近红外光谱快速无损检测仿瓷材料及制品的研究
摘要
近年来,仿瓷制品由于美观坚固耐用的特性,广泛使用于生活中的各个方面。按照国家标准要求,仿瓷餐具应由纯三聚氰胺甲醛树脂制作而成,但是市场中充斥着很多用脲醛树脂制作的伪劣仿瓷餐具,对人们身体健康会造成严重危害,使仿瓷制品的安全性饱受争议。目前,仿瓷制品仅规定了理化指标,并不包含检测制品成分的方法。现有通过核磁共振或红外方法鉴别仿瓷制品主要成分的研究报道,但这两种方法仪器昂贵,耗时长、并均会对样品造成破坏。因此,研究快速无损检测方法对仿瓷制品质量管理和市场监督具有重要的现实意义。
近红外光谱技术由于其分析速度快,操作简便,适用于现场和在线分析的技术特点,广泛应用于石油化工,农业,生物医药等领域。目前尚未见到使用近红外光谱技术对仿瓷制品进行分析的文献和报道,因此,本课题提出了一种近红外光谱鉴定仿瓷餐具及制品质量的分析方法,实现了仿瓷制品成分鉴定,为识别市场上密胺餐具产品的真伪提供了一种快速无损分析技术。
论文共收集具有代表性仿瓷样品112个,研究了样品的近红外光谱测量条件,采用主成分马氏距离及SMICA分类方法,处理光谱集对样品进行分类,并通过FT-IR法对分类结果进行了验证；研究发现了鉴别仿瓷制品的特征波长,为研制低成本手持式仿瓷餐具质量检测仪提供了可行性依据；论文还在密胺树脂中混兑不同比例的脲醛树脂粉,制成板材,通过建立预测仿瓷餐具中伪劣成分含量预警模型,研究了近红外光谱预测仿瓷餐具中脲醛树脂含量的可行性。
论文还结合仿瓷制品无损检测方法研究,对光谱信号处理方法---正交信号校正法(OSC)进行了研究。(OSC)应用于近红外光谱建模可显著改善光谱与待测性质之间的相关性,但存在过拟合现象问题—直没有得到有效解决。本文深度剖析了其原因,提出了有效解决方法,并通过多种建模实验进行了验证。
Melamine material has been widely used in our daily lives, owing to their good characteristics of beauty, firmness and durableness. Melamine tableware must be made from melamine-formaldehyde resin (MF) according to the Chinese National Standard. However, a large number of inferior melamine tableware made from urea-formaldehyde resin (UF) or UF-MF mixture appeared in the market, which are very harmful to health and has caused severe safety problems about melamine tableware. At present the melamine identification still relies on the physical and chemical indices, with which the ingredients of melamine cannot be authenticated effectively. Therefore, the development of fast screen method is very meaningful to the supervision and control on melamine tableware market.
Near infrared spectroscopic (NIR) technology has been applied in agricultural and petrochemical fields in virtue of its merits of fast and nondestructive analysis for long. There are many successful examples about distinguishing materials with NIR. In this paper, a rapid method to identify melamine tableware with near infrared reflectance spectroscopy was proposed
In this thesis, more than 112 melamine tableware samples were collected from the markets around Beijing. An optimal condition suitable for measuring spectra of melamine table-wares was studied, and identification models using Mahalanobis distance and SIMCA methods was built. The results showed that melamine tableware and the fake ones can be discriminated by NIR, and the recognition rates of up to 100% have been obtained. In order to determine the MF-UF content in melamine tableware, many polymer samples with different contents of MF-UF powder were prepared in Lab. Feasibility of establishing quantitative model for determining MF-UF content in melamine table-wares were studied. The SECV and SEP are 0.06 and 0.28, respectively. Although orthogonal signal correction, OSC, is very effective for improving correlation curve of spectra -property, the over-fitting phenomenon in building PLS model using OSC has been not resolved yet. In the quantitative analysis study the reason to bring about the over-fitting has been discussed..An effective application method of OSC has been found using MLR modeling, which can avoid the over fitting occurred in PLS modeling.
近红外光谱技术由于其分析速度快,操作简便,适用于现场和在线分析的技术特点,广泛应用于石油化工,农业,生物医药等领域。目前尚未见到使用近红外光谱技术对仿瓷制品进行分析的文献和报道,因此,本课题提出了一种近红外光谱鉴定仿瓷餐具及制品质量的分析方法,实现了仿瓷制品成分鉴定,为识别市场上密胺餐具产品的真伪提供了一种快速无损分析技术。
论文共收集具有代表性仿瓷样品112个,研究了样品的近红外光谱测量条件,采用主成分马氏距离及SMICA分类方法,处理光谱集对样品进行分类,并通过FT-IR法对分类结果进行了验证；研究发现了鉴别仿瓷制品的特征波长,为研制低成本手持式仿瓷餐具质量检测仪提供了可行性依据；论文还在密胺树脂中混兑不同比例的脲醛树脂粉,制成板材,通过建立预测仿瓷餐具中伪劣成分含量预警模型,研究了近红外光谱预测仿瓷餐具中脲醛树脂含量的可行性。
论文还结合仿瓷制品无损检测方法研究,对光谱信号处理方法---正交信号校正法(OSC)进行了研究。(OSC)应用于近红外光谱建模可显著改善光谱与待测性质之间的相关性,但存在过拟合现象问题—直没有得到有效解决。本文深度剖析了其原因,提出了有效解决方法,并通过多种建模实验进行了验证。
Melamine material has been widely used in our daily lives, owing to their good characteristics of beauty, firmness and durableness. Melamine tableware must be made from melamine-formaldehyde resin (MF) according to the Chinese National Standard. However, a large number of inferior melamine tableware made from urea-formaldehyde resin (UF) or UF-MF mixture appeared in the market, which are very harmful to health and has caused severe safety problems about melamine tableware. At present the melamine identification still relies on the physical and chemical indices, with which the ingredients of melamine cannot be authenticated effectively. Therefore, the development of fast screen method is very meaningful to the supervision and control on melamine tableware market.
Near infrared spectroscopic (NIR) technology has been applied in agricultural and petrochemical fields in virtue of its merits of fast and nondestructive analysis for long. There are many successful examples about distinguishing materials with NIR. In this paper, a rapid method to identify melamine tableware with near infrared reflectance spectroscopy was proposed
In this thesis, more than 112 melamine tableware samples were collected from the markets around Beijing. An optimal condition suitable for measuring spectra of melamine table-wares was studied, and identification models using Mahalanobis distance and SIMCA methods was built. The results showed that melamine tableware and the fake ones can be discriminated by NIR, and the recognition rates of up to 100% have been obtained. In order to determine the MF-UF content in melamine tableware, many polymer samples with different contents of MF-UF powder were prepared in Lab. Feasibility of establishing quantitative model for determining MF-UF content in melamine table-wares were studied. The SECV and SEP are 0.06 and 0.28, respectively. Although orthogonal signal correction, OSC, is very effective for improving correlation curve of spectra -property, the over-fitting phenomenon in building PLS model using OSC has been not resolved yet. In the quantitative analysis study the reason to bring about the over-fitting has been discussed..An effective application method of OSC has been found using MLR modeling, which can avoid the over fitting occurred in PLS modeling.
引文
[1]程军.通用塑料手册[M].北京：国防工业出版社,2007.
[2]王玲.仿瓷餐具产业前景[N].广阔中国医药报,2009.2.12(A06)
[3]商贵芹等.浅析我国密胺(仿陶瓷)餐具新国标GB9690-2009[J].检验检疫科学,2009(5)
[4]王珊.仿瓷餐具安全性探究[J].湖南包装,2009(3)
[5]网温.“毒原料”袭击仿瓷餐具行业[J].声音,2009.5.23
[6]GB/T 9690-1988《食品包装用三聚氰胺成型品卫生标准》[S].
[7]GB/T 9690-2009《食品容器、包装材料用三聚氰胺-甲醛成型品卫生标准》[S].
[8]GB/T 9685-2008《食品容器、包装材料用添加剂使用卫生标准》[S].
[9]邬建平.《食品用包装容器工具等制品生产许可教程》[M].2006.9.1
[10]EN ISO 4614-1999, Plastics-Melamine-formaldehyde moulding-Determination of extractable formaldehyde (ISO 4614:1977)
[11]张巍,高峡,刘伟丽,等.利用热重-质谱(TG-MS)研究密胺餐具和脲醛餐具热释放成分[C].2010年全国高分子材料科学与工程研讨会,2010.10
[12]张巍,高峡,王朝晖,等.ART-IR和固体NMR法分析鉴别仿瓷餐具的材质[J].现代仪器,2010(3)：39-41
[13]吴瑾光.近代傅里叶变换近红外光谱技术及应用[M].北京：科学技术文献出版社.1994.12
[14]杨伟,渠荣遴.固体核磁共振在高分子材料分析中的应用进展[J].高分子通报.2006 12(12)：69-74
[15]Fabio Durante P. Alves, G. Karunasiri, N. Hanson, M. Byloos, H.C. Liu, A. Bezinger, M.Buchanan. NIR, MWIR and LWIR quantum well infrared photo-detector using inter-band and intersubband transitions[J]. Infrared Phys. Teehn. (2006)021.
[16]Sierler H. W., Ozaki Y., Kawano S., Heise H. M. Near Infrared Spectroscopy[M]. Wiley-VCH,2004
[17]严衍禄,赵龙莲,韩东海.近红外光谱分析基础及应用[M].北京：中国轻工业出版社,2005
[18]Ciurczak E, rennen J. Near-Infrared Spectroscopy in Pharmaceutical and Medical Applications [M]. New York:Marcel-Dekker, Inc.,2002
[19]陆婉珍,袁洪福,徐光通.等.现代近红外光谱分析技术[M].北京：中国石化出版社,2007.1
[20]David L. Wetzel. Near-infrared reflectance analysis[J]. Aanlytical Chemistry,1983,55 (12):1165-1176
[21]McClure W F. Near-Infrared Spectroscopy:The giant is running strong [J]. Analytical Chemistry,1994, 66(1):43-51
[22]Christopher J. B.,Robert G D., Allison J. F., et al., Varietal discrimination of Australian wines by means of mid-infrared spectroscopy and multivariate analysis[J]. Analytica Chimica Acta,2008,621(1):19-23
[23]Alison N., Angela M., Ross'T. B., et al., Comparison of non-invasive NIR and Raman spectrometries for determination of alcohol content of spirits[J]. Analytica Chlmica Acta,2005,548(1-2):148-158
[24]马广,傅霞萍,周莹,等.大白桃糖度的近红外漫反射光谱无损检测试验研究[J],光谱学与光谱分析,2007,27(5)：907-910
[25]Yang H., Joseph I.,Manish M. P., Discriminate analysis of edible oils and fats by FT-IR,FT-NIR and FT-Raman spectroscopy[J]. Food Chemistry,2005,93(1):25-32
[26]徐广通,袁洪福,陆婉珍.现代近红外光谱技术及其应用进展[J].光谱学与光谱分析,2000,20(2)：134-142
[27]Aucott LS, Garthwaite PH, Buckland ST. Transformations to reduce the effect of particle size in near-infrared spectra. Analyst,1988,113(12):1849
[28]Heitor L.F, Ivo M.R.J., Celio P., etal., Simultaneous determination of methanol and ethanol in gasoline using NIR spectroscopy[J]. Effect of gasoline composition, Talanta,2008(75):804-810
[29]胡钢亮,吕秀阳,罗玲,等.近红外光谱法同时测定银杏提取液中总黄酮和总内酯含量[J].分析化学,2004,32(8)：1061-1063
[30]李代禧,吴智勇,徐端钧,等.啤酒主要成分的近红外光谱法测定[J].分析化学,2004,32(8)：1070-1073
[31]Isaksson Tomas, Kowalski Bruce. Piece-wise multiplicative scatter correction appliedto near-infrared diffuse transmittance data from meat products[J]. Applied Spectroscopy,1993,47:702
[32]Candolfi A, De Maesschalck R, Jouan-Rinbaud D, et al. The influence of date pre-processing in the pattern recognition of excipients near-infrared spectra[J]. Pharm Biomed Anal,1992,21(1):115
[33]吴静珠,张一鸣,王小超.样品状态与装样条件对近红外光谱测定的影响研究[J].现代科学仪器,2006,1：69
[34]王芳,陈达,邵学广.近红外光谱与卷烟样品常规成分的关系模型研究[J].烟草科技,2002,(5)：23-26
[35]A. S. Bangalore, R. E. Shaffer, G. W. Small, M. A. Arnold[J]. Anal. Chem,1996,4200:68
[36]J.-H. Jiang, R. J. Berry, H. W. Siesler, Y. Ozaki, Anal.Chem.74(2002)3555.
[37]Hongdong Li, Yizeng Liang, Qingsong Xu, et al. Key wavelengths screening using competitive adaptive reweighted sampling method for multivariate calibration. Journal of computational chemistry [J].2010,3(3):592-599
[38]Wold S, Antti H, Lindgren R, Ohman J. Orthogonal signal correction of near-infrared spectra[J]. Chelnometrics and Intelligent Laboratory Systems,1998,44:175-185
[39]褚小立,袁洪福,陆婉珍.近红外分析中光谱预处理及波长选择方法进展与应用[J].化学进展,2004,16(4)：528-542
[40]田高友,袁洪福,刘慧颖,陆婉珍.小波变换用于近红外光谱数据压缩[J].分析测试学报,2005,24(1)：17-20
[41]田高友,袁洪福,刘慧颖,陆婉珍.小波变换用于近红外光谱性质分析[J].分析化学,2004,32(9)：1125-1130
[42]Cowe, Ian A, McNicol, James W. The Use of principal components in the analysis of near-infrared spectra[J]. Applied Spectroscopy,1985,39(2):257-266
[43]Mark Howard. Normalized distances for qualitative near-infrared reflectance analysis[J]. Analytical Chemistry,1986,58(2):379-384
[44]金同铭,刘铃,唐晓伟,潘沈云.现代近红外光谱技术及应用进展[J].分析测试学报,1997,16(1)：32
[45]Davies A M C and Williams Phil. Near Infrared Spectroscopy, The Future Waves[C].7th Proc. Int. Conf. Near Infrared Spectroscopy,1995,389-392
[46]褚小立,袁洪福,陆婉珍.基础数据准确性对近红外光谱分析结果的影响[J].光谱学与光谱分析,2005,25(6)：886-88
[47]Lima. F. S. G, Leite. L. F. M. Determination of Asphalt Cement Properties by Near-Infrared Spectroscopy and Chemometrics[J]. Petroleum Science and Technology,2004,22(5-6):589-600
[48]王艳斌,袁洪福,陆婉珍,齐洪祥,殷宗玲.人工神经网络用于近红外光谱测定柴油闪点[J].分析化学,2000,28(9)：1070-1073
[49]王艳斌,刘伟,袁洪福,陆婉珍.人工神经网络在近红外分析方法中的应用及深色油品的分析[J].石油炼制与化工,2002,33(7)：62.67
[50]Perez-Marin D, Garrido-Varo A, Guerrero JE. Non-linear regression methods in NIRS quantitative analysis[J]. Talanta,2006.10(036)
[51]王韬,杨丽明,赵丽丽,等.傅里叶变换近红外全谱回归分析的应用研究[J].光谱学与光谱分析,2005,25(1)：33-35
[52]刘沭华,张学工,孙素琴.中药材产地的近红外光谱自动鉴别和特征谱段选择[J].科学通报,2005,50(4)：393-398
[53]褚小立,袁洪福,王艳斌,陆婉珍.近红外稳健分析校正模型的建立--样品温度的影响[J].光谱学与光谱分析,2004,24(6)：666-671
[54]褚小立,袁洪福,陆婉珍.一种消除在线多通道近红外分析仪各通道光谱差异的方法[J].分析化学,2005,33(6)：745-750
[55]Xie L.J., Ye X. Q., Liu D. H., et al., Quantification of glucose, fructose and sucrose in bayberry juice by NIR and PLS[J]. Food Chemistry,2009,114(3):1135-1140
[56]赵羚志,任玉秋,窦英,等.短波近红外光谱-偏最小二乘法非破坏分析复方头孢氨卞片[J].生命科学仪器,2006,4(8)：39-41
[57]Heidy S., Richard J., Roggy J. C., Robert L., Domenach A.M. Evaluation of the recovery of microbial functions during soil restoration using near-infrared spectroscopy[J]. Applied soil Ecology,2007, 37(3):223-232
[58]Jouan R. D., Walczak B., Massart D. L., et al., Comparison of multivariate methods based on latent vectors and methods based on wavelength selection for the analysis of near-infrared spectroscopic data[J]. Analytica Chimica Acta,1995,304(3):285-295
[59]Cecilia P., Anders N.. Partitioning the variation of microbial measurements in forest soils into heavy metal and substrate quality dependent parts by use of near infrared spectroscopy and multivariate statistics[J]. Soil Biology and Biochemistry,1996,28(6):711-720
[60]David R.E., Markus T.M., Teresa C., Analysis of the effects of Particles size and densification on NIR Spectra[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2008 331(10):63-67
[61]梁逸曾,俞汝勤.分析化学手册第十分册--化学计量学[M].北京：化学工业出版社,2000.12
[62]许禄.化学计量学一些重要方法的原理及应用[M].北京：科学出版社,2004.2
[63]Wold S, Antti H, Lindgren F, Ohman J. Orthogonal signal correction of near-infrared spectra[J]. Chemometrics and Intelligent Laboratory Systems,44(1998):175-185.
[64]张琳,等.正交信号校正用于傅里叶变换红外光谱的模型传递[J].分析化学,33(12),(2005)：1709-1712
[65]宋宁,等.基于正交信号校正和iPLS的烃源岩红外漫反射光谱定量分析[J].光谱学与光谱分析,29(2)(2009)：378-381
[66]E. Bertran, H. Iturriaga, S. Maspoch, I. Montoliu, Effect of orthogonal signal correction on the determination ofcompounds with very similar near infrared spectra[J]. Analytica Chimica Acta 431 (2001)303-311
[67]Fearn T. On orthogonal signal correction[J]. Chemometries and Intelligent Laboratory Systems,50 (2000):47-52.
[68]Andersson CA. Direct orthogonalization[J], Chemometrics and Intelligent Laboratory Systems, 47(1999):51-63
[69]Trygg J, Wold S. Orthogonal Projections to latent structures(O-PLS)[J]. Journal of Chemometrics, 16(2002):119-128.
[70]余浩.基于正交信号校正算法的近红外光谱预处理[D].浙江大学硕士论文,(2004)：27-37
[71]褚小立,许育鹏,田高友,译.近红外光谱解析使用指南[M].北京：化学工业出版社,2009.10
[2]王玲.仿瓷餐具产业前景[N].广阔中国医药报,2009.2.12(A06)
[3]商贵芹等.浅析我国密胺(仿陶瓷)餐具新国标GB9690-2009[J].检验检疫科学,2009(5)
[4]王珊.仿瓷餐具安全性探究[J].湖南包装,2009(3)
[5]网温.“毒原料”袭击仿瓷餐具行业[J].声音,2009.5.23
[6]GB/T 9690-1988《食品包装用三聚氰胺成型品卫生标准》[S].
[7]GB/T 9690-2009《食品容器、包装材料用三聚氰胺-甲醛成型品卫生标准》[S].
[8]GB/T 9685-2008《食品容器、包装材料用添加剂使用卫生标准》[S].
[9]邬建平.《食品用包装容器工具等制品生产许可教程》[M].2006.9.1
[10]EN ISO 4614-1999, Plastics-Melamine-formaldehyde moulding-Determination of extractable formaldehyde (ISO 4614:1977)
[11]张巍,高峡,刘伟丽,等.利用热重-质谱(TG-MS)研究密胺餐具和脲醛餐具热释放成分[C].2010年全国高分子材料科学与工程研讨会,2010.10
[12]张巍,高峡,王朝晖,等.ART-IR和固体NMR法分析鉴别仿瓷餐具的材质[J].现代仪器,2010(3)：39-41
[13]吴瑾光.近代傅里叶变换近红外光谱技术及应用[M].北京：科学技术文献出版社.1994.12
[14]杨伟,渠荣遴.固体核磁共振在高分子材料分析中的应用进展[J].高分子通报.2006 12(12)：69-74
[15]Fabio Durante P. Alves, G. Karunasiri, N. Hanson, M. Byloos, H.C. Liu, A. Bezinger, M.Buchanan. NIR, MWIR and LWIR quantum well infrared photo-detector using inter-band and intersubband transitions[J]. Infrared Phys. Teehn. (2006)021.
[16]Sierler H. W., Ozaki Y., Kawano S., Heise H. M. Near Infrared Spectroscopy[M]. Wiley-VCH,2004
[17]严衍禄,赵龙莲,韩东海.近红外光谱分析基础及应用[M].北京：中国轻工业出版社,2005
[18]Ciurczak E, rennen J. Near-Infrared Spectroscopy in Pharmaceutical and Medical Applications [M]. New York:Marcel-Dekker, Inc.,2002
[19]陆婉珍,袁洪福,徐光通.等.现代近红外光谱分析技术[M].北京：中国石化出版社,2007.1
[20]David L. Wetzel. Near-infrared reflectance analysis[J]. Aanlytical Chemistry,1983,55 (12):1165-1176
[21]McClure W F. Near-Infrared Spectroscopy:The giant is running strong [J]. Analytical Chemistry,1994, 66(1):43-51
[22]Christopher J. B.,Robert G D., Allison J. F., et al., Varietal discrimination of Australian wines by means of mid-infrared spectroscopy and multivariate analysis[J]. Analytica Chimica Acta,2008,621(1):19-23
[23]Alison N., Angela M., Ross'T. B., et al., Comparison of non-invasive NIR and Raman spectrometries for determination of alcohol content of spirits[J]. Analytica Chlmica Acta,2005,548(1-2):148-158
[24]马广,傅霞萍,周莹,等.大白桃糖度的近红外漫反射光谱无损检测试验研究[J],光谱学与光谱分析,2007,27(5)：907-910
[25]Yang H., Joseph I.,Manish M. P., Discriminate analysis of edible oils and fats by FT-IR,FT-NIR and FT-Raman spectroscopy[J]. Food Chemistry,2005,93(1):25-32
[26]徐广通,袁洪福,陆婉珍.现代近红外光谱技术及其应用进展[J].光谱学与光谱分析,2000,20(2)：134-142
[27]Aucott LS, Garthwaite PH, Buckland ST. Transformations to reduce the effect of particle size in near-infrared spectra. Analyst,1988,113(12):1849
[28]Heitor L.F, Ivo M.R.J., Celio P., etal., Simultaneous determination of methanol and ethanol in gasoline using NIR spectroscopy[J]. Effect of gasoline composition, Talanta,2008(75):804-810
[29]胡钢亮,吕秀阳,罗玲,等.近红外光谱法同时测定银杏提取液中总黄酮和总内酯含量[J].分析化学,2004,32(8)：1061-1063
[30]李代禧,吴智勇,徐端钧,等.啤酒主要成分的近红外光谱法测定[J].分析化学,2004,32(8)：1070-1073
[31]Isaksson Tomas, Kowalski Bruce. Piece-wise multiplicative scatter correction appliedto near-infrared diffuse transmittance data from meat products[J]. Applied Spectroscopy,1993,47:702
[32]Candolfi A, De Maesschalck R, Jouan-Rinbaud D, et al. The influence of date pre-processing in the pattern recognition of excipients near-infrared spectra[J]. Pharm Biomed Anal,1992,21(1):115
[33]吴静珠,张一鸣,王小超.样品状态与装样条件对近红外光谱测定的影响研究[J].现代科学仪器,2006,1：69
[34]王芳,陈达,邵学广.近红外光谱与卷烟样品常规成分的关系模型研究[J].烟草科技,2002,(5)：23-26
[35]A. S. Bangalore, R. E. Shaffer, G. W. Small, M. A. Arnold[J]. Anal. Chem,1996,4200:68
[36]J.-H. Jiang, R. J. Berry, H. W. Siesler, Y. Ozaki, Anal.Chem.74(2002)3555.
[37]Hongdong Li, Yizeng Liang, Qingsong Xu, et al. Key wavelengths screening using competitive adaptive reweighted sampling method for multivariate calibration. Journal of computational chemistry [J].2010,3(3):592-599
[38]Wold S, Antti H, Lindgren R, Ohman J. Orthogonal signal correction of near-infrared spectra[J]. Chelnometrics and Intelligent Laboratory Systems,1998,44:175-185
[39]褚小立,袁洪福,陆婉珍.近红外分析中光谱预处理及波长选择方法进展与应用[J].化学进展,2004,16(4)：528-542
[40]田高友,袁洪福,刘慧颖,陆婉珍.小波变换用于近红外光谱数据压缩[J].分析测试学报,2005,24(1)：17-20
[41]田高友,袁洪福,刘慧颖,陆婉珍.小波变换用于近红外光谱性质分析[J].分析化学,2004,32(9)：1125-1130
[42]Cowe, Ian A, McNicol, James W. The Use of principal components in the analysis of near-infrared spectra[J]. Applied Spectroscopy,1985,39(2):257-266
[43]Mark Howard. Normalized distances for qualitative near-infrared reflectance analysis[J]. Analytical Chemistry,1986,58(2):379-384
[44]金同铭,刘铃,唐晓伟,潘沈云.现代近红外光谱技术及应用进展[J].分析测试学报,1997,16(1)：32
[45]Davies A M C and Williams Phil. Near Infrared Spectroscopy, The Future Waves[C].7th Proc. Int. Conf. Near Infrared Spectroscopy,1995,389-392
[46]褚小立,袁洪福,陆婉珍.基础数据准确性对近红外光谱分析结果的影响[J].光谱学与光谱分析,2005,25(6)：886-88
[47]Lima. F. S. G, Leite. L. F. M. Determination of Asphalt Cement Properties by Near-Infrared Spectroscopy and Chemometrics[J]. Petroleum Science and Technology,2004,22(5-6):589-600
[48]王艳斌,袁洪福,陆婉珍,齐洪祥,殷宗玲.人工神经网络用于近红外光谱测定柴油闪点[J].分析化学,2000,28(9)：1070-1073
[49]王艳斌,刘伟,袁洪福,陆婉珍.人工神经网络在近红外分析方法中的应用及深色油品的分析[J].石油炼制与化工,2002,33(7)：62.67
[50]Perez-Marin D, Garrido-Varo A, Guerrero JE. Non-linear regression methods in NIRS quantitative analysis[J]. Talanta,2006.10(036)
[51]王韬,杨丽明,赵丽丽,等.傅里叶变换近红外全谱回归分析的应用研究[J].光谱学与光谱分析,2005,25(1)：33-35
[52]刘沭华,张学工,孙素琴.中药材产地的近红外光谱自动鉴别和特征谱段选择[J].科学通报,2005,50(4)：393-398
[53]褚小立,袁洪福,王艳斌,陆婉珍.近红外稳健分析校正模型的建立--样品温度的影响[J].光谱学与光谱分析,2004,24(6)：666-671
[54]褚小立,袁洪福,陆婉珍.一种消除在线多通道近红外分析仪各通道光谱差异的方法[J].分析化学,2005,33(6)：745-750
[55]Xie L.J., Ye X. Q., Liu D. H., et al., Quantification of glucose, fructose and sucrose in bayberry juice by NIR and PLS[J]. Food Chemistry,2009,114(3):1135-1140
[56]赵羚志,任玉秋,窦英,等.短波近红外光谱-偏最小二乘法非破坏分析复方头孢氨卞片[J].生命科学仪器,2006,4(8)：39-41
[57]Heidy S., Richard J., Roggy J. C., Robert L., Domenach A.M. Evaluation of the recovery of microbial functions during soil restoration using near-infrared spectroscopy[J]. Applied soil Ecology,2007, 37(3):223-232
[58]Jouan R. D., Walczak B., Massart D. L., et al., Comparison of multivariate methods based on latent vectors and methods based on wavelength selection for the analysis of near-infrared spectroscopic data[J]. Analytica Chimica Acta,1995,304(3):285-295
[59]Cecilia P., Anders N.. Partitioning the variation of microbial measurements in forest soils into heavy metal and substrate quality dependent parts by use of near infrared spectroscopy and multivariate statistics[J]. Soil Biology and Biochemistry,1996,28(6):711-720
[60]David R.E., Markus T.M., Teresa C., Analysis of the effects of Particles size and densification on NIR Spectra[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2008 331(10):63-67
[61]梁逸曾,俞汝勤.分析化学手册第十分册--化学计量学[M].北京：化学工业出版社,2000.12
[62]许禄.化学计量学一些重要方法的原理及应用[M].北京：科学出版社,2004.2
[63]Wold S, Antti H, Lindgren F, Ohman J. Orthogonal signal correction of near-infrared spectra[J]. Chemometrics and Intelligent Laboratory Systems,44(1998):175-185.
[64]张琳,等.正交信号校正用于傅里叶变换红外光谱的模型传递[J].分析化学,33(12),(2005)：1709-1712
[65]宋宁,等.基于正交信号校正和iPLS的烃源岩红外漫反射光谱定量分析[J].光谱学与光谱分析,29(2)(2009)：378-381
[66]E. Bertran, H. Iturriaga, S. Maspoch, I. Montoliu, Effect of orthogonal signal correction on the determination ofcompounds with very similar near infrared spectra[J]. Analytica Chimica Acta 431 (2001)303-311
[67]Fearn T. On orthogonal signal correction[J]. Chemometries and Intelligent Laboratory Systems,50 (2000):47-52.
[68]Andersson CA. Direct orthogonalization[J], Chemometrics and Intelligent Laboratory Systems, 47(1999):51-63
[69]Trygg J, Wold S. Orthogonal Projections to latent structures(O-PLS)[J]. Journal of Chemometrics, 16(2002):119-128.
[70]余浩.基于正交信号校正算法的近红外光谱预处理[D].浙江大学硕士论文,(2004)：27-37
[71]褚小立,许育鹏,田高友,译.近红外光谱解析使用指南[M].北京：化学工业出版社,2009.10