) to prevent the signal from reaching the detector of the Raman instrument via internal and external reflections.
    The radiation from the radiation sources interacts with the product to be analyzed and the return signal is sent by means of lenses (3) to the radiation guides (6 and 6') towards the analysis instruments. These lenses are specifically designed to send as much signal as possible to the individual conductors. The return signal may still be partially detrimental to the accuracy of some connected techniques, so it may be beneficial to install an additional filter in the return signal path, either in the probe, before or after the lens, or outside the probe, just for the analysis tool.
    Some spectroscopic or photometric techniques are very sensitive to product adhesion to the viewing window. If this happens, the quality of the analysis will be negatively affected. It has been shown in the literature that heating the viewing window can offer a solution by preventing adhesion for certain products. The probe may be provided with an internal electrical heating foil (1) as shown in FIG.1.
    A slightly modified form of the embodiment described above where the radiation guides at the end of the probe terminate in connectors is depicted in FIG. The use of the connectors can facilitate placement of the probe in hard-to-reach locations. Also, in case of damage to the conductors or the probe, a repair can be carried out more easily and cheaper.
    Example 2: Detailed Description of a Preferred Embodiment for a Combined NIR Raman Probe.
    Figure 5 shows a cross-section of a preferred embodiment of a combined NIR Raman probe: the NIR light source is fitted with a cut-off filter (both not visible in the drawing) and the radiation from the light source is directed to the surface by means of an optical beam. brought sin. The optical bundle enters through the top of the probe and the individual fibers of the bundle (2) terminate in a geometric annular configuration above the parabolic concentrator (3). This concentrator minimizes losses and internal reflections while focusing the light through the viewing window (1) in the product. The Raman Laser radiation source is introduced into the probe via an optical radiation guide (4) where the radiation is subsequently converted into a collimated beam of desired diameter via an integrated lens system (5). The collimated laser beam is then introduced via a combination of mirror (6) and dichroic mirror (7) into the space created by the expansion of the fibers of the NIR part and directed towards the product via the viewing window (1). Both radiations interact with the product and part of the resulting signal re-enters the probe through the same viewing window (1). The dichroic mirror (7) prevents internally reflected laser light from reaching the radiation guides (9 and 10) towards the analysis devices, while a lens (8) located behind the mirror focuses the signal on the radiation guide (9) towards the NIR analysis device . After this lens, a second dichroic mirror (7) splits off a part of the signal destined for the Raman analyzer and sends it via a second mirror (6') through an additional filter (11), in order to eliminate the last possible causes of stray light, in the radiation guide (10) to the Raman analyzer. Figure 6 shows additional detail of another embodiment of the NIR Raman probe of FIG. 5 both techniques have an individual viewing window in the tip of the probe.
    Example 3: Improved models by using NIR and Raman simultaneously. In order to clarify the advantages that the invention can offer in building spectroscopic models, an example is given on the basis of a possible application of a NIR Raman probe, which can in no way be regarded as limiting the application possibilities of the probe.
    In NIR spectroscopy it is generally assumed that for powdered product in pharmaceutical industry information is obtained from product to a depth of 0.5 to 1 mm. According to the same literature, the laser beam of the Raman spectroscopy generates a response that can be detected far beyond imm depth. This last signal will therefore suffer much less from adhesion of product on the viewing window of the probe in the product space. Although when applying models in NIR spectroscopy, a quality parameter is usually used on data to evaluate the quality of each spectrum taken for representativeness with respect to the population used to build the model, when adhering part of the product mixture, this method will unable to distinguish at the viewing window between the spectrum obtained and a spectrum richer in the component of the mixture that has adhered to the viewing window. By adding a Raman component to the model, the NIR part will show a shift in case of adhesion while the Raman part remains much more stable and in this way a warning can be given to the user that there is adhesion on the viewport.
    It should be understood that the present invention can in no way be limited to any embodiment described above and that modifications can be added to the embodiments without changing the claims. For example, the above-described version of NIR Raman probe that was used to explain the invention can be easily performed with two or more other techniques such as the combination LIF and NIR, a combination LIF, NIR and photometric, or any other combination of spectroscopic or photometric techniques.
    It is also clear that the method set forth in the example is not limiting to the application of the method of the invention. The present invention is in no way limited to the embodiments as described in the examples and/or shown in the figures. The method as described in the invention can be extended in various ways without this being considered an extension of the scope of the invention.
    权利要求:
    Claims (13)
    [1]
    1. A probe, which permits simultaneous application of two spectroscopic or photometric techniques, comprising at least one radiation source, at least one analysis instrument, a viewing window placed in the path of radiation, and a mechanical optical assembly to detect the different radiations from different radiation sources through the path to the product and the resulting signal back to the analysis instruments while eliminating interference between the different techniques, the probe further comprising at least one lens, a first and a second source radiation guide, a central radiation guide, at least one mirror, an expanded radiation guide, a parabolic concentrator and at least one filter, wherein monochromatic source radiation is transformed into a collimated beam by means of the lenses on the end of the first source radiation guide within the probe; and then introduced into the central radiation guide by means of mirrors selected so as to reflect only the monochromatic wavelength of the radiation source but to be otherwise transparent; the central radiation guide bounded by a cylinder formed by the expanded radiation guide of the second radiation source before this cylinder terminates in an annular configuration; the radiation from the second radiation source, which, once it comes out of the annular end configuration, is brought into focus by means of the parabolic concentrator through the viewing window at a point inside the product, i.e. beyond the viewing window, where the radiation from the first radiation source is directed so that both radiations interact with the same volume of product; the return resulting signal from the product passes through the same central radiation guide and through the mirror reflecting only the monochromatic radiation of the first light source; the return signal which, after this mirror, is split by filters and lenses into parts desired for each connected technology, stripped of further negative influences and focused in the radiation conductors that go to the analysis instruments of the specific connected technologies, characterized in that the probe has a device in the tip so that the temperature of the mechanical housing and the viewing window can be controlled by heating or cooling it, preferably this device is electrically controlled and includes a temperature sensor for more precise regulation to make.
    [2]
    The probe as set forth in claim 1, wherein the central optical channel is split into a channel by spectroscopic or photometric technique.
    [3]
    The probe as described in claim 2, wherein the probe has at least two viewing windows, each viewing window preferably being made to be transparent to the particular spectroscopic or photometric technique for which it is used.
    [4]
    The probe as set forth in any one of claims 1 to 3, wherein some or all of the filters from the probe have been moved to the radiation sources or analysis instruments.
    [5]
    The probe as set forth in any one of claims 1-4, wherein one or more radiation sources are integrated into the probe itself.
    [6]
    The probe as described in any one of the preceding claims 1-5, wherein a mechanical or optical system is integrated that can be used to nullify or calibrate the attached spectroscopic or photometric technique.
    [7]
    A method of using the probe according to any one of claims 1 to 6 in a mixer, vessel, dispenser or the like comprising: 1) a first step considering the best spectroscopic or photometric technique is to analyze the product; 2) an analysis of the device or vessel in which the probe is to be installed in order to find the best place where the process is least disturbed and the product can be measured most representatively; 3) the adaptation of the vessel or device and the probe to mount the latter smoothly on the inside or slightly protruding without hindering the movement of the product in the device and also preventing product from reaching the viewing window of the probe linger; 4) the creation of spectroscopic or photometric models as one trained in the art would do except that the two or more models are combined in at least one meta-model.
    [8]
    The method as set forth in claim 7 to analyze a chemical, biological or biochemical composition, preferably in the form of a pure or mixed powder, bulk or granulated material, slurry, paste or the like in a batch or continuous blender, tablet machine, product transport channel or reactor.
    [9]
    The method as set forth in claim 7 or 8, wherein the data from the analysis tools is sent to a machine learning system before one trained in the art would normally analyze them.
    [10]
    The method as claimed in claim 7, 8 or 9, wherein the end result is used to perform a feed-forward process control and thus alter parameters of a process step further in the production process than where the probe is used to maintain the quality of the end product at a constant level.
    [11]
    The method as set forth in claims 7-9, wherein the end result is used to perform a feed-back process control and thus alter parameters of a process step prior to the production process than where the probe is used to improve the quality of keep the end product at a constant level.
    [12]
    The method as set forth in any one of claims 7-9, wherein the final result is used to perform feed-back process control and thus modify parameters of a process step prior to the production process than where the probe is used to keep the quality of the end product at a constant level and perform a feed-forward process control and thus change parameters of a process step further in the production process than where the probe is used to keep the quality of the end product at a constant level to keep.
    [13]
    The use of a probe of claims 1-6 according to a method as set forth in claims 7-13 for the analysis of the concentration in relative or absolute form of one or more active pharmaceutical ingredients or other components in a pharmaceutical production or transport process.
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    同族专利:
    公开号 | 公开日
    EP3748337A1|2020-12-09|
    BE1027312A1|2020-12-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5044755A|1989-03-03|1991-09-03|Lt Industries|Probe for transmitting and receiving light from a sample|
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    US20150377787A1|2013-02-14|2015-12-31|British Columbia Cancer Agency Branch|Integrated spectral probe for raman, reflectance and fluorescence spectral measurements|
    US20160299060A1|2015-04-10|2016-10-13|Blaze Metrics, LLC|System and method for simultaneously performing multiple optical analyses of liquids and particles in a fluid|
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    US6873409B1|1998-11-17|2005-03-29|Kaiser Optical Systems|Optical probe with sampling window cleaning configuration|
    DE202005011177U1|2005-07-15|2006-11-23|J & M Analytische Mess- Und Regeltechnik Gmbh|Device for analysis, in particular photometric or spectrophotometric analysis|
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    CN104081189B|2012-01-25|2017-04-19|拜耳股份公司|Reflection probe|
    法律状态:
    2021-08-11| FG| Patent granted|Effective date: 20210713 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP19178822.3A|EP3748337A1|2019-06-06|2019-06-06|Probe for simultaneous analysis using different spectroscopic techniques, and corresponding method|
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