Technical Field
[0001] The present invention relates to a lubricant for hot rolling, which is mainly used
for the production of a seamless steel pipe or tube by the Mannesmann process.
Background Art
[0002] As is well known, in the production of a seamless metal pipe or tube by the Mannesmann
process, a billet or bloom heated is made into a hollow blank with piercing mill,
and then the hollow blank is finished into a product by means of a continuance mill
(mandrel mill) and a sizing mill. On the step of elongation in Mannesmann process,
inside face of a hollow blank is forcibly lubricated with a lubricant in order to
prevent seizing. The lubricant is a graphite-based lubricant made mainly of granular
graphite, scaly graphite, soil-form graphite or the like. It is used in a solid state
or in the state of a liquid wherein a graphite is mixed with a binder.
[0003] In lubricity a graphite-based lubricant is suitable for hot rolling of a hard-to-work
material such as stainless steel or high-alloy steel. However, the corrosion resistance
of the material is hindered by carburization. Specifically, when a graphite-based
lubricant is used for hot rolling of a hard-to-work material such as stainless steel
or high-alloy, the inside face of a mother pipe or tube is carburized; therefore,
grain boundaries due to grain-boundary - precipitation and the vicinity thereof are
selectively corroded, so that the corrosion resistance thereof lowers, thereby losing
the performance of product.
[0004] In order to improve this problem, Patent Document 1 suggests, instead of a conventional
graphite-based lubricant, a lubricant composition based on a combination of an oxide-based
layered compound, boric acid, and an alkali metal borate. Patent Document 2 suggests
a lubricant composition' based on a combination of artificial mica, vermiculite or
bentonite, Li, Na or K borate, a metaborate or pyroborate, and a hydrate thereof.
These lubricants, wherein an oxide-based layered compound is combined with boric acid,
are effective as non-carburizable lubricant that is excellent in lubricity.
[0005] On the other hand, non-carburizability is not required for ordinary graphite-based
lubricant. Accordingly, these graphite-based lubricants can give the above-mentioned
various properties when an ordinary organic thickener (for example, a water-soluble
acrylic resin, or a water-soluble cellulose such as sodium carboxymethylcellulose)
is sufficiently added to the graphite-based lubricants. For example, Patent Document
3 discloses a lubricant wherein both of a water-soluble polymer and a water-dispersible
polymer are blended in large amounts, whereby the above-mentioned various properties
are attained.
[0006] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 64-16894
[0007] Patent Document 2: JP-A No. 5-171165
[0008] Patent Document 3: JP-A No. 2-51592
Disclosure of the Invention
Problems to be Solved by the Invention
[0009] The lubricants disclosed in the Patent Documents 1 and 2 are supplied in a solid
state onto a face of a tool (for example mandrel bar), or are applied to a tool in
a state that they are dispersed intowater. Accordingly, in order to use the lubricants
in a continuance mill (mandrel mill), it becomes necessary that they have various
properties totally, such as storage stability before use, transferability inside an
apparatus tube, sprayability to a lubricated site, and property of uniform adhesion
to a high - temperature mandrel bar. However, it is difficult to attain these properties
totally.
[0010] In elongating a hollow blank of stainless steel or high-alloy steel by a continuance
mill(mandrel mill), non-carburizability is persistently required in order to keep
corrosion resistance thereof. Thus, the above-mentioned polymers cannot be blended
in large amounts.
[0011] Accordingly, an object of the present invention is to provide a lubricant composition
which totally has various properties, such as storage stability, transferability inside
an apparatus tube, sprayability to a lubricated site, and property of uniform adhesion
to a high-temperature mandrel bar without losing non-carburizability or excellent
lubricity in elongating hard-to-work materials (for example, such as 13 chromium steel
and stainless steel) by a continuance mill(mandrel mill).
Means for Solving the Problems
[0012] The present invention is a lubricant composition for seamless steel pipes or tubes
working which has a viscosity property represented by the following approximate expression:

wherein Y: viscosity (mPa·s) X: shear rate (s
-1) ; and
a: 4000 to 40000 and b: -1.0 to -3.0 while a lubricant composition is stored still,
and a: 1000 to 20000, and b: -1.0 to -0.15 after 90 seconds from the time when shearing
a lubricant composition is finished.
[0013] The wording "90 seconds from the time when shearing a lubricant composition is finished"
means the time of 60 seconds after the following measurement start: a lubricant composition
is stirred; and at 30 seconds from the end of the stirring, the viscosity of lubricant
composition is measured at a given shear rate. Consequently, the wording "90 seconds"
corresponds to the total value of the above-mentioned 30 seconds and 60 seconds. The
wording "the time when shearing a lubricant composition is finished" means the time
when the above-mentioned stirring operation is finished.
[0014] It is preferred that the lubricant composition for seamless steel pipes or tubes
working comprises 10 to 40% by mass of an oxide-based layered compound, 5 to 30% by
mass of one or more alkali metal salts or amine salts of boric acid, 0.11 to 3.0%
by mass of one or more water-soluble polymers which are soluble in an aqueous solution
of the alkali metal salt (s) or amine salt (s) of boric acid, and water as the balance.
[0015] It is preferred that the lubricant composition for seamless steel pipes or tubes
working comprises, as water-soluble polymer(s), a pseudo plastic fluidity water-soluble
polymer, or a pseudo plastic fluidity water-soluble polymer and a thixotropic fluidity
water-soluble polymer.
[0016] Alternatively, it is preferred that the lubricant composition for seamless steel
pipes or tubes working comprises, as water-soluble polymer(s)
, a pseudo plastic fluidity water-soluble polymer in an amount of 0.01 to 1.0% by mass
of the whole of the lubricant composition, and a thixotropic fluidity water-soluble
polymer in an amount of 0.1 to 2.0% by mass of the whole of the lubricant composition.
Effects of the Invention
[0017] According to the invention, it is possible to provide a lubricant composition for
seamless steel pipes or tubes working which totally has various properties, such as
storage stability, transferability inside an apparatus tube, sprayability to lubricated
sites, and property of uniform adhesion to a high-temperature mandrel bar without
losing non-carburizability or excellent lubricity to hard-to-work materials such as
13 chromium steel and stainless steel.
Best Mode for Carrying Out the Invention
[0018] An oxide-based layered compound used as main agent in a lubricant composition for
seamless steel pipes or tubes working of the invention is, for example, any natural
mica or artificial mica. Examples of the mica include:
Potassium tetrasilicone mica {KMg2.5(Si4O10)F2},
Sodium tetrasilicone mica {NaMg2.5(Si4O10) F2}, and
Natural golden mica {KMg3(AlSi2O10) (OH)2}.
In the lubricant composition for seamless steel pipes or tubes working of the invention,
one or more therefrom can be used. Instead of the mica, or together with the mica,
vermiculite, bentonite or the like can be used. Sodium tetrasilicone mica is the most
preferable for the lubricant composition for seamless steel pipes or tubes working
of the invention.
[0019] The average particle diameter of the oxide-based layered compound is from 1 to 40
µm, preferably from 5 to 30 µm. If the particle diameter is too small, the effect
of interlayer slip becomes small. On the other hand, if the particle diameter is too
large, problems such that a nozzle is blocked when the lubricant composition is sprayed
are caused. The adding amount of the oxide-based layered compound is from 10 to 40%
by mass of the lubricant composition of the lubricant of the invention for seamless
steel pipes or tubes working, preferably from 20 to 30% by mass thereof. If the adding
amount of the oxide-based layered compound is too small, the seizing resistance becomes
low so that a problem is caused about the lubricity thereof. On the other hand, if
the adding amount of the oxide-based layered compound is too large, the viscosity
of the lubricant composition becomes too high so that a problem is caused about the
workability.
[0020] Alkali metal salt(s) or amine salt(s) of boric acid in a lubricant composition help
(s) the oxide-based layered compound, which is a main agent, spreading on a high-temperature
mandrel bar, or the salt (s) itself/themselves work(s) as a single or plural lubricating
auxiliaries. Examples of the alkali metal salt(s) of boric acid include lithium borate,
sodium borate, and potassium borate. Ametaborate, a pyroborate and/or a hydrate, such
as borax (Na
2B
4O
7·10H
2O) can be used.
[0021] The adding amount of alkali metal salt (s) or amine salt (s) of boric acid into the
lubricant composition is from 5 to 30% by mass, preferably from 10 to 20% by mass.
If the adding amount of the salt (s) is too large, the salt (s) hinder (s) the lubricity
of the main agent. If the adding amount of the salt(s) is too small, it hinders a
main object, that is, the property of uniform adhesion to a mandrel bar caused by
the main agent. Moreover, the lubricity is insufficient, so that shortage of lubricity
is induced.
[0022] Aswater-solublepolymer(s) used ina lubricant composition for seamless steel pipes
or tubes working of the invention, the following can be used: a single or a combination
of two or more selected from natural, semi-natural and synthetic water-soluble polymers
having the viscosity conditions prescribed in the present invention. These water-soluble
polymers will be specifically described later.
[0023] Next, an ideal viscosity which has been found by the present inventors is shown in
FIG. 1. FIG. 1, wherein viscosity is represented by its vertical axis and time is
represented by its horizontal axis, is a graph of the viscosity variation of a lubricant
composition changed with time under the following conditions:
(i): a lubricant composition is kept still,
(ii) to (iii): a lubricant composition is sheared at a constant rate, and
(iii) to (iv) : the shearing of a lubricant composition is finished.
[0024] The inventors have found out that a lubricant composition of which viscosity property
is as the following (1) to (4), has excellent lubricity in the production of a seamless
metal pipe or tube according to the Mannesmann process:
- (1) In order to store a lubricant in a state that solid particles of the oxide-based
layered compound is even and stable, the viscosity at the time (i) when a lubricant
composition is kept still has to be high. If the viscosity is low, the solid particles
settle down.
- (2) In order to keep the transferability inside an apparatus tube and the sprayability,
the viscosity at the time (ii) to (iii) when a lubricant composition is sheared needs
to be low.
- (3) For the property of fine and even adhesion to a high-temperature bar, which gives
a great influence on lubricity, the viscosity at the time (ii) has to be high. From
a microscopic viewpoint, a lubricant is continuously sprayed and adheres onto a tool
surface. On a coat of lubricant adhered formerly, a lubricant sprayed later arrives.
That is, a coat of lubricant adhered formerly is sheared. Accordingly, if the viscosity
at the time (ii) is low, the lubricant is unfavorably peeled down or scattered by
the pressure of spraying lubricant.
- (4) In order to keep uniform and stable retention property of the solid particles
on a tool surface, the viscosity needs to rise immediately after the finish of the
shearing at the times of (iii) to (iv). If it takes much time that the viscosity recovers
or the viscosity does not recover, the lubricant unfavorably flows down from the tool
surface.
[0025] In order to realize that a lubricant has the viscosity showed as FIG, 1, and attains
various properties, such as storage stability, transferability inside an apparatus
tube, sprayability to lubricated sites, and property of uniform adhesion to a high-temperature
mandrel bar without adding a large amount of a polymer, the inventors have found out
that the lubricant viscosityhas to fulfill the expression described below. In other
words, the inventors have measured the viscosity property of the present invention
lubricant having the above-mentioned various properties by a viscosity-measuring method
described in Examples which is described later, so as to find that the parameters
a and b which are counted from the measured viscosity curve has to be within the range
described in the following approximate expression:

wherein Y: viscosity (mPa·s) X: shear rate (s
-1); and
a: 4000 to 40000 and b: -1.0 to -0.3 while a lubricant composition is stored still;
and
a: 1000 to 20000, and b: -1.0 to -0.7.5 after 90 seconds from the time when shearing
a lubricant composition is finished.
[0026] In the approximate expression:

a and b are set into the range of 4000 to 40000 and that of -1.0 to -0.3, respectively,
while a lubricant composition is stored to be kept still. If a is less than 4000,
the viscosity of a lubricant composition is low while a lubricant composition is kept
still. Consequently, the oxide-based layered compound settles down while a lubricant
composition is stored. If a is more than 40000, the fluidity of a lubricant composition
is substantially lost, so as to cause a problem about the transfer thereof.
[0027] Further, if b is more than -0.3, the difference between the viscosity of a lubricant
composition while it is kept still and that while a lubricant composition is sheared
(i.e., transferred or sprayed) is small, so as to cause a problem about the transfer
or spray thereof. If b is less than -1.0, the viscosity of a lubricant composition
becomes too low when it is sprayed. Consequently, at the time of applying a lubricant
composition onto a tool, the lubricant adhered formerly is peeled down or scattered
by the pressure of spraying lubricant itself. More preferably a and b are as follows:
a: 7000 to 30000, and
b: -0.5 to -0.8.
[0028] The approximate expression: Y = a·X
b is described herein with reference to FIG. 1. As the value a is larger and the value
b is smaller while a lubricant composition is stored still (that is, when the value
X is limitlessly near 0), the viscosity at the time (i) in FIG. 1 is higher so that
the stability is better. For example, in the case of X = 0.01, a = 100000 and b =
-1, Y = 10,000,000 mPa·s.
[0029] In the approximate expression:

a and b are set into the range of 1000 to 20000 and that of -1.0 to -0.15, respectively,
after 90 seconds from the time when shearing a lubricant composition is finished.
If a, is less than 1000 or b is less than -1.0, the water-soluble polymer (s) is /are
sheared and thus it takes much time that the viscosity recovers. Alternatively, a
lubricant composition is sheared and its viscosity does not recover, and at this time
the lubricant flows down. If a is more than 20000 or b is more than -0.15, a problem
is caused when a lubricant composition is transferred or sprayed. More preferably,
a and b are as follows:
a: 3000 to 20000, and
b: -0.3 to -0.8.
[0030] As the value a is larger and the value b is smaller while a lubricant composition
is sheared (that is, when the value X is larger immediately after a lubricant composition
is stirred), the viscosity at the time (ii) and (iii) in FIG. 1 is higher. If a is
too large and b is too small, the viscosity does not become low and that hinders the
transferability and sprayability. For example, in the case of X = 10, a = 100000 and
b = -1, Y = 10,000 mPa·s.
[0031] The time after a lubricant composition is sheared (that is, when the value X just
after the stirring is small) is (iv) in FIG. 1. In the case that numerical values
of a and bare similar to the numerical values when a lubricant composition is stored
still, the viscosity rapidly recovers. In this case, the lubricant that adheres to
a tool does not easily flow down. Accordingly, such an appropriate viscosity property
as in the invention described above is crucial.
[0032] The inventors have made eager investigations on conditions for attaining the above-mentioned
viscosity property, so as to find out the following: the use of only a pseudo plastic
fluidity water-soluble polymer, as the water-soluble polymer(s) used in a lubricant
composition of the invention, may cause the above mentioned property to be attained;
however, the addition of both of a pseudo plastic fluidity water-soluble polymer and
a thixotropic fluidity water-soluble polymer easily causes the above mentioned property
to be attained.
[0033] Typical examples of the pseudo plastic fluidity water-soluble polymer include bio-gums
such as xanthan gum, welan gum and ramsan gum. The chemical structure of xanthan gum
is a water-soluble polymer polysaccharide wherein linking blocks each having two glucoses,
two mannoses and one glucuronic acid as constituents are recurred. A model of the
chemical structure is illustrated in FIG. 2.
[0034] Typical examples of the thixotropic fluiditywater-soluble polymer include carboxymethylcelulose
salts (Na, K, and amine salts). As an example thereof, a chemical structure model
of a long-chain polymer wherein glucoses are subjected to glucoside bonding is illustrated
in FIG. 3.
[0035] Pseudo plastic fluidity and/or thixotropic fluidity can also be attained by incorporating,
into a lubricant composition, one or more selected from the following materials which
are different from the above and cannot be easily distinguished from each other dependently
on the molecular weight, another component or other components (for example, a metal
(such as Ca) ion), or pH: bio-gums such as gellan gum, and succinoglucan; natural
polysaccharides such as tamarind, tara gum, locust bean gum, and carrageenan; cellulose
derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,
hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose; polyacrylic acid salts
(Na, K, and amine salts), and alginic acid salts (Na, K, and amine salts).
[0036] Next, the viscosity property of a pseudo plastic fluidity water-soluble polymer in
static and dynamic states is shown in FIG. 4, and that of a thixotropic fluidity water-soluble
polymer is shown in FIG. 5. According to only the pseudo plastic fluidity water-soluble
polymer, a change from the static state to the dynamic state is like a straight line.
Thus, the change comes under the scope of the invention, but satisfaction is not sufficiently
given. On the other hand, the viscosity change of the thixotropic fluidity water-soluble
polymer, wherein the viscosity difference from the static state to the dynamic state
is small, is gentler than the viscosity change of the pseudo plastic fluidity water-soluble
polymer. About the thixotropic fluidity water-soluble polymer, some amount of time
(yield value) is necessary from the start of the dynamic state to a drop in the viscosity.
About the thixotropic fluidity water-soluble polymer, time is also necessary for a
rise in the viscosity in the case that the dynamic state is shifted to the static
state. In the case that time is required for such a viscosity change, the lubricant
sprayed onto a mandrel bar cannot undergo viscosity change for ideal film-formation
in a film-forming step from the spray to drying. As a result, the lubricant does not
adhere evenly onto the mandrel bar at ease. Accordingly, the object of the invention
cannot be sufficiently realized by only the thixotropic fluidity water-soluble polymer.
[0037] In order to realize the ideal viscosity form shown in FIG. 1, it is desired to add
the above-mentioned two polymers together. Specifically, the addition percentage of
the pseudo plastic fluidity water-soluble polymer is from 0.01 to 1.0% by mass of
the whole of the lubricant composition and the addition percentage of the thixotropic
fluidity water-soluble polymer is from 0.1 to 2.0% by mass of the whole of the lubricant
composition. More preferably, the addition percentage of the pseudo plastic fluidity
water-soluble polymer is from 0.05 to 0.5% by mass of the whole of the lubricant composition
and in connection therewith the addition percentage of the thixotropic fluidity water-soluble
polymer is from 0.5 to 1.5% by mass of the whole of the lubricant composition. If
the addition percentage of the pseudo plastic fluidity water-soluble polymer gets
larger than that of the thixotropic fluidity water-soluble polymer, the viscosity
change by shear becomes too large so that a lubricant composition does not adhere
evenly onto a mandrel bar at ease. If the percentage of the thixotropic fluidity water-soluble
polymer becomes too large, the dispersion stability of the oxide-based layered compound
and the spreading property to a high-temperature mandrel bar are deteriorated so that
the property of the uniform adhesion gets worse.
[0038] A lubricant which includes each fluidity water-soluble polymer of the above-mentioned
two has a mixed viscosity property of that shown in FIG. 4 and FIG. 5. A qualitative
viscosity property thereof is as follows: in FIG. 1, at time(i)when a lubricant composition
is kept still, the viscosity is high because of the nature of the pseudo plastic fluidity
water-soluble polymer; when shear is applied thereto thereafter, a drop in the viscosity
at (i) to (iii), having a synthetic form of pseudo plastic fluidity and thixotropic
fluidity states, is exhibited; and at last the viscosity property is converted into
a rise in the viscosity shown at (iv) immediately after shearing is finished.
[0039] If the total percentage of the two polymers is more than 3.0% by mass of the total
of a lubricant composition, a problem of carburization is unfavorably caused. If the
percentage of the two polymers is less than 0.11% by mass of the total of a lubricant
composition, the dispersion stability of the oxide-based layered compound is deteriorated
so that the resultant is not suitable for a lubricant composition of the invention.
[0040] The addition of an ordinary antifoaming agent or dispersing agent causes a risk of
carburization if the agent is an organic compound; therefore, the addition of a small
amount (0.5% or less by mass of the total of the lubricant composition) thereof is
permissible. Inorganic agents, which do not contain carbon, are allowed to be added
as long as the agents do not give a significant influence onto basic performances
of the invention.
Examples
(1) Preparations of samples for evaluation
[0041] Eighteen working examples shown in Tables 1 to 2 and 10 comparative examples shown
in Table 3, that is, 28 samples in total were prepared. Tables 1 to 3 also show peculiar
numeric constants "a" and "b" in the approximate expressions of these samples while
they were stored still, and those after 90 seconds from the time when shearing thereto
was finished.
(2) Performance-evaluating tests
1) Viscosity
(i) Measuring conditions
[0042] Measuring device: B-model rotary viscometer was used.
Measuring temperature: It was set to 25°C.
Shearing conditions:
[0043] a 500-mL of the samples were respectively put into a 500-mL beaker, and then stirred
at 3000 rpm for 1 minute by means of a propeller of 50 mm diameter.
Rotation number:
[0044] Low rotation (1.5 rpm) [shear rate: 0.323 to 0.366 S
-1]
[0045] High rotation (60 rpm) [shear rate: 12.9 to 14.6 s
-1]
[0046] The reason why the shear rate of the samples had a numerical range was that in the
rotary viscometer, wherein viscosity is measured while a cone is rotated on its plate,
cones actually used for the samples were different from each sample.
(ii) Measuring method
[0047] Stationary viscosity: After each of the samples was stirred and kept still for 24
hours, it started to measure the viscosity at low shear rate. After 60 seconds from
the start of the measurement, data of the viscometer was read out and was multiplied
by a coefficient. Subsequently, it started to measure the viscosity at high shear
rate. After 60 seconds from the start of the measurement, data of the viscometer was
read out and was multiplied by a coefficient. The result was recorded as stationary
viscosity.
[0048] Shear viscosity: Each of samples was stirred to shear thereto with the propeller.
After 30 seconds from the finish of shearing, it started to measure the viscosity
at low shear rate. After 60 seconds from the start of the measurement, data of the
viscometer was read out and was multiplied by a coefficient. The sample was again
stirred, and after 30 seconds therefrom it started to measure the viscosity at high
shear rate. After 60 seconds from the start of the measurement, data of the viscometer
was read and was multiplied by a coefficient. The result was recorded as shear viscosity.
[0049] In the measurements, the time "90 seconds from the time when shearing was finished
(or after 90 seconds from the finish of the shearing)" means the time of 60 seconds
after the following measurement start: an operation of shearing a sample was performed
by stirring the lubricant composition; and after 30 seconds from the finish of the
operation, it started to measure the viscosity at a given shear rate. Thus, the time
"90 seconds" corresponds to the total value of the above-mentioned 30 seconds and
60 seconds. The "time when shearing was finished (or the time of the finish of the
shearing" means the time when rotating the propeller for the above-mentioned stirring
is stopped.
(iii) Decision of the peculiar numeric constants "a" and "b"
[0050] Logarithms of both sides of the approximate expression Y = a·X
b are given as follows: log (Y) = blog (X) + log (a)
[0051] According to X and Y obtained in the above-mentioned measurements, log (X) and log
(Y) are calculated. These are plotted in a graph corresponding to its vertical axis
and its horizontal axis, respectively. As a result, there is a substantially linear
relationship (relationship of a linear function) between them. From the graph, "b",
which is the gradient of the linear function and "a", which is the vertical axis intercept,
can be obtained by the least-squares method.
2) Storage stability
(i) Test method
[0052] The samples were respectively stored in a 500-mL glass container, and kept still
for 7 days. Thereafter, a state of separation thereof was observed.
(ii) Evaluating method: The samples were evaluated inaccordance with the following
evaluating criterion:
[0053]

: No supernatant was generated, and no sedimentation was caused on the bottom.
○: Supernatant was generated in an amount of less than 5%, and no sedimentation was
caused on the bottom.
Δ: Supernatant was generated in an amount of 5% or more, and no sedimentation was
caused on the bottom.
x: Sedimentation was caused on the bottom regardless of the generation of supernatant.
[0054] The word "supernatant" means a substantially transparent liquid portion containing
no solid. By observing a beaker of sample from a side-direction, the height of a supernatant
in the beaker is measured. The height of a supernatant in the beaker was evaluated
as the percentage thereof into the height of the liquid in the beaker.
[0055] The wording "sedimentation on the bottom" means a state that a solid lubricant settles
down on the bottom and thus a hard layer having no fluidity can be perceived.
3) Carburization
(i) Test method
[0056] Four examples 4, 11 and 13 and Comparative Examples 6 were respectively sprayed and
applied onto a mandrel bar made of SKD61 and having an outer diameter of 140.5 mm
and an effective portion length of 18 m, and then dried and solidified to form a substantially
uniform lubricant coat having a film thickness of 100
µm on the surface of the mandrel bar. The mandrel bar, onto which the lubricant was
applied, was inserted into an hollow shell. Continuance mill (mandrel mill) composed
of 7 stands was used to roll a hollow blank into an mother pipe or tube.
[0057] Specification of a hollow blank before elongation:
Material: Austenite stainless steel (SUS304L);
Working: piercing by piercing mill with inclined-roll;
Shape: outer diameter: 181.0 mm, thickriess: 16.0 mm, and length: 7000 mm.
Shape of a mother pipe or tube after elongation:
Outer diameter: 151.0 mm, thickness: 5.0 mm, and length: 25300 mm.
[0058] After the hollow blanks were respectively rolled with continuance mill (mandrel mill),
the mother pipe or tube was rolled to determined outer diameter by sizing mill. A
product had an outer diameter of 63.5 mm, thickness of 7.0 mm and a length of 40000
mm. An arc-form test piece having a thickness of 5 mm, a width of 25 mm and a length
of 50 mm was made from a product. This test piece was used to make a sulfuric acid-copper
sulfate corrosion test prescribed in JIS G0575, and then the state of a grain boundary
corrosive crack generated in the inside surface was observed.
(ii) Evaluating method: An evaluation was made in accordance with the following criterion:
[0059]

: No crack.
x: A crack was generated.
4) Sprayability
(i) Test conditions
[0060] Spray manner: an airless spray.
[0061] Spraying pressure: It was set to 3.0 MPa.
[0062] Nozzle: 1/4MVVP5010 (manufactured by Kabushiki Kaisha Ikeuchi (transliteration)).
[0063] Spray pattern: Fan-shaped
[0065] 50 degrees (angle at which water was spread into a fan shape when water was sprayed)
[0066] Sample temperature: It was set to 25°Ctomake an evaluation.
(ii) Evaluation: The spreading property was evaluated by measuring the spray angle.
The result of the evaluation was recorded in accordance with the following evaluating
criterion:
[0067]

: The spray angle was a almost predetermined angle (50 degrees).
O: The spray angle was somewhat narrower than the predetermined angle (40 to 45 degrees).
△: The spray angle was far narrower than the predetermined angle (20 to 39 degrees).
x: The spray angle was hardly spread (less than 20 degrees), or sprayed particles
were large.
5) Adhesion property (adhesion amount)
i) Test conditions
[0068] Spray manner: an airless spray.
[0069] Spraying pressure: It was set to 3.0 MPa.
[0070] Nozzle: 1/4MVVP5010 (manufactured by Kabushiki Kaisha Ikeuchi (transliteration)).
[0071] Spray angle: 50 degrees
[0072] Test piece temperatures: The temperatures were set to 60, 80, 100, and 120°C.
[0073] Nozzle/test-piece distance: It was set to 250 mm to make the test.
[0074] Test speed: It was set to 2 m/second.
(ii) Evaluating method: Each sample was sprayed onto a test piece (a 65 mm x 120 mm
x 30 mm steel plate) under the test conditions. After spraying, the test piece was
heated up to 120°C to dry the lubricant . Thereafter, the test piece naturally cooled
down to 20-40°C. The lubricant coat was shaved off with a knife and its weight was
measured. The weight of the coat was divided by the adhesion area (0.0078 m2) and the result was defined as the adhesion amount. It was evaluated in accordance
with the following evaluating criterion:
[0075]

: The coat adhered evenly, and the adhesion amount was 50 g/m2 or more.
0: The coat adhered substantially evenly, and the adhesion amount was 50 g/m2 or more.
△ : The lubricant somewhat flowed down, and the adhesion amount was 40 g/m2 or more.
x: The lubricant flowed down largely, and the adhesion amount was 30 g/m2 or less.
xx: The adhesion property was bad because of repellency, and the adhesion amount was
30 g/m2 or less.
(3) Test results
[0076] The results of the tests 1) to 5) are shown in Tables 1 to 3.
[Table 1]
|
Example 1 |
Example2 |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Sodium tetrasilicone mica |
10.00 |
10.00 |
20.00 |
15.00 |
20.00 |
20.00 |
20.00 |
20.00 |
30.00 |
Natural golden mica |
|
|
|
|
|
|
|
|
|
Bentonite |
|
|
|
|
|
|
|
|
|
Potassium borate |
|
10.00 |
13.00 |
8.00 |
10.00 |
10.00 |
15.00 |
15.00 |
12.00 |
Amine borate |
5.00 |
5.00 |
|
8.00 |
|
5.00 |
5.00 |
5.00 |
3.00 |
Xanthan gum |
0.50 |
0.40 |
0.70 |
0.10 |
|
0.40 |
0.50 |
0.30 |
0.30 |
Welan gum |
|
|
|
|
0.05 |
|
|
|
|
CMC (A) |
0.50 |
|
|
|
|
|
0.50 |
|
|
CMC (B) |
|
0.50 |
|
|
|
|
|
|
0.30 |
CMC (C) |
|
|
|
1.00 |
1.00 |
|
|
0.50 |
|
CMC (D) |
|
|
|
|
|
|
|
|
|
Na polyacrylate (A) |
|
|
|
|
|
|
|
|
|
Na polyacrylate (B) |
|
|
|
|
|
0.20 |
|
|
|
Water (Calculated amount) |
84.00 |
74.10 |
66.30 |
67.90 |
68.95 |
64.40 |
59.00 |
59.20 |
54.40 |
Liquid state |
|
|
|
|
|
|
|
|
|
Stationary viscosity |
(low shear rate) |
18850 |
15930 |
53500 |
14180 |
15400 |
15800 |
22080 |
26000 |
30900 |
|
(high shear rate) |
1080 |
1390 |
1750 |
1780 |
1870 |
1040 |
1720 |
1700 |
1860 |
After shearing |
(low shear rate) |
19520 |
17400 |
48420 |
6325 |
2250 |
18900 |
25000 |
18000 |
24130 |
|
(high shear rate) |
1090 |
1410 |
1690 |
1410 |
1170 |
1060 |
1630 |
1600 |
1710 |
|
|
|
|
|
|
|
|
|
|
At a time of stationary storage |
(coefficient a) |
8154 |
7795 |
19638 |
7719 |
8302 |
7119 |
10451 |
11691 |
13562 |
|
(coefficient b) |
-0.777 |
-0.663 |
-0.929 |
-0.564 |
-0.573 |
-0.739 |
-0.693 |
-0.741 |
-0.763 |
Immediately after the shearing |
(coefficient a) |
8380 |
8332 |
18115 |
4074 |
1858 |
8125 |
11232 |
8856 |
11110 |
|
(coefficient b) |
-0.784 |
-0.683 |
-0.911 |
-0.408 |
-0.178. |
-0.783 |
-0.742 |
-0.657 |
-0.719 |
|
|
|
|
|
|
|
|
|
|
Storage stability |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
Carburization |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
Sprayability |
(25°C) |
⊚ |
⊚ |
○ |
⊚ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
Adhesive property |
(60°C) |
⊚ |
⊚ |
⊚ |
○ |
○ |
Δ |
⊚ |
⊚ |
⊚ |
|
(80°C) |
⊚ |
⊚ |
⊚ |
⊚ |
○ |
Δ |
⊚ |
⊚ |
⊚ |
|
(100°C) |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
|
(120°C) |
⊚ |
⊚ |
○ |
⊚ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
[Table 2]
|
Example 10 |
Example 11 |
EXample 12 |
Example 13 |
Example 14 |
Example 15 |
Example 16 |
Example 17 |
Example 18 |
Sodium tetrasilicone mica |
40.00 |
|
|
10.00 |
|
5.00 |
5.00 |
|
20.00 |
Natural golden mica |
|
20.00 |
|
10.00 |
10.00 |
5.00 |
5.00 |
10.00 |
|
Bentonite |
|
|
20.00 |
|
10.00 |
5.00 |
5.00 |
|
|
Potassium borate |
12.00 |
12.00 |
10.00 |
10.00 |
20.00 |
5.00 |
5.00 |
30.00 |
30.00 |
Amine borate |
3.00 |
3.00 |
10.00 |
5.00 |
|
10.00 |
10.00 |
|
|
Xanthan gum |
|
0.60 |
|
|
|
|
0.10 |
0.20 |
|
Welan gum |
0.05 |
|
0.15 |
0.20 |
0.15 |
0.10 |
|
|
0.02 |
CMC (A) |
|
|
|
1.50 |
|
|
|
|
|
CMC (B) |
|
|
|
|
|
|
|
|
0.50 |
CMC (C) |
|
|
|
|
|
1.00 |
1.00 |
1.00 |
|
CMC (D) |
0.50 |
|
|
|
|
|
|
|
|
Na polyacrylate (A) |
|
2.00 |
|
|
1.00 |
|
|
|
|
Na polyacrylate (B) |
|
|
0.30 |
|
|
|
|
|
|
Water (Calculated amount) |
44.45 |
62.40 |
59.55 |
63.30 |
58.85 |
68.90 |
68.90 |
58.80 |
49.48 |
Liquid state |
|
|
|
|
|
|
|
|
|
Stationary viscosity |
(low shear rate) |
12070 |
42400 |
32000 |
45100 |
17800 |
50000 |
9500 |
18000 |
9225 |
|
(high shear-rate) |
1740 |
2480 |
1450 |
4230 |
1650 |
3050 |
1800 |
2150 |
1680 |
After shearing |
(low shear rate) |
8920 |
32100 |
17500 |
9830 |
7200 |
8500 |
5800 |
133300 |
1975 |
|
(high shear rate) |
1580 |
2500 |
1100 |
2230 |
900 |
2100 |
1560 |
1980 |
835 |
|
|
|
|
|
|
|
|
|
|
At a time of stationary storage |
(coefficient a) |
6843 |
18453 |
12923 |
22542 |
8866 |
22031 |
5835 |
9657 |
5600 |
|
(coefficient b) |
-0.526 |
-0.771 |
-0.841 |
-0.643 |
-0.646 |
-0.76 |
-0.452 |
-0.577 |
-0.463 |
Immediately after the shearing |
(coefficient a) |
5371 |
15193 |
7779 |
6364 |
3915 |
5643 |
3947 |
7611 |
1534 |
|
(coefficient b) |
-0.47 |
-0.693 |
-0.752 |
-0.403 |
-0.565 |
-0.38 |
-0.357 |
-0.517 |
-0.234 |
|
|
|
|
|
|
|
|
|
|
|
Storage stability |
⊚ |
⊚ |
⊚ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
○ |
Carburization |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
Sprayabilily |
(25°C) |
⊚ |
⊚ |
○ |
○ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
Adhesive property |
(60°C) |
⊚ |
⊚ |
Δ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
Δ |
|
(80°C) |
⊚ |
⊚ |
Δ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
Δ |
|
(100°C) |
⊚ |
○ |
○ |
⊚ |
⊚ |
⊚ |
⊚ |
⊚ |
○ |
|
(120°C) |
⊚ Δ |
|
○ |
⊚ |
○ |
⊚ |
⊚ |
⊚ |
Δ |
[Table 3]
|
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
Comparative Example 4 |
Comparative Example 5 |
Comparative Example 6 |
Comparative Example 7 |
Comparative Example 8 |
Comparative Example 9 |
Comparative Example 10 |
Sodium tetrasilicone mica |
20.00 |
30.00 |
|
|
20.00 |
10.00 |
20.00 |
7.00 |
42.00 |
|
Natural golden mica |
|
|
15.00 |
50.00 |
|
10.00 |
|
|
|
20.00 |
Bentonite |
|
|
|
|
10.00 |
|
|
|
|
10.00 |
Potassium borate |
10.00 |
|
5.00 |
30.00 |
10.00 |
15.00 |
20.00 |
2.00 |
30.00 |
10.00 |
Amine borate |
|
10.00 |
5.00 |
|
5.00 |
5.00 |
|
2.00 |
5.00 |
5.00 |
Xanthan gum |
3.00 |
|
|
|
|
0.50 |
0.30 |
0.30 |
|
0.005 |
Welan gum |
|
|
|
0.30 |
2.00 |
|
|
|
0.005 |
|
CMC (A) |
|
1.00 |
|
|
|
|
|
1.00 |
|
0.05 |
CMC (B) |
|
|
|
|
|
|
5.00 |
|
|
|
CMC (E) |
|
|
|
|
|
5.00 |
|
|
|
|
Na polyacrylate (A) |
|
|
|
|
|
|
|
|
|
|
Na polyacrytate (B) |
|
|
1.00 |
|
|
|
|
|
0.15 |
|
Water (Calculated amount) |
67.00 |
59.00 |
74.00 |
19.70 |
53.00 |
54.50 |
54.70 |
87.70 |
22.845 |
54.945 |
Liquid state |
Unable to be prepared |
|
|
Unable to be prepared |
Unable to be prepared |
|
Unable to be prepared |
|
|
|
Stationary viscosity |
(low shear rate) |
|
400 |
2100 |
|
|
26800 |
|
4400 |
87600 |
800 |
|
(high shear rate) |
|
340 |
570 |
|
|
3870 |
|
520 |
100000 |
130 |
After shearing |
(low shear rate) |
|
350 |
700 |
|
|
11000 |
|
1000 |
100000 |
1200 |
|
(high shear rate) |
|
314 |
500 |
|
|
2300 |
|
468 |
8700 |
140 |
|
|
|
|
|
|
|
|
|
|
|
At a time of stationary storage |
(coefficient a) |
|
381 |
1433 |
|
|
15201 |
|
2353 |
91065 |
469 |
|
(coefficient b) |
|
-0.044 |
-0.354 |
|
|
-0.526 |
|
-0.58 |
-0.038 |
-0.494 |
Immediately after the shearing |
(coefficient a) |
|
339 |
63.4 |
|
|
6954 |
|
800 |
48892 |
639 |
|
(coefficient b) |
|
-0.03 |
-0.091 |
|
|
-0.425 |
|
-0.206 |
-0.663 |
-0.584 |
|
|
|
|
|
|
|
|
|
|
|
Storage stability |
|
X |
X |
|
|
⊚ |
|
⊚ |
⊚ |
X |
Carburization |
|
⊚ |
⊚ |
|
|
X |
|
⊚ |
⊚ |
⊚ |
Sprayability |
(25°C) |
|
⊚ |
○ |
|
|
○ |
|
⊚ |
X |
⊚ |
Adhesive property |
(60°C) |
|
X |
X |
|
|
○ |
|
X |
X |
X |
|
(80°C) |
|
X |
X |
|
|
○ |
|
X |
X |
X |
|
(100°C) |
|
X |
X |
|
|
○ |
|
X |
X |
X |
|
(120°C) |
|
XX |
XX |
|
|
○ |
|
X |
X |
XX |
CMC*(A): molecular weight (100,000), viscosity (800/2%**) |
CMC*(B): molecular weight (250,000), viscosity (1600/1%**) |
CMC*(C): molecular weight (175,000), viscosity (2500/2%) |
CMC*(D): molecular weight (195,000), viscosity (3500/2%) |
CMC*(E): molecular weight (30,000), viscosity (15/2%) |
Na polyacrylate (A): molecular weight (500,000), viscosity |
(75/1%) |
Na polyacrylate (B): molecular weight (1,650,000), viscosity |
(300/0.2%) |
*CMC = Na salt of carboxymethylcellulose |
**: It means that the viscosity of a 2% solution thereof in water |
at 25°C was 800 mPa·s. |
(4) Conclusion
[0077] From the above-mentioned test results, it was proved that a lubricant composition
of the invention has performances good in all of storage stability, sprayability,
and adhesion property. On the other hand, about the group of a lubricant compositions
of Comparative Examples, satisfactory performances therefor were unable to be obtained.
[0078] The above has described the invention in connection with embodiments which appear
to be most practical and preferable at the present time. However, the invention is
not limited to the embodiments disclosed in the specification of the present application,
and can be appropriately varied within a scope not contrary to the subject matter
and the conception of the invention read out from the claims and the whole of the
specification. It should be understood that any lubricant composition for seamless
steel pipes or tubes working with such a variation is also included in the technical
scope of the invention.
Industrial Applicability
[0079] A lubricant composition for seamless steel pipes or tubes working of the invention
is useful for working in the Mannesmann process for producing a seamless steel pipe.
Brief Description of the Drawings
[0080]
FIG. 1 is a chart showing an ideal viscosity form as a lubricant composition for seamless
steel pipes or tubes working.
FIG. 2 is a view of a chemical structure model of an example of the pseudo plastic
fluidity water-soluble polymer.
FIG. 3 is a view showing a chemical structure model of a long-chain polymer wherein
glucoses are subjected to glucoside bonding, the polymer being an example of the thixotropic
fluidity water-soluble polymer.
FIG. 4 is a chart showing viscosity properties of static and dynamic states of a pseudo
plastic fluidity water-soluble polymer.
FIG. 5 is a chart showing viscosity properties of static and dynamic states of a thixotropic
fluidity water-soluble polymer.