WO2003062818A1 - Method for the spectroscopic analysis of viscose constituents - Google Patents

Method for the spectroscopic analysis of viscose constituents Download PDF

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Publication number
WO2003062818A1
WO2003062818A1 PCT/AT2003/000016 AT0300016W WO03062818A1 WO 2003062818 A1 WO2003062818 A1 WO 2003062818A1 AT 0300016 W AT0300016 W AT 0300016W WO 03062818 A1 WO03062818 A1 WO 03062818A1
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WO
WIPO (PCT)
Prior art keywords
viscose
determined
na
method
constituents
Prior art date
Application number
PCT/AT2003/000016
Other languages
German (de)
French (fr)
Inventor
Thomas Baldinger
Johann Moosbauer
Susanne Jary
Original Assignee
Lenzing Aktiengesellschaft
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
Priority to ATA108/2002 priority Critical
Priority to AT1082002 priority
Application filed by Lenzing Aktiengesellschaft filed Critical Lenzing Aktiengesellschaft
Publication of WO2003062818A1 publication Critical patent/WO2003062818A1/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/36Textiles
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • 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 infra-red, visible or ultra-violet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection

Abstract

The invention relates to a method for the spectroscopic analysis of viscose constituents, whereby the ATR technique is used for said analysis.

Description

A method for the spectroscopic determination of Niskosebestandteilen

The present invention relates to a method for the spectroscopic determination of Viskosebestandteilen, in particular by infrared spectroscopy. With the process especially viscose staple solutions will be studied spectroscopically.

The chemical composition of viscose staple Solutions has a decisive influence on the quality of viscose fibers. For the spinning process, it is particularly important to achieve a consistent product quality. It is therefore essential to know the chemical composition of the dope and monitor the process.

The classical methods for determining the quality parameter of viscose spinning solutions consist, for example, in the iodometric determination of the Cellulosexanthogenates (gamma-value), a acidometrischen titration of ΝaOH content, a spectroscopic (UV-VIS) determining the trithiocarbonate content (TTC) and a gravimetric determination of the cellulose content. This provision is time-consuming and was replaced by spectroscopic methods.

The simultaneous determination of the main components of viscose staple solutions in the near infrared (VIS-ΝIR) is known (see, eg, S. M. Sollinger and Nõges, J. Νear Infrared Spectrosc. 5, 135-148 (1997)). According to this method, the simultaneous determination of the following ingredients viscose succeeds: ΝaOH, trithiocarbonate (TTC), cellulose xanthogenate and cellulose by means of spectroscopic measurements in the visible range ΝIR- coupled with mathematical methods, such as multivariate data analysis.

In general, the infrared spectroscopy is now regarded as an important instrument for the analysis of mixtures and process monitoring. This was based on the development of Fourier transform infrared spectrometer (FTIR). In combination with an attenuated-total-eflection Meßsondensystem (ATR), this method for the analysis of fast chemical reactions has been proven, and this system is installed directly in the reaction chamber.

However, spectroscopic methods for investigation of viscose spinning solutions described have the disadvantage that they require extensive sample preparation, since the under investigation spinning solutions having a high viscosity, the measuring cuvette is bubble-free as possible to attack, and the temperature are kept constant during the measuring process got to. Sample preparation and measurement should be completed as soon as possible in addition, since the spinning solutions are sensitive in chemical terms, quickly change and falsify the measurement result.

The present invention has as its object to provide a method of analysis is available, which does not have the above disadvantages.

This object is achieved with a method of the type shown in that to determine the ATR technique is used.

It has been shown that the ATR technique is advantageous for studying the viscose and very accurate measurement allowed, even though the analysis beam does not pass through the sample. This allows easy sample preparation, as for measuring only a drop viscose Spinnlöung to a high refractive index medium, for example a Diamantplät Chen, needs to be applied and the sample is detected in total reflection.

With the inventive method, at least one of cellulose, total alkali, sulfur, NaOH, Na 2 CO 3 can be in the sample, determine Na 2 CS 3 and gamma-value.

A preferred Ausfurhrungsform of the inventive method is that the four constituents cellulose, total alkali and sulfur are determined.

A further preferred embodiment of the inventive method is that NaOH, Na 2 CO 3, Na 2 CS 3 and gamma-value can be determined additionally.

The inventive method has furthermore the advantage that the spectroscopic analysis in the mid-infrared can be carried out with a wavelength in the region from 600 to 4000 cm "1 (MIR range). This allows a better allocation of the individual absorbances with the groups of atoms or molecular moieties of is to be determined Bestabdteile than in the near infrared (NCR). possible. in NDR. Obeschwingungen the molecules are mainly registered with the association to the individual is not so easy to be determined constituents. It is the skilled worker it clear that in this case, the medium used for the ATR technique, high refractive index must be matched to the wavelength range of the measuring light.

With the following examples the invention is explained in more detail. Calibration (calibration)

Of a sufficiently large set (A) of measuring samples the parameters of interest or constituents to be determined as accurately as possible by means of conventional methods and in each case was added a spectrum. The distribution of the individual parameter values ​​is to cover as the expected range going advantageous is when the individual parameters vary not parallel (eg no dilutions as "independent" samples). The required number of samples depends in part on the number to be determined of parameters and the reliability of the individual conventional analysis methods.

If necessary, a pretreatment spectra is tested (for example, baseline correction, Norminierung, derivative) or empirically selected. From the vectors of parameters and spectra of these samples, a suitable spectral range for the calibration is now selected by a suitable multivariate calibration program and generates a set of spectra factor. Each sample spectrum can be represented by a linear combination of these spectra factor plus a residual error spectrum. From the coefficients of a certain value is obtained for each parameter. By minimizing the residual error the optimal number to be used factor spectra can be determined. Both for the election of the spectra and the spectral pretreatment and to determine the optimal number of factor spectra of most commercial software packages offer automatic routines.

In a next step, any outliers are searched for and eliminated (mostly also programmed cluster analytical routines in the software packages) and with the remaining samples recalculated factor spectra. From the calculations, a degree of correlation (R 2) and a standard calibration error, a measure of the quality of the calibration results in this case for each parameter.

validation

From another sufficiently large set (B) of samples the parameters of interest (X) can be determined as accurately as possible by means of conventional methods and in each case added again a spectrum; resulting calculated parameters from these spectra and the above calibration. The comparison with directly specific parameters again results in a degree of correlation (R 2) and a standard prediction error which practically relevant variables for assessing the quality of the analysis. If these values ​​are in a predetermined by the requirements of the framework, it can be determined in a very short time from a recorded in the same manner spectrum of an unknown sample of the entire set of calibrated parameters.

provisions

A set of approximately 400 Viskoseproben was measured for 8 Parameter cellulose content, total alkali, sulfur, NaOH content, Na 2 CO 3, Na 2 CS 3, gamma value and spin maturity, as completely as possible characterized and of all the samples an infrared spectrum in the range between 4,000 and was added 600 cm '1.

For recording the spectra FT-ER spectrometer from Bruker was used (DFS 66) and a horizontal diamond ATR unit with hermetically sealed beam path. the resolution was 2 cm '1.

The evaluations (spectra pretreatment and multivariate calibration for a PLS algorithm) with the software "opus" and the additive package "Opus Quant 2" from. Bruker or the PLS package GRAMS software of Fa. Galactic (PLS = "Partial Least Squares ").

Part of the data sets (60, all full characterized) was reserved for future validation, with the remaining 340 data sets was performed multivariate calibration after a PLS algorithm by first determined for each parameter the optimal spectra pretreatment and the appropriate spectral range were (range 2000-675 cm "1). In the next step the factor spectra were calculated and the number of color active spectra used against residual error from an application, the optimum for each number of parameters to be used factor spectra (=" determined Rank ").

With this "Rank" now a first calibration were prepared and subjected to all the samples an outlier test. Then, with the elimination of outlier (it remained up to 314 samples) repeats the calibration and the statistical parameters standard calibration error and regression coefficient R 2 of calibration determined.

In a final step of the IR spectra of the reserved validation samples were calculated (as quasi unknowns) the calibrated parameter and these statistically compared with the directly measured values (standard prediction error and regression coefficient R 2 of the validation). The results are shown in the following table:

Figure imgf000006_0001

The table shows satisfactory results (standard prediction error) for all seven calibrated parameters. As a further parameter the ripeness of the viscose can be determined with the inventive method, wherein the calibration range [Ηo] is 8 to 15

Claims

claims:
1. A method for the spectroscopic determination of viscous' sebestandteilen, characterized in that, to determine the ATR technique is used.
2. The method according to claim 1, characterized in that at least one of cellulose, total alkali, sulfur, NaOH, Na 2 CO, Na 2 CS 3 and gamma-value can be determined.
3. The method according to claim 2, characterized in that the four constituents cellulose, total alkali, sulfur, and gamma-value can be determined.
4. The method according to claim 3, characterized in that NaOH, Na 2 CO 3, Na 2 CS 3 and gamma-value can be determined additionally.
5. The method according to any one of claims 1 to 4, characterized in that the determination of mid-infrared is carried out with a wavelength in the region from 600 to 4000 cm "1 (MER range).
PCT/AT2003/000016 2002-01-23 2003-01-17 Method for the spectroscopic analysis of viscose constituents WO2003062818A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ATA108/2002 2002-01-23
AT1082002 2002-01-23

Publications (1)

Publication Number Publication Date
WO2003062818A1 true WO2003062818A1 (en) 2003-07-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2003/000016 WO2003062818A1 (en) 2002-01-23 2003-01-17 Method for the spectroscopic analysis of viscose constituents

Country Status (1)

Country Link
WO (1) WO2003062818A1 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0440472A1 (en) * 1990-02-01 1991-08-07 James River Corporation Of Virginia High bulking resilient fibers through cross linking of wood pulp fibers with polycarboxylic acids

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0440472A1 (en) * 1990-02-01 1991-08-07 James River Corporation Of Virginia High bulking resilient fibers through cross linking of wood pulp fibers with polycarboxylic acids

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DIAS C R ET AL: "Structure of water in asymmetric cellulose ester membranes - an ATR-FTIR study", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER SCIENTIFIC PUBL.COMPANY. AMSTERDAM, NL, vol. 138, no. 2, 21 January 1998 (1998-01-21), pages 259 - 267, XP004107200, ISSN: 0376-7388 *
MASCARENHAS M ET AL: "CHARACTERIZATION OF PLANT CARBOHYDRATES AND CHANGES IN LEAF CARBOHYDRATE CHEMISTRY DUE TO CHEMICAL AND ENZYMATIC DEGRADATION MEASURED BY MICROSCOPIC ATR FT-IR SPECTROSCOPY", APPLIED SPECTROSCOPY, THE SOCIETY FOR APPLIED SPECTROSCOPY. BALTIMORE, US, vol. 54, no. 5, May 2000 (2000-05-01), pages 681 - 686, XP001130460, ISSN: 0003-7028 *
MURPHY D ET AL: "An ATR-FTIR study of water in cellulose acetate membranes prepared by phase inversion", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER SCIENTIFIC PUBL.COMPANY. AMSTERDAM, NL, vol. 106, no. 3, 31 October 1995 (1995-10-31), pages 245 - 257, XP004041257, ISSN: 0376-7388 *
YOUNG GUN KO ET AL: "Physicochemical and thermal studies of viscose rayon borate fiber and its carbon fiber", J POLYM SCI PART A;JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY NOV 15 2001, vol. 39, no. 22, 15 November 2001 (2001-11-15), pages 3875 - 3883, XP002237204 *

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