WO2002082063A1 - Method and device for surface evaluation - Google Patents

Method and device for surface evaluation Download PDF

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Publication number
WO2002082063A1
WO2002082063A1 PCT/EP2002/003682 EP0203682W WO02082063A1 WO 2002082063 A1 WO2002082063 A1 WO 2002082063A1 EP 0203682 W EP0203682 W EP 0203682W WO 02082063 A1 WO02082063 A1 WO 02082063A1
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WO
WIPO (PCT)
Prior art keywords
light
sample
light source
imaging device
recording
Prior art date
Application number
PCT/EP2002/003682
Other languages
English (en)
French (fr)
Inventor
Klaas Hendrik De Haas
Gerrit Cornelis Dubbeldam
Ivo Bernardus Nicolaas Van Der Lans
Robin Paul Fries
Original Assignee
Akzo Nobel Coatings International B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Coatings International B.V. filed Critical Akzo Nobel Coatings International B.V.
Priority to BR0208660-3A priority Critical patent/BR0208660A/pt
Priority to AU2002338353A priority patent/AU2002338353B2/en
Priority to JP2002579783A priority patent/JP3933581B2/ja
Priority to EP02742872A priority patent/EP1373867A1/en
Priority to KR1020037012945A priority patent/KR100875806B1/ko
Publication of WO2002082063A1 publication Critical patent/WO2002082063A1/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • 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
    • G01N21/55Specular reflectivity
    • G01N21/57Measuring gloss
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0216Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using light concentrators or collectors or condensers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/10Arrangements of light sources specially adapted for spectrometry or colorimetry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/50Measurement of colour; Colour measuring devices, e.g. colorimeters using electric radiation detectors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/50Measurement of colour; Colour measuring devices, e.g. colorimeters using electric radiation detectors
    • G01J3/504Goniometric colour measurements, for example measurements of metallic or flake based paints
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/52Measurement of colour; Colour measuring devices, e.g. colorimeters using colour charts
    • G01J3/524Calibration of colorimeters

Definitions

  • the invention relates to a method and a device for recording the visual properties of a surface, for example the colour, gloss, texture, etc. of pigmented coating films, using an imaging device, a light source, and a sample area for positioning a sample with a surface to be examined.
  • the visual appearance of a surface can be dependent on optical geometry, optical geometry being defined as the positioning of an observed object relative to an observer and a light source. This dependency can occur for example in films of coatings comprising effect pigments.
  • the dependency of visual properties on optical geometry is generally called goniochromatism, or flop behaviour.
  • the observation direction is the line between the observer and an observed point on the observed object
  • the illumination direction is the line between the light source and the observed point.
  • the specular direction is the direction of a line mirroring the illumination direction by a mirror plane perpendicular to the sample surface.
  • the flop angle also called the aspecular angle, is the angle between the observation direction and the specular direction.
  • gloss of either effect or non-effect films, is dependant on the optical geometry.
  • Effect pigments are used in coatings to obtain optical effects, such as a metallic or pearlescent look.
  • optical effects such as a metallic or pearlescent look.
  • lightness is dependent on the optical geometry
  • pearlescent pigments the hue changes with the optical geometry. This complicates the characterization of the visual appearance of such coating films.
  • a further complication in this respect is the appearance of local strong scattering spots in the coating film when it is observed from a short distance, due to the presence of pigment flakes.
  • coatings comprising effect pigments require taking the angular and spatial dependency into account.
  • US 5,550,632 discloses a method and an arrangement for evaluating paint films using a digital photo camera. Only one optical geometry is used per recording, and since the camera is focussed, only one flop angle. Since the appearance of a coating layer comprising effect pigments is dependent on the flop angle, this method cannot be used for the evaluation of such effect coatings in one recording.
  • the object of the invention is a system allowing the evaluation of a surface in a single recording over a continuous range of flop angles.
  • a device for recording the flop angle dependent properties of a surface comprising an imaging device for recording light interaction by a surface, a light source, and a sample area for positioning a sample with a surface to be examined, characterized in that the scope of the imaging device covers a continuous range of observation directions and in that the imaging device, the light source, and the sample area are arranged in such a way that in one image at least one of the surface properties is recorded as a function of the flop angle.
  • the recording can be used for visual inspection and comparison or, depending on the capability of the imaging device to quantify recorded signals, for measurement or data processing. Particular examples of use are gloss measurement and colour matching.
  • a device or arrangement according to the present invention is particularly suitable for evaluating the flop behaviour, or goniochromatism, of a surface coated with a coating containing effect pigments.
  • the range of flop angles should preferably span more than 40 degrees, more preferably more than 50 degrees.
  • the colour is darker at larger flop angles.
  • the light distribution is preferably varied over the viewing scope of the imaging device, preferably according to an increasing or decreasing function. This function is dependent on the type of material.
  • the light distribution can be varied by varying the light output of the light source as a function of the illumination angle. Alternatively, the light distribution can be varied by using suitable filters.
  • the light source can be a line source, such as a TL strip light, a horizontal slit in a light diffusor, an array of point sources, such as LEDs or glass fibres, etc.
  • the light source may be a point source.
  • a suitable imaging device in an arrangement according to the invention is a CCD camera, or Charge Coupled Device camera.
  • Suitable CCD photo cameras are for instance the Ricoh ® RDC 5000, the Olympus ® C-2000Z, the Minolta ® Dimage ® RD 3000, and the Nikon ® Coolpix ® 950.
  • Digital video cameras form another group of suitable devices which can be used to implement the present invention.
  • the flop angle can be varied not only as a function of location, but, alternatively or additionally, as a function of time.
  • Using a video camera also makes it possible to monitor time- dependent changes in the visual appearance of the examined surface over a period of time, for instance the appearance of a coating film during curing.
  • every recorded image is composed of a large number of pixels. Every pixel has a red value R, a green value G, and a blue value B. Ideally, calibrated R, G, and B values for a purely black surface should all be 0, whereas for an ideal purely white surface, each of these three values should be equal to a predefined maximum value.
  • the maximum value is equal to 2 ⁇ -1 , wherein n is the number of bits defining a pixel. If an 8-bits pixel depth is used, this maximum value is 255.
  • the lightness can exceed the lightness of white locally. This should be taken into account, for example by choosing a maximum white value lower than 2 n -1.
  • calibration can for example be carried out by first separately recording a black sample and a white sample.
  • the R,G,B values of the black value are subtracted from the R, G, and B values of the white sample and of the measured sample in question.
  • the R, G, and B values of the measured sample are divided by the corresponding values of the white calibration sample and are multiplied with the maximum white value. This means that for every pixel in the image, a calibrated value R ca ⁇ of the R value is calculated using the following formula:
  • R b ia ck is the R value of a pixel in the black sample
  • R Wh i te is the R value of a pixel in the white sample.
  • the R, G, and B values can be corrected for time-dependent variations in light intensity. This can be done for example by applying a parallel white strip to the sample.
  • the sample and the white strip are considered to be divided along the longitudinal axis of the sample by a large number of virtual parts.
  • the average R, G, and B values R av , G av , and B av are determined.
  • the average R, G, and B values Rwhite-av, G w hjt e -a , and B W hite-av are determined.
  • the corrected R value R cor for each sample part is then calculated using the following formula:
  • CIE Commission International de I'Eclairage
  • CIELab L*, a*, b*
  • CIEXYZ X, Y, Z
  • CIELuv L*, u * , v*
  • the mathematical model selected may be any model known to the skilled person. Examples are mentioned in H.R. Kang, Color Technology for Electronic Imaging Devices, SPIE Optical Engineering Press, 1997, chapters 3 and 11 , and in U.S. 5,850,472.
  • the model may be non-linear or linear.
  • One example of a non-linear model is a 2 nd order polynomial having 10 parameters or a 3 rd order polynomial having 20 parameters.
  • use is made of a linear model. More preferably, the linear model used has 4 model parameters.
  • Rj, G,-, B,- are the measured signals and L * , a *, and b * are the colorimetric data of calibration colour i.
  • Linear regression is used to calculate the 12 model parameters c 0 -c 3 , d 0 -d 3 , and e 0 -e 3 from the measured RGB data and the known CIELab data (CIE 1964 standard colorimetric observer) of the calibration colours. These model parameters are used to convert the measured RGB data of the selected colour to CIELab data.
  • Linear regression is used to calculate the 60 model parameters c 0 -c 9 , d 0 -d ⁇ g, and e 0 -e ⁇ g from the measured RGB data and the known CIELab data of the calibration colours. These model parameters are used to convert the measured RGB data of the selected colour to CIELab data. Notwithstanding the above, it is possible to lend greater weight to the calibration colours in the vicinity of the selected colour when calculating the model parameters. In the case of the above example of a linear model having 4 parameters, this means that during the linear regression each calibration colour is given a weighting factor based on the distance in the RGB colour space between the calibration colour in question and the selected colour. In the linear regression procedure the following sum of squares is minimized:
  • w is a weighting factor
  • y is the L * ,, a , *, or b , * based on spectral measurements and y, is the calculated value for L* , a , *, or b , * based on the RGB to CIELab conversion.
  • n is the number of calibration colours R, G, B: are the measured signals of the selected colour
  • image processing software such as the computer program Optimas ® commercially available from Media Cybernetics, or the program Image ProPlus ® available from the same company
  • individual particles can be identified by recognition of differing luminance relative to the particle's background.
  • These particles can for instance be metallic pigments or clusters of metallic pigments.
  • the number of particles, and image parameters like particle size, particle shape, the length of the shortest and the longest axis, as well as the R, G, and B values of the particles can be determined by the image processing software. This data optionally can be averaged per strip part, or per larger part if so required.
  • the data determined on the basis of the images can for example be used to search for a coating formulation giving a matching surface coating.
  • the measured data can be compared with data from a colour formulation database.
  • the light source can optionally comprise a set of mirrors. It has been found that using mirrors in a suitable arrangement can enhance the scope to about 90 degrees or even more.
  • the light source may be a permanent light source, a flash light is preferred to minimize the use of energy. If permanent light sources are used, the camera should be set at a suitable exposure time. Suitable light sources are for instance tungsten halogen lamps or xenon lamps.
  • the light source comprises a light diffusing housing discharging light via a slit. The longitudinal side of the slit is arranged substantially parallel to the sample surface, whereas the short side is substantially perpendicular to the sample surface.
  • a light sensor can be used to control the light output.
  • the slit is bordered by a substantially horizontal wall at the inner side of the diffusor. This way, the light intensity at the sample surface is a function of the flop angle. On positions at a smaller angular distance to the diffusor, the light intensity is less than at larger angles.
  • the spectral distribution of the light is varied in one image as a function of the position on the sample, e.g., by using different light sources or using a set of filters, a grating, or a prism.
  • This enhances the number of independent measurement data and thus improves colour accuracy.
  • This can be done for example by varying the light from the light source or by varying the spectral distribution of the light just before it enters the imaging device.
  • the spectral distribution of the illumination is varied perpendicular to the variation of optical geometry.
  • the device according to the invention preferably comprises a housing.
  • the present invention includes a method of surface evaluation as described above wherein, in general, the recorded light interaction is the light reflection of a sample. However, if the sample is transparent or semi-transparent, the recorded light interaction can be light transmission. In that case, the sample is positioned between the imaging device and the light source.
  • Fig. 1 shows a schematic overview of a recording arrangement according to the invention
  • Fig. 2 shows a recording by the arrangement of Figure 1 ;
  • Fig. 3 shows schematically an alternative arrangement according to the invention;
  • Fig. 4 shows a plot of the flop angle as a function of the position, as recorded by the arrangement of Figure 3;
  • Fig. 5 shows a third alternative arrangement according to the invention
  • Fig. 6 shows a fourth alternative embodiment of the invention
  • Fig. 7 shows the change in the filtered wavelength ranging over a sample imaged in a device according to Figure 6.
  • Fig. 8 shows a sample with a parallel reference sample for gloss measurement.
  • Figure 1 shows an arrangement 1 according to the present invention, comprising a light source 2, a CCD camera 3 as a recording device, having a viewing angle ⁇ ranging from a first outer end observation direction 4 closest to the light source to a second outer end observation direction 5.
  • a coated sample 6 is located under the camera 3.
  • the light source 2 is a line source parallel to the sample surface.
  • the light source 2 is located outside the direct scope of the CCD camera 3.
  • the line between the light source 2 and the point where the observation direction 4 meets the sample 6 defines a first illumination direction 7, which is reflected by the sample 6 in a direction defined as the first specular direction 8.
  • the line between the light source 2 and the point where the observation direction 5 meets the sample 6 defines a second illumination direction 9, which is reflected by the sample 6 in a direction defined as the second specular direction 10.
  • the outer flop angle ⁇ - ⁇ is the angle between the first observation direction 4 and the first specular direction 8
  • the outer flop angle 0 is the angle between the second observation direction 5 and the second specular direction 10.
  • the angular range between ⁇ 1 and ⁇ 2 may span up to about 90 degrees.
  • Figure 2 shows a recorded image recorded by the arrangement of Figure 1. It is the image of a sample coated with a metallic paint. The figure shows how brightness varies with the flop angle. The image in Figure 2 also shows a change in coarseness over the length of the sample, as would also be experienced by the human eye.
  • Figure 3 shows an alternative arrangement according to the invention, where the flop angle scope is enhanced by the use of a mirror 11.
  • the mirror 11 is arranged in such a way that it reflects the sample part right next to the outer end of the camera's viewing angle scope most distant from the light source 2.
  • the scope closest to the light source 2 is replaced by an extension of the scope on the other side. From right to left, the recording shows the scope from ⁇ 3 to ⁇ 5 and subsequently the scope from ⁇ 4 to 0 2 .
  • the scope from ⁇ to ⁇ is not visible anymore on the recording.
  • Figure 4 shows the flop angle as a function of the position in an arrangement similar to the arrangement of Figure 3, position 0 being right under the camera.
  • the mirrored part of the sample overlaps the part from about 20 mm to 25 mm.
  • the sample can be recorded in two (or even more) separate parallel strips, one with a mirror enhanced scope and the other without. This way, the full enlarged scope ranging from ⁇ -j to ⁇ 2 and the scope ranging from 0 5 to ⁇ 3 can be recorded. If O 5 is equal to ⁇ 2 , then a closed range from ⁇ -i to ⁇ 3 is covered.
  • Figure 5 shows an arrangement similar to the arrangement of Figure 1 with a camera 3 right above a sample 6 where a light source 12 comprises a standard flash light 13, available under the trademark Metz 45CT-1.
  • the flash light 13 comprises a transparent side 14.
  • the flash light is connected to the flat upper side 15 of a diffusor 16 comprising a semi-cylindrical part 17.
  • This flat side 15 is open where it is in connection with the transparent side 14 of the flash light 13.
  • the inner side of the diffusor 16 is covered with a white coating.
  • the flat side 15 is closed by a horizontal wall 18, which on its inside is provided with a white coating.
  • the edge between the outer end of the horizontal wall 18 and the semi-cylindrical part 17 is provided with a vertical slit 19 extending over the width of the diffusor 16.
  • the light is diffused by the reflective coatings at the inner side of the diffusor 16. Part of the light is reflected by the reflective layer of the horizontal wall 18 through the slit 19 onto the part of the sample 6 to be imaged.
  • the sample 6 is illuminated by a considerably smaller part of the reflective horizontal wall 17 than at the camera's outer viewing direction distant from the diffusor 16. This way, the light density is a function of the angular distance from the light source. The function can be varied with the orientation of the slit with respect to the sample surface.
  • a glass fibre cable 20 connects the space enclosing the flash light 13 to a light sensor 21 controlling the time interval at which the flash light 13 flashes. Part of the light diffused in the diffusor 16 escapes via the glass fibre cable 20 to the light sensor 21. The quantity of light passing the glass fibre cable 20 is measured by the light sensor 21. When a pre-defined quantity of light has passed the glass fibre cable 20, the sensor 21 stops the flash light 13. This way, it is ensured that every flash gives exactly the same quantity of light.
  • Figure 6 shows a further alternative embodiment of a device according to the invention, comprising an imaging device 3 and a light source 2. A sample 6 is located under the imaging device 3. A set of filters and a grating or a prism 24 are positioned between the light source 2 and the sample 6. The spectral distribution of the illumination is varied in one image as a function of the position on the sample.
  • Figure 7 shows the result of the preferred embodiment where the spectral distribution of the illumination is varied perpendicular to the variation of optical geometry.
  • Figure 8 shows that the gloss behaviour of a sample can be characterized as a function of optical geometry. This particular example shows in one image the difference between a high gloss sample 25 and a low gloss sample26.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Spectrometry And Color Measurement (AREA)
  • Investigating Materials By The Use Of Optical Means Adapted For Particular Applications (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
PCT/EP2002/003682 2001-04-06 2002-03-28 Method and device for surface evaluation WO2002082063A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR0208660-3A BR0208660A (pt) 2001-04-06 2002-03-28 Método e dispositivo para avaliação de superfìcie
AU2002338353A AU2002338353B2 (en) 2001-04-06 2002-03-28 Method and device for surface evaluation
JP2002579783A JP3933581B2 (ja) 2001-04-06 2002-03-28 表面評価の方法および装置
EP02742872A EP1373867A1 (en) 2001-04-06 2002-03-28 Method and device for surface evaluation
KR1020037012945A KR100875806B1 (ko) 2001-04-06 2002-03-28 표면 평가를 위한 방법 및 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01201276.1 2001-04-06
EP01201276 2001-04-06

Publications (1)

Publication Number Publication Date
WO2002082063A1 true WO2002082063A1 (en) 2002-10-17

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EP (1) EP1373867A1 (ja)
JP (1) JP3933581B2 (ja)
KR (1) KR100875806B1 (ja)
CN (1) CN100403011C (ja)
AU (1) AU2002338353B2 (ja)
BR (1) BR0208660A (ja)
RU (1) RU2292037C2 (ja)
WO (1) WO2002082063A1 (ja)
ZA (1) ZA200307712B (ja)

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RU2463162C2 (ru) * 2006-12-23 2012-10-10 Колорматрикс Холдингс, Инк. Полимерные материалы
US9823130B2 (en) 2012-04-20 2017-11-21 Office Color Science Co., Ltd. Multi-angle spectral imaging measurement method and apparatus
US11280743B2 (en) 2015-03-30 2022-03-22 Gemological Institute Of America, Inc. (Gia) Apparatus and method for assessing optical quality of gemstones
CN114502266A (zh) * 2019-10-09 2022-05-13 株式会社日立制作所 粉体混合系统及粉体混合方法

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US9880098B2 (en) * 2014-10-28 2018-01-30 Axalta Coatings Systems Ip Co., Llc Method and systems for quantifying differences between colored surfaces
CN106908149A (zh) * 2017-04-11 2017-06-30 上海电机学院 一种机器人物体颜色识别系统及方法
KR102047206B1 (ko) * 2018-10-31 2019-11-20 한국과학기술원 체적함수비별 반사율 측정을 위한 함수특성곡선-초분광 캠 테스트 방법 및 장치

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2463162C2 (ru) * 2006-12-23 2012-10-10 Колорматрикс Холдингс, Инк. Полимерные материалы
US9823130B2 (en) 2012-04-20 2017-11-21 Office Color Science Co., Ltd. Multi-angle spectral imaging measurement method and apparatus
US11280743B2 (en) 2015-03-30 2022-03-22 Gemological Institute Of America, Inc. (Gia) Apparatus and method for assessing optical quality of gemstones
US11921051B2 (en) 2015-03-30 2024-03-05 Gemological Institute Of America, Inc. (Gia) Apparatus and method for assessing optical quality of gemstones
CN114502266A (zh) * 2019-10-09 2022-05-13 株式会社日立制作所 粉体混合系统及粉体混合方法
CN114502266B (zh) * 2019-10-09 2024-03-05 株式会社日立制作所 粉体混合系统及粉体混合方法

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BR0208660A (pt) 2004-03-09
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JP2004526969A (ja) 2004-09-02
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KR20040012743A (ko) 2004-02-11
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