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Patent 2417546 Summary

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(12) Patent: (11) CA 2417546
(54) English Title: AGE-HARDENABLE COPPER ALLOY
(54) French Title: ALLIAGE DE CUIVRE DURCISSABLE PAR VIEILLISSEMENT
Status: Deemed expired
Bibliographic Data
(51) International Patent Classification (IPC):
  • C22C 9/06 (2006.01)
  • B22D 11/06 (2006.01)
(72) Inventors :
  • HELMENKAMP, THOMAS (Germany)
  • RODE, DIRK (Germany)
(73) Owners :
  • KME GERMANY GMBH & CO. KG (Germany)
(71) Applicants :
  • KM EUROPA METAL AG (Germany)
(74) Agent: G. RONALD BELL & ASSOCIATES
(74) Associate agent:
(45) Issued: 2015-03-31
(22) Filed Date: 2003-01-28
(41) Open to Public Inspection: 2003-08-15
Examination requested: 2007-11-23
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
102 06 597.7 Germany 2002-02-15

Abstracts

English Abstract




An age-hardenable copper alloy made of 1.2 to 2.7 wt. % cobalt, which is able
to be
partially replaced by nickel, 0.3 to 0.7 wt. % beryllium, 0.01 to 0.5 wt. %
zirconium,
optionally 0.005 to 0.1 wt. % magnesium and/or iron and in some instances up
to a
maximum of 0.15 wt. % of at least one element from the group including
niobium,
tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium. The
remainder is copper and includes production-conditioned impurities and usual
processing additives. This copper alloy is used as the material for producing
mold
blocks for the side dams of continuous strip-casting installations.


French Abstract

Alliage de cuivre à durcissement par vieillissement composé de 1,2 à 2,7 % en poids de cobalt, qui peut être partiellement remplacé par du nickel, de 0,3 à 0,7 % en poids de béryllium, de 0,01 à 0,5 % en poids de zirconium, facultativement, de 0,005 à 0,1 % en poids de magnésium ou de fer et, dans certains cas, jusquà un maximum de 0,15 % en poids dau moins un élément du groupe comprenant du niobium, du tantale, du vanadium, du hafnium, du chrome, du manganèse, du titane et du cérium. Le reste est du cuivre et comprend des impuretés conditionnées par la production et des additifs de traitement habituels. Cet alliage de cuivre est utilisé comme matériau pour produire des blocs à mouler pour les faces latérales dinstallations de coulée de bande continue.

Claims

Note: Claims are shown in the official language in which they were submitted.




THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An age-hardenable copper alloy suitable as a material for producing block
for the
side dams of strip-casting installations, comprising: 1.2 to 2.7 weight %
cobalt, which may be
partially substituted with nickel, 0.3 to 0.7 weight % beryllium, 0.01 to 0.5
weight %
zirconium, optionally 0.005 to 0.2 weight % magnesium, optionally 0.005 to 0.2
weight %
iron, optionally up to a maximum of 0.15 weight % of at least one element
selected from the
group consisting of niobium, tantalum, vanadium, hafnium, chromium, manganese,
titanium
and cerium, and a balance of copper, in which the alloy has a grain size
between 30 and
90µm, ascertained according to ASTM E 112, wherein the copper alloy is
cast, hot formed,
cold formed up to 40%, solution treated at a temperature lying in the
temperature range of
850 to 970 °C, and subsequently submitted to a 0.5 to 16-hour age-
hardening treatment at 400
to 550 °C.
2. A copper alloy according to Claim 1, comprising: 1.8 to 2.4 weight %
cobalt, 0.45
to 0.65 weight % beryllium, 0.15 to 0.3 weight % zirconium, 0.005 to 0.05
weight %
magnesium, 0.005 to 0.1 weight % iron, and a balance of copper.
3. A copper alloy according to Claim 1 or 2, wherein up to 80% of the cobalt
content
is replaced by nickel.
4. A copper alloy according to any one of Claims 1 to 3, wherein a part of the

zirconium content is replaced by up to 0.15 weight % of at least one element
selected from
the group consisting of cerium, hafnium, niobium, tantalum, chromium,
manganese, titanium
and vanadium.
5. A copper alloy according to any one of Claims 1 to 4, wherein after the
copper
alloy is hot formed, it is cold formed up to 30%.
6. A copper alloy according to any one of Claims 1 to 4, wherein after the
copper



alloy is hot formed, it is cold formed by 5 to 30%.
7. A copper alloy according to any one of Claims 1 to 4, wherein after the
copper
alloy is hot formed, it is cold formed by 10 to 15%.
8. A copper alloy according to any one of Claims 1 to 7, wherein in the age-
hardened
state, the copper alloy has a tensile strength of at least 650 MPa, a Vickers
hardness of at least
210 HV, an electrical conductivity of at least 40% IACS, a hot tensile
strength at 500 °C of at
least 400 MPa, and a minimum hardness of 160 HV after 500 hours of constant
ageing at 500
°C.
9. A copper alloy according to any one of Claims 1 to 7 wherein in the age-
hardened
state, the copper alloy has a tensile strength of at least 700 to 900 MPa, a
Vickers hardness of
230 to 280 HV, an electrical conductivity of 45 to 60% IACS, a hot tensile
strength at 500 °C
of at least 450 MPa and a minimum hardness of 160 HV after 500 hours of
constant ageing at
500 °C.
10. An age-hardenable copper alloy suitable as a material for producing block
for the
side dams of strip-casting installations, comprising: 1.2 to 2.7 weight %
cobalt, 0.3 to 0.7
weight % beryllium, 0.01 to 0.5 weight % zirconium, 0.005 to 0.2 weight %
magnesium,
optionally 0.005 to 0.2 weight % iron, optionally up to a maximum of 0.15
weight % of at
least one element selected from the group consisting of niobium, tantalum,
vanadium,
hafnium, chromium, manganese, titanium and cerium, and a balance of copper, in
which the
alloy has a grain size between 30 and 90 µm, ascertained according to ASTM
E112, wherein
up to 80% cobalt may be partially substituted with nickel, and wherein the
copper alloy is
cast, hot formed, cold formed up to 40%, solution treated at a temperature
lying in the
temperature range of 850 to 970 °C, and subsequently submitted to a 0.5
to 16-hour age-
hardening treatment at 400 to 550 °C.
11

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02417546 2003-01-28
[364/104]
AGE-HARDENABLE COPPER ALLOY
BACKGROUND OF THE INVENTION
Field _of the Invention
The invention relates to an age-hardenable copper alloy as material for
producing blocks for the side dams of continuous strip-casting installations.
Description of Related Art
The worldwide aim, especially in the steel and copper industries, to cast
semifinished material to as close to the final dimensions as possible, in
order to
save hot forming and/or cold forming steps, led even before .1970 to the
development of the so-called Hazelettstrip-casting installations, in which the

molten metal solidifies in the gap between two bands guided in parallel. The
side dams, in, for example, the strip-casting installation known from U.S.
Patent
No. 3,865,176, are made of metallic mold blocks or darn blocks having a T
groove, which are lined up on a fle.xible continuous band such as one made of
steel, and which move in the longitudinal direction, synchronously with the
casting bands. In this context, the dam blocks bound the casting mold cavity
formed by the casting bands. .- ,-== -
Also !mown, from EP 0 974 413 Al are dam block chains for continuous
strip-casting, formed by blocks having a slot and key. The advantage of these
further developed mold blocks having a slot and key comes about due to a more
exact alignment, and guidance of the blocks during the casting process, and
leads to an improvement of the surface quality of the cast strip. In order to
prevent premature wear of the side edges of the blocks by plastic deformation
and the formation of cracks, a suitable material has to have great hardness
and
strength, a fine-grained microstructure and a good long-term resistance to
softening. In order to remove the heat of solidification from the liquid
molten
material, a high thermal conductivity of the mold block material is
additionally

CA 02417546 2003-01-28
=
required.
Finally, optimum fatigue behavior of the material is of the most decisive
significance, which will ensure that, after leaving the casting segment, the
thermal stresses appearing during the cooling off of the blocks do not lead to

cracking of the blocks at the corners of the T groove incorporated for the
accommodation of the steel band. In this context, particularly great thermal
stresses are to be expected in dam blocks having the design using slot and
key,
on account of the unfavorable geometry and mass distribution.
If such cracks caused by thermal shock appear, the respective mold block will
fall out of the dam block chain of the continuous strip-casting machine after
even a short period, molten metal being able to run uncontrollably from the
casting mold cavity and to damage parts of the installation. For the purpose
of
exchanging the damaged mokLblocks, the entire strip-casting installation has
to
be stopped and the casting process has to be interrupted.
A testing method has proven itself for checking the tendency to crack, in
which
the mold blocks are submitted to heat treatment for two hours at 500 C and
are subsequently quenched in water at 20 to 25 C. Even if this thermal shock
test is repeated several times, in the case of a suitable material no cracks
may
appear in the T groove surface.
EP 0 346 645 Bi describes an age-hardenable copper-based alloy which is
made of 1.6 to 2.4 % nickel, 0.5 to 0.8 % silicon, 0.01 to 0.2 % zirconium,
optionally up to 0.4 % chromium and/or up to 0.2 % iron, the remainder being
copper including production-caused impurities. This known copper alloy
basically satisfies the prerequisites for a long service life, if used as the
material
for producing standard mold blocks for the side darns of continuous
,
2

CA 02417546 2003-01-28
strip-casting installations. The following combination of properties is even
for
this copper alloy:
Rm at 20 C: 635 to 6601VIPa
Rm at 500 C: 286 to 372 MPa
Brinell hardness: 185 to 191 HB (corresponds to about 195 to 210
HV)
=
Conductivity: 4L4 to 42.4 % IACS.
No cracks are to appear during the thermal shock test. One advantage
compared to beryllium-containing copper-based alloys is the possibility of
being
able to regrind the mold blocks manually, since no beryllium is contained in
the
grinding dust. The reprocessing of used dam blocks having slot and key is
considerably more costly and, as a rule, requires machine (wet) cleaning of
the T
groove and the casting surfaces (e.g. in closed chambers), whereby the
liberation
of grinding dusts is prevented, Thus, using beryllium-containing alloys would
basically be possible under these circumstances.
A dam block made of the CuNiSiZr alloy described in EP 0 346 645 81, however,
disadvantageously tends to premature wear of the side edges and casting
surfaces, at very high mechanical and thermal stresses in the casting
operation
of a continuous strip-casting installation. As the results of investigations
have
shown, this wear may be attributed to a material softening of the casting
edges
and surfaces to a value below 160 FN. Furthermore, the thermal shock
resistance of the known CuNiSiZr alloy is not always sufficient for
effectively
preventing the formation of cracks in the T groove during casting use, when
the
alloy is used for a dam block having a slot and key.
It is an object of the invention to create an age-hardenable copper alloy as a

material for producing dam blocks for continuous strip-casting installations,
3

CA 02417546 2010-02-03
especially in a slot and key embodiment, which is stable to changing
temperature
stresses even at high casting speeds, and which has a great resistance to wear
and
resistance to softening, as well as great resistance to crack formation in the
T groove.
Thus, according to an aspect of the present invention, there is provided an
age-
hardenable copper alloy suitable as a material for producing block for the
side dams
of strip-casting installations, comprising: 1.2 to 2.7 weight % cobalt, which
may be
partially substituted with nickel, 0.3 to 0.7 weight % beryllium, 0.01 to 0.5
weight
% zirconium, optionally 0.005 to 0.2 weight % magnesium, optionally 0.005 to
0.2
weight % iron, optionally up to a maximum of 0.15 weight % of at least one
element
selected from the group consisting of niobium, tantalum, vanadium, hafnium,
chromium, manganese, titanium and cerium, and a balance of copper, in which
the =
alloy has a grain size between 30 and 90tim, ascertained according to ASTM E
112.
DETAILED DESCRIPTION OF THE INVENTION
By using a copper-based alloy made of 1.2 to 2.7 wt.% cobalt, 0.3 to 0.7 wt.%
beryllium, 0.01 to 0.5 wt.% zirconium, optionally 0.005 to 0.2 wt.% magnesium
and/or iron and of the remainder copper, including production-caused
impurities and
the usual processing additives, on the one hand, a sufficient age-
hardenability of the
material for achieving great strength, hardness and conductivity may be
ensured. On
the other hand, only a relatively slight cold working of up to a maximum of
40% is
required for establishing a fine-grained microstructure having a sufficient
plasticity.
Because of the deliberately graduated zirconium content, both the fatigue
resistance
and the heat resistance properties are improved.
A further improvement of the mechanical properties of the dam blocks,
especially an increase in tensile strength, may advantageously be achieved by
having the copper alloy contain 1.8 to 2.4 wt.% cobalt, 0.45 to 0.65 wt.%
beryllium, 0.15 to 0.3 wt.% zirconium, up to 0.05 wt.% magnesium and/or up
4

CA 02417546 2003-07-31
to 0.1 wt. % iron.
The invention permits that, in the copper alloy, up to 80% of the cobalt
content
may be replaced by nickel.
Further improvements of the mechanical properties of a dam block may be
achieved if the copper alloy contains up to a maximum of 0.15 wt.% of at least

one element of the group including niobium, tantalum, vanadium, hafnium,
chromium, manganese, titanium and cerium. Usual deoxidants such as boron,
lithium, potassium and phosphorus may also be added up to a maximum of
0.03 vit.%, without negatively influencing the mechanical properties of the
copper alloy of the present invention.
According to another specific embodiment, a part of the zirconium content may
be replaced by up to 0.15 wt.% by at least one element of the goup including
cerium, hafnium, niobium, tantalum, vanadium, chromium, manganese and
titanium.
Advantageously, the blocks for the side darns of double strip-casting
installations are produced using the age-hardenable copper alloy, by the
method steps: casting, hot forming, cold forming up to, 40 %, solution
treating
at a temperature in the range of 850 to 970 C, as well as a 0.5 to 16-hour
age-hardening treatment at 400 to 550 C.
As a particular advantage, the copper alloy may be cold formed by 5 to 30 %
after hot forming. A cold forming degree of 10 to 15 % lying within this range
is
particularly preferred in this context.
It is especially advantageous if the dam blocks in the age-hardened condition
have a tensile strength of at least 650 Mpa, particularly 700 to 900 Mpa, a
Vickers hardness of at least 210 MV, particularly 230 to 280 MV, an electrical

CA 02417546 2003-01-28
=
conductivity of at least 40 % 1ACS, particularly 45 to 50 A) IACS, a hot
tensile
strength at 500 C of at least 400 Mpa, particularly of at least 450 Mpa, a
minimum hardness of 160 MV after 500-hour ageing at 500 C, and a maximum
grain size according to ASTM E 112 of 0.5 mm.
Particularly preferred are dam blocks made of the copper alloy, if, in the
age-hardened condition they have a grain size, ascertained according to ASTM E

112, between 30 and 90 pm.
In a preferred embodiment, the copper alloy, after the hot forming of the cast

blank, is cold formed up Ito 40%, is then solution treated at a temperature
lying
in the temperature range of 850 to 970*C, and is subsequently submitted to a
0.5 to 16-hour age-hardening treatment at 400 to 550*C. In a surprisingly
simple way one may succeed in getting rid of the bad recrystallization
behavior
observed in the known CuCoBe alloys during the hot forming and solution
treatment. The bad recrystallization behavior, in the production of mold
blocks
made of CuCoBe alloys, in the hot formed, solution treated and age-hardened
condition leads to a coarse microstructure, that is not acceptable for the
application purpose, having grain sizes up to more than 1 min. However, if,
between the hot forming and the solution treatment, the material is submitted
to cold forming up to a maximum of 40 %, preferably up to a maximum of 15 %,
this additional processing step leads to a considerably more fine-grained
microstructure. Relevant investigative series have confirmed that materials
for
mold blocks for the side dams of strip-casting machines, which are cold formed

below the recrystAllizAtion temperature, and are subsequently solution
treated,
have a clearly finer microstructure at grain sizes below 0.5 mm, while higher
degrees of cold =forming, above approximately 40 %, lead during subsequent
solution treatment to a coarsening of the grain by secondary
recrysta11i7ation, at
grain sizes above 1 mm.
=
= = 6

CA 02417546 2003-01-28
.'EXAMPLES
The invention is explained below in greater detail, with the aid of exemplary
embodiments. The advantages of the copper alloys are demonstrated using õ
three alloys according to the invention (A, B and C) and three alloys for
reference (D, E and F). The composition of the copper alloys in wt.% is given
below in Table 1.
Table 1.
Alloy Co (%) Ni (%) Be (%) Zr (%) Si (%) Cr (%) Cu N
A 2.1 0.54 0,18
Remainder
B 2.2 0.56 0.24
Remainder
1.3 1.0 0.48 0.15 - Remainder
2.0 -= 0.16 0.62 0.34
Remainder
2.1 - 0.55 - - Remainder
1.0 1.1 0.62 - - - Remainder
In the case of the composition of alloy D, a known CuNiSi-based alloy is
involved, whereas E and F are normalized CuCo2Be or CuCoNiBe materials.
All the copper alloys were smelted in an induction crucible oven and were cast

by the continuous strip-casting method to round billets having a diameter of
280 mm. The round billets of exemplary alloy A, B and C were extruded on an
extrusion press at a temperature above 900 C to flat bar of a dimension 79 x
59 mm, and subsequently were drawn, at a loss in cross section of 12 %, to a
dimension of 75 x 55 mm. The blocks of the reference alloys D, E and F were
extruded at the same temperature, directly to the dimension 75 x 55 mm, and
were not submitted to additional cold forming. The CuCoBe and CuCoNiBe
materials were subsequently solution-treated at 900 to 950 C and were
age-hardened at a temperature range between 450 and. $50 C for 0.5 to 16
7

CA 02417546 2003-01-28
=
=
hours.
The CuNiSi-based alloy was solution-treated at 800 to 850 C and age-hardened
under the same conditions. In the age-hardened condition, the tensile strength

Rm, the Vickers hardness HVIO, the electrical conductivity (as substitute
quantity for the heat conductivity), the gain size according to ASTM El12, the

heat resistance Rm at 500 C and the resistance to softening via Vickers
hardness measurement (liV10) after ageing at 500 C after 500 hours were
ascertained,
The thermal shock behavior was finally tested on mold blocks (1) of dimensions

70 x 50 x 40 mm and mold blocks (2), having slot and key, of dimensions 70 x
50 x 47 mm. For this, the mold blocks were first annealed for two hours at 500

C and then quenched in water at 20 to 25 C. The T groove of the blocks were
=then searched for cracks with the naked eye and a microscope at 10-fold
magnification.
All the test results are summarized in Table 2 below.
Table 2
Alloy Tensile Vickers Conductivity Grain Tensile
Vickers Hardness Behavior Alter
Strength Hardness (eketrical) % Size Strength 10 After Aget4 at
Theroloshock Test
2dPa liv10 IACS (500 C) 500 =C over SOO Block
(1) Block(2)
MF's Ii
A 801 254 50 . 30-90 523 173 crack-free
crack-free
B 804 24$ 51.5 45-90 464 175 crack-
free crack-free
C 812 255 49.5 45-90 485 167 crack-free
crack-free
1) 652 205 43 45-90 387 118 crack-free
cracked
E 786 260 50.5 10 5000 423 ISO
cracked cracked
P 807 248 49.5 to 3000 434 252
cracked cracked
In the mold blocks classified as "cracked", the extension of determined cracks
in
8

CA 02417546 2003-01-28
=
the groove was 2 to 5 mm, and in individual cases, the length of the crack was

up to 10 mm. One may see from the reference that, as compared to materials E
and F, only copper alloys A, B and C, and produced using slight cold working,
at optimum properties, have a surprisingly uniform and fine-grained
microstructure, and have the necessary resistance to the formation of cracks
when used as mold block having slot and key. Even when used in a usual mold
block, the copper alloys in accordance with the invention have a clearly
better
resistance to softening compared to the known CuNiSi alloys D, and a
somewhat better resistance to softening when compared to alloys E and F.
Therefore, the copper alloy in accordance with the invention is eminently
suitable as the material for producing all mold blocks, that are submitted to
typically changing temperature stress during the casting process, for the side

dams of strip-casting instAl tions. These are both the mold blocks used up to

the present and the mold blocks embodied with slot and key as in
EP 0 974 413 A1.
. .
9

Representative Drawing

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 2015-03-31
(22) Filed 2003-01-28
(41) Open to Public Inspection 2003-08-15
Examination Requested 2007-11-23
(45) Issued 2015-03-31
Deemed Expired 2017-01-30

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $300.00 2003-01-28
Registration of a document - section 124 $100.00 2003-03-11
Maintenance Fee - Application - New Act 2 2005-01-28 $100.00 2005-01-11
Maintenance Fee - Application - New Act 3 2006-01-30 $100.00 2006-01-27
Maintenance Fee - Application - New Act 4 2007-01-29 $100.00 2007-01-26
Request for Examination $800.00 2007-11-23
Maintenance Fee - Application - New Act 5 2008-01-28 $200.00 2008-01-21
Maintenance Fee - Application - New Act 6 2009-01-28 $200.00 2009-01-09
Maintenance Fee - Application - New Act 7 2010-01-28 $200.00 2009-12-30
Maintenance Fee - Application - New Act 8 2011-01-28 $200.00 2011-01-06
Maintenance Fee - Application - New Act 9 2012-01-30 $200.00 2012-01-18
Maintenance Fee - Application - New Act 10 2013-01-28 $250.00 2013-01-09
Maintenance Fee - Application - New Act 11 2014-01-28 $250.00 2014-01-09
Final Fee $300.00 2014-12-11
Maintenance Fee - Application - New Act 12 2015-01-28 $250.00 2015-01-26
Registration of a document - section 124 $100.00 2015-08-31
Registration of a document - section 124 $100.00 2015-08-31
Registration of a document - section 124 $100.00 2015-08-31
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
KME GERMANY GMBH & CO. KG
Past Owners on Record
HELMENKAMP, THOMAS
KM EUROPA METAL AG
KME GERMANY AG
KME GERMANY AG & CO. KG
RODE, DIRK
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 2003-01-28 1 22
Description 2003-01-28 9 509
Claims 2003-01-28 3 118
Cover Page 2003-07-22 1 28
Claims 2011-07-08 2 75
Abstract 2003-07-31 1 18
Claims 2003-07-31 3 79
Description 2003-07-31 9 487
Description 2010-02-03 9 486
Claims 2010-02-03 2 67
Claims 2013-12-13 2 84
Cover Page 2015-02-24 1 29
Fees 2005-01-11 1 40
Correspondence 2003-02-27 1 24
Assignment 2003-01-28 2 81
Assignment 2003-03-11 5 194
Prosecution-Amendment 2003-07-31 9 273
Prosecution-Amendment 2011-07-08 7 295
Fees 2006-01-27 1 36
Fees 2007-01-26 1 35
Prosecution-Amendment 2007-11-23 1 33
Fees 2008-01-21 1 36
Prosecution-Amendment 2008-06-19 2 39
Fees 2009-01-09 1 36
Prosecution-Amendment 2009-08-13 2 79
Prosecution-Amendment 2010-02-03 7 261
Prosecution-Amendment 2011-01-14 3 94
Prosecution-Amendment 2011-11-21 3 112
Prosecution-Amendment 2012-05-22 6 271
Prosecution-Amendment 2013-06-14 3 127
Prosecution-Amendment 2013-12-13 7 319
Assignment 2015-08-31 26 1,069
Correspondence 2014-12-11 1 25
Fees 2015-01-26 1 33