JPH07306137A - Near-infrared spectrochemical analyzer - Google Patents

Abstract

PURPOSE:To analyze such a substance that interacts with light in a specific wavelength region by providing a probe which makes light from a light source guided through multiple fluoride optical fibers to interact with an object to be analyzed and another multiple optical fibers which guide the interacted light to the photodetector of a near-infrared spectrochemical analyzer. CONSTITUTION:A transmissive cell type probe 4 is connected to the front end of a fluoride optical fiber bundle (light-source light guiding bundle) 2 for guiding light from a light source so that the light emitted from the light-source light guiding bundle 2 can be coupled with another fluoride optical fiber bundle (detecting light guiding bundle) 3. A liquid sample 5 is subjected to near-infrared analysis by putting the sample 5 in the probe 4 and measuring the near-infrared absorption spectrum produced by the sample 5. When the fluoride optical fiber bundles 2 and 3 are used, all of the spectral information of a specific wavelength region from 800nm to 2,500nm can be utilized, because even the spectral information of a wavelength region from 2,000nm to 2,500nm can be utilized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near infrared spectroscopic analyzer.

[0002]

2. Description of the Related Art As a near-infrared spectroscopic analyzer, there is an analyzer equipped with a multi-core or single-core silica glass optical fiber as an optical waveguide.

[0003]

The wavelength range used in this type of near infrared spectroscopy is 800 nm to 2500 nm.
Is. 2000 nm to 250 in this wavelength range
The wavelength region of 0 nm contains very useful spectral information in spectroscopic analysis. That is, in this wavelength region, for example, absorption by carbon double bonds, absorption by proteins / starches / oils and fats, absorption by hydroxyl ions and the like exist. Therefore, the realization of a near-infrared spectroscopic analyzer that makes use of this spectral information is to realize food industry, agriculture, chemical industry, petrochemical industry, fermentation industry, polymer chemistry industry, textile industry, pharmaceutical industry, medical treatment, and biometrics. -It will make a great contribution to a wide range of industries such as environmental measurement. But,
In the quartz glass optical fiber used as an optical waveguide in the conventional technique, the wavelength range from 2000 nm to 2500 nm is a region where the light transmission deteriorates as shown in FIG. Especially when the fiber length is 100 m or more, 2100
There is a problem that light is not transmitted in the wavelength range of nm or more. Therefore, the effective transmission wavelength range is from 800 nm to 200
Since it is 0 nm, it is difficult to use the spectrum information from 2000 nm to 2500 nm with low accuracy in the near infrared spectroscopic analyzer using the conventional silica glass fiber.

The object of the present invention was made in view of this drawback of the conventional near-infrared spectroscopic analyzer using a quartz fiber, and it is difficult to use the conventional device from 800 nm to 2500 n.
It is to provide a near-infrared spectroscopic analyzer that effectively analyzes a substance having absorption / scattering characteristics in this wavelength range, that is, a substance that interacts with light in this wavelength range, using all the spectral information of m. .

[0005]

To achieve this object, a near-infrared spectroscopic analyzer according to the present invention guides a near-infrared spectroscopic analyzer and light source light of the near-infrared spectroscopic analyzer. A multi-core or single-core fluoride glass optical fiber, a probe having a function of interacting a light source light guided using the fluoride glass optical fiber with an analyte, and a light after interaction with the probe. And a multi-core or single-core fluoride glass optical fiber that guides light to a photodetector of a near-infrared spectrophotometer. If necessary, a configuration in which the light source optical waveguide fiber and the detector fiber are combined may be used.

[0006]

As shown in the transmission characteristics shown by the solid line in FIG. 6, in contrast to the case of the quartz fiber shown by the dotted line, the fluoride glass fiber does not deteriorate above 2000 nm. Therefore, by adopting the above-mentioned configuration, 800n
It is possible to provide a near-infrared spectroscopic analyzer that can effectively use all spectral information in the wavelength range of m to 2500 nm. Furthermore, the fact that this transmission characteristic is excellent means that
It is equivalent to being able to guide light to a longer distance. That is, the optical waveguide length of the near-infrared spectroscopic analyzer can be made longer than that of the conventional method using a silica glass optical fiber, which brings about an effect that the use as a remote analyzer is advantageous. .

[0007]

EXAMPLE An example of the near infrared spectroscopic analyzer according to the present invention will be described below.

[0008]

EXAMPLE 1 FIG. 1 shows an example of a near-infrared spectroscopic analyzer according to the present invention equipped with a multi-core fluoride glass optical fiber (hereinafter referred to as a fluoride glass optical fiber bundle) as an optical waveguide. . As shown in FIG. 1, the present apparatus comprises a near infrared spectrophotometer 1 and a fluoride glass optical fiber bundle 2.
3 and a transmission cell type probe 4 were used. A 10 m long light source optical waveguide fluoride glass optical fiber bundle (hereinafter referred to as a light source optical waveguide bundle) 2 for guiding the light source light of the near infrared spectrometer 1 and a near infrared spectroscopy A 10 m long detection optical waveguide fluoride glass optical fiber bundle (hereinafter referred to as a detection optical waveguide bundle) 3 for returning light to the photodetector of the analyzer 1 was used. The fluoride glass optical fiber forming the bundle has a three-layered concentric structure consisting of a core layer having a diameter of 110 μm, a cladding layer having a thickness of 20 μm surrounding the core layer, and an ultraviolet curable resin coating layer having a thickness of 10 μm surrounding the core layer. The fiber has a configured outer diameter of 170 μm, and the core / clad is expressed in mol percentage,
_{a% ZrF 4 -b% HfF 4} -c% BaF 4 -d% La
F ₄ −e% AlF ₄ −f% NaF ₄ (a + b + c + d +
e + f = 100: 0: ≦ a, b, c, d, e, f ≦ 10
0) type fluoride glass was used. The number of fluoride glass fibers forming the bundle is 20 each.
It was set to 0.

A transmission cell type probe 4 was connected to the tip of the light source optical waveguide bundle 2. The transmission cell type probe 4 is
Light emitted from the light source optical waveguide bundle 2 was effectively coupled to the detection light bundle 3 by attaching an appropriate optical system. The near-infrared spectroscopic analysis was performed by putting the liquid sample 5 in this probe 4 and measuring the near-infrared absorption spectrum. By using a fluoride glass fiber bundle for the optical waveguide, this device also has a wavelength of 800 nm to 25 nm.
This brings about the effect that all spectral information in the wavelength range of 00 nm can be effectively used.

[0010]

[Embodiment 2] FIG. 2 shows another example of a near-infrared spectroscopic analyzer equipped with a single-core fluoride glass optical fiber as an optical waveguide. As shown in FIG. 2, the present apparatus comprises a near-infrared spectroscopic analyzer 1, a single-core fluoride glass optical fiber and a transmission cell type probe 4 which are connected to a pipeline 9 in a tubular form to connect a fluid flowing in the pipe. A so-called permeation flow cell type probe 8 which was made possible to analyze was used. Guide the light from the light source of the near infrared spectrometer 1 through the single-core fluoride glass optical fiber 10
The light source optical waveguide single-core fiber 6 having a length of 0 m and the detection optical waveguide bundle 7 having a length of 100 m for returning light to the photodetector of the near-infrared spectroscopic analyzer 1 were used. The fluoride glass fiber was the same as in Example 1 except that the core diameter was 0.6 mm, the clad layer thickness was 50 μm, and the ultraviolet curable resin layer thickness was 50 μm.

A transmission flow cell type probe 8 was connected to the tip of the light source optical waveguide single core fiber 6. The transmission flow cell probe 8 has an appropriate optical system attached thereto, and the light emitted from the light source optical waveguide single core fiber 6 is effectively coupled to the detection optical waveguide single core fiber 7. By connecting the transmission flow cell type probe 8 to the pipeline 9, measuring the near-infrared absorption spectrum of the liquid sample body flowing through the pipeline 9 and performing near-infrared spectroscopic analysis, in-line analysis target in the liquid is obtained. I was able to monitor at 9. Also in this device,
By using the fluoride glass fiber bundle for the optical waveguide, it was possible to bring about the effect that all spectral information in the wavelength range of 800 nm to 2500 nm can be effectively used.

[0012]

[Embodiment 3] FIG. 3 shows still another example of a near-infrared spectroscopic analyzer equipped with a fluoride glass optical fiber bundle as an optical waveguide. As shown in FIG. 3, the near-infrared spectroscopic analyzer 1, the fluoride glass optical fiber bundles 2 and 3, and the reflection type probe 14 were used. 1m that guides the light source light of the near infrared spectrometer 1 through the fluoride glass optical fiber bundle
The light source optical waveguide bundle 2 having a long length, the detection optical waveguide bundle 3 having a length of 1 m for returning light to the photodetector of the near-infrared spectrophotometer, and the combined bundle 13 having a length of 9 m in which both bundles are combined. The same fluoride glass fiber as in Example 1 was used.

As shown in the sectional view of FIG. 4, the structure of the united bundle 13 has a coaxial type (a) centered on the light source optical waveguide bundle, a coaxial type (b) centered on the detection optical waveguide bundle, and a random arrangement type (c). ), Or any other than those shown here may be selected according to the purpose and use. In this embodiment, the random arrangement type is adopted. In FIG. 4, black circles represent fibers of the light source waveguide bundle, and white circles represent fibers of the cable optical waveguide bundle. Coalesced bundle 1
A reflection type probe 14 was connected to the tip of 3. The probe 14 was inserted into the powdery solid sample body 15, the near infrared reflection spectrum was measured using the diffuse reflection light from the sample, and the near infrared spectroscopic analysis was performed. Also in this apparatus, the use of the fluoride glass fiber bundle for the optical waveguide brings about the effect that all spectral information in the wavelength range of 800 to 2500 nm can be effectively used.

In the first to third embodiments, the near-infrared spectroscopic analyzer equipped with a multi-core or single-core fluoride glass fiber as an optical waveguide has been described. In each of the embodiments, a multi-core or single-core fluoride fiber is used. Even if each of the fluoride glass fibers is replaced with a single-core or multi-core fluoride glass fiber, the same effect as in the embodiment can be obtained. Further, although examples of the transmission cell type probe, the transmission flow cell type probe, and the reflection type probe have been given as the sample portion, the same action as that of the embodiment can be brought about for other probes.

The core-clad composition of the fluoride glass fiber constituting the fluoride glass bundle is expressed as mol% in terms of a% ZrF ₄ -b% HfF ₄ -c% Ba.
_{F 4 -d% LaF 4 -e%} AlF 4 -f% NaF 4 (a
+ B + c + d + e + f = 100: 0: a, b, c, d,
e, f ≦ 100) system was used, but other fluoride glass systems such as a% AlF ₃ -b% ZrF ₃ -c% Y.
_{F 3 -d% MgF 2 -e%} CaF 2 -f% SrF 2 -g
% BaF ₂ -h% NaF (a + b + c + d + e + f + g
+ H = 100: 0 ≦ a, b, c, d, e, f, g, h ≦
_{100), a% InF 3 -b} % ZnF 2 -c% SrF 2
_{-D% BaF 2 -e% CdF 2} , a% InF 3 -b% Z
_{nF 2 -c% SrF 2 -d%} BaF 2 -e% PbF 2,
_{a% InF 3 -b% ZnF 2} -c% SrF 2 -d% Ba
_{F 2 -e% CaF 2, a} % InF 3 -b% ZnF 2 -c
_{% SrF 2 -d% BaF 2 -e} % NaF (a + b + c +
The same action as that of the present embodiment can be produced for d + e = 100: 0: a ≦ b, c, d, e ≦ 100).
Furthermore, the core diameter, the clad layer thickness, the coating layer thickness, and the number of fibers in the bundle of the fluoride glass fiber described in the above examples are not limited to these examples.

[0016]

INDUSTRIAL APPLICABILITY The near-infrared spectroscopic analyzer according to the present invention has a multi-core or single-core fluoride glass optical fiber as an optical waveguide, and therefore is used in a conventional near-infrared spectroscope using a quartz fiber. I couldn't do 2000 to 2500
Since the spectral information in the wavelength region of nm can be used, it becomes possible to analyze the sample body, which was difficult to analyze by the conventional device. Further, the near-infrared spectroscopic analyzer according to the present invention,
Since all the near-infrared spectrum information from 800 nm to 2500 nm can be effectively used, there is a peculiar effect that it becomes possible to analyze a sample body that can be analyzed by a conventional apparatus with higher accuracy.

Further, since the fluoride glass fiber has better transmission characteristics than the quartz fiber, it has a unique effect that the waveguide distance can be increased and the distance between the probe and the near-infrared spectrophotometer can be increased. This produces a great safety and health advantage when the substance to be analyzed is a dangerous substance such as an irritant, a poison, an inflammable substance, an explosive substance, or a radioactive substance. As described above, the near-infrared spectroscopic analyzer according to the present invention is used in the food industry, agriculture, chemical industry, petrochemical industry,
It will make a great contribution to a wide range of industries such as fermentation industry, polymer chemistry industry, textile industry, pharmaceutical industry, medical treatment, biometrics, and environmental measurement.

[Brief description of drawings]

FIG. 1 is a system diagram showing an embodiment of a near-infrared spectroscopic analyzer of the present invention equipped with a transmission cell type probe and a fluoride glass optical fiber bundle.

FIG. 2 is a connection system diagram showing an embodiment of a near-infrared spectroscopic analyzer of the present invention equipped with a transmission flow cell type probe and a single-core fluoride glass fiber.

FIG. 3 is a connection system diagram showing an embodiment of the near-infrared spectroscopic analyzer of the present invention equipped with a reflection type probe and a fluoride glass optical fiber bundle.

FIG. 4 is a cross-sectional view showing a specific example of a fluoride glass optical fiber bundle used for the probe tip portion in the device of the present invention.

FIG. 5 is a transmission characteristic diagram of a quartz fiber.

FIG. 6 is a transmission characteristic diagram of a fluoride glass optical fiber.

[Explanation of symbols]

 1 near infrared spectrophotometer 2 light source optical waveguide fluoride glass optical fiber bundle 3 detection optical waveguide fluoride glass optical fiber bundle 4 transmission cell type probe 5 liquid sample 6 light source optical waveguide single core fiber 7 detection optical waveguide single core fiber 8 Transmission flow cell type probe 9 Pipeline 10 Analysis / control room 11 Central controller 12 Combined part 13 Combined bundle 14 Reflective probe 15 Powder solid sample

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Shinbori 2-32 Nishishinjuku, Shinjuku-ku, Tokyo International Telegraph and Telephone Corporation

Claims (1)

[Claims] 1. A near-infrared spectroscopic analyzer, a multi-core or single-core fluoride glass optical fiber for guiding the light source light of the near-infrared spectrophotometer, and a guide using the fluoride glass optical fiber. A probe having a function of interacting an oscillated light source light with an analyte, and a multi-core or single-core fluoride glass for guiding the interacted light to a photodetector of the near-infrared spectrometer A near-infrared spectroscopic analyzer characterized by comprising an optical fiber.