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CN106872226A - By making the method that the imitative body of solid is corrected to agricultural product optical characteristics detection means by oneself - Google Patents

By making the method that the imitative body of solid is corrected to agricultural product optical characteristics detection means by oneself Download PDF

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CN106872226A
CN106872226A CN201710005065.9A CN201710005065A CN106872226A CN 106872226 A CN106872226 A CN 106872226A CN 201710005065 A CN201710005065 A CN 201710005065A CN 106872226 A CN106872226 A CN 106872226A
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solid
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imitative body
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CN106872226B (en
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饶秀勤
何学明
傅霞萍
李庭苇
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Zhejiang University ZJU
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/314Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N2001/2893Preparing calibration standards
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/314Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
    • G01N2021/3155Measuring in two spectral ranges, e.g. UV and visible

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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

The invention discloses a kind of by making the method that the imitative body of solid is corrected to agricultural product optical characteristics detection means by oneself.Make the imitative body of the solid with different optical property parameters, and the reference value of its optical property parameter is obtained according to standard method and theoretical formula method, detected under visible near-infrared wave band by agricultural product optical property parameter detection means, obtain the measured value of the optical property parameter under different wave length, measured value relation corresponding with reference value according to imitative optical property parameter of the body under each wavelength of different solids is fitted acquisition fitting parameter, after actual sample is measured by agricultural product optical property parameter detection means, the measured value of the optical property parameter obtained to measurement with fitting parameter is modified.Die module low cost of the invention, the making solid imitative body time is short, and the imitative body of fixed solid of making can be preserved for a long time, complete the correction to detection means, improve the accuracy of detection of agricultural product optical characteristics.

Description

通过自制固体仿体对农产品光学特性检测装置校正的方法Method for calibrating the optical characteristic detection device of agricultural products by self-made solid phantom

技术领域technical field

本发明涉及一种装置的校正方法,尤其是涉及了一种通过自制固体仿体对农产品光学特性检测装置校正的方法。The invention relates to a method for calibrating a device, in particular to a method for calibrating an optical characteristic detection device of agricultural products by self-made solid phantom.

背景技术Background technique

生物组织光学特性的检测技术在食品和农产品品质检测中得到了广泛的研究和应用。自从Norris在1964年将近红外光谱技术用于农产品检测中,大多数传统近红外光谱技术研究都是将该技术用于农产品化学成分的无损检测。The detection technology of the optical properties of biological tissue has been widely studied and applied in the quality detection of food and agricultural products. Since Norris used near-infrared spectroscopy in the detection of agricultural products in 1964, most of the traditional research on near-infrared spectroscopy has focused on the non-destructive testing of chemical components in agricultural products.

然而,光在生物组织的传播与衰减主要存在两种形式:吸收与散射,可以用吸收系数与约化散射系数来表征。可见-近红外波段下的吸收系数与农产品中的一些重要的化学成分(如:SSC)相关,而散射通常与其微观物理结构相关。所以对于农产品品质检测,测量这两种参数有很大意义。However, there are two main forms of light propagation and attenuation in biological tissues: absorption and scattering, which can be characterized by the absorption coefficient and the reduced scattering coefficient. The absorption coefficient in the visible-near-infrared band is related to some important chemical components (such as: SSC) in agricultural products, and the scattering is usually related to its microscopic physical structure. Therefore, for the quality inspection of agricultural products, it is of great significance to measure these two parameters.

在农产品检测领域,有一些已有研究:时间分辨反射光谱法;空间分辨光谱法;基于高光谱的空间分辨法;空间频域成像法以及积分球法。在这些方法用于实际检测之前,需要使用标准物质对这些光谱或图像装置与仪器以及相应的算法进行校正与精度验证。这些标准物质被称为固体仿体。固体仿体的光学特性参数应包含农产品光学特性参数的范围,这样可以实现对不同检测系统较大光学特性参数范围内的校正。In the field of agricultural product detection, there are some existing researches: time-resolved reflectance spectroscopy; spatially resolved spectroscopy; spatially resolved method based on hyperspectral; spatial frequency domain imaging method and integrating sphere method. Before these methods are used in actual detection, it is necessary to use standard substances to calibrate and verify the accuracy of these spectral or imaging devices and instruments as well as the corresponding algorithms. These reference materials are called solid analogues. The optical characteristic parameters of the solid phantom should include the range of the optical characteristic parameters of agricultural products, so that the correction of the larger optical characteristic parameters of different detection systems can be realized.

目前已有研究中的固体仿体有固体与液体两类,但是固体仿体能够长期保存且可以制作成不同形状,更能够满足农产品检测的实际情况。目前对于农产品的固体仿体制作在国内还属空白,国外有商品化的固体仿体但是成本较高。由于不同的农产品光学特性参数检测装置需要大量的,且形状大小不同的固体仿体,所以需要开发出一套低成本且制作简单的固体仿体制作方法,以及相应的校正方法。At present, there are two types of solid phantoms in research: solid and liquid, but solid phantoms can be stored for a long time and can be made into different shapes, which can better meet the actual situation of agricultural product testing. At present, the production of solid phantoms for agricultural products is still blank in China, and there are commercial solid phantoms abroad, but the cost is relatively high. Since different agricultural product optical characteristic parameter detection devices require a large number of solid phantoms of different shapes and sizes, it is necessary to develop a set of low-cost and easy-to-manufacture solid phantom manufacturing methods and corresponding calibration methods.

发明内容Contents of the invention

为了解决背景技术中存在的问题,本发明的目的在于提供一种通过自制固体仿体对农产品光学特性检测装置校正的方法。In order to solve the problems in the background technology, the object of the present invention is to provide a method for calibrating the optical characteristic detection device of agricultural products by self-made solid phantom.

本发明的技术方案如下步骤:Technical scheme of the present invention has the following steps:

1)制作具有不同光学特性参数的固体仿体,并根据标准方法与理论公式计算获得其光学特性参数的参考值;1) Make solid phantoms with different optical characteristic parameters, and calculate the reference values of their optical characteristic parameters according to standard methods and theoretical formulas;

2)针对步骤1)中制作成的固体仿体,通过农产品光学特性参数检测装置在可见-近红外波段下进行检测,获得不同波长下的光学特性参数(吸收系数和约化散射系数)的测量值;2) For the solid phantom made in step 1), the optical characteristic parameter detection device of agricultural products is used for detection in the visible-near-infrared band, and the measured values of optical characteristic parameters (absorption coefficient and reduced scattering coefficient) at different wavelengths are obtained ;

3)根据不同固体仿体在各波长下的光学特性参数的测量值与参考值一一对应的关系进行拟合获得拟合参数;3) According to the one-to-one correspondence relationship between the measured values of the optical characteristic parameters of different solid phantoms at each wavelength and the reference value, the fitting parameters are obtained by fitting;

4)在通过农产品光学特性参数检测装置测量实际样品后,通过步骤3)获得的拟合参数对测量获得的光学特性参数的测量值进行修正。4) After the actual sample is measured by the agricultural product optical characteristic parameter detection device, the measured value of the optical characteristic parameter obtained by the measurement is corrected by the fitting parameters obtained in step 3).

所述的光学特性参数是包括吸收系数与约化散射系数。The optical characteristic parameters include absorption coefficient and reduced scattering coefficient.

所述的步骤3)和步骤4)具体是:Described step 3) and step 4) specifically are:

先制作用于校正检测装置吸收系数的n个约化散射系数相同且吸收系数不同的固体仿体,同时制作用于校正检测装置约化散射系数的m个吸收系数相同且约化散射系数不同的固体仿体;First make n solid phantoms with the same reduced scattering coefficient and different absorption coefficients for correcting the absorption coefficient of the detection device, and at the same time make m solid bodies with the same absorption coefficient and different reduced scattering coefficients for correcting the reduced scattering coefficient of the detection device Mimic body;

然后根据不同固体仿体在同一波长下的吸收系数与约化散射系数的测量值与参考值采用以下公式进行计算获得n个固体仿体吸收系数的参考值与测量值比值的均值k(μa)λ和m个固体仿体约化散射系数的参考值与测量值比值的均值k(μ’s)λ作为拟合参数:Then, according to the measured values and reference values of absorption coefficients and reduced scattering coefficients of different solid phantoms at the same wavelength, the following formula is used to calculate the average value k(μ a ) λ and the average value k(μ' s ) λ of the ratio of the reference value and the measured value of the reduced scattering coefficient of m solid phantoms as the fitting parameter:

其中,λ表示波长,μa(i)ref与μa(i)mea分别代表所有n个固体仿体中第i个固体仿体的吸收系数的参考值与测量值,μ’s(j)ref与μ’s(j)mea分别代表所有m个固体仿体中j个固体仿体的约化散射系数的参考值与测量值;Among them, λ represents the wavelength, μ a (i) ref and μ a (i) mea respectively represent the reference value and measurement value of the absorption coefficient of the i-th solid phantom in all n solid phantoms, μ' s (j) ref and μ' s (j) mea respectively represent the reference value and measured value of the reduced scattering coefficient of j solid phantoms among all m solid phantoms;

最后对于该波长下,通过农产品光学特性参数检测装置测量实际样品获得的吸收系数和约化散射系数采用以下公式进行线性修正,即将检测装置测得的吸收系数和约化散射系数分别乘以各自的拟合参数k(μa)λ与k(μ’s)λFinally, for this wavelength, the absorption coefficient and reduced scattering coefficient obtained by measuring the actual sample through the optical characteristic parameter detection device of agricultural products are linearly corrected by the following formula, that is, the absorption coefficient and reduced scattering coefficient measured by the detection device are respectively multiplied by their fitting Parameters k(μ a ) λ and k(μ' s ) λ :

μa(i)calibrated=k(μa)λa(i)mea μ a (i) calibrated = k(μ a ) λ * μ a (i) mea

μ's(j)calibrated=k(μ's)λ*μ's(j)mea μ' s (j) calibrated = k(μ' s ) λ *μ' s (j) mea

其中,μa(i)calibrated与μa(i)mea分别代表所有n个固体仿体中第i个固体仿体的吸收系数的校正后值与测量值,μ’s(j)ref与μ’s(j)mea分别代表所有m个固体仿体中第j个固体仿体的约化散射系数的校正后值与测量值。Among them, μ a (i) calibrated and μ a (i) mea respectively represent the corrected value and measured value of the absorption coefficient of the i-th solid phantom among all n solid phantoms, μ' s (j) ref and μ ' s (j) mea represents the corrected value and the measured value of the reduced scattering coefficient of the jth solid phantom among all m solid phantoms, respectively.

所述的固体仿体的制作是以印度墨水(India Ink)作为吸收子、以二氧化钛(TiO2)作为散射子、以聚氨酯AB料作为基底材料使用不同模具制作形成不同形状的的固体仿体。The solid phantom is made by using India Ink as an absorber, titanium dioxide (TiO 2 ) as a scatterer, and polyurethane AB material as a base material, using different molds to form solid phantoms of different shapes.

所述的固体仿体的制作具体步骤为:The concrete steps of making described solid analog body are:

1.1)根据农产品光学特性参数值的吸收系数与约化散射系数值的范围和所需制作的固体仿体的大小,确定固体仿体中印度墨水、二氧化钛和聚氨酯AB料的质量,三者分别为a份、b份、c份;1.1) According to the range of the absorption coefficient and the reduced scattering coefficient value of the optical characteristic parameter value of the agricultural product and the size of the solid phantom to be made, determine the quality of India ink, titanium dioxide and polyurethane AB material in the solid phantom, the three are respectively a part, b part, c part;

1.2)将0.5a份印度墨水混合到0.5c份的聚氨酯A料中得到混合液Ⅰ,将b份TiO2和0.5a份印度墨水一起混合到0.5c份的聚氨酯B料中得到混合液Ⅱ;1.2) Mix 0.5a part of Indian ink into 0.5c part of polyurethane material A to obtain mixed solution I, and mix b part of TiO2 and 0.5a part of Indian ink into 0.5c part of polyurethane material B to obtain mixed solution II;

1.3)将混合液Ⅰ与混合液Ⅱ放到超声波清洗机振荡并使用玻璃棒搅拌,使其均匀混合,得到混合液Ⅲ;1.3) Put the mixed solution I and the mixed solution II in an ultrasonic cleaning machine to vibrate and stir with a glass rod to make them evenly mixed to obtain the mixed solution III;

1.4)将混合液Ⅲ放入真空干燥箱抽真空10-15分钟,每1分钟取出放到超声波清洗机振荡并使用玻璃棒搅拌一次;1.4) Put the mixture III in a vacuum drying oven to vacuum for 10-15 minutes, take it out every 1 minute, put it in an ultrasonic cleaner to vibrate and stir once with a glass rod;

1.5)将抽真空后的混合液Ⅲ注入到模具中,放置常温下待其凝固,获得固体仿体。1.5) Inject the vacuumized mixture III into the mold, and place it at room temperature until it solidifies to obtain a solid analog.

从所述步骤1.3)制成的混合液I中取一部分放入比色皿中,通过使用QUANTUMNORTHWEST公司的温控比色皿支架测其吸光度和比色皿的厚度,根据吸光度和比色皿的厚度通过朗伯比尔定律计算获得吸收系数μa的参考值,通过米氏理论计算获得约化散射系数μ’s的参考值。From the mixed solution I that described step 1.3) is made, get a part and put into cuvette, measure its absorbance and the thickness of cuvette by using the temperature control cuvette support of QUANTUMNORTHWEST company, according to the absorbance and cuvette The reference value of the absorption coefficient μ a is obtained by calculating the thickness through Lambert-Beer's law, and the reference value of the reduced scattering coefficient μ 's is obtained through the calculation of the Mie theory.

所述的比色皿是采用QUANTUM NORTHWEST公司的温控比色皿。Described cuvette is to adopt the temperature control cuvette of QUANTUM NORTHWEST company.

针对不同的平台与方法的校正需求,所述模具包括三种针对不同使用需求的模具,分别是用于制作薄平板型固体仿体的模具、用于制作厚平板型固体仿体的模具和用于制作带半球厚板型固体仿体的模具,模具通过模块化组件搭建而成;模块化组件具体包括底座板、薄中间板、注射器、厚中间板、烧杯和半球板,薄中间板和厚中间板均为中部开有通槽的环形结构,环形结构的侧壁开有用于注入液体的径向通道,底座板为一块平板结构,半球板为一端中心带有凸台的平板结构,半球板非凸台端面中心开有半球形孔。For the correction requirements of different platforms and methods, the mold includes three kinds of molds for different usage requirements, namely, a mold for making a thin flat solid phantom, a mold for making a thick flat solid phantom, and a mold for making a thick flat solid phantom. It is used to make a mold with a hemispherical thick plate solid imitation body. The mold is built by modular components; the modular components include a base plate, a thin middle plate, a syringe, a thick middle plate, a beaker and a hemispherical plate, a thin The middle plate is an annular structure with a through groove in the middle. The side wall of the annular structure is opened with a radial channel for injecting liquid. The base plate is a flat plate structure. The hemispherical plate is a flat plate structure with a boss in the center of one end. A hemispherical hole is opened in the center of the non-boss end face.

所述的用于制作薄平板型固体仿体的模具主要由两块底座板以及两块底座板之间的薄中间板构成,注射器中的混合液通过薄中间板侧壁的径向通道注入。The mold for making a thin flat solid phantom is mainly composed of two base plates and a thin middle plate between the two base plates, and the mixed liquid in the syringe is injected through the radial channel of the side wall of the thin middle plate.

所述的用于制作厚平板型固体仿体的模具主要由一块底座板和置于底座板上的厚中间板构成,烧杯中的混合液倒入厚中间板中间的通槽和底座板形成的容腔中。The mold for making a thick plate-shaped solid body is mainly composed of a base plate and a thick middle plate placed on the base plate. The mixed solution in the beaker is poured into the through groove in the middle of the thick middle plate and the base plate forms In the cavity.

所述的用于制作带半球厚板型固体仿体的模具主要由一块半球板和置于半球板非凸台端面上的厚中间板构成,烧杯中的混合液倒入厚中间板中间的通槽和半球板形成的容腔中。The mold for making a thick plate-shaped solid body with a hemisphere is mainly composed of a hemispherical plate and a thick middle plate placed on the non-bossed end face of the hemispherical plate. In the cavity formed by the groove and the hemispherical plate.

本发明根据不同检测装置的校正需求特别设计并制作上述模具来制作不同形状和尺寸的固体仿体。对于积分球系统,要求测得样本的反射率与透射率,所以样本不能太厚,因此本发明特别地采用薄平板型固体仿体的模具,厚度约为10mm。对于时间分辨光谱系统、空间分辨光谱系统和基于高光谱的空间分辨系统,空间频域成像系统要求样本为半无限介质,因此本发明特别地采用厚平板型固体仿体的模具,厚度约为50mm。另外对于成像系统来说,由于很多农产品并不是平板状,所以设计有带半球形的固体仿体以校正成像系统检测曲面样本的精度,因此本发明特别地采用带半球厚板型固体仿体的模具。According to the correction requirements of different detection devices, the present invention specially designs and manufactures the above-mentioned molds to make solid phantoms of different shapes and sizes. For the integrating sphere system, it is required to measure the reflectance and transmittance of the sample, so the sample should not be too thick. Therefore, the present invention specially adopts a thin plate solid imitation mold with a thickness of about 10mm. For time-resolved spectroscopy systems, spatially resolved spectroscopy systems, and hyperspectral-based spatially resolved systems, the spatial frequency domain imaging system requires the sample to be a semi-infinite medium, so the present invention particularly uses a thick plate-type solid phantom mold with a thickness of about 50mm . In addition, for the imaging system, since many agricultural products are not flat, a solid phantom with a hemispherical shape is designed to correct the accuracy of the imaging system for detecting curved surface samples. mold.

本发明的有益效果是:The beneficial effects of the present invention are:

本发明的模具采用模块化设计,成本低,制作固体仿体时间短,制作的固定固体仿体能够长期保存。The mold of the invention adopts a modular design, has low cost, and takes a short time to manufacture the solid analog body, and the manufactured fixed solid analog body can be preserved for a long time.

本发明能在满足农产品光学特性参数范围前提下,完成对检测装置的校正,提高农产品光学特性的检测精度。The invention can complete the calibration of the detection device under the premise of satisfying the range of the optical characteristic parameters of the agricultural products, and improve the detection accuracy of the optical characteristics of the agricultural products.

附图说明Description of drawings

图1是薄平板型固体仿体的模具结构示意图;Fig. 1 is the mold structure schematic diagram of thin plate type solid imitation body;

图2是厚平板型固体仿体的模具结构示意图;Fig. 2 is the mold structure schematic diagram of thick plate type solid imitation body;

图3是带半球厚板型固体仿体的模具结构示意图;Fig. 3 is the mold structure schematic diagram of band hemispherical thick plate type solid imitation body;

图4是底座板的结构示意图;Fig. 4 is the structural representation of base plate;

图5是半球板主视图;Fig. 5 is a front view of a hemispherical plate;

图6是半球板俯视图;Figure 6 is a top view of the hemispherical plate;

图7是半球板剖面图;Fig. 7 is a sectional view of a hemispherical plate;

图8是薄中间板示意图;Fig. 8 is a schematic diagram of a thin middle plate;

图9是厚中间板示意图。Figure 9 is a schematic diagram of a thick middle plate.

图10是本发明实施例的流程图。Fig. 10 is a flowchart of an embodiment of the present invention.

图中:1、底座板,2、薄中间板,4、注射器,5、厚中间板,6、烧杯,7、半球板。In the figure: 1. Base plate, 2. Thin middle plate, 4. Syringe, 5. Thick middle plate, 6. Beaker, 7. Hemispherical plate.

具体实施方式detailed description

下面结合附图与具体实施例对本发明作进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

本发明的实施例如下,过程如图10所示:Embodiments of the present invention are as follows, and the process is as shown in Figure 10:

1)固体仿体制作:1) Solid body imitation production:

本实施例制作固体仿体选用的材料有:基底材料,吸收物质与散射物质。其中基底材料选用聚氨酯AB料(水清)(WC-781,BJB,USA),吸收物质为印度墨水(Talens,Netherlands),散射物质为二氧化钛(T105415,Aladdin,China),其粒径范围为0.2-0.4um。The materials selected for making the solid phantom in this embodiment include: base material, absorbing material and scattering material. Among them, the base material is polyurethane AB material (water clear) (WC-781, BJB, USA), the absorbing material is Indian ink (Talens, Netherlands), the scattering material is titanium dioxide (T105415, Aladdin, China), and its particle size range is 0.2 -0.4um.

1.1)根据所需测量的样品类型,来确定所需要的光学特性参数范围,再根据光学特性参数范围,来确定所需的TiO2的体积分数与印度墨水的体积分数。这里TiO2的体积分数确定为0.02%,0.03%,0.05%,印度墨水的体积分数为0.04%,0.07%,0.1%。根据TiO2的体积分数,算出所需的TiO2的体积,再根据TiO2的密度为ρTiO2=4g/cm3,算出所需的TiO2的重量。根据印度墨水的体积分数,算出所需印度墨水的体积。1.1) Determine the required range of optical characteristic parameters according to the type of sample to be measured, and then determine the required volume fraction of TiO2 and India ink according to the range of optical characteristic parameters. Here the volume fraction of TiO2 was determined to be 0.02%, 0.03%, 0.05%, and that of India ink was 0.04%, 0.07%, 0.1%. According to the volume fraction of TiO 2 , calculate the required volume of TiO 2 , and then calculate the required weight of TiO 2 according to the density of TiO 2 as ρ TiO2 =4g/cm 3 . According to the volume fraction of India ink, calculate the volume of required India ink.

1.2)根据所校正平台和方法,制作三种不同的固体仿体,模具通过模块化组件搭建而成,模块化组件具体包括底座板1、薄中间板2、注射器4、厚中间板5、烧杯6和半球板7,薄中间板2和厚中间板5均为中部开有通槽的环形结构,环形结构的侧壁开有用于注入液体的径向通道,分别如图8和图9所示;底座板1为一块平板结构如图4所示;半球板7为一端中心带有凸台的平板结构,半球板7非凸台端面中心开有半球形孔,如图5-7所示。其对应的模具为:1.2) According to the calibrated platform and method, three different solid phantoms are made. The mold is built by modular components. The modular components specifically include the base plate 1, the thin middle plate 2, the syringe 4, the thick middle plate 5, and the beaker 6 and the hemispherical plate 7, the thin middle plate 2 and the thick middle plate 5 are all annular structures with a through groove in the middle, and radial channels for injecting liquid are opened on the side walls of the annular structure, as shown in Figure 8 and Figure 9 respectively The base plate 1 is a flat plate structure as shown in Figure 4; the hemispherical plate 7 is a flat plate structure with a boss in the center of one end, and the center of the non-bossed end surface of the hemispherical plate 7 has a hemispherical hole, as shown in Figure 5-7. The corresponding molds are:

(1)10mm厚的薄平板型固体仿体(用于校正积分球系统和IAD方法),对应模具为图1,主要由两块底座板1以及两块底座板1之间的薄中间板2构成,注射器4中的混合液通过薄中间板2侧壁的径向通道注入;(1) 10mm thick thin flat solid phantom (used to correct the integrating sphere system and IAD method), the corresponding mold is shown in Figure 1, mainly composed of two base plates 1 and a thin middle plate 2 between the two base plates 1 Composition, the mixed solution in the syringe 4 is injected through the radial channel of the side wall of the thin middle plate 2;

(2)50mm厚的厚平板型固体仿体(用于校正空间频域成像系统,空间分辨漫反射光谱系统等需要样品为半无限介质的系统),对应的模具为图2,主要由一块底座板1和置于底座板1上的厚中间板5构成,烧杯6中的混合液倒入厚中间板5中间的通槽和底座板1形成的容腔中;(2) 50mm thick thick plate solid phantom (used to correct the spatial frequency domain imaging system, spatial resolution diffuse reflectance spectroscopy system and other systems that require the sample to be a semi-infinite medium), the corresponding mold is shown in Figure 2, mainly composed of a base plate 1 and a thick middle plate 5 placed on the base plate 1, the mixed solution in the beaker 6 is poured into the cavity formed by the through groove in the middle of the thick middle plate 5 and the base plate 1;

(3)50mm厚的带半球厚板型固体仿体(用于轮廓校正),对应的模具为图3,主要由一块半球板7和置于半球板7非凸台端面上的厚中间板5构成,烧杯6中的混合液倒入厚中间板5中间的通槽和半球板7形成的容腔中。(3) 50mm thick hemispherical thick plate type solid imitation body (for contour correction), the corresponding mold is shown in Figure 3, which mainly consists of a hemispherical plate 7 and a thick middle plate 5 placed on the non-bossed end surface of the hemispherical plate 7 The mixed solution in the beaker 6 is poured into the cavity formed by the through groove in the middle of the thick middle plate 5 and the hemispherical plate 7 .

1.3)其中制作第(1)类固体仿体,所需的聚氨酯A料和B料分别为75mL,75mL;系列1:印度墨水含量相同,TiO2含量不同。用电子天平分别称取0.128g,0.192g,0.320g的TiO2放入3份B料中,用移液枪量取52.5uL的的印度墨水分别放入3份A料和上述B料中,分别得到混合液Ⅰ和Ⅱ;系列2:TiO2含量相同,印度墨水含量不同。用电子天平分别称取0.192g的TiO2放入3份B料中,用移液枪分别量取30uL,52.5uL,75uL的印度墨水分别放入3份A料和上述3份B料中,分别得到混合液Ⅰ和Ⅱ。1.3) Among them, to make solid analogs of type (1), the required polyurethane materials A and B are 75mL and 75mL respectively; series 1: the content of Indian ink is the same, but the content of TiO 2 is different. Weigh 0.128g, 0.192g, 0.320g of TiO2 into 3 parts of material B with an electronic balance, and put 52.5uL of Indian ink into 3 parts of material A and the above material B with a pipette gun, respectively. Mixed solutions Ⅰ and Ⅱ were obtained respectively; series 2: same content of TiO 2 , different content of India ink. Use an electronic balance to weigh 0.192g of TiO 2 and put them into 3 parts of material B, and use a pipette gun to measure 30uL, 52.5uL, and 75uL of Indian ink respectively and put them into 3 parts of material A and the above-mentioned 3 parts of material B. Mixtures I and II were obtained respectively.

制作第(2)(3)类固体仿体,所需的聚氨酯A料和B料分别为200mL,200mL;系列1:印度墨水含量相同,TiO2含量不同。用电子天平分别称取0.341g,0.512g,0.853g的TiO2放入3份B料中,用移液枪分别量取140uL的印度墨水分别放入3份A料和上述B料中,分别得到混合液Ⅰ和Ⅱ;系列2:TiO2含量相同,印度墨水含量不同。用电子天平分别称取0.512g的TiO2放入3份B料中,用移液枪分别量取80uL,140uL,200uL的印度墨水分别放入3份A料和上述B料中,分别得到混合液Ⅰ和Ⅱ。To make solid analogs of categories (2) and (3), the required polyurethane materials A and B are 200mL and 200mL respectively; series 1: the content of Indian ink is the same, but the content of TiO 2 is different. Weigh 0.341g, 0.512g, and 0.853g of TiO with an electronic balance respectively and put them into 3 parts of material B, and use a pipette gun to measure 140uL of Indian ink respectively and put them into 3 parts of material A and the above-mentioned material B respectively. Mixtures I and II were obtained; series 2 : same content of TiO2, different content of India ink. Use an electronic balance to weigh 0.512g of TiO 2 into 3 parts of material B, and use a pipette gun to measure 80uL, 140uL, and 200uL of Indian ink respectively into 3 parts of material A and the above-mentioned material B to obtain a mixture Liquid I and II.

1.4)吸收系数与约化散射系数参考值的计算1.4) Calculation of absorption coefficient and reference value of reduced scattering coefficient

对于三类固体仿体的系列2,取出其混合液Ⅰ的一部分放入比色皿中,通过使用温控样品池支架(CUV-qpot-ABSKIT,QUANTUM NORTHWEST,USA),卤钨灯(model HL-2000-FHSA,Ocean Optics,USA),QE 65Pro光谱仪(Ocean Optics,USA)与两根光纤(modelP1000-2-VIS-NIR,Ocean Optics,USA),测得混合液Ⅰ的吸光度,再根据朗伯比尔定律计算得到。For the series 2 of the three types of solid phantoms, take a part of the mixture I into the cuvette, and use the temperature-controlled sample cell holder (CUV-qpot-ABSKIT, QUANTUM NORTHWEST, USA) and the tungsten-halogen lamp (model HL -2000-FHSA, Ocean Optics, USA), QE 65Pro spectrometer (Ocean Optics, USA) and two optical fibers (modelP1000-2-VIS-NIR, Ocean Optics, USA), measured the absorbance of the mixture Ⅰ, and then according to the Calculated by Berber's law.

朗伯比尔定律的数学表达式:A=lg(1/T)=Kbc,其中A为吸光度,T为透射比,K摩尔吸收系数,c为吸光物质的浓,b为吸收层厚度,即为样品层的厚度。吸收系数μa=Kc=A/b,只要知道溶液的吸光度与比色皿的厚度(这里为10mm),即可计算出μaThe mathematical expression of Lambert-Beer's law: A=lg(1/T)=Kbc, wherein A is the absorbance, T is the transmittance, K molar absorption coefficient, c is the concentration of the light-absorbing substance, and b is the thickness of the absorbing layer, which is The thickness of the sample layer. Absorption coefficient μ a =Kc=A/b, as long as the absorbance of the solution and the thickness of the cuvette (here 10mm) are known, μ a can be calculated.

约化散射系数的参考值是通过Mie算法(Christian“MATLAB Functionsfor Mie Scattering and Absorption.”,2002)计算得到。需要输入的参数为聚氨酯的折射率:1.50,TiO2在527nm折射率:2.6738,TiO2的直径:这里取中值0.3um,以及TiO2的体积分数:0.02%,0.03%,0.05%。The reference value of the reduced scattering coefficient is obtained through the Mie algorithm (Christian "MATLAB Functions for Mie Scattering and Absorption.", 2002). The parameters that need to be input are the refractive index of polyurethane: 1.50, the refractive index of TiO 2 at 527nm: 2.6738, the diameter of TiO 2 : the median value here is 0.3um, and the volume fraction of TiO 2 : 0.02%, 0.03%, and 0.05%.

1.5)将混合液Ⅰ与混合液Ⅱ放到超声波清洗机振荡15分钟并使用玻璃棒搅拌,使其均匀混合,得到混合液Ⅲ。将混合液Ⅲ放入真空干燥箱抽真空,在0.1MPa下抽真空10-15分钟。1.5) Put the mixed solution I and the mixed solution II in an ultrasonic cleaning machine to vibrate for 15 minutes and stir with a glass rod to make them evenly mixed to obtain the mixed solution III. Put the mixed solution III into a vacuum drying oven for vacuuming at 0.1 MPa for 10-15 minutes.

1.6)对于第(1)类固体仿体,通过注射器4,将混合液Ⅲ注入到如图1所示的模具组合1中。对于第(2)(3)类固体仿体,直接通过烧杯6倒入如图2和3所示的模具组合2和3中。放置常温下待其凝固成固体。1.6) For the solid analog of category (1), inject the mixed solution III into the mold combination 1 shown in FIG. 1 through the syringe 4 . For (2) (3) type solid analogs, pour directly through the beaker 6 into the mold combinations 2 and 3 as shown in FIGS. 2 and 3 . Place it at room temperature until it solidifies into a solid.

制作完成的第(1)类固体仿体,其4个边角部分有一点缺口,但不影响校正测量使用。制作完成的第(3)类固体仿体,形状完整,没有缺陷。第(2)类固体仿体与第(3)类固体仿体类似,不同的是没有半球。The finished type (1) solid phantom has a little gap in the 4 corners, but it does not affect the use of calibration measurement. The finished (3) solid phantom has a complete shape and no defects. The solid phantom of category (2) is similar to the solid phantom of category (3), except that there is no hemisphere.

制作完成的第一类(1)(3)类固体仿体,其对应的相同样品号的固体仿体,组分含量相同,各块组分含量如下表所示:For the completed first type (1) (3) solid analogs, the corresponding solid analogs of the same sample number have the same component content, and the component content of each block is shown in the following table:

表1Table 1

2)空间频域成像系统校正2) Calibration of the spatial frequency domain imaging system

通过制作的第三类固体仿体中的系列1中的3个固体仿体(吸收系数相同,约化散射系数不同)用于校正检测装置的约化散射系数,系列2中的3个固体仿体(约化散射系数相同,吸收系数不同)用于校正检测装置的吸收系数。The three solid phantoms in series 1 (same absorption coefficient but different reduced scattering coefficients) in the third type of solid phantoms made by making are used to correct the reduced scattering coefficient of the detection device, and the three solid phantoms in series 2 Volumes (same reduced scattering coefficient, different absorption coefficient) are used to correct the absorption coefficient of the detection device.

在上述的固体仿体制作过程中,已经得到吸收系数与约化散射系数的参考值。在527nm波长下,通过空间频域成像系统检测得到各个固体仿体的吸收系数与约化散射系数。In the process of making the above-mentioned solid phantom, the reference values of the absorption coefficient and the reduced scattering coefficient have been obtained. At a wavelength of 527nm, the absorption coefficient and reduced scattering coefficient of each solid phantom are obtained through the detection of the spatial frequency domain imaging system.

分别对吸收系数和约化散射系数进行线性校正,即分别将空间频域成像系统测得的吸收系数和约化散射系数乘以一个系数:k(μa)λ与k(μ’s)λ。k(μa)λ是系列2中3个固体仿体吸收系数的参考值与测量值比值的均值,k(μ’s)λ是系列1中3个固体仿体约化散射系数的参考值与测量值比值的均值。The absorption coefficient and the reduced scattering coefficient are linearly corrected respectively, that is, the absorption coefficient and the reduced scattering coefficient measured by the spatial frequency domain imaging system are multiplied by a coefficient: k(μ a ) λ and k(μ' s ) λ . k(μ a ) λ is the mean value of the ratio of the reference value to the measured value of the absorption coefficient of the three solid phantoms in series 2, and k(μ' s ) λ is the reference value of the reduced scattering coefficient of the three solid phantoms in series 1 The mean of the ratios to the measured values.

其中,μa(i)ref与μa(i)mea分别代表系列2中的3个固体仿体中第i个固体仿体的吸收系数的参考值与测量值。μ’s(j)ref与μ’s(j)mea分别代表系列1中的3个固体仿体中第j个固体仿体的约化散射系数的参考值与测量值,λ的值为:527nm。Among them, μ a (i) ref and μ a (i) mea represent the reference value and measured value of the absorption coefficient of the i-th solid phantom among the three solid phantoms in series 2, respectively. μ' s (j) ref and μ' s (j) mea respectively represent the reference value and measured value of the reduced scattering coefficient of the jth solid phantom among the three solid phantoms in series 1, and the value of λ is: 527nm.

校正后的检测结果如下表2所示:The corrected test results are shown in Table 2 below:

表2Table 2

约化散射系数检测的相对误差最大为2.39%,吸收系数检测的相对误差最大为13.48%,完成系统的校正过程,由此可见本发明方法能针对农产品光学特性检测装置进行校正,提高农产品光学特性的检测精度。The maximum relative error in the detection of the reduced scattering coefficient is 2.39%, and the maximum relative error in the detection of the absorption coefficient is 13.48%, and the correction process of the system is completed. It can be seen that the method of the present invention can correct the optical characteristic detection device for agricultural products and improve the optical characteristics of agricultural products. detection accuracy.

并且本发明成本相比于使用购买的商品化的固体仿体所用的成本降低了20倍,使用3000元人民币左右即可实现模具和固体仿体的制作以及系统的校正。In addition, the cost of the present invention is 20 times lower than that of commercially purchased solid phantoms, and the production of molds and solid phantoms as well as system calibration can be realized with about RMB 3,000.

Claims (7)

1. it is a kind of by making the method that the imitative body of solid is corrected to agricultural product optical characteristics detection means by oneself, it is characterised in that method Step is:
1) the imitative body of the solid with different optical property parameters is made, and its light is obtained according to standard method and theoretical formula method Learn the reference value of characterisitic parameter;
2) for step 1) in the imitative body of the solid that is fabricated to, by agricultural product optical property parameter detection means visible-near red Detected under wave section, obtained the measured value of the optical property parameter under different wave length;
3) the measured value relation corresponding with reference value according to imitative optical property parameter of the body under each wavelength of different solids is carried out Fitting obtains fitting parameter;
4) by agricultural product optical property parameter detection means measure actual sample after, by step 3) obtain fitting parameter The measured value of the optical property parameter obtained to measurement is modified.
2. a kind of by making what the imitative body of solid was corrected to agricultural product optical characteristics detection means by oneself according to claims 1 Method, it is characterised in that:Described optical property parameter is to include absorption coefficient and reduced scattering coefficient.
3. a kind of by making what the imitative body of solid was corrected to agricultural product optical characteristics detection means by oneself according to claims 1 Method, it is characterised in that:Described step 3) and step 4) be specifically:
The solid that n reduced scattering coefficient is identical and absorption coefficient is different for correcting detection means absorption coefficient is first made to imitate Body, while making for correcting, m absorption coefficient of detection means reduced scattering coefficient is identical and reduced scattering coefficient is different Solid imitates body;
Then according to imitative absorption coefficient of the body under Same Wavelength of different solids and the measured value and reference value of reduced scattering coefficient Using below equation calculate the average k (μ of the reference value with measured value ratio that obtain absorption coefficienta)λAnd reduced scattering coefficient Reference value and measured value ratio average k (μ 's)λAs fitting parameter:
k ( μ a ) λ = Σ i = 1 n μ a ( i ) r e f / μ a ( i ) m e a n
k ( μ ′ s ) λ = Σ j = 1 m μ ′ s ( j ) r e f / μ ′ s ( j ) m e a m
Wherein, λ represents wavelength, μa(i)refWith μa(i)meaI-th suction of the imitative body of solid in the imitative body of all n solids is represented respectively Receive the reference value and measured value of coefficient, μ 's(j)refWith μ 's(j)meaThe j imitative body of solid in the imitative body of all m solids is represented respectively Reduced scattering coefficient reference value and measured value;
Under finally for the wavelength, the absorption coefficient that actual sample is obtained is measured by agricultural product optical property parameter detection means Linearly corrected using below equation with reduced scattering coefficient:
μa(i)calibrated=k (μa)λa(i)mea
μ's(j)calibrated=k (μ 's)λ*μ's(j)mea
Wherein, μa(i)calibratedWith μa(i)meaI-th absorption coefficient of the imitative body of solid in the imitative body of all n solids is represented respectively Correction after value and measured value, μ 's(j)refWith μ 's(j)meaJ-th solid imitates body in representing the imitative body of all m solids respectively Value and measured value after the correction of reduced scattering coefficient.
4. a kind of by making what the imitative body of solid was corrected to agricultural product optical characteristics detection means by oneself according to claims 1 Method, it is characterised in that:
The making of the imitative body of described solid is as absorption, with titanium dioxide (TiO using india ink (India Ink)2) conduct Scattering is sub, use different Mold Makings to form the imitative body of solid of different shapes as base material using polyurethane AB material.
5. a kind of by making what the imitative body of solid was corrected to agricultural product optical characteristics detection means by oneself according to claims 4 Method, it is characterised in that:
The making of the imitative body of described solid is concretely comprised the following steps:
1.1) scope of the absorption coefficient according to agricultural product optical property parameter value and reduced scattering coefficient value and required making The size of the imitative body of solid, determines the quality of india ink, titanium dioxide and polyurethane AB material in the imitative body of solid, and three is respectively a Part, b parts, c parts;
1.2) 0.5a parts of india ink is mixed into 0.5c parts of polyurethane A material and obtains mixed liquor I, by b parts of TiO2 and 0.5a Part india ink obtains mixed liquor II in being mixed together in 0.5c parts of polyurethane B material;
1.3) mixed liquor I and mixed liquor II are put into ultrasound cleaner vibrator to swing and stirred using glass bar, make its uniform mixing, Obtain mixed liquor III;
1.4) mixed liquor III is put into vacuum drying chamber to vacuumize 10-15 minutes, taking-up in every 5 minutes is put into ultrasound cleaner vibrator Swing and use glass bar to stir once;
1.5) mixed liquor III after vacuumizing is injected into mould, treats that its solidifies under placement normal temperature, obtains the imitative body of solid.
6. a kind of by making what the imitative body of solid was corrected to agricultural product optical characteristics detection means by oneself according to claims 5 Method, it is characterised in that:
From the step 1.3) part is taken in the mixed liquor I that is made is put into cuvette, by using QUANTUM The temperature control cuvette support of NORTHWEST companies surveys the thickness of its absorbance and cuvette, according to absorbance and the thickness of cuvette Degree is calculated by langbobier law and obtains absorption coefficient μaReference value, by Mie theory calculate obtain reduced scattering coefficient μ’sReference value.
7. a kind of by making what the imitative body of solid was corrected to agricultural product optical characteristics detection means by oneself according to claims 5 Method, it is characterised in that:Described mould includes three kinds of moulds for different use demands, namely for making thin flat plate Type solid imitates the mould of body, the mould for making the imitative body of thick flat-plate-type solid and for making the imitative body of band hemisphere thick plate type solid Mould, mould built by modular assembly;Modular assembly specifically includes bedplate (1), thin intermediate plate (2), note Emitter (4), thick intermediate plate (5), beaker (6) and hemisphere plate (7), thin intermediate plate (2) and thickness intermediate plate (5) be in the middle part of be provided with it is logical The loop configuration of groove, the side wall of loop configuration is provided with the radial passage for injecting liquid, and bedplate (1) is one flat plate knot Structure, hemisphere plate (7) is slab construction of one end center with boss, and the non-raised head face center of hemisphere plate (7) is provided with hemispherical-shaped aperture;
Described is main by two pieces of bedplates (1) and two pieces of bedplates (1) for making the mould of the imitative body of Boping template solid Between thin intermediate plate (2) constitute, mixed liquor in syringe (4) is injected by the radial passage of thin intermediate plate (2) side wall;
The described mould for making the imitative body of thick flat-plate-type solid mainly by one piece of bedplate (1) and is placed in bedplate (1) Thick intermediate plate (5) constitute, what the groove and bedplate (1) that the mixed liquor in beaker (6) is poured into the middle of thick intermediate plate (5) were formed In cavity volume;
It is described that for making, the mould with the imitative body of hemisphere thick plate type solid is main by one piece of hemisphere plate (7) and to be placed in hemisphere plate (7) thick intermediate plate (5) on non-raised head face is constituted, groove that the mixed liquor in beaker (6) is poured into the middle of thick intermediate plate (5) and In the cavity volume that hemisphere plate (7) is formed.
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