FIELD OF THE INVENTION
[0001] This invention relates to a heat transfer tube for an LNG (liquid natural gas) vaporizer
which has an excellent corrosion resistance, and an LNG vaporizer produced by using
such heat transfer tubes.
BACKGROUND OF THE INVENTION
[0002] Liquid natural gas (hereinafter referred to as LNG) is generally transported and
stored in liquid form at a low temperature and a high pressure, and vaporized before
its use.
For such vaporization, an open rack vaporizer (hereinafter referred to as ORV) is
often used since the ORV can vaporize a large amount of LNG. FIG. 1 shows a typical
ORV, and as shown in this FIGURE, an ORV is a heat exchanger in which LNG is heated
for vaporization by heat exchange with seawater (see, for example, Patent Document
1). The seawater enters at a seawater header 6, flows through a sprinkling nozzle
7 to be stored in a trough 8. The seawater flowing over the edge of the trough 8 flows
down along the outer surface of panel 3 composed of heat transfer tubes 3a arranged
in a row in curtain form wetting the outer surface of the heat transfer tubes 3a.
In the meanwhile, LNG enters an LNG manifold 1, and flows through a lower header 2
connected to the lower end of the panel 3, where the LNG is heated by heat exchange
with the seawater. The LNG is then vaporized in each heat transfer tube 3a of the
panel 3, and the vaporized natural gas (NG) flows upward through the heat transfer
tube 3a to headers 4 and 4, and then, to NG manifold 5.
[0003] The material used for the heat transfer tubes 3a constituting the panel 3 should
have satisfactory heat conductivity as well as high workability that allows the material
to be worked into the complicated profile required for the panel 3, and an aluminum
alloy is typically used for the heat transfer tubes. However, an aluminum alloy is
susceptible to corrosion when it is immersed in seawater, and once the corrosion starts,
pitting corrosion is likely to take place wherein the corrosion is concentrated to
the corroded part resulting in a hole. Accordingly, extensive studies on corrosion
protective treatment have been made on the aluminum alloy for use in applications
in which the alloy is immersed in seawater, and currently, the most popular anti-corrosive
treatment is the one using sacrificial corrosion protection. Patent Document 1 as
mentioned above discloses a corrosion protection wherein a metal such as zinc (Zn)
which is more susceptible to corrosion than the aluminum alloy used for the panel
3 (heat transfer tubes 3a) having the LNG flowing therethrough, namely, a bulk of
a metal or an alloy which has a high ionization tendency is electrically connected
to the lower header 2 which is immersed in the pond of the seawater flown down along
the outer surface of the panel 3 wetting the outer surface for use as a sacrificial
anode so that this sacrificial anode undergoes electrochemical dissolution and consumption
and the surface of the lower header 2 and the panel 3 acting as a counter electrode
is prevented from undergoing corrosion. However, in the LNG vaporizer, the seawater
flowing over the edge of the trough 8 directly hits the surface of the heat transfer
tubes 3a constituting the panel 3, and therefore, corrosion by the so called "erosion
corrosion" inevitably proceeds even if such sacrificial anode were provided. Therefore,
an alloy having an ionization tendency higher than the aluminum alloy of the heat
transfer tube 3a (hereinafter referred to as "coating alloy") is preferably coated
on the surface of the heat transfer tubes 3a so that the seawater is prevented from
directly contacting with the surface, and so that the corrosion of the heat transfer
tube surface is prevented by its corrosion protective effect even if local peeling
of the coating alloy should occur. Exemplary alloys that have been known to have such
protective effects of sacrificial corrosion include Al - Zn alloy, and those commonly
used include Al-2% Zn alloy and Al - 15% Zn alloy. Accordingly, effective prevention
of the corrosion is realized by thermally spraying such coating alloy to form a coating
on the surface of the heat transfer tube.
[0004] In order to further improve the corrosion resistance of the coating formed on the
surface of the heat transfer tube, Patent Document 2, for example, discloses a tube
for use in an aluminum tube for a heat exchanger having an improved corrosion resistance
wherein a heat transfer tube (tube produced by extrusion) of aluminum or an aluminum
alloy has formed on its surface a first layer including a Zn layer which electrochemically
acts as a sacrificial layer, and Al or an Al alloy of Al - Ca or Al - Zn - Ca metal
thermally sprayed on the first layer to thereby prevent evaporation of the zinc during
blazing in the production of the heat exchanger. Patent Document 3 discloses an Al
alloy heat transfer tube having an improved corrosion resistance wherein the heat
transfer tube has formed on its surface an Al - Zn alloy layer, and further on this
layer, an Al - Zn alloy layer containing at least one element selected from In, Sn,
Hg, and Cd. On the other hand, Patent Document 4 discloses a finned tube (a fin type
heat transfer tube) for an ORV type vaporizer including an Al alloy tube having a
thick sacrificial anode coating formed by cladding an Al - Zn alloy material.
SUMMARY OF THE INVENTION
[0009] However, lower part of the panel 3 of the ORV and the lower header 2 are the parts
cooled to a temperature below freezing point by the LNG, namely, by the natural gas
in liquid state flowing therethrough. When the surface of the heat transfer tube and
the overflow of the seawater flowing thereon become in contact with each other in
such low temperature part of the ORV, the oxide coating is not readily formed on the
aluminum alloy surface of the heat transfer tube substrate, and the electrode potential
of the heat transfer tube substrate including the aluminum alloy will be lower than
the electrode potential of the Al - Zn ally coating described in Patent Documents
1 to 4. In such case, there is a risk that the protection by sacrificial corrosion
of the Al - Zn alloy coating will not be realized, and the heat transfer tube substrate
will be left unprotected. In a certain circumstance, for example, when the seawater
is at a high temperature, or when the panel 3 is excessively cooled by the LNG flowing
therethrough, there is a risk that the high potential of the Al - Zn alloy coating
affects the heat transfer tube substrate and the heat transfer tube substrate undergoes
galvanic corrosion.
[0010] The coating formed on the surface of the heat transfer tube is required to have durability
in addition to the corrosion resistance. Even if the coating had excellent sacrificial
corrosion protection for Al alloy heat transfer tube substrate, the heat transfer
tube substrate will be ultimately damaged if the corrosion proceeds at a high speed
and the coating has inferior durability. In addition, in the case of the LNG vaporizer,
the seawater flowing over the edge of the trough 8 hits the surface of the heat transfer
tubes 3a constituting the panel 3 as described above, and countermeasure for erosion
corrosion is also required.
SUMMARY OF THE INVENTION
[0011] The present invention has been completed in view of such situation, and an object
of the present invention is to provide a heat transfer tube for an LNG vaporizer in
which damage in the surface of the Al alloy substrate by corrosion is effectively
prevented even when it is used in the lower portion of the panel or in the lower header
where the surface is vigorously cooled and formation of the oxide coating is less
likely to take place. Another object of the present invention is to provide a method
for producing such heat transfer tube and an LNG vaporizer using such a heat transfer
tube.
[0012] In order to achieve such objects, the present invention has employed the constitution
as described below.
DISCLOSURE OF THE INVENTION
[0013] In a first aspect of the invention, accordingly, the heat transfer tube for an LNG
vaporizer is a heat transfer tube wherein the LNG is passed through its interior and
seawater is supplied to its exterior surface for vaporization of the LNG by heat exchange
between the LNG and the seawater, and which comprises an A1 alloy having a corrosion
protective coating on its exterior surface. The corrosion protective coating comprises
an Al alloy coating containing Mg.
[0014] In a second aspect of the invention, the heat transfer tube for an LNG vaporizer
is a heat transfer tube wherein the corrosion protective coating contains Mg at an
amount higher than that of the Al alloy constituting the heat transfer tube.
[0015] As described above, under the conditions in which the oxide coating is not readily
formed on the surface of the aluminum alloy substrate of the heat transfer tube, natural
electrode potential of Zn will be higher than that of the substrate alloy, and the
Al - Zn sprayed coating will be a higher potential compared to the substrate alloy
of the heat transfer tube or the lower header detracting from the effects of protection
by sacrificial corrosion. Accordingly, in order to enable the protection by sacrificial
corrosion to be realized even under such conditions in which the oxide coating is
not readily formed on the surface of the aluminum alloy substrate of the heat transfer
tube, a coating of a metal having a potential thermodynamically lower than that of
the Al should be formed, for example, by thermal spraying. Such metal is most preferably
Mg, and suitable sacrificial corrosion protective coatings include coatings of an
Mg - containing alloy which are "meaner" than the Al alloy substrate material of the
heat transfer tube or the lower header. Exemplary metals having a potential thermodynamically
lower than that of the Al include, in addition to Mg, Hf (hafnium), Ti (titanium),
and Be (beryllium). Among these, oxide coatings of Ti and Be are stronger than the
oxide coating of Al, and even if these metals were thermodynamically "meaner" than
Al, the oxides of these metals are substantially more "noble" than Al when the environment
of the LNG vaporizer operation is taken into consideration. In addition, a metal containing
Hf or Ti suffer from extremely poor drawability, and production of such metal into
the spraying target to be used in the flame spraying employed in the formation of
the coating is difficult.
Therefore, Hf and Ti can not be used for the coating formed for the purpose of protection
by sacrificial corrosion. In the meanwhile, Be is also unsuitable for use as a sacrificial
corrosion protection coating since Be is toxic and in view of the risk involved in
the formation of the coating and the marine pollution during the operation of the
ORV. Be is also a very expensive material.
[0016] Accordingly, an Al alloy coating containing Mg is most suitable for use as a coating
which is provided to protect the Al alloy heat transfer tube by sacrificial corrosion,
and such corrosion protective coating is effective if the coating contains Mg at an
amount higher than that of the Al alloy.
[0017] In the third aspect of the invention, the heat transfer tube for an LNG vaporizer
has such Al alloy corrosion protective coating with a thickness of 100 to 1000 µm.
[0018] When such Al alloy coating is used in an ORV, an adequate control of the thickness
of the coating is important in order to improve the resistance to blister peeling.
When the thickness is less than 100 µm, corrosion resistance of the thermally sprayed
coating will be insufficient, and the aluminum alloy substrate of the heat transfer
tube or the lower header is readily exposed to the seawater. The minimum thickness
typically at least 100 µm, preferably at least 150 µm, and more preferably at least
200 µm. While a thicker coating is preferable in view of preventing the corrosion
at an early stage, peeling is promoted by the residual stress from the formation of
the coating by the thermal spraying when the thickness is in excess of 1000 mm. Accordingly,
the coating is typically formed to a thickness of up to 1000 µm, preferably up to
800 µm, and more preferably up to 600 µm.
[0019] In the fourth aspect of the invention, the heat transfer tube for an LNG vaporizer
is the one wherein the Al alloy corrosion protective coating has a Mg content in the
range of 1 to 80% by mass.
[0020] When the A1 alloy coating has a Mg content of less than 1% , the protection by sacrificial
corrosion will be insufficient, and in order to realize effective protection by the
sacrificial corrosion, the Mg content is preferably at least 1.5% by mass, and more
preferably at least 2% by mass, and such Mg content will realize effective protection
by the sacrificial corrosion. In the meanwhile, while the protection by the sacrificial
corrosion of the Al - Mg alloy coating becomes stronger with the increase in the Mg
content, the speed of the coating consumption will be too high under some environments,
for example, under some temperature conditions. Therefore, the Mg content is preferably
up to 80% by mass, more preferably up to 50% by mass, and most preferably up to 20%
by mass. When the Mg content is in the range of 2 to 20% by mass, good adhesion of
the coating, protection by the sacrificial corrosion, and durability of the coating
are simultaneously realized.
[0021] In the fifth aspect of the invention, in the heat transfer tube for an LNG vaporize,
the Al alloy corrosion protective coating is formed by thermal spraying, and boundary
between the coating and the heat transfer tube has a center line mean roughness (Ra
75) in the range of 10 to 100 µm.
[0022] When the roughness of the boundary between the thermally sprayed coating and the
heat transfer tube or the lower header, namely, the Al alloy substrate is increased,
speed of the expansion of the area of the preferential dissolution caused by the oxygen
concentration cell formed between the internal defects of the thermally sprayed coating
and the thermally sprayed coating to the surrounding area of the defects is suppressed,
and this results in the improved resistance to blister peeling of the thermally sprayed
coating. This method is quite effective in improving the adhesion of the thermally
sprayed coating of A1 - Mg alloy whose improvement in the adhesion is difficult compared
to other thermally sprayed coatings such as those including an Al - Zn alloy. An intensive
study was conducted on this improvement in the adhesion, and the inventors found that
resistance to peeling of the thermally sprayed coating from the Al alloy substrate
under the circumstance that the moving seawater comes into contact with the thermally
sprayed coating at a low temperature range will be improved when the boundary between
the thermally sprayed coating and the Al alloy substrate has a center line mean roughness
(Ra 75) of at least 10 µm, and excellent adhesion properties are thereby realized.
In view of improving the adhesion, the center line mean roughness Ra 75of the boundary
is preferably at least 12 µm, and more preferably at least 14 µm. On the other hand,
when the boundary between the sprayed coating and the Al alloy substrate is excessively
rough, spaces not filled by the thermally sprayed coating are likely to be left at
the boundary, and the seawater entering such space will promote preferential corrosion
at the boundary. Therefore, the roughness at the boundary is preferably not more than
100 µm, more preferably not more than 80 µm, and most preferably 60 µm in terms of
the center line mean roughness Ra 75.
[0023] In a sixth aspect of the invention, in the heat transfer tube for an LNG vaporizer,
the roughness of the boundary as described above has been formed by spraying a blast
agent containing blast particles of #16 or higher to the exterior surface of the heat
transfer tube on which the sprayed coating is to be formed.
[0024] Such blast surface roughening using a blast agent containing blast particles of #16
or higher enables adjustment of the roughness of the boundary to the range of 10 to
100 µm.
[0025] In a seventh aspect of the invention, in the heat transfer tube for an LNG vaporizer,
the Al alloy coating has a percentage of pore area of not more than 15% in the region
from the uppermost surface to the depth of 100 µm in the cross section including the
central axis of the heat transfer tube.
[0026] When the percentage of the pore area in the surface layer part of the Al alloy coating
is suppressed to not more than 15%, and preferably not more than 10%, the area percentage
of blister peeling will be markedly reduced, and a satisfactory protection by sacrificial
corrosion is thereby realized.
[0027] It is in view of the situation as described above that the present invention has
adopted the constitution as described below.
[0028] In an eighth aspect of the invention, in the heat transfer tube for an LNG vaporizer
according to claim 8, the corrosion protective coating comprises an Al alloy coating
containing Zn and/or Mn and Mg wherein content of (Zn + Mn), Zn, or Mn is in the range
of 0.3 to 3.0% by mass and content of Mg is 0.3 to 5.0% by mass.
[0029] To provide resistance to erosion, addition of an element which forms a solid solution
in the Al to strengthen the matrix to the Al alloy substrate of the heat transfer
tube is effective, and it is necessary that the electrode potential of the Al alloy
coating does not becomemore "noble" than the electrode potential of the Al alloy substrate
of the heat transfer tube when such element precipitates as a compound. Exemplary
elements used for such strengthening include Zn, Nb, Mn, Zr, and Ti. Among these,
Nb, Zr, and Ti are inadequate for use in such purpose because these elements form
oxide coatings harder than the Al and these elements are expensive and difficult to
alloy with the Al. Therefore, preferable element (s) added for the erosion protection
is Zn and/or Mn. While it is preferable that Zn and/or Mn forms a solid solution in
the Al alloy matrix, Zn and/or Mn and the Mg may form a compound such as Zn - Mg,
Mn - Mg, or Zn - Mn - Mg depending on the amount added, and even if such compounds
were formed, the electrode potential "meaner" than the Al alloy substrate will still
be retained.
[0030] When the content of Zn + Mn or the content of Zn or Mn is less than 0.3%, strengthening
by formation of the solid solution will be insufficient detracting from the required
erosion protection. The content in excess of 3.0% by mass is unfavorable since the
effect of strengthening the Al alloy matrix will be saturated at such content, and
the Zn and/or Mn segregated in the Al alloy coating may adversely affect the anti-erosive
properties. When the Mg content is less than 0.3%, substantially all of the Mg will
form solid solution in the Al matrix irrespective the coating conditionsemployed,failing
to realize the effect of reducing the electrode potential of the Al alloy coating
to a level sufficiently lower than that of the Al alloy matrix of the heat transfer
tube. An Mg content in excess of 5% by mass is also unfavorable since the electrode
potential of the Al alloy coating will be "mean" to an unnecessary degree resulting
in the increased amount of Mg dissolution and excessively high speed of the corrosion
under some the conditions of use.
[0031] In a ninth aspect of the invention, the LNG vaporizer is an LNG vaporizer equipped
with a panel unit including a panel composed of the plural heat transfer tubes having
a thermally sprayed coating formed thereon arranged in a row in curtain form, and
an upper header for discharging the LNG and a lower header for supplying the LNG respectively
connected to the panel at its upper end portion and its lower end portion; wherein
the LNG is vaporized by heat exchange between seawater flowing down along the surface
of the panel from the upper end portion of the panel unit and the LNG flowing through
the heat transfer tubes from the side of the lower header to the side of the upper
header.
[0032] In a tenth aspect of the invention, in the LNG vaporizer, the thermally sprayed coating
of the heat transfer tubes is formed at least on the exterior surface of the lower
portion of the panel and the lower header.
[0033] As described above, LNG is in liquid form in the lower header and the lower portion
of the panel in the LNG vaporizer of this type, and therefore, such part of the vaporizer
are cooled to a temperature below freezing point. When the exterior surfaces of such
portion of the LNG vaporizer become in contact with the overflow seawater flowing
down along such surfaces, oxide coating is less likely to be formed on the aluminum
alloy surface of the heat transfer tube substrate. Under such circumstance, favorable
corrosion protection is realized when the surface of the lower portion of the panel
and the lower header in the low temperature region are covered with the thermally
sprayed coating as described above.
[0034] In an eleventh aspect of the invention, in the method for producing a heat transfer
tube for an LNG vaporizer which is used by passing the LNG in its interior and applying
seawater to its exterior surface for vaporization of the LNG by heat exchange between
the LNG and the seawater, and which has a corrosion protective coating formed on its
exterior surface, the corrosion protective coating is formed by thermally spraying
an Al alloy containing Mg and subjecting the surface of the thermal spray coating
to mechanical processing.
[0035] In a twelfth aspect of the invention, in the method for producing a heat transfer
tube for an LNG vaporizer, the corrosion protective coating is formed by thermally
spraying an A1 alloy containing Zn and/or Mn and Mg and subjecting the surface of
the spray coating to a mechanical processing.
[0036] When the surface of the thermally sprayed coating is subjected to mechanical processing
such as grinding or shot peening, pore defects in the sprayed coating are reduced
and damages such as blistering or peeling during the use are suppressed to realize
favorable protection by sacrificial corrosion.
[0037] In a thirteenth aspect of the invention, in the method for producing a heat transfer
tube for an LNG vaporizer, a sealing treatment of the sprayed coating is carried out
as a pretreatment and/or a post-treatment of the mechanical processing.
[0038] When a sealing treatment is carried out in addition to the mechanical processing,
pores in the thermally sprayed coating is further reduced, and the damages such as
blistering or peeling are further suppressed.
[0039] In this invention, an Al alloy coating containing Mg which is a metal thermodynamically
meaner than Al is formed on the outer surface of the alloy heat transfer tubes including
an Al alloy at least in the lower end portion of the panel and the outer surface of
the lower header which comes into contact with the seawater in the low temperature
region of the LNG vaporizer. Therefore, even in the environment in which an oxide
coating is less likely to be formed on the surface of the aluminum alloy of the heat
transfer tube and the lower header, a satisfactory sacrificial corrosion protection
is realized since the alloy coating containing Mg has an electrode potential meaner
than the A1 alloy substrate of the heat transfer tube and the lower header. An even
better sacrificial corrosion protection is realized when the Al alloy coating formed
contains Mg at a higher content than the Al alloy as described above. In addition,
when the roughness of the boundary was controlled to the predetermined range of center
line mean roughness (Ra 75) by blasting with a blast agent having a suitable particle
size, peeling resistance of the Al alloy coating in the environment where overflow
of the seawater contacts the Al alloy coating was improved to the level acceptable
in practical use. Since an Al alloy coating containing Mg which is a metal thermodynamically
meaner than Al having Zn and/or Mn added as a solid solution strengthening element
of the heat transfer tube substrate is formed on the surface of the heat transfer
tube for an LNG vaporizer in order to improve erosion resistant properties, favorable
protection by sacrificial corrosion realizing excellent erosion resistant properties
as well as high durability is achieved on the outer surface of the heat transfer tubes
in the lower end portion of the panel and the outer surface of the lower header of
the LNG vaporizer used in the environment in which the oxide coating is less likely
to be formed due to the contact of the seawater in the low temperature region, and
therefore, more susceptible to the damage by corrosion. Furthermore, a dramatic improvement
in peeling resistance is achieved when the coating is mechanically processed or impregnated
with a sealant after the formation of the alloy coating, and such improvement contributes
to the prevention of the damage of the heat transfer tubes by corrosion, and hence,
in the increase in the operation efficiency and service life of the LNG vaporizer.
BRIEF DESCRIPTION OF THE DRAWING
[0040]
FIG. 1 is a perspective view of the LNG vaporizer.
DETAILED DESCRIPTION OF THE INVENTION
[0041] Next, embodiments of the present invention are described by referring to FIG. 1.
[0042] FIG. 1 shows an LNG vaporizer wherein the heat transfer tubes according to an embodiment
of the present invention are incorporated. The LNG vaporizer comprises a plurality
of panel units U made from an Al alloy (for example, an Al - Mn based alloy such as
A3203, an Al - Mg based alloy such as A5083, or an Al - Mg - Si based alloy such as
A6063), and these panel units U are arranged in parallel. Each panel unit U comprises
a panel 3 composed of plural heat transfer tubes 3a arranged in a row in the form
of a curtain, and a lower header 2 for supplying the LNG and an upper header 4 for
discharging the vaporized natural gas (NG) respectively connected to the upper end
portion and lower end portion of the panel 3. The lower header 2 and the upper header
4 are respectively connected to a lower LNG manifold 1 and an upper NG manifold 5.
Above the space defined between the adjacent panels 3 of the unit U is provided a
trough 8 which makes the downward flow of the seawater used as a heat source for vaporizing
the LNG. The LNG is supplied from the LNG manifold 1 to the lower header 2, and then,
passes through the heat transfer tubes 3a of each panel 3. The LNG is vaporized during
this upward flowing of the LNG in the heat transfer tube by the heat exchange with
the seawater. The vaporized LNG is fed to the gas line (not shown) through the upper
header 4 and the NG manifold 5.
[0043] On the exterior surface of the heat transfer tube 3a and the lower header 2 is formed
a coating of an Al - Mg alloy, and more specifically, a coating of an Al alloy containing
1 to 80% by mass of Mg, and preferably 3 to 30% by mass of Mg. This coating is formed
by thermal spraying to a thickness of 100 to 1000 µm, and preferably, to a thickness
of 200 to 600 µm. In order to improve adhesion of the thermally sprayed Al - Mg alloy
coating to the heat transfer tube 3a and the lower header 2, namely, to the underlying
Al alloy substrate, the surface is treated with a blast agent for surface roughening
as a pretreatment of the thermal spraying to thereby adjust roughness of the boundary
between the thermally sprayed coating and the Al alloy substrate. The blast treatment
is carried out using a blast agent containing fine blast particles of at least #16
until the exterior surface of the Al alloy substrate has a center line mean roughness
Ra 75 of 10 to 100 µm, and preferably 14 to 60 µm. After the formation of the thermally
sprayed coating, the coating is preferably subjected to a sealing treatment in which
a compound such as epoxy polymer resin having excellent permeability to the Al - Mg
alloy coating is coated at least once on the surface of the sprayed coating. The covering
of the entire surface of the heat transfer tube 3a with the Al - Mg alloy coating
is not necessarily required, and the heat transfer tube should be covered to at least
about 1 m from the lower end of the panel 3.
[0044] The acceptable range of roughness, namely, the Ra 75 in the range of 10 to 100 µm
at the broadest of the boundary between the Al alloy substrate of the heat transfer
tube and the lower header and the thermally sprayed coating is useless if realized
locally, and such acceptable range of roughness should be realized for the entire
surface covered with the thermally sprayed coating. Accordingly, in this embodiment,
at least 10 locations are randomly chosen from the area of the Al alloy substrate
to be coated by the thermally sprayed coating before the application of the coating,
and center line mean roughness Ra 75 is measured by the measurement method defined
in the annexed paper of JIS B 0031 and JIS B 0061. It is after confirming that arithmetic
mean of the all Ra 75 values measured is within the defined range that the coating
is formed by thermal spraying. The roughness of the boundary between the Al alloy
substrate and the sprayed coating can also be measured after the formation of the
thermally sprayed coating. In this case, at least 10 locations are randomly chosen
from the area coated by the thermally sprayed coating for the Al alloy substrate randomly
sampled from the lot of the same blast treatment and the same thermal spray coating,
and the cross section of the surface coated with the thermally sprayed coating is
observed by SEM, and Ra 75 can be calculated by image processing. It is also necessary
in this case that the arithmetic mean of the all Ra 75 values measured is within the
defined range. The roughness of the boundary can also be provided by a mechanical
processing instead of the blast treatment.
[0045] On the exterior surface of the heat transfer tube 3a and the lower header 2, it is
effective to form a coating of an Al - Zn - Mn - Mg alloy having a Mg content of 0.3
to 5% by mass, and preferably 2 to 4% by mass, and a (Zn + Mn) content of 0.3 to 3%
by mass. This coating may be formed by thermal spraying to a thickness of 100 to 1000
µm. In order to improve adhesion of the thermally sprayed Al - Zn - Mn - Mg alloy
coating to the heat transfer tube 3a and the lower header 2, namely, to the underlying
Al alloy substrate, the surface may be treated with a blast of fine particles for
surface roughening as a pretreatment of the thermal spraying to thereby adjust roughness
of the boundary between the thermally sprayed coating and the Al alloy substrate.
The roughness of the boundary can also be provided by a mechanical processing instead
of the blast treatment. The Al alloy coating may also be a Al - Zn - Mg alloy coating
or a Al - Mn - Mg alloy coating, and in such a case, content of the Zn or Mg is in
the range of 0.3 to 3% by mass. The covering of the entire surface of the heat transfer
tube 3a with such Al alloy coating is not necessarily required, and the heat transfer
tube 3a should be covered to at least about 1 m from the lower end of the panel 3.
After the formation of the thermally sprayed coating, the coating is preferably subjected
to a sealing treatment in which a compound such as epoxy polymer resin having excellent
permeability to the Al - Zn - Mn - Mg alloy coating is coated at least once on the
surface of the sprayed coating. In addition, a mechanical processing such as grinding
or shot peening is preferably carried out before or/and after such sealing treatment
in order to remove the pore defects in the surface layer of the thermally sprayed
coating.
Example 1
[0046] In order to simulate the environment near the panel 3 and the lower header 2 of the
LNG vaporizer (ORV) (see FIG. 1), a disk of pure aluminum having a diameter of 16
mm and a thickness of 4 mm was prepared, and a coating of the composition shown in
Table 1 was thermally sprayed to a thickness of 300 µm on one surface of the disk
defined by the straight line passing through the center of the disk. No further treatment
was conducted after the thermal spraying, and the test specimen was thereby provided.
Peltier element was brought in close contact with the rear surface of the test specimen
on the side that have not been subjected to the thermal spraying to thereby cool the
rear surface of the test specimen to 20°C below the freezing point. The surface of
the side formed with the thermally sprayed coating at 20°C below the freezing point
was exposed to a commercially available artificial seawater (Marine Art Hi manufactured
by Tomita Pharmaceutical Co. , Ltd.) at 30°C for 20 hours, and extent of the recess
formed by the corrosion was measured for both the disk substrate and the thermally
sprayed coating. The results of the measurement are shown in Table 1. As demonstrated
in Table 1, extent of the recess in the thermally sprayed coating was as low as 1
to 2 µm in the case of conventional thermally sprayed Al - Zn based coating (Nos.
15 and 16), while extent of the recess in the disk substrate was as high as approximately
12 µm, indicating that protective effect by the sacrificial corrosion was not fully
exerted in the seawater exposure conditions as described above. In contrast, in the
case of the thermally sprayed Al - Mg based coating, extent of the recess in the thermally
sprayed coating was higher and extent of the recess in the disk substrate was lower
compared to the case of the Al - Zn based sprayed coating. In particular, when the
Mg content was 1% or higher, extent of the recess in the thermally sprayed coating
was as high as 5 µm or higher indicating the realization of the protective effect
by the sacrificial corrosion, and extent of the recess in the disk substrate decreased
to the level of 8 µm or lower. In particular, in view of reducing the extent of recess
of the pure aluminum disk substrate, Mg content is preferably 1% by mass or higher,
preferably 3% by mass or higher, and most preferably 5% by mass or higher. When the
Mg content is 5% by mass or higher, the extent of recess of the thermally sprayed
Al - Mg coating increases while the extent of recess of the disk substrate does not
substantially change. When the Mg content increases to over 80% by mass and reaches
90% by mass, consumption of the thermally sprayed coating becomes significant, and
therefore, the Mg content preferably does not exceed 80% by mass. In view of preventing
excessive consumption of the thermally sprayed coating, the Mg content is more preferably
up to 50% by mass, and most preferably up to 30% by mass. In Table 1, G1, G2, and
G3 indicate the level of the sacrificial corrosion protection, and the level of the
sacrificial corrosion protection increases in the order of G1 < G2 < G3.
Table 1
No. |
Composition of thermally sprayed coating |
Recess in Al alloy substrate (µm) |
Recess in thermally sprayed coating (µm) |
Note |
1 |
Al - 1% Mg |
5.2 |
8.3 |
Example(G1) |
2 |
Al - 2% Mg |
5.1 |
8.1 |
Example(G1) |
3 |
Al - 3% Mg |
3.7 |
10.1 |
Example(G2) |
4 |
Al - 4% Mg |
3.4 |
9.9 |
Example(G2) |
5 |
Al - 5% Mg |
1.1 |
11.2 |
Example(G3) |
6 |
Al - 10% Mg |
0.9 |
12.1 |
Example(G3) |
7 |
Al - 30% Mg |
1.2 |
12.5 |
Example(G3) |
8 |
Al - 40% Mg |
0.8 |
15.2 |
Example(G2) |
9 |
Al - 50% Mg |
1.2 |
16.5 |
Example(G2) |
10 |
Al-60% Mg |
0.9 |
19.2 |
Example(G1) |
11 |
Al-70% Mg |
0.8 |
20.5 |
Example(G1) |
12 |
Al - 80% Mg |
0.9 |
19.8 |
Example(G1) |
13 |
Al-90% Mg |
1 |
30.5 |
Comparative Example |
14 |
Al- 0.5% Mg |
8.5 |
5.2 |
Comparative Example |
15 |
Al - 2% Zn |
12.5 |
1.2 |
Comparative Example |
16 |
Al- 15% Zn |
11.4 |
2.1 |
Comparative Example |
Example 2
[0047] One side of an aluminum alloy (A5083) plate of 200 mm x 200 mm having a thickness
of 5 mm was mechanically processed to various degree of surface roughness, and this
plate was used for the aluminum substrate. Immediately after the mechanical processing,
the aluminum substrate was evaluated for its center line mean roughness Ra 75 using
a surface roughness meter. 10 aluminum substrates (n = 10) which had been mechanically
processed with the same target surface roughness were prepared for each set of test
conditions, and average of Ra 75 for these 10 aluminum substrates is shown in Table
2 as the roughness (Ra 75) of the boundary between the aluminum substrate and the
thermally sprayed coating. In order to realize satisfactory adhesion with the aluminum
substrate, a coating of Al - 5% by mass Mg was formed to a thickness of 300 µm on
the mechanically processed aluminum substrate immediately after the machine processing
by flame spraying using a wire of Al - 5% by mass. On a part of the mechanically processed
aluminum substrate, a coating of Al - 90% Mg was formed to a thickness of 300 µm by
flame spraying using a wire of Al - 90% by mass Mg. No further treatment was conducted
after the thermal spraying, and the test specimen was thereby provided. The composition
and the thickness of the thermally sprayed coating are shown in Table 2 for each set
of conditions.
Table 2
NO. |
Composition of thermally sprayed coating |
Thickness of thermally sprayed coating (µm) |
Boundary roughness (Ra 75, µm) |
Area of blister peeling (%) |
Note |
1 |
Al - 5% Mg |
300 |
5.2 |
64.2 |
Example |
2 |
Al - 5% Mg |
300 |
10.8 |
22.4 |
Example |
3 |
Al - 5% Mg |
300 |
11.3 |
21 |
Example |
4 |
Al - 5% Mg |
300 |
12.5 |
13.4 |
Example |
5 |
Al - 5% Mg |
300 |
13.2 |
11.5 |
Example |
6 |
Al - 5% Mg |
300 |
14.5 |
2.8 |
Example |
7 |
Al - 5% Mg |
300 |
16.8 |
2.3 |
Example |
8 |
Al - 5% Mg |
300 |
20.5 |
2.1 |
Example |
9 |
Al - 5% Mg |
300 |
38.5 |
2.5 |
Example |
10 |
Al - 5% Mg |
300 |
42.4 |
3.2 |
Example |
11 |
Al - 5% Mg |
300 |
58.5 |
8.5 |
Example |
12 |
Al - 5% Mg |
300 |
65.2 |
12.9 |
Example |
13 |
Al - 5% Mg |
300 |
79.2 |
17.5 |
Example |
14 |
Al - 5% Mg |
300 |
86.2 |
21.2 |
Example |
15 |
Al - 5% Mg |
300 |
98.5 |
25.3 |
Example |
16 |
Al - 5% Mg |
300 |
115.2 |
65.2 |
Comparative Example |
17 |
Al - 5% Mg |
175 |
20 |
5.5 |
Example |
18 |
Al - 5% Mg |
120 |
19.8 |
14.2 |
Example |
19 |
Al - 5% Mg |
50 |
20.4 |
50.2 |
Comparative Example |
20 |
Al - 90% Mg |
300 |
20.1 |
59.3 |
Comparative Example |
21 |
Al - 90% Mg |
300 |
75.2 |
98.3 |
Comparative Example |
[0048] Blister peeling test was conducted for the aluminum substrates of No. 1 to 21 having
the thermally sprayed coating formed thereon as shown in Table 2. 10 test specimens
of the aluminum substrate were used for each type. First, the test piece was immersed
for 3 months in an artificial seawater (Marine Art Hi manufactured by Tomita Pharmaceutical
Co. , Ltd.) at 20°C and pH 8.2 flowing at a flow rate 3 m/s to measure and calculate
area percentage of blister peeling on the thermally sprayed coating after the immersion
by means of image analysis. The average of the 10 test specimens is indicated in Table
2 as the area percentage of blister peeling of the aluminum substrates of No. 1 to
21 having the thermally sprayed coating formed thereon. The relationship between the
roughness (Ra 75) of the boundary between the thermally sprayed coating and the aluminum
substrate and the area percentage of blister peeling was noteworthy in Table 2, and
when the roughness (Ra 75) of the boundary increased to the level of about 10 µm or
higher (test piece Nos. 2 and 3), the area percentage of blister peeling rapidly decreased
to the level of approximately 20% to demonstrate improvement in the peeling resistance
in the environment of moving seawater. The area percentage of blister peeling further
reduced to about its half when the roughness (Ra 75) of the boundary was about 12
µm or higher (test piece Nos. 4 and 5), and even further reduced to the level of approximately
2 to 3% when the roughness (Ra 75) of the boundary was about 14 µm or higher (test
piece No. 6). Accordingly, in order to improve the peeling resistance of the thermally
sprayed coating in the environment of moving seawater, it would be effective to control
the roughness (Ra 75) of boundary to the level of 10 µm or more, preferably to 12
µm or more, and more preferably to 14 µm or more.
[0049] In the meanwhile, when the roughness (Ra 75) of the boundary reached about 60 µm
(test piece No. 11), the area percentage of blister peeling started to increase again,
and in the case of test piece No. 16 with the boundary roughness exceeding 100 µm,
the area percentage of blister peeling rapidly increased to the level equivalent with
test piece No. 1 wherein the boundary roughness was less than 10 µm. As described
above, when the roughness (Ra 75) of the boundary is excessively high, space not filled
by the coating is apt to be formed between the thermally sprayed coating and the aluminum
substrate, and the seawater entering such space will promote preferential corrosion
at the boundary. As a consequence, area percentage of the peeling will be increased
to detract from the peeling resistance of the thermally sprayed coating. Accordingly,
it would be effective to control the roughness (Ra 75) of the boundary to the range
of up to 100 µm, preferably up to 80 µm, and more preferably up to 60 µm.
[0050] It is to be noted that, when the content of Mg is as high as 90% by mass which is
outside the scope of the present invention (test piece Nos. 20, 21), the area percentage
of blister peeling is quite high even if the roughness (Ra 75) of the boundary were
within the scope of the present invention (i.e. 10 to 100 µm). In addition, even if
the Mg content and the roughness (Ra 75) of the boundary were both within the scope
of the present invention, the area percentage of blister peeling will also be high
if the thermally sprayed coating were thinner (i.e. 50 µm) than the thickness of the
present invention. When the Mg content is at the level as high as 90% by mass, consumption
of the thermally sprayed coating will be accelerated, and the seawater will penetrate
into the boundary between the aluminum substrate and the alloy coating at an earlier
timing and aluminum rust will occur at a faster rate at the boundary between the substrate
and the coating. This results blister or bulging of the alloy coating, and hence,
peeling, and significant increase in the area of blister peeling is thereby invited.
The situation is similar when the thermally sprayed coating is as thin as 50 µm, and
penetration of the seawater into the boundary between the aluminum substrate and the
alloy coating invites blister and peeling of the alloy coating and increase in the
area of blister peeling.
Example 3
[0051] An aluminum alloy (A5083) plate of 200 mm x 200 mm having a thickness of 5 mm was
used for the aluminum substrate. On one side of such aluminum substrate was thermally
sprayed an Al-5% by mass Mg alloy to form a coating of the Al-5% by mass Mg alloy.
Test specimen Nos. 1 to 7 were prepared as shown in Table 3 by subjecting the aluminum
substrate to different post treatments after forming the thermally sprayed coating.
11 test specimens were prepared for each type of post treatment.
Table 3
No. |
Thickness of thermally sprayed coating (µm) |
Mechanical processing after thermal spraying |
Treatment after thermal spraying |
Pore area (%) |
Area percentage of blister peeling (%) |
Note |
1 |
300 |
No |
No treatment |
17.1 |
44.2 |
Comparative Example |
2 |
300 |
No |
Sealer impregnation |
18.2 |
20.4 |
Comparative Example |
3 |
450 |
Yes |
Grinding |
10.4 |
4 |
Example |
4 |
400 |
Yes |
Shot peening |
6.6 |
2.4 |
Example |
5 |
400 |
Yes |
Sealer impregnation → Shot peening |
1.7 |
0.5 |
Example |
6 |
400 |
Yes |
Shot peening → Sealer impregnation |
1.6 |
0.8 |
Example |
7 |
400 |
Yes |
Sealer impregnation → Shot peening → Sealer impregnation |
1.6 |
0.3 |
Example |
[0052] The thermal spraying of test specimen Nos. 1 to 7 was conducted so that the coating
thickness after the post treatment (the treatment after the thermal spraying) was
300 µm as shown in Table 3. More specifically, the target thickness of the thermally
sprayed coating was 300 µm in test specimen Nos. 1 and 2 which were not treated by
mechanical processing after the thermal spraying; 470 µm in test specimen No. 3 which
was treated by grinding (for 10 seconds) after the thermal spraying; and 400 µm in
test specimen Nos. 4 to 7 which were treated by shot peening (for 60 seconds). While
the coating thickness in the test specimen Nos. 1 and 2 which was not subjected to
mechanical processing after the thermal spraying and the test specimen Nos. 3 to 7
which were treated by mechanical processing and other treatment after the thermal
spraying were variable among the 11 (N = 11) specimens of the same treatment, coating
thickness of the test specimen Nos. 1 to 7 were all within the range of 250 to 350
µm.
[0053] From the 11 specimens of each of the test specimen Nos. 1 to 7, 1 specimen was used
for measuring area percentage of pores of thermally sprayed coating in the region
from the uppermost surface to the depth of 100 µm of thermally sprayed coating. 10
locations were evenly selected from the entire area of 200 mm x 200 mm of each test
specimen, and a sample was sliced from each location. The cross section of the thermally
sprayed coating was examined by SEM as in the case of Examples 1 and 2, and area percentage
of pores observed in the region from the uppermost surface to the depth of 100 µm
of thermally sprayed coating was determined by image analysis. The average of the
thus determined area percentage of pores from the 10 location for test specimen Nos.
1 to 7 are shown in Table 3 as the area percentage of pores of the thermally sprayed
coating from the uppermost surface to the depth of 100 µm.
[0054] The remaining 10 specimens of the test specimen Nos. 1 to 7 were used for blister
peeling test. The test specimen was immersed for 3 months in an artificial seawater
at 20°C and pH 8.2 flowing at a flow rate 3 m/s to measure. The test specimen after
the immersion/exposure test was bent so that the side of the thermally sprayed coating
is in the inside to thereby apply compression stress to the thermally sprayed coating
and occurrence of the blister peeling was examined by SEM to measure and calculate
area percentage of the blister peeling on the surface of the thermally sprayed coating
by means of image analysis. The average of the 10 test specimens of test specimen
Nos. 1 to 7 is indicated in Table 3 as the area percentage of blister peeling.
[0055] The results in Table 3 indicate that the area percentage of pores of the thermally
sprayed coating was as high as approximately 17 to 18% in test specimen No . 1 which
was subjected to neither of the mechanical processing after the thermal spraying nor
the post-treatment and in test specimen No. 2 which was impregnated with the sealer
without the mechanical processing after the thermal spraying, and in accordance with
such high area percentage of pores, the area of blister peeling was also high. The
area percentage of pores decreased to approximately 6 to 10% in test specimen Nos.
3 and 4 which were treated only by mechanical processing of either grinding or shot
peening, and the area percentage of blister peeling also greatly reduced to 2 to 4%.
In test specimen Nos. 5 to 7 which were treated by the combination of the impregnation
with a sealer and the mechanical processing of the shot peening, the area percentage
of pores markedly reduced to approximately 1.6%, and the area percentage of blister
peeling also decreased to the level of 1% or less. It was therefore indicated that
a treatment by the combination of the impregnation with a sealer and the mechanical
processing after the thermal spraying was extremely effective in reducing the area
percentage of pores and the area percentage of blister peeling.
Example 4
[0056] In order to simulate the environment near the panel 3 and the lower header 2 of the
LNG vaporizer (ORV) (see FIG. 1), a disk of aluminum alloy A5083 having a diameter
of 16 mm and a thickness of 4 mm was prepared, and a coating of the composition shown
in Table 4 was thermally sprayed to a thickness of 300 µm on one surface of the disk
defined by the straight line passing through the center of the disk. No further treatment
was conducted after the thermal spraying, and the test specimen was thereby provided.
Peltier element was brought in close contact with the rear surface of the test specimen
on the side not subj ected to the thermally spraying to thereby cool the rear surface
of the test specimen to 20°C below the freezing point. The surface of the side formed
with the thermally sprayed coating at 20°C below the freezing point was exposed to
a commercially available artificial seawater (Marine Art Hi manufactured by Tomita
Pharmaceutical Co., Ltd.) at 30°C for 20 hours at a flow rate of 1 m/s, and extent
of the recess formed by the corrosion was measured for both the disk substrate and
the thermally sprayed coating. The results of the measurement are shown in Table 4.
[0057] As demonstrated in Table 4, extent of the recess in the thermally sprayed coating
was as low as 1 to 2 µm in the case of conventional thermally sprayed Al - Zn based
coating (Nos. 1 and 2), while extent of the recess in the in the disk substrate was
as high as approximately 8 µm, indicating that the protective effect by the sacrificial
corrosion was not fully exerted in the seawater exposure conditions as described above.
In the test specimens of Nos. 3, 4, and 5 in which content of the alloying elements
Zn, Mn, and Mg are outside the scope of the present invention, the extent of the recess
of the thermally sprayed coating was slightly lower than that of the Al alloy substrate
(disk substrate), and the protective effect by the sacrificial corrosion was not fully
exerted. In contrast, in the cases of the thermally sprayed coating having the alloying
composition of the present invention, the extent of the recess of the thermally sprayed
coating was approximately 5 to 10 µm, which was larger than the extent of the recess
(up to 4.5 µm) of the Al alloy substrate, and the protective effect by the sacrificial
corrosion was not exerted. In addition, the extent of the recess of the thermally
sprayed coating was relatively low, indicating that the durability of the thermally
sprayed coating was maintained at a satisfactory level. In particular, in the cases
of test specimen Nos. 10 to 13 in which the Mg content was up to 24% by mass and the
content of (Zn + Mn) was 1.5 to 2.5% by mass, the extent of the recess of the Al alloy
substrate was as low as 1. 5 µm or less and the corrosion protective effect was excellent.
In the cases of test specimen Nos. 16 to 19 in which the content of the alloying element
Zn, Mn, or (Zn + Mn), or Mg was outside the scope of the present invention, despite
the apparent satisfactory sacrificial corrosion protection, such composition was unsuitable
as described above due to the segregation caused by the increased content of the alloying
element in the thermally sprayed coating, or the excessively increased corrosion speed.
Table 4
No. |
Composition of thermally sprayed coating |
Recess in Al alloy substrate (µm) |
Recess in thermally sprayed coating (µm) |
Note |
1 |
Al - 2% Zn |
8.1 |
1.1 |
Comparative Example |
2 |
Al -15% Zn |
7.8 |
1.7 |
Comparative Example |
3 |
Al - 0.2% Zn - 0.2% Mg |
6 |
5 |
Comparative Example |
4 |
Al - 0.2% Mn- 0.2% Mg |
6 |
5.2 |
Comparative Example |
5 |
Al - 0.2% Mg |
6.3 |
5.6 |
Comparative Example |
6 |
Al - 0.3% Zn - 0.3% Mg |
4.3 |
6.2 |
Example |
7 |
Al - 0.3% Mn - 0.3% Mg |
4.2 |
6.5 |
Example |
8 |
Al - 0.2% Zn - 0.1 % Mn - 0.3% Mg |
4.4 |
6.9 |
Example |
9 |
Al -1% Mn - 1%Mg |
3.2 |
7.2 |
Example |
10 |
Al - 1.5% Zn - 0.5% Mn - 3% Mg |
0.9 |
9 |
Example |
11 |
Al - 1.5% Zn - 1 % Mn - 4% Mg |
0.8 |
9.1 |
Example |
12 |
Al - 1.5% Zn -1% Mn - 2% Mg |
1.5 |
7.9 |
Example |
13 |
Al - 1.5% Zn - 3% Mg |
1.3 |
8.6 |
Example |
14 |
Al - 1% Zn - 2% Mn - 2% Mg |
1.6 |
8.4 |
Example |
15 |
Al - 0.5% Zn -1% Mn - 5% Mg |
1 |
9.3 |
Example |
16 |
Al - 4% Zn - 3% Mg |
1 |
10.5 |
Comparative Example |
17 |
Al - 5% Mn - 3% Mg |
2.3 |
11.6 |
Comparative Example |
18 |
Al - 2% Zn - 2% Mn - 3% Mg |
2.1 |
9.8 |
Comparative Example |
19 |
Al - 3% Zn - 7% Mg |
1 |
12.1 |
Comparative Example |
1. A heat transfer tube for an LNG vaporizer,
wherein the LNG is passed through its interior and seawater is supplied to its exterior
surface for vaporization of the LNG by heat exchange between the LNG and the seawater,
wherein the heat transfer tube comprises an Al alloy and has a corrosion protective
coating on its exterior surface, and the corrosion protective coating includes an
Al alloy coating containing Mg.
2. The heat transfer tube for an LNG vaporizer according to claim 1,
wherein the corrosion protective coating contains Mg at an amount higher than that
of the Al alloy having the corrosion protective coating on its exterior surface.
3. The heat transfer tube for an LNG vaporizer according to claim 1 or 2,
wherein the Al alloy corrosion protective coating has a thickness of 100 to 1000 µm.
4. The heat transfer tube for an LNG vaporizer according to any one of claims 1 to 3,
wherein the Al alloy corrosion protective coating has a Mg content in the range of
1 to 80% by mass.
5. The heat transfer tube for an LNG vaporizer according to any one of claims 1 to 4,
wherein the Al alloy corrosion protective coating is formed by thermal spraying, and
boundary between the coating and the heat transfer tube has a center line mean roughness
(Ra 75) is in the range of 10 to 100 µm.
6. The heat transfer tube for an LNG vaporizer according to claim 5,
wherein the roughness of the boundary has been formed by spraying a blast agent containing
blast particles of #16 or higher to the exterior surface of the heat transfer tube
on which the sprayed coating is to be formed.
7. The heat transfer tube for an LNG vaporizer according to claim 5 or 6,
wherein the Al alloy coating has a percentage of pore area of not more than 15% in
the region from the uppermost surface to the depth of 100 µm in the cross section
including the central axis of the heat transfer tube.
8. The heat transfer tube for an LNG vaporizer according to claim 1,
wherein the corrosion protective coating comprises an Al alloy coating containing
Zn and/or Mn and Mg wherein content of (Zn + Mn), Zn, or Mn is in the range of 0.3
to 3.0% by mass and content of Mg is 0.3 to 5.0% by mass.
9. An LNG vaporizer comprising:
a panel unit including a panel composed of a plurality of heat transfer tubes having
a thermally sprayed coating formed thereon of any one of claims 1 to 8 arranged in
a row in curtain form; and
an upper header for discharging the LNG and a lower header for supplying the LNG respectively
connected to the panel at its upper end portion and its lower end portion,
wherein the LNG is vaporized by heat exchange between seawater flowing down along
the surface of the panel from the upper end portion of the panel unit and the LNG
flowing through the heat transfer tubes from the side of the lower header to the side
of the upper header.
10. The LNG vaporizer according to claim 9,
wherein the thermally sprayed coating of the heat transfer tubes is formed at least
on the exterior surface of the lower portion of the panel and on the exterior surface
of the lower header.
11. A method for producing a heat transfer tube for an LNG vaporizer which is used by
passing the LNG in its interior and supplying seawater to its exterior surface for
vaporization of the LNG by heat exchange between the LNG and the seawater, and which
has a corrosion protective coating formed on its exterior surface,
wherein the corrosion protective coating is formed by thermal spraying an Al alloy
containing Mg and subjecting the surface of the thermal spray coating to a mechanical
processing.
12. A method for producing a heat transfer tube for an LNG vaporizer,
wherein the LNG is passed through its interior and seawater is supplied to its exterior
surface for vaporization of the LNG by heat exchange between the LNG and the seawater,
and which has a corrosion protective coating formed on its exterior surface,
wherein the corrosion protective coating is formed by thermal spraying an Al alloy
containing Zn and/or Mn and Mg and subjecting the surface of the spray coating to
a mechanical processing.
13. The method for producing a heat transfer tube for an LNG vaporizer according to claim
11 or 12,
wherein a sealing treatment of the sprayed coating is carried out as a pretreatment
and/or a post-treatment of the mechanical processing.