Are chroma tolerances dependent on hue‐angle?

Relationships between suprathreshold chroma tolerances and CIELAB hue‐angles have been analyzed through the results of a new pair‐comparison experiment and the experimental combined data set employed by CIE TC 1–47 for the development of the latest CIE color‐difference formula, CIEDE2000. Chroma tolerances have been measured by 12 normal observers at 21 CRT‐generated color centers L*₁₀ = 40, C*_ab,10 = 20 and 40, and h_ab,10 at 30° regular steps). The results of this experiment lead to a chroma‐difference weighting function with hue‐angle dependence W_CH, which is in good agreement with the one proposed by the LCD color‐difference formula [Color Res Appl 2001;26:369–375]. This W_CH function is also consistent with the experimental results provided by the combined data set employed by CIE TC 1–47. For the whole CIE TC 1–47 data set, as well as for each one of its four independent subsets, the PF/3 performance factor [Color Res Appl 1999;24:331–343] was improved by adding to CIEDE2000 the W_CH function proposed by LCD, or the one derived by us using the results of our current experiment together with the combined data set employed by CIE TC 1–47. Nevertheless, unfortunately, from the current data, this PF/3 improvement is small (and statistically nonsignificant): 0.3 for the 3657 pairs provided by CIE TC 1–47 combined data set and 1.6 for a subset of 590 chromatic pairs (C*_ab,10>5.0) with color differences lower than 5.0 CIELAB units and due mainly to chroma. © 2004 Wiley Periodicals, Inc. Col Res Appl, 29, 420–427, 2004; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/col.20057     

Interior and exterior daylight illuminants for the colorimetry of fluorescent materials

The difficulties in simulating CIE Standard Illuminant D₆₅ are considered and an interior daylight illuminant is described, Illuminant ID₆₅, representing exterior daylight attenuated by average window glass. The benefits of Illuminant ID₆₅ are that it represents the daylight source which most commonly occurs in the viewing of critically coloured merchandise, and that it can be practically simulated using a filtered tungsten-halogen source. Its applicability to measurements, particularly to the assessment of fluorescent samples, is considered. The results of measurements on the two common classes of fluorescent samples are discussed and indicate that an Illuminant ID₆₅ simulator can be used validly for the measurement of fluorescent materials, even including materials intended specifically for exterior use.     

Color scales in simulated daylight

The pigmentation plan used for production of the color cards made available by the Optical Society of America (OSA) for its Committee on Uniform Color Scales (UCS) was designed in such a manner that the color scales should, within the production tolerances, appear uniform in all phases of daylight. The production specifications were based on D₆₅ of the Commission International de L'Eclairage (CIE) and the CIE supplementary observer (1964) for 10° visual-field subtense. To test for the intended invariance of uniformity of the scales in daylight, for normal observers, the effects on color differences between all nearest neighbors of the OSA colors have been studied for CIE Illuminant C with the 1931 observer, and for a “daylight” fluorescent luminaire (color temperature 6500 K) with both the 1931 and 1964 CIE observers. Although the colorimetric specifications (Y, x, y) of each color card are different for those three illuminant + observer combinations, the color differences computed with the formula of the OSA-UCS committee are, within the production tolerances, unchanged. The purpose of this article is to show how well the aim and expectation is fulfilled—that the uniformity of color differences between nearest neighbors in the scales of the OSA-UCS colors be essentially unchanged for normal observers and for ordinary variations of the quality of natural and artificial daylight. This invariance is found, even for daylight-quality fluorescent-lamp light.     

Detailed optical analysis of Dy3+ and Pr3+ co-doped alumino-borate glasses for visible lighting applications

A new glass series with nominal molar composition of 60B₂O₃ + 30NaF + 10Al₂O₃ co-doped with Dy³⁺ and Pr³⁺, synthesized by melt quench was reported. The influence of Rare Earth (RE) ratio variation on prepared glasses was investigated by using Fourier Transform Infra-Red spectroscopy, UV–Vis–NIR absorption spectroscopy, Photoluminescence, Decay curves and Density measurements. Their X-Ray Diffraction and FTIR spectra revealed the glassy nature and confirmed that AlO₆, AlO₄, BO₃ and BO₄ units are the main structural units of that matrix. A non-linear variation following the same trend for tetragonal borate units (N₄), Band gap, non-linear optical properties, Density, Molar Volume etc. was observed. Different optical parameters were obtained by UV–Vis–NIR spectroscopy. The Bonding parameter obtained from Nephelauxetic study indicated ionic nature of Dy³⁺ and covalent nature of Pr³⁺ ions. Photoluminescence excitation and emission spectra were recorded under variety of excitation wavelengths and corresponding color parameters were calculated using 1931 CIE standards. A detailed yellow to blue ratio analysis was reported as a function of RE ion concentration and excitation wavelengths. Composition DPNAB(x = 0.7) displayed the best performance with CIE coordinates (0.33, 0.37). Existence of Energy transfer from Dy³⁺ and Pr³⁺ was evidenced by the spectral overlap diagram and lifetime values obtained from fitting of Decay curves. From the obtained results, prepared glasses can be suggested for solid-state lighting devices like WLEDs and display devices.     

Development of a comprehensive visual dataset based on a CIE blue color center: Assessment of color difference formulae using various statistical methods

The objectives of this work were to develop a comprehensive visual dataset around one CIE blue color center, NCSU‐B1, and to use the new dataset to test the performance of the major color difference formulae in this region of color space based on various statistical methods. The dataset comprised of 66 dyed polyester fabrics with small color differences ($\Delta E_{{\rm ab}}^* < 5$ ) around a CIE blue color center. The visual difference between each sample and the color center was assessed by 26 observers in three separate sittings using a modified AATCC gray scale and a total of 5148 assessments were obtained. The performance of CIELAB, CIE94, CMC(l:c), BFD(l:c), and CIEDE2000 (K_L:K_C:K_H) color difference formulae based on the blue dataset was evaluated at various K_L (or l) values using PF/3, conventional correlation coefficient (r), Spearman rank correlation coefficient (ρ) and the STRESS function. The optimum range for K_L (or l) was found to be 1–1.3 based on PF/3, 1.4–1.7 based on r, and 1–1.4 based on STRESS, and in these ranges the performances of CIEDE2000, CMC, BFD and CIE94 were not statistically different at the 95% confidence level. At K_L (or l) = 1, the performance of CIEDE2000 was statistically improved compared to CMC, CIE94 and CIELAB. Also, for NCSU‐B1, the difference in the performance of CMC (2:1) from the performance of CMC (1:1) was statistically insignificant at 95% confidence. The same result was obtained when the performance of all the weighted color difference formulae were compared for K_L (or l) 1 versus 2. © 2009 Wiley Periodicals, Inc. Col Res Appl, 2011     

The influence of iron content on the promotion of the zircon structure and the optical properties of pink coral pigments

A sol–gel reaction starting from Si and Zr alkoxides, in water-ethanol mixtures, was employed to obtain iron doped zirconium silicate powders (zircon). The starting amount of the ferric salt in the sol–gel reacting mixture was varied in order to obtain Fe₂O₃/Zr molar ratios in the range 0.7–10%. The products of the sol–gel reaction were calcined in the range 800–1300 °C. X-ray diffractograms, EDX analyses and diffuse reflectance spectra were obtained and analysed for all the calcined powders; the colour of the pigments was characterised on the grounds of the CIE (Commission Internationale de l’Eclairage) standard procedure (CIE L¹a¹b¹ measurements). Results from the structural and spectral characterisations are examined and cross-compared to produce a consistent picture of the role played by iron on the promotion of the zircon lattice and on the optical properties of the reaction products.     

Deep-red-emitting Ca2ScSbO6:Mn4+ phosphors with a double perovskite structure: Synthesis,characterization and potential in plant growth lighting

Mn⁴⁺-activated double-perovskite type Ca₂ScSbO₆ (CSS) phosphors were synthesized via a high-temperature solid-state reaction. The phase purity and crystal structure of obtained samples were investigated by powder X-ray diffraction (XRD). The successful incorporation of Mn⁴⁺ ions into CSS lattice was confirmed by the combination of energy-dispersive X-ray spectra (EDX) and X-ray photoelectron spectra (XPS) results. The luminescent properties of the CSS phosphors, including the photoluminescence (PL) and PL excitation (PLE) spectra, commission international de l'clairage (CIE) chromaticity coordinates, fluorescence decay curves, quantum yields and temperature-dependent PL spectra, were investigated in detail. Under 310-nm excitation, the optimized CSS:0.3%Mn⁴⁺ phosphor exhibited bright deep-red emission covering a narrow band from 640 nm to 720 nm, which overlaps with the absorbance of phytochromes. The Racah parameters B, C, and local crystal strength Dq were calculated to be 870, 2703, and 1984 cm^–1, respectively. Particularly, the emission intensity of CSS:0.3%Mn⁴⁺ still remained 61.4% at 423 K compared with that at room temperature. Therefore, all these outstanding luminescent properties provided the as-synthesized phosphors a great potential in plant growth lighting.     

Analysis of five sets of color difference data

In a systematic optimization process five sets of recent color difference data have been analyzed for commonalities. Adjustment of the X tristimulus values and application of a systematic, surround dependent S_L function was found to be beneficial in all cases. Other modifications of the CIE94 color‐difference formula were found to bring improvements only in some cases and may be spurious. Application of what seem to be nonsystematic scale factors in a range of 0.78–1.38 improve correlation between calculated and visual color differences in all cases. After optimization, calculated color difference values explain between 80–90% of the variation in visual color differences. Some of the datasets are shown not to be well suited for formula optimization. Optimization in all cases by set, for three sets of data by quadrant in the a^*b^* diagram, and for one set by subset did not reveal any additional systematic trends for improvement. It appears that the basic structure of CIE94, with the recommended modifications, is a good approximation as a model for color‐difference evaluation in the range from 0.5–10 units of difference. The model is surround dependent. A number of issues remain to be resolved. © 2001 John Wiley & Sons, Inc. Col Res Appl, 26, 141–150, 2001     

Random copolymerization of 2,2‐dimethyltri methylene carbonate and ε‐caprolactone using a rare‐earth tris(4‐tert‐butylphenolate)s as a single‐component initiator

Highly random copolymers of 2,2‐dimethyltrimethylene carbonate (DTC) and ε‐caprolactone (CL) were synthesized by single component rare‐earth tris(4‐tert‐butylphenolate)s [Ln(OTBP)₃] for the first time. The influences of reaction conditions on the copolymerization initiated by La(OTBP)₃ have been examined in detail. The monomer reactivity ratios of DTC and CL determined by the Fineman–Ross method are 4.0 for r_DTC and 0.27 for r_CL. The microstructure of the copolymer was determined by the analyses of the diads DTC–DTC, DTC–CL, CL–DTC and CL–CL of the ¹H NMR spectra. The high degree of randomness of the chain structure was further confirmed by the ¹³C NMR spectra and differential scanning calorimetry. The thermal properties of the copolymers as a function of composition are reported. The mechanism investigated by ¹H NMR data indicates that the rare‐earth tris(4‐tert‐butylphenolate)s initiate the ring‐opening copolymerization of DTC and CL with acyl‐oxygen bond cleavages of the monomers. Copyright © 2004 Society of Chemical Industry     

Optical Investigation of Ce3+‐Activated Borogermanate Glass Induced by Substitution of BaF2 for BaO

Transparent and colorless CeO₂‐activated borogermanate glasses, with the nominal molar composition of 25B₂O₃–40GeO₂–14Gd₂O₃–1CeO₂–(20?x) BaO–xBaF₂ (x = 0, 2.5, 5, 10, 15 and 20), were synthesized by a melt‐quenching method in air. Their optical investigation on the transmittance, photoluminescence (excitation and emission spectra), the luminescence decay curves, as well as the temperature‐dependent Ce³⁺ emission are studied systematically with the gradual substitution of BaF₂ for BaO. The room‐temperature photoluminescence results reveal that the emission intensity can be improved by about 2.5 times with the full substitution of BaF₂ for BaO. The blue shift of the cut‐off edge, excitation and emission spectra of Ce³⁺‐activated borogermanate glass, and the emission intensity of Ce³⁺ ions as a function of temperature range in 80–500 K are also discussed.     

Effect of the composition of the initiating complex acyl halides/aluminium bromide on the cationic polymerization of isobutylene

On the basis of ¹H and ¹³C spectra obtained for solutions of complexes of acyl halides with aluminium bromide RCOX·nAlBr₃ (X = Cl, Br; n = 1, 2), it is shown that these adducts can exist in solution as donor–acceptor complexes, acyl salts, or combinations of both forms. The nature of the cationic initiating species for each case is predicted. The predictions coincide well with experimental results obtained by analysis of the isobutylene polymers prepared with these initiating complexes. Initiation by the 1:2 complexes allows polymeric molecules to be synthesized with an acyl group at one end. These polymerization processes have some of the characteristics of living polymerizations. The possibility for quantitative estimation of such systems using the criteria of ‘approach to livingness’ is demonstrated. © 2000 Society of Chemical Industry     

Effect of Tm3+ Ions on the White Light Emission of Dy3+–Tm3+ Codoped SrMg2La2W2O12 Phosphors

Dy³⁺–Tm³⁺ ions codoped SrMg₂La₂W₂O₁₂ (strontium magnesium lanthanum tungstate) phosphors were synthesized by conventional high‐temperature solid‐state reaction method. X‐ray analysis of the end products revealed the well‐crystallized phases with orthorhombic structure. The functional groups present in the phosphors were studied by the Fourier transform infrared measurements. To know the potential applicability of these phosphors for white light emission, the excitation and emission spectra were recorded. The excitation spectra exhibited an intense broad band at 313 nm, pertaining to the O → W ligand‐to‐metal charge‐transfer state (LMCT) of the host. With the excitation of LMCT band (313 nm), the decay curves of singly doped SrMg₂La₂W₂O₁₂:Dy phosphors exhibited single exponential, where as the codoped SrMg₂La₂W₂O₁₂:DyTm phosphors exhibited double exponential nature. The luminescence colors of these phosphors were estimated from Commission Internationale de L'Eclairage (CIE) coordinates using the photoluminescence data. The color of singly doped SrMg₂La₂W₂O₁₂:Dy phosphor has been tuned by codoping with Tm³⁺ ions. It has been noticed that the CIE chromaticity coordinates (x,y) determined from the luminescence spectrum of singly Dy³⁺ doped SrMg₂La₂W₂O₁₂ phosphor shifted toward the white light region, when codoped with Tm³⁺ ions. The increase in correlated color temperatures (T_cct) has been noticed with the increase of Tm³⁺ ions concentration in SrMg₂La₂W₂O₁₂:DyTm phosphors.     

Studies on silk fabric dyed with a hemicyanine dye

Silk fabric was dyed with a hemicyanine dye, DHEASPBr‐C₄, to create the fluorescent silk fabric in this article. The study initially focuses on the dyeing properties of the dyed silk fabric, followed by the reflectance and emission spectra. The results show that the sorption isotherms are the Langmuir type and the dyed silk fabrics using DHEASPBr‐C₄ have an obvious fluorescent effect in the spectral range 570–720 nm, while their peak locations of ca. 590 nm in the emission spectra are under the excitation of 365 nm. Finally, the CIE coordinates of the dyed silk fabric are discussed in order to investigate further potential applications.     

Intrinsic dielectric properties of columbite ZnNb2O6 ceramics studied by P–V–L bond theory and Infrared spectroscopy

In this study, intrinsic dielectric properties of ZnNb₂O₆ ceramics were investigated using P–V–L chemical bond theory and far-infrared reflectivity spectra. The largest bond ionicity and bond susceptibility of Nb–O bonds suggest that the dielectric polarizability is mainly determined by Nb–O bonds. Relative permittivity, calculated via P–V–L bond theory, is close to experimental value determined using TE₀₁₁ mode. The Nb–O bonds are also crucial for the structural stability. According to far-infrared reflectivity spectra and complex dielectric function analysis, a relatively consistent result between calculated and measured dielectric properties, fit using classical damped oscillator mode, indicate that the B_1u mode at 168.87 cm⁻¹ provides majority contribution to the dielectric properties.     

Stereochemical and compositional assignments of trans‐4‐methacryloyloxyazobenzene–methyl methacrylate copolymers by one‐ and two‐dimensional NMR spectroscopy

The microstructure of trans‐4‐methacryloyloxyazobenzene–methyl methacrylate copolymers prepared by solution polymerization process using AIBN as initiator is analyzed by one‐and two‐dimensional spectroscopy. Sequence distribution was calculated from the ¹³C(¹H)‐NMR spectra of the copolymers. Comonomer reactivity ratios were determined using the Kelen–Tudos and the nonlinear error‐in‐variables methods are r_A = 1.14 ± 0.08 and r_M = 0.51 ± 0.03; r_A = 1.13 ± 0.1 and r_M = 0.50 ± 0.04, respectively. The sequence distribution of A‐ and M‐centered triads determined from ¹³C(¹H)‐NMR spectra of copolymer is in good agreement with triad concentration calculated from a statistical model. The 2‐D heteronuclear single‐quantum correlation and correlated spectroscopy (TOCSY) was used to analyze the complex ¹H‐NMR spectrum. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3016–3025, 1999     

Structural investigations of (9‐ethyl‐carbazol‐6‐yl) methyl methacrylate/methyl acrylate copolymers using two‐dimensional NMR spectroscopy

(9‐Ethyl‐carbazol‐6‐yl) methyl methacrylate/methyl acrylate (E/A) copolymers of different compositions were prepared by solution polymerization by varying the molar infeed ratio, using AIBN as initiator at 60°C. The reactivity ratios calculated by Kelen–Tudos (KT) method were found to be r_E = 1.16 ± 0.02 and r_A = 0.69 ± 0.01 whereas those calculated from RREVM method were found to be r_E = 1.18 and r_A = 0.68. The molecular weights (M_w) and polydispersity index (PDI, M_w/M_n) were determined using gel permeation chromatography (GPC). Glass transition temperatures (T_g) for different compositions of E/A copolymers were determined using differential scanning calorimetry (DSC). Copolymer molar outfeed ratio (F_E) was calculated from ¹H NMR spectra. The α‐methyl, methine, backbone methylene, and quaternary carbon resonance signals of the copolymers were distinguished using ¹³C{¹H}, DEPT‐45, ‐90, and ‐135 NMR techniques. The α‐methyl and β‐methylene showed compositional and configurational sensitivity up to pentad and tetrad level, respectively, whereas methine showed only compositional sensitivity up to pentad level. Unambiguous assignments for ¹H and ¹³C{¹H} NMR spectra were done by correlating 1D (¹H, ¹³C{¹H}, DEPT) and 2D (HSQC, TOCSY) NMR data. The spectral assignments for carbonyl region were done by studying higher bond order couplings by heteronuclear multibond correlation (HMBC) spectra. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5595–5606, 2006     

A benign approach for novel synthesis of Eu3+ doped MgNb2O6: Its photoluminescence and photocatalytic studies

The Present work involves the production of Eu³⁺ (1–11 mol %) doped MgNb₂O₆ nanophosphors (NPs) by combustion technique using ODH as a fuel for the first time and well characterized. The average crystallite and the energy gap of the samples were found to be in the range of 20–45 nm and 4.65–5.66 eV respectively, TEM results reflects the same crystallite size values. The effect of doping was confirmed by the characteristic emission peaks recorded at ~535, 590, 614, 642 and 698 nm may be attributed to the 4f–4f intra shell transitions (⁵D₀→⁷F_j=0,1,2,3,4) of Eu³⁺ cations when bombarded at 395 nm energy. Judd–Ofelt parameters (Ω₂, Ω₄), transition probabilities (A_T), quantum efficiency (η), luminescence lifetime (τ_rad) are discussed in detail. From the emission spectra, CIE (Commission International de I’ Eclairage) chromaticity co-ordinates and Correlated color temperature (CCT) were estimated. Langmuir-Hinshelwood model was used to study the photocatalytic degradation of AR-88 dye. The above results confirmed that the present phosphor can be potentially used for display and photocatalytic applications.     

Effective sensitization of Eu3+ ions on Eu3+/Nd3+ co-doped multicomponent borosilicate glasses for visible and NIR luminescence applications

Eu³⁺/Nd³⁺ co-doped multicomponent borosilicate glasses (ND1E: 10BaO +10ZnF₂+10K₂O +20SiO₂+(49-x) B₂O₃+1Nd₂O₃+xEu₂O₃) were prepared by conventional melting and rapid quench technique to evaluate the effect of Eu³⁺ ions in the Nd³⁺ doped glasses. Thermal stability, structural and spectroscopic characteristics of the ND1E glasses were investigated by using DSC, XRD, FTIR, Optical absorption, excitation and emission measurements. The Judd – Ofelt (JO) analysis is implemented to the absorption spectrum of the prepared glassy matrix in order to identify their potential applicability in lasing devices. Enhancement of ⁷F₀ → ⁵L₆ band (394 nm) with the increasing concentration of Eu³⁺ ion in the Nd³⁺ excitation spectra (λ_emi = 1060 nm) reveals the possibility of obtaining the characteristic fluorescence spectra of Nd³⁺ ion with the typical excitation wavelengths (Nd³⁺ = 584 nm and Eu³⁺ = 394 nm) of both rare earth ions and it is further verified from the emission spectrum. This interesting luminescence effect of showing excellent visible and NIR emission under 394 nm excitation mainly attributes the energy transfer mechanism between the RE³⁺ ions and the reason underlying this effect is discussed in detail with the help of partial energy level diagram. Energy transfer efficiency between the Eu³⁺ and Nd³⁺ ions were evaluated by using the radiative lifetimes of the prepared glasses. Also, a comparison of radiative properties and lasing characteristics of Eu³⁺/Nd³⁺ co-doped glasses with other Nd³⁺ glasses are reported. The emission intensities were characterized using CIE chromaticity diagram and the observed CIE coordinates shows a shift towards reddish – orange region with the increase in Eu³⁺ concentration. The quantum efficiency of the prepared glasses was determined experimentally. The obtained results suggest that the ND1E glassy system can be considered as a potential candidate for visible and NIR luminescence applications.     

Synthesis,energy transfer mechanism,and tunable emissions of novel Na3La(VO4)2:Re3+ (Re3+ = Dy3+, Eu3+, and Sm3+) vanadate phosphors for near-UV-excited white LEDs

In this study, novel Eu³⁺-, Dy³⁺-, and Sm³⁺-activated Na₃La(VO₄)₂ phosphors were synthesized using a solid state reaction method. X-ray diffraction analysis results indicated that the Na₃La(VO₄)₂ phosphors had an orthorhombic crystal structure with the Pbc21 space group. There were two different La(1)O₈ and La(2)O₈ polyhedra with high asymmetry in the crystal structure. Scanning electron microscopy revealed that the product had a sheet morphology with an irregular particle size. Further, the luminescence properties, including the excitation and emission spectra, and luminescence decay curve, were investigated using a fluorescence spectrometer. The results showed that the Na₃La(VO₄)₂ compound was an excellent host for activating the luminescence of Eu³⁺ (614 nm), Dy³⁺ (575 nm), and Sm³⁺ (647 nm) ions. Further, Dy³⁺/Eu³⁺ co-doped Na₃La(VO₄)₂ phosphors were exploited, and the energy transfer from Dy³⁺ to Eu³⁺ was demonstrated in detail by the photoluminescence excitation, photoluminescence spectra, and luminescent decay curves. The results showed that the energy transfer efficiency from Dy³⁺ to Eu³⁺ was highly efficient, and the energy transfer mechanism was dipole–dipole interactions. Finally, tunable emissions from the yellow region of CIE (0.3925, 0.4243) to the red region of CIE (0.6345, 0.3354) could be realized by rationally controlling the Dy³⁺/Eu³⁺ concentration ratio. These phosphors may be promising materials for the development of solid-state lighting and display systems.     

Visual Evaluation of Daylight Simulators for the Colorimetry of Luminescent Materials

The accuracy of several methods for assessing the colorimetric performance of daylight simulators as practical realizations of CIE standard daylight illuminants such as D₆₅ was studied by visual methods. Eight luminescent samples containing various fluorescent whitening agents were used. Visual differences between sample pairs, each consisting of a luminescent sample and its nonluminescent substrate, were judged under a reference source simulating D₆₅ and six test sources with different ultraviolet content from the reference source but nearly the same spectral irradiance in the visible region. Over 3000 observations were made by eight observers. Visual scale values were derived and compared to indices calculated by five published methods. The results show that four methods based on colorimetric weighting gave significantly better correlations than one based on radiometric weighting, with little choice among them; that the CIELAB color-difference equation was preferred to CIELUV; and that the choice of 2° or 10° standard observer had no effect.