WO2000008446A1 - Galvanised metal coating analysis by laser ablation - Google Patents

Galvanised metal coating analysis by laser ablation Download PDF

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Publication number
WO2000008446A1
WO2000008446A1 PCT/GB1999/002418 GB9902418W WO0008446A1 WO 2000008446 A1 WO2000008446 A1 WO 2000008446A1 GB 9902418 W GB9902418 W GB 9902418W WO 0008446 A1 WO0008446 A1 WO 0008446A1
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WIPO (PCT)
Prior art keywords
galvanised
laser ablation
metal
spectrophotometry
phase information
Prior art date
Application number
PCT/GB1999/002418
Other languages
French (fr)
Inventor
David Charles Richards
Ian Robert Crosby Whiteside
Original Assignee
Corus Uk Limited
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 Corus Uk Limited filed Critical Corus Uk Limited
Priority to AU51755/99A priority Critical patent/AU5175599A/en
Publication of WO2000008446A1 publication Critical patent/WO2000008446A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0459—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples
    • H01J49/0463—Desorption by laser or particle beam, followed by ionisation as a separate step
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/208—Coatings, e.g. platings

Definitions

  • This invention relates to galvanised metal. More especially, but not exclusively, the invention relates to a method and apparatus for analysing the surface composition of a galvanised layer, in particular gaivanneal.
  • Galvanised metal for example, gaivanneal
  • the gaivanneal layer is of the order of 8-1 O ⁇ m thick and comprises several phases wherein the iron concentration decreases and the zinc concentration increases towards the surface of the layer. Adjacent to a steel substrate surface is a gamma phase (Fe 5 Zn 21 ) which is followed by a delta phase (FeZn 7 ).
  • the outer layer is predominantly a zeta phase (FeZn 13 ) but if under-alloyed, free zinc (Zn), or an eta phase, may be present. It is possible to manipulate the ratio of the three main phases, while maintaining a constant concentration of iron, by changing the annealing cycle used in the post-galvanising process.
  • Zinc-iron galvanised steel sheet has excellent spot weldability, paint adhesion and corrosion resistance, but suffers poor formability due to a flaking phenomenon during pressing which is known as "powdering".
  • paint adhesion is dependent on alloy composition, with good adhesion properties observed with an iron content of less than 10%, marginal adhesion with an iron content of between 10 and 1 1 % and poor adhesion for an iron content greater than 1 1 %. This correlates with an increase in more iron-rich and brittle phases of gaivanneal.
  • X-ray diffraction and X-ray fluorescence studies have indicated that there is also a correlation between the composition of an alloy layer and the degree of powdering. Therefore, the ability to measure alloy composition and control it on galvannealling process lines will be extremely important.
  • Iron content is only one component of the phases present in the gaivanneal layer and detailed phase information is required to fully understand the relationship between composition and properties such as powdering.
  • the molten zinc bath used in the galvanising process contains aluminium which is also known to affect coating phase composition and properties. Some studies have indicated that an aluminium concentration in the coating of less than 0.1 % offers good resistance to powdering.
  • the gamma phase of the gaivanneal layer is known to be the hardest. Therefore, it has been suggested that powdering will be reduced most effectively by minimising the thickness of the gamma phase. For good coating properties, some experts believe that the gamma phase should comprise less than 5% of the total thickness. However, this theory is not universal because of the complexity of factors which contribute to the final formability of the steel. For example, higher bath aluminium concentrations delay the formation of the gamma phase and for given annealing conditions produce thinner layers.
  • coatings consisting mainly of a zeta phase exhibit lower incidences of powdering.
  • the zeta phase has a low hardness and resists cracking by relaxing compressive stresses by deforming itself. Unfortunately, this property leads to higher friction during pressing and hence poor drawability.
  • Table I shows the properties exhibited by different phases in the gaivanneal layer.
  • the invention provides a method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry.
  • laser ablation may be used as a method of removing small samples from metal surfaces. Control of the laser power density and the focus spot diameter enables the sample volume to be controlled. Each laser pulse produces a discrete plasma which emits wavelengths characteristic of the atom or ion population produced from the ablated specimen. The intensities of the element-specific wavelengths may be directly related to composition using a conventional optical emission spectrophotometer.
  • pulsed lasers with wavelengths ranging from the ultraviolet to the infra-red spectrum may be used, that is, between 1 0 ⁇ and 1 0 "4 cm.
  • the laser ablated material may be transferred as an aerosol using an inert carrier gas to a secondary excitation source, such as a mass spectrophotometer, for qualification.
  • a secondary excitation source such as a mass spectrophotometer
  • Laser ablation will fragment the metal sample into positive, negative and neutral fragments.
  • a mass spectrophotometer will deflect the fragments in a strong magnetic field in which the fragments will be deflected according to their mass-to- charge ratio. Analysis of the spectrum produced provides detailed information about the composition of the laser ablated material.
  • the invention provides a method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation to excite atoms/ions at the surface and optical emission spectrophotometry to identify the atoms/ions so excited.
  • the invention provides a method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation to remove a sample of atoms/ions at the surface, collecting the sample and analysing the sample by mass spectrophotometry.
  • depths of sample ablated from the surface are as little as 0.3 ⁇ m, preferably between 0.1 and 0.2 ⁇ m, for example 0.1 5 ⁇ m.
  • the galvanised metal is galvanised steel, that is gaivanneal.
  • the invention provides apparatus for identifying phase information on the surface of galvanised metal by the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry.
  • the invention provides a method for controlling the physical properties of galvanised metal by altering the composition of the galvanised layer, including the steps of:-

Abstract

A method for obtaining phase information from the surface of galvanised metal (8) comprises the use of laser ablation to excite atoms/ions (10) at the surface and optical emission spectrophotometry to identify the atoms/ions so excited. Pulsed lasers (2) with wavelengths ranging from the ultraviolet to the infra-red spectrum may be employed. Alternatively, or additionally, the laser ablated material may be transferred as an aerosol using an inert carrier gas to a secondary excitation source, such as a mass spectrophotometer, for qualification.

Description

GALVANISED METAL COATING ANALYSIS BY LASER ABLATION
This invention relates to galvanised metal. More especially, but not exclusively, the invention relates to a method and apparatus for analysing the surface composition of a galvanised layer, in particular gaivanneal.
Galvanised metal, for example, gaivanneal, has a dull and rough surface appearance. The gaivanneal layer is of the order of 8-1 Oμm thick and comprises several phases wherein the iron concentration decreases and the zinc concentration increases towards the surface of the layer. Adjacent to a steel substrate surface is a gamma phase (Fe5Zn21) which is followed by a delta phase (FeZn7). The outer layer is predominantly a zeta phase (FeZn13) but if under-alloyed, free zinc (Zn), or an eta phase, may be present. It is possible to manipulate the ratio of the three main phases, while maintaining a constant concentration of iron, by changing the annealing cycle used in the post-galvanising process.
Zinc-iron galvanised steel sheet has excellent spot weldability, paint adhesion and corrosion resistance, but suffers poor formability due to a flaking phenomenon during pressing which is known as "powdering". Studies have suggested that paint adhesion is dependent on alloy composition, with good adhesion properties observed with an iron content of less than 10%, marginal adhesion with an iron content of between 10 and 1 1 % and poor adhesion for an iron content greater than 1 1 %. This correlates with an increase in more iron-rich and brittle phases of gaivanneal. X-ray diffraction and X-ray fluorescence studies have indicated that there is also a correlation between the composition of an alloy layer and the degree of powdering. Therefore, the ability to measure alloy composition and control it on galvannealling process lines will be extremely important.
Iron content is only one component of the phases present in the gaivanneal layer and detailed phase information is required to fully understand the relationship between composition and properties such as powdering. For example, the molten zinc bath used in the galvanising process contains aluminium which is also known to affect coating phase composition and properties. Some studies have indicated that an aluminium concentration in the coating of less than 0.1 % offers good resistance to powdering.
The gamma phase of the gaivanneal layer is known to be the hardest. Therefore, it has been suggested that powdering will be reduced most effectively by minimising the thickness of the gamma phase. For good coating properties, some experts believe that the gamma phase should comprise less than 5% of the total thickness. However, this theory is not universal because of the complexity of factors which contribute to the final formability of the steel. For example, higher bath aluminium concentrations delay the formation of the gamma phase and for given annealing conditions produce thinner layers.
It is, however, widely agreed that coatings consisting mainly of a zeta phase exhibit lower incidences of powdering. The zeta phase has a low hardness and resists cracking by relaxing compressive stresses by deforming itself. Unfortunately, this property leads to higher friction during pressing and hence poor drawability.
Table I shows the properties exhibited by different phases in the gaivanneal layer. Hence, the powdering behaviour of the galvanised product must be minimised by finding a balance between phase layers that lies between the limits of over- and under-alloying. Under-alloying causes stickiness as a result of the zeta and eta phases at the coating surface, whereas over-alloying results in hardness and brittleness at the surface.
TABLE I
Figure imgf000005_0001
It is an object of the present invention to provide a means to analyse the surface layer of a gaivanneal coating in order to control the galvannealling process and provide an optimum coating which reduces or substantially eliminates the problems associated with powdering.
Accordingly, in one aspect the invention provides a method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry.
It is known that laser ablation may be used as a method of removing small samples from metal surfaces. Control of the laser power density and the focus spot diameter enables the sample volume to be controlled. Each laser pulse produces a discrete plasma which emits wavelengths characteristic of the atom or ion population produced from the ablated specimen. The intensities of the element-specific wavelengths may be directly related to composition using a conventional optical emission spectrophotometer.
In one example, pulsed lasers with wavelengths ranging from the ultraviolet to the infra-red spectrum may be used, that is, between 1 0 δ and 1 0"4 cm.
Alternatively, or additionally, the laser ablated material may be transferred as an aerosol using an inert carrier gas to a secondary excitation source, such as a mass spectrophotometer, for qualification. Laser ablation will fragment the metal sample into positive, negative and neutral fragments. A mass spectrophotometer will deflect the fragments in a strong magnetic field in which the fragments will be deflected according to their mass-to- charge ratio. Analysis of the spectrum produced provides detailed information about the composition of the laser ablated material.
In another aspect, the invention provides a method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation to excite atoms/ions at the surface and optical emission spectrophotometry to identify the atoms/ions so excited.
In yet another aspect, the invention provides a method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation to remove a sample of atoms/ions at the surface, collecting the sample and analysing the sample by mass spectrophotometry.
Typically, depths of sample ablated from the surface are as little as 0.3μm, preferably between 0.1 and 0.2μm, for example 0.1 5μm.
Preferably, the galvanised metal is galvanised steel, that is gaivanneal.
In another aspect, the invention provides apparatus for identifying phase information on the surface of galvanised metal by the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry. In yet another aspect, the invention provides a method for controlling the physical properties of galvanised metal by altering the composition of the galvanised layer, including the steps of:-
(a) identifying phase information on the surface of galvanised metal with the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry; and,
(b) adjusting annealing cycles to produce the required composition.
It is to be understood that the foregoing is merely exemplary of the invention and that various modifications can be made thereto without departing from the true scope of the invention as set out in the claims.

Claims

1 . A method for obtaining phase information from the surface of a coated metal comprising the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry.
2. A method as claimed in claim 1 wherein the metal is galvanised metal.
3. A method as claimed in claim 1 or claim 2 wherein pulsed lasers are employed with wavelengths ranging from the ultraviolet to the infrared spectrum.
4. A method as claimed in any one of claims 1 to 3 wherein the laser ablated material is transferred as an aerosol using an inert carrier gas to a secondary excitation source for qualifications.
5. A method as claimed in claim 4 wherein the secondary excitation source is a mass spectrophotometer.
6. A method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation to excite atoms/ions at the surface and optical emission spectrophotometry to identify the atoms/ions so excited.
7. A method for obtaining phase information from the surface of galvanised metal comprising the use of laser ablation to remove a sample of atoms/ions at the surface, collecting the sample and analysing the sample by mass spectrophotometry.
8. A method as claimed in claim 7 wherein the depths of sample ablated from the surface are between 0. 1 and 0.2╬╝m.
9. A method as claimed in any one of claims 2 to 8 wherein the galvanised metal is galvanised steel.
10. Apparatus for identifying phase information on the surface of galvanised metal by the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry.
1 1 . A method for controlling the physical properties of galvanised metal by altering the composition of the galvanised layer, including the steps of:-
(a) identifying phase information on the surface of galvanised metal with the use of laser ablation and optical emission spectrophotometry and/or mass spectrophotometry; and,
(b) adjusting annealing cycles to produce the required composition.
1 2. A method substantially as herein described.
1 3. Apparatus substantially as herein described.
PCT/GB1999/002418 1998-08-07 1999-08-06 Galvanised metal coating analysis by laser ablation WO2000008446A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (2)

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GB9817129A GB2340598A (en) 1998-08-07 1998-08-07 Determining composition of galvanised metal coating
GB9817129.1 1998-08-07

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003006967A1 (en) * 2001-07-12 2003-01-23 National Research Council Of Canada Method and apparatus for depth profile analysis by laser induced plasma spectroscopy
US6532068B2 (en) 2001-07-17 2003-03-11 National Research Council Of Canada Method and apparatus for depth profile analysis by laser induced plasma spectros copy
JP2012526265A (en) * 2009-05-07 2012-10-25 シーメンス ヴェ メタルス テクノロジーズ エスアーエス Method and apparatus for spectral analysis of a metal coating layer deposited on the surface of a steel strip

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3002635B1 (en) * 2013-02-27 2015-04-10 Areva Nc SYSTEM FOR THE ANALYSIS, BY LASER-INDUCED PLASMA SPECTROMETRY, OF THE COMPOSITION OF THE SURFACE LAYER OF A MATERIAL AND FOR THE SAMPLING OF SAMPLES FOR COMPLEMENTARY ANALYZES OR CONTROLS OF THIS SURFACE LAYER, AND METHOD RELATING THERETO

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0176625A2 (en) * 1984-10-05 1986-04-09 Kawasaki Steel Corporation Method of laser emission spectroscopical analysis of steel and apparatus therefor
US4740692A (en) * 1985-06-13 1988-04-26 Mitsubishi Denki Kabushiki Kaisha Laser mass spectroscopic analyzer and method
DE4138157A1 (en) * 1991-11-21 1993-05-27 Krupp Ag Measuring thickness of coating, e.g. of zinc@ on steel, - counting repeatedly applied laser pulses until spectral lines in plasma generated changes
EP0654663A1 (en) * 1993-11-19 1995-05-24 Commissariat A L'energie Atomique Method for elementary analysis through optical emission spectroscopy in a plasma produced by a laser beam in presence of Argon
US5537206A (en) * 1993-11-02 1996-07-16 Nkk Corporation Method for analyzing steel and apparatus therefor

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8322709D0 (en) * 1983-08-24 1983-09-28 British Steel Corp Analysis of materials
DE3718672A1 (en) * 1987-06-04 1988-12-15 Metallgesellschaft Ag METHOD FOR ANALYZING METAL PARTICLES
US5135870A (en) * 1990-06-01 1992-08-04 Arizona Board Of Regents Laser ablation/ionizaton and mass spectrometric analysis of massive polymers
JPH0750033B2 (en) * 1991-03-22 1995-05-31 株式会社島津製作所 Emission spectroscopy
US5628044A (en) * 1995-06-02 1997-05-06 Old Dominion University Pure iron-zinc intermetallic galvanneal calibration standards
DE19637480C2 (en) * 1996-09-13 2001-02-08 Thorald Bergmann Device for mass spectrometric analysis of surfaces
US5844149A (en) * 1996-09-19 1998-12-01 Nkk Corporation Method for analyzing solid specimen and apparatus therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0176625A2 (en) * 1984-10-05 1986-04-09 Kawasaki Steel Corporation Method of laser emission spectroscopical analysis of steel and apparatus therefor
US4740692A (en) * 1985-06-13 1988-04-26 Mitsubishi Denki Kabushiki Kaisha Laser mass spectroscopic analyzer and method
DE4138157A1 (en) * 1991-11-21 1993-05-27 Krupp Ag Measuring thickness of coating, e.g. of zinc@ on steel, - counting repeatedly applied laser pulses until spectral lines in plasma generated changes
US5537206A (en) * 1993-11-02 1996-07-16 Nkk Corporation Method for analyzing steel and apparatus therefor
EP0654663A1 (en) * 1993-11-19 1995-05-24 Commissariat A L'energie Atomique Method for elementary analysis through optical emission spectroscopy in a plasma produced by a laser beam in presence of Argon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANDERSON D R ET AL: "DEPTH PROFILE STUDIES USING LASER-INDUCED PLASMA EMISSION SPECTROMETRY", APPLIED SPECTROSCOPY,US,THE SOCIETY FOR APPLIED SPECTROSCOPY. BALTIMORE, vol. 49, no. 6, pages 691-701, XP000508969, ISSN: 0003-7028 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003006967A1 (en) * 2001-07-12 2003-01-23 National Research Council Of Canada Method and apparatus for depth profile analysis by laser induced plasma spectroscopy
US6532068B2 (en) 2001-07-17 2003-03-11 National Research Council Of Canada Method and apparatus for depth profile analysis by laser induced plasma spectros copy
JP2012526265A (en) * 2009-05-07 2012-10-25 シーメンス ヴェ メタルス テクノロジーズ エスアーエス Method and apparatus for spectral analysis of a metal coating layer deposited on the surface of a steel strip
US9212998B2 (en) 2009-05-07 2015-12-15 Primetals Technologies SAS France Method and device for the spectral analysis of a metal coating layer deposited on the surface of a steel strip
KR101737139B1 (en) 2009-05-07 2017-05-17 프리메탈스 테크놀로지스 프랑스 에스에이에스 Method and device for the spectral analysis of a metal coating layer deposited on the surface of a steel strip

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GB2340598A (en) 2000-02-23
GB9817129D0 (en) 1998-10-07

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