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US 9,851,342 B2Granted
Deterioration analyzing method
AssigneeSumitomo Rubber Industries, Ltd.
InventorsFusae Kaneko, Hiroyuki Kishimoto
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Abstract
The present invention provides a method of deterioration analysis that enables detailed analysis of the deterioration, especially of the surface, of a polymer material containing at least two diene polymers. The present invention relates to a method of deterioration analysis including: irradiating a polymer material containing at least two diene polymers with high intensity x-rays; and measuring x-ray absorption while varying the energy of the x-rays, to analyze the deterioration of each diene polymer.
Claims20
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a polymer material containing at least two diene polymers to oxygen and/or ozone deterioration;
- irradiating the polymer material containing at least two diene polymers with high intensity x-rays at multiple different wavelengths in sequence in the energy range of 260 to 400 eV;
- and
- measuring x-ray absorption correspondingly for each energy irradiation in sequence while varying the energy of the x-rays, to analyze deterioration of each diene polymer;
- wherein the method comprises:
- calculating normalization constants α and β using Equations 1-1 from x-ray absorption spectra obtained by scanning over a range of high intensity x-ray energies around the carbon K-shell absorption edge within the range of 260 to 400 eV;
- performing waveform separation of the x-ray absorption spectra around the carbon K-shell absorption edge corrected with the normalization constants α and β to obtain peaks attributed to π* transition at around 285 eV;
- and
- determining degree of deterioration of each diene polymer using Equation 1-2 with areas of the obtained peaks:
- [Total area of x-ray absorption spectrum over measurement range of sample before deterioration]×α=1, and
- [Total area of x-ray absorption spectrum over measurement range of sample after deterioration]×β=1;
- and (Equations 1-1)
- [1−[(π*peak area of each diene polymer after deterioration)×β]/[(π*peak area of each diene polymer before deterioration)×α]]×100=Degree (%) of deterioration. (Equation 1-2)
10 more elements
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a polymer material containing at least two diene polymers to oxygen and/or ozone deterioration;
- irradiating the polymer material containing at least two diene polymers with high intensity x-rays at multiple different wavelengths in sequence in the energy range of 260 to 400 eV;
- and
- measuring x-ray absorption correspondingly for each energy irradiation in sequence in a micro area of the polymer material while varying the energy of the x-rays, to analyze deterioration of each diene polymer,
- wherein the method comprises:
- calculating normalization constants α and β using Equations 2-1 from x-ray absorption spectra of each diene polymer obtained by scanning over a range of high intensity x-ray energies around the carbon K-shell absorption edge within the range of 260 to 400 eV;
- performing waveform separation of the x-ray absorption spectra around the carbon K-shell absorption edge corrected with the normalization constants α and β to obtain peak areas attributed to π* transition at around 285 eV;
- and
- determining degree of deterioration of each diene polymer using Equation 2-2 with the obtained peak areas:
- [Total area of x-ray absorption spectrum of diene polymer Ai in sample before deterioration]×αAi=1, and
- [Total area of x-ray absorption spectrum of diene polymer Ai in sample after deterioration]×βAi=1, (Equations 2-1)
- wherein Ai represents each diene polymer contained in the polymer material;
- and
- [1−[(π* peak area of diene polymer Ai after deterioration)×βAi]/[(π* peak area of diene polymer Ai before deterioration)×αAi]]×100=Degree (%) of deterioration of diene polymer Ai, (Equation 2-2)
- wherein Ai represents each diene polymer contained in the polymer material.
12 more elements
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a polymer material containing at least two diene polymers to oxygen and/or ozone deterioration;
- irradiating the polymer material containing at least two diene polymers with high intensity x-rays at multiple different wavelengths in sequence in the energy range of 500 to 600 eV;
- and
- measuring x-ray absorption correspondingly for each energy irradiation in sequence in a micro area of the polymer material while varying the energy of the x-rays, to analyze deterioration of each diene polymer,
- wherein the method comprises:
- performing waveform separation of an x-ray absorption spectrum of each diene polymer around the oxygen K-shell absorption edge obtained by scanning over a range of high intensity x-ray energies of 500 to 600 eV;
- and
- calculating contribution rates of oxygen deterioration and ozone deterioration of each diene polymer according to Equations 2-3, wherein the oxygen deterioration corresponds to a peak on the low energy side with a peak top energy in the range of at least 532 eV but lower than 532.7 eV, and the ozone deterioration corresponds to a peak on the high energy side with a peak top energy in the range of at least 532.7 eV but not higher than 534 eV:
- [Peak area of oxygen deterioration of diene polymer Ai]/[(Peak area of ozone deterioration of diene polymer Ai)+(Peak area of oxygen deterioration of diene polymer Ai)]×100=Contribution rate (%) of oxygen deterioration of diene polymer Ai, and
- [Peak area of ozone deterioration of diene polymer Ai]/[(Peak area of ozone deterioration of diene polymer Ai)+(Peak area of oxygen deterioration of diene polymer Ai)]×100=Contribution rate (%) of ozone deterioration of diene polymer Ai, (Equations 2-3)
- wherein Ai represents each diene polymer contained in the polymer material.
8 more elements
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a polymer material containing at least two diene polymers to oxygen and/or ozone deterioration;
- irradiating the polymer material containing at least two diene polymers with high intensity x-rays at multiple different wavelengths in sequence in the energy range of 260 to 400 eV;
- and
- measuring x-ray absorption correspondingly for each energy irradiation in sequence in a micro area of the polymer material while varying the energy of the x-rays, to analyze deterioration of each diene polymer,
- wherein the method comprises:
- determining a normalization constant γ using Equation 2-4 from an x-ray absorption spectrum of each diene polymer after deterioration around the carbon K-shell absorption edge;
- and
- correcting a total area of an x-ray absorption spectrum of each diene polymer around the oxygen K-shell absorption edge using Equation 2-5 with the normalization constant γ to determine the amount of oxygen and ozone bonded to each diene polymer:
- [Total area of x-ray absorption spectrum of diene polymer Ai around carbon K-shell absorption edge]×γAi=1, (Equation 2-4)
- wherein Ai represents each diene polymer contained in the polymer material;
- and
- [Total area of x-ray absorption spectrum of diene polymer Ai around oxygen K-shell absorption edge]×γAi=Amount (index) of oxygen and ozone bonded to diene polymer Ai, (Equation 2-5)
- wherein Ai represents each diene polymer contained in the polymer material.
10 more elements
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a sulfur cross-linked polymer material to oxygen and/or ozone deterioration;
- irradiating the sulfur cross-linked polymer material with x-rays at multiple different wavelengths in sequence in the energy range of 260 to 400 eV, and measuring x-ray absorption correspondingly for each energy irradiation in sequence while varying the energy of the x-rays, to determine deterioration of polymers;
- irradiating the sulfur cross-linked polymer material with constant energy x-rays, and measuring excited and emitted photoelectrons to determine deterioration of sulfur crosslinks;
- and
- determining a deterioration ratio between polymers and sulfur crosslinks from the deterioration of polymers and the deterioration of sulfur crosslinks,
- wherein the method comprises:
- calculating normalization constants α and β using Equations 3-1 from x-ray absorption spectra obtained by scanning over a range of x-ray energies around the carbon K-shell absorption edge within the range of 260 to 400 eV;
- performing waveform separation of the x-ray absorption spectra around the carbon K-shell absorption edge corrected with the normalization constants α and β to obtain peak areas attributed to π* transition at around 285 eV;
- and
- determining degree (%) of deterioration of polymers using Equation 3-2 with the obtained peak areas:
- [Total area of x-ray absorption spectrum over measurement range of sample before deterioration]×α=1, and
- [Total area of x-ray absorption spectrum over measurement range of sample after deterioration]×β=1;
- and (Equations 3-1)
- [1−[(π*peak area after deterioration)×β]/[(π*peak area before deterioration)×α]]×100=Degree (%) of deterioration of polymers. (Equation 3-2)
11 more elements
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a sulfur cross-linked polymer material to oxygen and/or ozone deterioration;
- irradiating the sulfur cross-linked polymer material with x-rays at multiple different wavelengths in sequence in the energy range of 260 to 400 eV, and measuring x-ray absorption correspondingly for each energy irradiation in sequence while varying the energy of the x-rays, to determine deterioration of polymers;
- irradiating the sulfur cross-linked polymer material with constant energy x-rays, and measuring excited and emitted photoelectrons to determine deterioration of sulfur crosslinks;
- and
- determining a deterioration ratio between polymers and sulfur crosslinks from the deterioration of polymers and the deterioration of sulfur crosslinks,
- wherein the method comprises:
- dispersing the photoelectrons excited and emitted by irradiation with the constant energy x-rays;
- measuring S2p photoelectron intensity to obtain an x-ray photoelectron spectrum;
- performing waveform separation of the spectrum to obtain a peak area attributed to sulfur oxides;
- and
- determining degree (%) of deterioration of sulfur crosslinks using Equation 3-3 with the obtained peak area:
- (S2p peak area attributed to sulfur oxides)/(Total S2p peak area)×100=Degree (%) of deterioration of sulfur crosslinks. (Equation 3-3)
9 more elements
A method of oxygen and/or ozone deterioration analysis, comprising:
- subjecting a sulfur cross-linked polymer material to oxygen and/or ozone deterioration;
- irradiating the sulfur cross-linked polymer material with x-rays at multiple different wavelengths in sequence in the energy range of 260 to 400 eV, and measuring x-ray absorption correspondingly for each energy irradiation in sequence while varying the energy of the x-rays, to determine deterioration of polymers;
- irradiating the sulfur cross-linked polymer material with constant energy x-rays, and measuring excited and emitted photoelectrons to determine deterioration of sulfur crosslinks;
- and
- determining a deterioration ratio between polymers and sulfur crosslinks from the deterioration of polymers and the deterioration of sulfur crosslinks,
- wherein the method comprises:
- dispersing the photoelectrons excited and emitted by irradiation with the constant energy x-rays;
- measuring S1s photoelectron intensity to obtain an x-ray photoelectron spectrum;
- performing waveform separation of the spectrum to obtain a peak area attributed to sulfur oxides;
- and
- determining degree (%) of deterioration of sulfur crosslinks using Equation (3-4) with the obtained peak area:
- (S1s peak area attributed to sulfur oxides)/(Total S1s peak area)×100=Degree (%) of deterioration of sulfur crosslinks. (Equation 3-4)
9 more elements
Dependencies are inferred from the claim text.