EP2077949A2 - Manufacturing process to produce litho sheet - Google Patents

Manufacturing process to produce litho sheet

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Publication number
EP2077949A2
EP2077949A2 EP07759824A EP07759824A EP2077949A2 EP 2077949 A2 EP2077949 A2 EP 2077949A2 EP 07759824 A EP07759824 A EP 07759824A EP 07759824 A EP07759824 A EP 07759824A EP 2077949 A2 EP2077949 A2 EP 2077949A2
Authority
EP
European Patent Office
Prior art keywords
less
equal
alloy
current
sheet
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP07759824A
Other languages
German (de)
French (fr)
Other versions
EP2077949B1 (en
Inventor
Juan Francisco Del Rio Martin
Jose Alberola Fuster
Gemma Mora Azuar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Acr Ii Aluminium Group Cooperatief Ua
Original Assignee
Alcoa Corp
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
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Application filed by Alcoa Corp filed Critical Alcoa Corp
Publication of EP2077949A2 publication Critical patent/EP2077949A2/en
Application granted granted Critical
Publication of EP2077949B1 publication Critical patent/EP2077949B1/en
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Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon

Definitions

  • This invention in one embodiment relates to an Al alloy and yet in another
  • Lithographic sheet manufacturing typically includes a
  • electrograining roughening
  • a finished printing plate formed of lithographic sheet is inserted into the
  • Al-materials for offset printing plates must exhibit sufficiently high fatigue strength or reversed bending fatigue strength
  • the present invention provides an alloy suitable for
  • the aluminum alloy includes:
  • the aluminum alloy includes:
  • a lithographic sheet including a electrolytic pre-etching step.
  • method for producing a lithographic sheet includes:
  • peaks may be obtained from a thyristor power supply which conducts in either one or
  • Figure 1 shows the sinusoidal wave form of current used in the prior art
  • Figures 2a-2c represent micrographs of a lithographic sheet surface formed
  • Figures 3a-3c represent micrographs of a lithographic sheet surface formed
  • Figures 4a-4c represent micrographs of a lithographic sheet surface formed
  • Figures 5a-5c represent micrographs of a lithographic sheet surface formed
  • Lithographic sheet is used in printing
  • aluminum alloy means aluminum alloy
  • the alloy of the present invention includes:
  • the Mg content may range from 0.31 wt % to about
  • the Si content may range from about 0.05 wt % to about
  • the Si content may range from about 0.8 wt % to
  • Si in solution may alter the reactivity of the lithographic sheet during
  • Low pitting density may be have a surface characterized
  • plateaus that may be detected by
  • S negative skewness
  • the Si content is too great, too few pits may form during electro-graining, in which the
  • excess pitting may be
  • a surfacing having at least two pits with a diameter greater than 10 ⁇ m
  • the Fe content may range from about 0.25 wt % to
  • the Fe content may range from about
  • Mg present ranging from 0.31 wt % to approximately
  • mixtures further including additives selected from the group including but not limited to
  • the Mg content may range from 0.31 wt
  • Mg is one element in the alloy that may provide for
  • electrograining acids such as HNO 3 or HCl.
  • the temi increased mechanical strength means that a
  • present invention and work hardened to H 18, may have an ultimate tensile strength
  • inventive aluminum alloy has a higher ultimate
  • the H 18 designation means that the material was cold rolled at a temperature not
  • a hard material denotes a Brinell hardness greater than about 50.
  • Zn may be present in less than or equal to about 0.03
  • the Zn content may range from 0.01 wt % to 0.03 wt %.
  • Zn is advantageous for electro-graining in nitric acid.
  • Zn is electrochemically anodic with respect to aluminum and functions as
  • the initiator for pit formation during electrograining.
  • Ti may be present in less than or equal to about 0.03
  • micrographs do not include isolated pits having a diameter greater than about 10 ⁇ m in
  • Grain refiner such as TiB 2 , may or may not be present. Ti combined with
  • Mn is present in less than about 0.25 wt %, preferably
  • Mn may have a strengthening effect.
  • Mn may be present within a range of about 0.01 wt % to about 0.25 wt %. In one embodiment, Mn may be present from about 0.05 wt % to about 0.25 wt % to
  • Cu may be present in up to about 0.04 %, and in one embodiment of the
  • present invention is limited to about 0.007 wt % or less.
  • the alloy includes about 0.8 wt % to about 0.12 wt %
  • the lithographic sheet forming process begins with providing a direct cast
  • titanium boride may be employed as a grain refiner.
  • the ingot is scalped in a machining
  • the pre-heat step prepares the ingot for hot rolling and provides for a
  • the pre-heat step is
  • heat time may range from 2-20 hours depending on the heat up cycle of the furnace.
  • the ingot is then hot rolled to a thickness ranging from about 7.5 mm to
  • the hot rolling apparatus may be single stand or multi-stand hot mill.
  • the strip is then coiled, in which the coiling temperature is
  • the sheet may experience surface defects including but not limited to
  • the strip is cold rolled
  • the annealing atmosphere may or may not be an inert atmosphere.
  • the strip is then cold rolled to a final gauge, i.e. ranging from about 0.1 mm to about 0.5
  • the aluminum strip is then treated with an electrolytic pre- etching or
  • an electrolytic pre-etching step including a
  • coating may be an aluminum oxide having a thickness of about 100 nm or less, and in yet
  • another embodiment may be a thickness ranging from about 1 nm to about 30 nm. It is
  • the electrolytic pre-etching step includes passing the
  • the mineral acid bath may include any one of the minerals acid bath (electrolyte)
  • mineral acid is in a concentration of about 5% to about 35%, and yet in an even further
  • the mineral acid bath may be about 15% to about 25%. In one embodiment,
  • the mineral acid includes sulfuric, phosphoric, or sulfuric-phosphoric mixtures.
  • the aluminum content of the electrolyte should be kept below about 15 g/1
  • the mineral acid wherein higher levels may decrease conductivity.
  • the mineral acid is sodium tartrate
  • bath includes phosphoric acid ranging from about 10% to about 30%, and in yet another
  • embodiment approximately 20% phosphoric acid, and containing about 2 g/1 to about 15
  • the temperature of the mineral acid bath is the temperature of the mineral acid bath
  • acid bath may include chromic, boric, and tartaric acids and combinations thereof.
  • Figure 1 shows the non-sinusoidal wave form 10 of the current generated
  • a thyristor power supply which is used during pre-etching when practicing this
  • the operating frequency of the thyristor power supply is at least several
  • form 10 here disclosed can be generated by a thyristor power supply where the
  • conduction angle is selected for the exact current density applied to the aluminum sheet.
  • the peak voltage ranges from about 35 to about 60 volts.
  • the thyristor power supply maintains a constant peak voltage. Degreasing
  • Peak current is related to peak voltage.
  • cathodic and anodic current the current having a non-sinusoidal wave form 10
  • the aluminum strip may be roughened by
  • electrograining and may be treated by similar processes used to provide lithographic sheet and plates. Suitable electrograining response may be achieved with the alloy and
  • the present alloy and processing method provides a lithographic sheet
  • form 10 which can be asymmetrical or symmetrical and has a constant peak voltage.
  • Table 1 below shows the composition of an alloy within the scope of the
  • Lithographic sheets were formed using the alloy representative of the
  • the comparison sheet formed from AA 1050 was
  • Figures 2a-2c represent micrographs of electrogram roughened lithographic
  • Figures 3a-3c represent micrographs of a comparative example of an
  • Figures 4a-4c represent micrographs of a comparative example of an
  • AA 1050 similar to AA 1050, which included about 0.2 wt % Mg and about 0.07 wt % Mn.
  • alloy composition including 0.090 wt % Si, 0.34 wt % Fe, 0.004 wt % Cu, 0.07 1 wt %
  • the alloy was composed of .096

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)

Abstract

The present invention provides an aluminum alloy for lithographic sheet including about 0.05 wt % to about 0.25 wt % Si; about 0.25 wt % to about 0.4 wt % Fe; less than or equal to about 0.04 wt % Cu; less than or equal to about 0.25 wt % Mn; 0.31 wt % to 0.35 wt % Mg; less than or equal to about 0.03 wt % Zn; less than or equal to about 0.03 wt % Ti; and incidental impurities. Another aspect of the invention is a method of processing a lithographic sheet including the steps of providing an aluminum sheet; contacting the aluminum sheet with an electrolyte bath; and applying a current having a non-sinusoidal wave form with a constant peak voltage to said electrolyte bath.

Description

MANUFACTURING PROCESS TO PRODUCE LITHO SHEET
[0001] This application claims the benefit of U.S. Provisional Application No.
60/787,826 filed March 31, 2006.
Field of the Invention [0002] This invention in one embodiment relates to an Al alloy and yet in another
embodiment relates to a process suitable for producing lithographic sheet having
increased strength and improved electro-graining response.
Background of the Invention [0003] Lithographic sheet manufacturing places high requirements on purity and
uniformity of litho strip surfaces. Lithographic sheet manufacturing typically includes a
roughening process step. It is standard practice to perform electrochemical (EC)
roughening, also referred to as electrograining. It is desirable for electro-graining of the
lithographic sheet to result in a plate that is rough across its entire surface and exhibits a
very uniform non-directional appearance (no streakiness effects).
[0004] A finished printing plate formed of lithographic sheet is inserted into the
printing machine, wherein the exact clamping of the plate on the printing cylinder so that
no play will result during the printing process. When the printing plate is not perfectly
secured and is thus cyclically subjected to bending or torsional loads during printing,
plate cracking occurs according to practical experience in the fast running rotary offset
printing machines. The reason for plate cracking is fatigue fracture, and the result is an
immediate interruption of the printing process. Therefore, Al-materials for offset printing plates must exhibit sufficiently high fatigue strength or reversed bending fatigue strength
so that plate cracking can be prevented.
Summary of the Invention [0005] In one embodiment, the present invention provides an alloy suitable for
lithographic sheet applications that provides increased strength and suitable graining
response performance.
[0006] In one embodiment, the aluminum alloy includes:
[0007] about 0.05 wt % to about 0.25 wt % Si;
[0008] about 0.25 wt % to about 0.4 wt % Fe;
[0009] less than or equal to about 0.04 wt % Cu;
[0010] less than or equal to about 0.25 wt % Mn;
[0011] 0.31 wt % to about 0.40 wt % Mg;
[0012] less than or equal to about 0.03 wt % Zn; and
[0013] less than or equal to about 0.03 wt % Ti;
[0014] In another embodiment, the aluminum alloy includes:
[0015] about 0.8 wt % to about 0.12 wt % Si;
[0016] about 0.28 wt % to about 0.32 wt % Fe;
[0017] less than or equal to about 0.007 wt % Cu;
[0018] less than or equal to about 0.02 wt % Mn;
[0019] 0.31 wt % to about 0.35 wt % Mg;
[0020] less than or equal to about 0.03 wt % Zn; and
[0021] less than or equal to about 0.014 wt % Ti. [0022] In another aspect of the present invention, a method is provided for forming
a lithographic sheet including a electrolytic pre-etching step. In one embodiment, the
method for producing a lithographic sheet includes:
[0023] providing an aluminum sheet;
[0024] contacting the aluminum sheet with an electrolyte bath; and
[0025] applying a current having a non-sinusoidal wave form and substantially
constant peak values to said electrolyte bath.
[0026] The current having a non-sinusoidal wave form with substantially constant
peaks may be obtained from a thyristor power supply which conducts in either one or
both directions to provide a desired current density applied to the aluminum sheet by
controlling the phase angle of the switching point of the power supply.
Brief Description of the Drawings [0027] The following detailed description, given by way of example and not
intended to limit the invention solely thereto, will best be appreciated in conjunction with
the accompanying drawings, wherein like reference numerals denote like elements and
parts, in which:
[0028] Figure 1 shows the sinusoidal wave form of current used in the prior art and
the non-sinusoidal wave form with constant peak values here disclosed, in accordance
with the present invention.
[0029] Figures 2a-2c represent micrographs of a lithographic sheet surface formed
using the alloy and process of the invention, wherein the sheet was treated to an electro graining treatment with 8% HNO3 acid and current densities of 10A/dm2 for a
period of 90 seconds.
[0030] Figures 3a-3c represent micrographs of a lithographic sheet surface formed
of an alloy outside the scope of the present invention, which includes 0.2 wt % Mg,
wherein the sheet was treated to an electro-graining treatment with 8% HNO3 acid and
current densities of 10 A/dm2 for a period of 90 seconds.
[0031] Figures 4a-4c represent micrographs of a lithographic sheet surface formed
an alloy outside the scope of the present invention, which includes 0.2 wt % Mg and 0.07
wt % Mn, wherein the sheet was treated to an electro-graining step with 8% HNO3 acid
and current densities of 10 A/dm2 for a period of 90 seconds.
[0032] Figures 5a-5c represent micrographs of a lithographic sheet surface formed
using the alloy and process of the present invention, wherein the sheet was treated to an
electrograining treatment with 8% HCl acid and current densities of 15 A/dm" for a period
of 20 seconds.
Detailed Description of Preferred Embodiments [0033] Detailed embodiments of the present invention are disclosed herein;
however, it is to be understood that the disclosed embodiments are merely illustrative of
the invention that may be embodied in various forms. In addition, each of the examples
given in connection with the various embodiments of the invention are intended to be
illustrative, and not restrictive. Further, the figures are not necessarily to scale, some
features may be exaggerated to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as
limiting, but merely as a representative basis for teaching one skilled in the art to
variously employ the present invention.
[0034] In accordance with one embodiment of the present invention, an aluminum
alloy is provided for forming lithographic sheet that provides increased strength and
suitable electro-graining performance. Lithographic sheet is used in printing
applications to provide a printing plate. As used herein the term aluminum alloy means
an aluminum metal with soluble alloying elements either in the aluminum lattice or in a
phase with aluminum. All component percentages herein are by weight percent unless
otherwise indicated. When referring to any numerical range of values, such ranges are
understood to include each and every number and/or fraction between the stated range
minimum and maximum. A range of about 5-15 wt. % Si, for example, would expressly
include all intermediate values of about 5.1 , 5.2, 5.3 and 5.5%, all the way up to and
including 14.5, 14.7 and 14.9% Si. The same applies to each other numerical property,
relative thickness and/or elemental range set forth herein.
[0035] In one embodiment, the alloy of the present invention includes:
[0036] about 0.05 wt % to about 0.25 wt % Si;
[0037] about 0.25 wt % to about 0.4 wt % Fe;
[0038] less than or equal to about 0.04 wt % Cu;
[0039] less than or equal to about 0.25 wt % Mn;
[0040] 0.31 wt % to about 0.40 wt% Mg;
[0041] less than or equal to about 0.03 wt % Zn; [0042] less than or equal to about 0.03 wt % Ti; and
[0043] a balance of Al and incidental impurities.
[0044] In one embodiment, the Mg content may range from 0.31 wt % to about
0.35 wt %. In one embodiment, the Si content may range from about 0.05 wt % to about
0.25 wt %. In yet another embodiment, the Si content may range from about 0.8 wt % to
about 0.12 wt %. Si in solution may alter the reactivity of the lithographic sheet during
electro-graining. If the Si content is too low, a low pitting density may
disadvantageously occur during electro-graining, which may render the surface not
suitable for lithographic sheet. Low pitting density may be have a surface characterized
as including flat areas, which may be referred to as plateaus, that may be detected by
scanning electron microscopy (SEM), wherein in one embodiment a low pitting density
may have a negative skewness (S) value, with absolute values being higher than 0.4. If
the Si content is too great, too few pits may form during electro-graining, in which the
size of the individual pits may be too large. In one embodiment, excess pitting may be
characterized as a surfacing having at least two pits with a diameter greater than 10 μm,
as observed in a 100x60 μm scanning electron microscopy (SEM) image.
[0045] In one embodiment, the Fe content may range from about 0.25 wt % to
about 0.4 wt % Fe. In yet another embodiment, the Fe content may range from about
0.28 wt % to about 0.32 wt %. Similar to Si, Fe in solution may alter the reactivity of the
lithographic sheet during electro-graining, wherein excess pitting may occur if the Fe
content is too low or insufficient pitting may occur when the Fe content is too great.
Additionally, increasing the Fe content above the specified range may result in increased intermetallic phases present as particles within the sheet, which are detrimental to the
sheet's electro-graining performance.
[0046] In one embodiment, Mg present ranging from 0.31 wt % to approximately
0.40 wt %, in accordance with the present invention, provides for an electrograining
response that may provide a topography of round pits having a diameter of less than five
microns when processed with acids, such as HNO3, HCl or combinations thereof, and
mixtures further including additives selected from the group including but not limited to
acetic acid and boric acid. In one embodiment, the Mg content may range from 0.31 wt
% to approximately 0.35 wt %. Mg is one element in the alloy that may provide for
strengthening in work hardening. The Mg content of the present alloy surprisingly
helped attained improved mechanical strength, while maintaining electro-graining
performance. Prior to the present invention, a suitable electrograining response was not
achievable in alloys having the Mg content of the present alloy with commercial
electrograining acids, such as HNO3 or HCl.
[0047] In one embodiment, the temi increased mechanical strength means that a
lithographic sheet formed from the inventive alloy and work hardened to Hl 8 temper has
a greater ultimate tensile strength (UTS) and yield strength (YS) being at least about 20
Mpa higher than similarly prepared lithographic sheets of AA 1050.
[0048] In one embodiment, the lithographic sheet formed in accordance with the
present invention and work hardened to H 18, may have an ultimate tensile strength
greater than about 165 MPa, in another embodiment being greater than about 175 MPa,
and a yield strength greater than about 155 MPa, in another embodiment being greater than about 160 MPa. Additionally, the inventive aluminum alloy has a higher ultimate
tensile strength and yield strength than AA 1050 when heat treated following working.
The H 18 designation means that the material was cold rolled at a temperature not
exceeding about 5O0C for significant periods of time to a reduction of about 74% or more
as the last processing step, thereby producing a hard material. For the purposes of this
disclosure a hard material denotes a Brinell hardness greater than about 50.
[0049] In one embodiment, Zn may be present in less than or equal to about 0.03
wt %. In another embodiment, the Zn content may range from 0.01 wt % to 0.03 wt %.
In some embodiments, Zn is advantageous for electro-graining in nitric acid. In one
embodiment, Zn is electrochemically anodic with respect to aluminum and functions as
the initiator for pit formation during electrograining.
[0050] In one embodiment, Ti may be present in less than or equal to about 0.03
wt %, preferably being less than about 0.014 wt %. In one embodiment, a lower Ti
content favors graining in producing a homogeneous finish, in which 100x60 μm SEM
micrographs do not include isolated pits having a diameter greater than about 10 μm in
diameter or flat areas (plateaus) having a topography with a surface area greater than
about 25 μmf. Grain refiner, such as TiB2, may or may not be present. Ti combined with
B is not detrimental to graining.
[0051] In one embodiment, Mn is present in less than about 0.25 wt %, preferably
being less that 0.02 wt%. In some embodiments, Mn may have a strengthening effect. In
one embodiment, Mn may be present within a range of about 0.01 wt % to about 0.25 wt %. In one embodiment, Mn may be present from about 0.05 wt % to about 0.25 wt % to
take advantage of Mn's presence in solid solution or intermetallic particles.
[0052] Cu may be present in up to about 0.04 %, and in one embodiment of the
present invention is limited to about 0.007 wt % or less.
[0053J The term "incidental impurities" refers to elements that are not purposeful
additions to the alloy, but that due to impurities and/or leaching from contact with
manufacturing equipment, trace quantities of such elements being no greater than about
0.05 wt % each and in combination no greater than about 0.15 wt % of the final alloy,
which may nevertheless find their way into the final alloy product.
[0054] In one embodiment, the alloy includes about 0.8 wt % to about 0.12 wt %
Si; about 0.28 wt % to about 0.32 wt % Fe; less than or equal to about 0.007 wt % Cu;
less than or equal to about 0.02 wt % Mn; 0.31 wt % to 0.35 wt % Mg; less than or equal
to about 0.03 wt % Zn; less than or equal to about 0.0 14 wt % Ti; and a balance of Al
and incidental impurities.
[0055] In another aspect of the invention, a method is provided for processing an
aluminum alloy, such as the alloy described-above, for producing a lithographic sheet.
[0056] The lithographic sheet forming process begins with providing a direct cast
ingot preferably in accordance with the above compositions. In one embodiment,
titanium boride may be employed as a grain refiner. The ingot is scalped in a machining
step to remove the non-uniformities from the ingot's surface that are typically formed
during the casting process. [0057] Following preparation of the ingot as described above, the ingot is treated
by a pre-heat step. The pre-heat step prepares the ingot for hot rolling and provides for a
uniform microstructure throughout ingot. In one embodiment, the pre-heat step is
conducted in a gas/electric furnace at a temperature between 5000C to 6000C. The pre¬
heat time may range from 2-20 hours depending on the heat up cycle of the furnace.
[0058] The ingot is then hot rolled to a thickness ranging from about 7.5 mm to
about 10 mm. The hot rolling apparatus may be single stand or multi-stand hot mill.
Following hot rolling, the strip is then coiled, in which the coiling temperature is
maintained between about about 3200C to about about 3600C to obtain a grain re-
crystallized structure (fine grain structure). The coiling temperature is maintained
between about 3200C and about 36O0C by cooling sprays. If the temperature drops below
about 3200C undesirable cold working effects may be observed. In one embodiment,
temperatures drops to below about 32O0C adversely effect recrystallization of the
structure, which may result in streaking during electro graining. If the temperature is
greater than 3600C the sheet may experience surface defects including but not limited to
welding laps, damages or pick ups that may result in physical defects on the lithographic
sheet product.
[0059] In a next series of process steps, in one embodiment, the strip is cold rolled
to a thickness ranging from about 1.0 mm to about 5.0 mm, in yet another embodiment to
a thickness ranging from about 1.5 mm to about 3.0 mm, and then annealed for
approximately 2 to approximately 6 hours at a temperature ranging from about 2800C to
about 5000C, in which the annealing atmosphere may or may not be an inert atmosphere. The strip is then cold rolled to a final gauge, i.e. ranging from about 0.1 mm to about 0.5
mm, with a minimal reduction of about 74%. Once cold rolled to its final gauge, the strip
is then trimmed and tension leveled.
[0060] The aluminum strip is then treated with an electrolytic pre- etching or
degreasing step, hereafter referred to as an electrolytic pre-etching step, including a
combination of chemical and electrical treatments that produce an anodized coating on
the sheet's surface, which provides for greater graining response. The electro-graining
response provided by the present invention is characterized as a topography having fine
round pits of a diameter of less than about 5 microns. In one embodiment, the anodized
coating may be an aluminum oxide having a thickness of about 100 nm or less, and in yet
another embodiment may be a thickness ranging from about 1 nm to about 30 nm. It is
noted that other thickness for the anodized coating have been contemplated and are
within the scope of the present invention, so long as the thickness of the anodized coating
should provide protection from oxidation, yet be thin enough to be easily removed in
subsequent operations.
[0061] In one embodiment, the electrolytic pre-etching step includes passing the
aluminum strip through a mineral acid bath (electrolyte), and applying a current density
ranging from about 4 A/dm2 to about 12 A/dm2 for dwell times of about 0.5 to about 3.0
seconds using silicon controller rectifier (SCR) pulse waves. In one embodiment, the
charge density is about 3000 Qm"2. In one embodiment, the electrolytic pre-etching step
is a continuous in-line process, wherein the aluminum strip enters the mineral acid bath, a
current is applied and the aluminum strip is removed with an anodized coating. [0062] In one embodiment, the mineral acid bath (electrolyte) may include any
mineral acid in a concentration of less than about 35%, and in another embodiment the
mineral acid is in a concentration of about 5% to about 35%, and yet in an even further
embodiment the mineral acid bath may be about 15% to about 25%. In one embodiment,
the mineral acid includes sulfuric, phosphoric, or sulfuric-phosphoric mixtures. In one
embodiment, the aluminum content of the electrolyte should be kept below about 15 g/1
(of Al ion) in phosphoric acid electrolytes, and below about 20 g/1 in sulphuric acid,
wherein higher levels may decrease conductivity. In one embodiment, the mineral acid
bath includes phosphoric acid ranging from about 10% to about 30%, and in yet another
embodiment approximately 20% phosphoric acid, and containing about 2 g/1 to about 15
g/1 aluminum, wherein the aluminum concentration may be equal to approximately 0 g/1
during start up operations. In one embodiment, the temperature of the mineral acid bath
may range from about 400C to about 1000C, and in another embodiment may range from
about 500C to about 800C. Alternatively, it has also been contemplated that the mineral
acid bath may include chromic, boric, and tartaric acids and combinations thereof.
[0063] Figure 1 shows the non-sinusoidal wave form 10 of the current generated
by a thyristor power supply which is used during pre-etching when practicing this
invention as compared to the sinusoidal wave form 5 generated by a prior art AC
autotrans former. The operating frequency of the thyristor power supply is at least several
cycles per second and is preferably at the commercial frequency. The wave form of the
current here disclosed is non-sinusoidal with constant peak voltage up to about 60 volts,
can be symmetrical or asymmetrical and provide a selected charge density up to about 30,000 Qcm. to the minus 2 which depends upon the strip width or final product
requirements. As depicted in Figure 1, in counter distinction to prior AC autotrans formers
which provide current having sinusoidal wave form 5, current with non-sinusoidal wave
form 10 here disclosed can be generated by a thyristor power supply where the
conduction angle is selected for the exact current density applied to the aluminum sheet.
In one embodiment, the peak voltage ranges from about 35 to about 60 volts.
[0064] The thyristor power supply maintains a constant peak voltage. Degreasing
of the aluminum sheet requires cathodic and anodic current. Cathodic current provides
mechanical cleaning of oil, debris, and fines from the aluminum sheet. Anodic current
provides the generation of thin aluminum oxide coating (anodized coating). Operating
with a current having a wave form here disclosed provides increase cathodic current and
anodic current. Peak current is related to peak voltage. By maintaining a constant peak
voltage and employing a current having a non-sinusoidal wave form 10, uniformity to the
cathodic and anodic current is obtained. Therefore, by providing uniformity to the
cathodic and anodic current, the current having a non-sinusoidal wave form 10, provides
uniformity to mechanical cleaning of the aluminum strip through gas generation and
uniformity to the formation of the anodized coating, resulting in a more reactive
degreasing step than is possible with a current having a sinusoidal wave form 5 from an
AC autotransformer.
[0065] Following the pre-etch step the aluminum strip may be roughened by
electrograining and may be treated by similar processes used to provide lithographic sheet and plates. Suitable electrograining response may be achieved with the alloy and
method of the invention using Hydrochloric or Nitric acid.
[0066] The present alloy and processing method provides a lithographic sheet
having higher mechanical properties than AA 1050, better fatigue behavior, and allows
for longer press runs.
[0067] In accordance with the principles of the invention, there is disclosed a
method of processing a lithographic sheet, in which the current has a non-sinusoidal wave
form 10 which can be asymmetrical or symmetrical and has a constant peak voltage.
[0068] By changing the switching point of the thyristor power supply, the exact
current density desired on the aluminum sheet can be obtained.
[0069] Although the invention has been described generally above, the following
examples are provided to further illustrate the present invention and demonstrate some
advantages that arise therefrom. It is not intended that the invention be limited to the
specific examples disclosed.
EXAMPLES
[0070] Table 1 below shows the composition of an alloy within the scope of the
present invention, designated "ALLOY", which is hereafter referred to as the inventive
alloy, and an alloy representative of Aluminum Associations (AA) 1050, which is
hereafter referred to as the comparative example. Table 1
[0074] Lithographic sheets were formed using the alloy representative of the
invention and the alloy representative of AA 1050. Each sheet was prepared from a DC
cast ingot, pre-heat treated, hot rolled, coiled, cold rolled with intermediate anneal steps
to a final gauge, and trimmed. In accordance with the present invention, the sheet formed
of the inventive alloy is degreased with a pre-etching step. The pre-etching step included
a sulphuric acid bath and a current having a non-sinusoidal wave form with constant peak
voltage to provide a current density ranging from about 4A/dm~ to about 12 A/dm" for
dwell times of about 0.5 to 3.0 seconds. The comparison sheet formed from AA 1050 was
not treated with the pre-etching step and was processed with a prior art sinusoidal AC
wave form current from an AC auto trans former.
[0075J The inventive alloy sheet and comparison sheet were then tested for
ultimate tensile strength (UTS), yield strength (YS), and Elongation (%) after being
worked to Hl 8 temper. Samples were also tested for ultimate tensile strength (UTS),
yield strength (YS), and Elongation (%) following a heat treatment at a temperature of
2800C for a period of 4 minutes.
Table 2
[0076] Table 2 shows the mechanical strength advantages of the inventive alloy
having increased Mg content and processed with the inventive pre-etching step, when
compared to a conventionally processed AA 1050 sheet. Specifically, the sheets
comprising the inventive alloy displayed greater than a 10% increase in ultimate tensile
strength (UTS) and yield strength (YS) when compared to similarly prepared AA 1050,
wherein the samples had been worked to H 18 temper. Similar results were observed in
the samples that had been heat treated. Specifically, after a heat treatment of 2800C for 4
minutes, (baking test) sheets prepared in accordance with the present invention displayed
greater than an 8% increase in ultimate tensile strength and greater than a 13% increase in
yield strength when compared to similarly prepared AA 1050.
[0077] Lithographic sheet prepared in accordance with the present invention and
comparative examples formed from compositions similar to AA 1050, where then tested
for electro-graining behavior. An electro-graining step was conducted using about 8%
HNO3 acid with current densities of about 10 A/dm2 for a time period of about 90
seconds.
[0078] Figures 2a-2c represent micrographs of electrogram roughened lithographic
sheet surface formed using the alloy and process in accordance with the present
invention, as designated in Table 1.
[0079] Figures 3a-3c represent micrographs of a comparative example of an
electrogram roughened lithographic sheet surface formed from an alloy composition
similar to AA 1050, which included about 0.2 wt % Mg. Specifically, the comparative example depicted in Figures 3a-3c was formed from an alloy composition including
0.082 wt % Si, 0.40 wt % Fe, 0.00 1 wt % Cu, 0.004 wt % Mn, 0.02 wt % Mg, 0.00 1 wt
% Cr, 0.002 wt % Ni, 0.015 wt % Zn, and 0.015 wt % Ti.
[0080] Figures 4a-4c represent micrographs of a comparative example of an
electrograin roughened lithographic sheet surface formed from an alloy composition
similar to AA 1050, which included about 0.2 wt % Mg and about 0.07 wt % Mn.
Specifically, the comparative example depicted in Figures 4a-4c was formed from an
alloy composition including 0.090 wt % Si, 0.34 wt % Fe, 0.004 wt % Cu, 0.07 1 wt %
Mn, 0.018 wt % Mg, 0.001 wt % Cr, 0.002 wt % Ni, 0.013 wt % Zn, and 0.013 wt % Ti.
[0081J Figures 5a-5c represent micrographs of a lithographic sheet surface formed
using the alloy and process in accordance with the present invention, wherein the sheet
was treated to an electrograining treatment with about 8% HCl acid and current density of
about 15A/dm2 for a period of 20 seconds. Specifically, the alloy was composed of .096
wt % Si, 0.33 wt % Fe, 0.002 wt % Cu, 0.005 wt % Mn, 0.34 wt % Mg, 0.001 wt % Cr,
0.005 wt % Ni, 0.002 wt % Zn and 0.015 wt % Ti.
[0082J The electro-graining aspect for the lithographic sheet formed in accordance
with the present invention was equal to the comparative examples of AA 1050.
[0083] It will be readily appreciated by those skilled in the art that modifications
may be made to the invention without departing from the concepts disclosed in the
foregoing description. Such modifications are to be considered as included within the
following claims unless the claims, by their language, expressly state otherwise.
Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention which is to be given the full breadth of
the appended claims and any and all equivalents thereof.

Claims

What is claimed is:
1. An aluminum alloy comprising:
about 0.05 wt % to about 0.25 wt % Si;
about 0.25 wt % to about 0.4 wt % Fe;
less than or equal to about 0.04 wt % Cu;
less than or equal to about 0.25 wt % Mn;
0.31 wt % to about 0.40 wt % Mg;
less than or equal to about 0.03 wt % Zn; and
less than or equal to about 0.03 wt % Ti;
2. The alloy of Claim 1 comprising Si ranging from about 0.8 wt % to about 0.12 wt
%.
3. The alloy of Claim 1 comprising Fe ranging from about 0.28 wt % to about 0.32
wt %.
4. The alloy of Claim 1 comprising Zn ranging from .01 wt % to .03 wt %.
5. The alloy of Claim 1 comprising Ti in less than or equal to about 0.0 14 wt %.
6. The alloy of Claim 1 comprising Mg ranging from 0.31 wt% to about 0.35 wt. %.
7. The alloy of Claim 1 comprising less than or equal to 0.007 wt % Cu.
8. An aluminum alloy comprising:
about 0.8 wt % to about 0.12 wt % Si;
about 0.28 wt % to about 0.32 wt % Fe;
less than or equal to about 0.007 wt % Cu;
less than or equal to about 0.02 wt % Mn;
0.31 wt % to about 0.35 wt % Mg;
less than or equal to about 0.03 wt % Zn; and
less than or equal to about 0.0 14 wt % Ti;
9. A method of producing a lithographic sheet comprising:
providing an aluminum sheet;
contacting the aluminum sheet with an electrolyte bath; and
applying a current having a non-sinusoidal wave form to said electrolyte bath at a
constant peak voltage.
10. The method of Claim 9 wherein the wave form of the non-sinusoidal current is
either symmetrical or asymmetrical and is generated by a thyristor power supply to
provide a desired current density to the aluminum sheet by moving the switching point of
the thyristor power supply.
1 1. The method of Claim 10 wherein the constant peak voltage ranges from about 35
to about 60 volts.
12. The method of Claim 10 further comprising applying the non-sinusoidal wave
form current with a current density ranging from about 4 to about 12 A/dnr.
13. The method of Claim 12 comprising applying the non-sinusoidal wave form
current for dwell times ranging from about 0.5 to about 3.0 seconds.
14. The method of Claim 10 wherein the electrolyte bath comprises a mineral acid in a
concentration of less than about 35%.
15. The method of Claim 13 wherein the electrolyte bath comprises sulfuric,
phosphoric, or sulfuric-phosphoric mixtures.
16. The method of Claim 15 wherein the electrolyte bath comprises less than 20 g/1.
17. The method of Claim 16 wherein the electrolyte bath comprises a temperature
ranging from about 400C to about 1000C.
18. The method of Claim 9 wherein providing the aluminum sheet comprises an alloy
comprising:
about 0.05 wt % to about 0.25 wt % Si;
about 0.25 wt % to about 0.4 wt % Fe;
less than or equal to about 0.04 wt % Cu;
less than or equal to about 0.25 wt % Mn;
0.31 wt % to about 0.40 wt % Mg;
less than or equal to about 0.03 wt % Zn; and
less than or equal to about 0.03 wt % Ti;
19. The method of Claim 18 further comprising using a thyristor power supply to
generate the current having a non-sinusoidal wave form, wherein the power supply is
configured to provide a current with a desired current density applied to the aluminum
sheet by moving the switching point of the thyristor power supply.
20. The method of Claim 19 wherein the electrolyte bath comprises sulphuric acid and
then applying the pulse wave current comprises a current density ranging from about 4-
12 A/dm" for dwell times of 0.5 to 3.0 seconds.
EP07759824.1A 2006-03-31 2007-03-30 Manufacturing process to produce litho sheet Revoked EP2077949B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78782606P 2006-03-31 2006-03-31
PCT/US2007/065635 WO2007115167A2 (en) 2006-03-31 2007-03-30 Manufacturing process to produce litho sheet

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EP2077949A2 true EP2077949A2 (en) 2009-07-15
EP2077949B1 EP2077949B1 (en) 2015-09-30

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EP (1) EP2077949B1 (en)
KR (1) KR101152169B1 (en)
CN (1) CN101484322A (en)
BR (1) BRPI0709691A2 (en)
WO (1) WO2007115167A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012059362A1 (en) 2010-11-04 2012-05-10 Novelis Inc. Aluminium lithographic sheet

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0709691A2 (en) 2006-03-31 2011-07-19 Alcoa Inc lithographic sheet
ES2556166T3 (en) * 2006-07-21 2016-01-13 Hydro Aluminium Rolled Products Gmbh Aluminum band for lithographic printing plate support
US20110039121A1 (en) * 2007-11-30 2011-02-17 Hydro Aluminium Deutschland Gmbh Aluminum strip for lithographic printing plate carriers and the production thereof
ES2407655T5 (en) * 2007-11-30 2023-02-23 Speira Gmbh Aluminum strip for supports for lithographic printing plates and their production
WO2009144108A1 (en) * 2008-05-28 2009-12-03 Novelis Inc. Composite aluminium lithographic sheet
ES2587024T3 (en) * 2008-11-21 2016-10-20 Hydro Aluminium Rolled Products Gmbh Aluminum band for lithographic printing plate supports with high alternating flexural strength
EP2427584B1 (en) 2009-05-08 2014-09-03 Novelis, Inc. Aluminium lithographic sheet
EP2499272B1 (en) * 2009-11-13 2017-08-16 Norsk Hydro ASA Process for production of magnesium containing aluminium strip or web material with improved adhesion
EP2495106B1 (en) 2011-03-02 2015-05-13 Hydro Aluminium Rolled Products GmbH Aluminium band for lithographic printing plate carriers with water-based coatings
KR102150366B1 (en) 2020-03-20 2020-09-01 주식회사 창신 Spuit type cosmetic comtaimers
CN117684055A (en) * 2023-12-19 2024-03-12 中铝材料应用研究院有限公司 Aluminum alloy plate and strip for treatment-free printing plate base and preparation method thereof

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59227494A (en) * 1983-06-09 1984-12-20 Fuji Photo Film Co Ltd Manufacture of support for lithographic plate
JPS6021298A (en) * 1983-07-18 1985-02-02 Fuji Photo Film Co Ltd Preparation of support for planographic printing plate
JPS61146598A (en) * 1984-12-20 1986-07-04 Furukawa Alum Co Ltd Supporter for lithographic printing plate and its manufacture
JPS61274993A (en) * 1985-05-31 1986-12-05 Nippon Light Metal Co Ltd Aluminum alloy support for offset printing
JPS62230946A (en) * 1986-04-01 1987-10-09 Furukawa Alum Co Ltd Aluminum alloy support for planographic printing plate
JPH07100837B2 (en) 1986-11-20 1995-11-01 スカイアルミニウム株式会社 Aluminum alloy for wrought and its manufacturing method
US4721552A (en) 1987-04-27 1988-01-26 Polychrome Corporation Two-step method for electrolytically graining lithographic metal plates
DE3714059C3 (en) 1987-04-28 1995-12-07 Vaw Ver Aluminium Werke Ag Material in ribbon or plate form and process for its production and its use as a support for planographic printing forms
IT1238055B (en) * 1989-03-01 1993-06-26 LAYERED MATERIAL FOR SLIDING BEARING ELEMENTS WITH ANTI-FRICTION LAYER FOR ALUMINUM-BASED BEARINGS.
GB9112211D0 (en) * 1991-06-06 1991-07-24 Alcan Int Ltd Treating a1 sheet
EP0795048B1 (en) * 1994-12-19 2000-03-15 Alcan International Limited Cleaning aluminium workpieces
ATE256205T1 (en) * 1996-06-17 2003-12-15 Alcan Int Ltd TREATMENT OF ALUMINUM WORKPIECES
JP3580462B2 (en) 1996-07-05 2004-10-20 富士写真フイルム株式会社 Method for producing aluminum support for lithographic printing plate
US6596150B2 (en) * 1998-05-28 2003-07-22 Fuji Photo Film Co., Ltd. Production method for an aluminum support for a lithographic printing plate
DE29924474U1 (en) * 1999-07-02 2003-08-28 Hydro Aluminium Deutschland GmbH, 53117 Bonn litho
JP4056682B2 (en) * 2000-07-11 2008-03-05 富士フイルム株式会社 Support for lithographic printing plate
ATE404383T1 (en) * 2000-09-14 2008-08-15 Fujifilm Corp ALUMINUM SUPPORT FOR FLAT PRINTING PLATE, METHOD FOR THE PRODUCTION THEREOF AND ORIGINAL FLAT PRINTING PLATE
EP1341942B1 (en) * 2000-12-11 2006-03-15 Novelis, Inc. Aluminium alloy for lithographic sheet
JP2003048379A (en) * 2001-05-30 2003-02-18 Fuji Photo Film Co Ltd Lithographic printing plate support and lithographic printing plate precursor
GB0117683D0 (en) * 2001-07-20 2001-09-12 Alcan Int Ltd Aluminium alloy sheet with roughened surface
GB2379669B (en) * 2001-09-12 2005-02-16 Alcan Int Ltd Al alloy for lithographic sheet
DE60329343D1 (en) * 2002-02-26 2009-11-05 Fujifilm Corp Aluminum support for a planographic printing plate and process for its production, and a presensitized printing plate using the same
JP4070587B2 (en) * 2002-12-02 2008-04-02 富士フイルム株式会社 Planographic printing plate precursor
JP4105042B2 (en) * 2003-06-12 2008-06-18 三菱アルミニウム株式会社 Aluminum alloy material for lithographic printing plate and method for producing the same
JP2005305690A (en) * 2004-04-19 2005-11-04 Konica Minolta Medical & Graphic Inc Printing plate material, printing method of printing plate material and offset press
ES2389051T5 (en) 2005-05-19 2021-07-07 Hydro Aluminium Rolled Prod Conditioning of a lithographic strip
BRPI0709691A2 (en) 2006-03-31 2011-07-19 Alcoa Inc lithographic sheet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007115167A2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012059362A1 (en) 2010-11-04 2012-05-10 Novelis Inc. Aluminium lithographic sheet

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US20080035488A1 (en) 2008-02-14
CN101484322A (en) 2009-07-15
BRPI0709691A2 (en) 2011-07-19
EP2077949B1 (en) 2015-09-30
WO2007115167A2 (en) 2007-10-11
KR20080109058A (en) 2008-12-16
KR101152169B1 (en) 2012-06-15

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