NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No.

106 JULY 2014

UDC 669 . 14 . 018 . 8

Technical Report

Development of Austenitic Stainless Steel Sheets for

Micro-Fabrication
Masayoshi SAWADA* Hayato KITA
Masayuki SHIBUYA Kazuyoshi FUJISAWA

Abstract
Austenitic stainless steels “304 H-SR”, “304 H-SR2” and “301L SE1” were developed
for microfabrications like photoetching and laser processing. 304 H-SR and 304 H-SR2
have superior flatness, low residual stress and improved surface wettability, which are re-
quired as the materials for microfabrications. These high performances are attained mainly
by Tension Leveling (T/L) process, Stress Relieving (S/R) process and Special Surface Treat-
ment. 301L SE1 with fine grained structure has been received high reputations as a mate-
rial with excellent smoothness of the fabricated surface, in addition to the above mentioned
characteristics. The grain refinement has been achieved through the use of α' → γ reverse
transformation and pining effects by minute precipitates with optimization of the alloy com-
position and manufacturing process.

1. Introduction ticle are considered as typical examples of precision-cutting meth-

Austenitic stainless steel sheets provide high mechanical proper- ods.3, 4) They process stainless steel sheets into desired product
ties through cold rolling, and are therefore used for mechanical and shapes by removing unnecessary portions through chemical dissolu-
electronic parts of precision machinery in automobiles and consum- tion or thermofusion.
er electrical appliances.1, 2) To respond to the recent trend toward The photo-etching process for metallic material utilizes printing
further miniaturization and sophistication in apparatus performance, and corroding technology. It is widely used to produce the following
stainless steel must now offer more sophisticated functions to meet parts: metallic parts with high dimensional accuracy; complicated
requirements. figures such as precision machinery parts; precision electronics and
Nippon Steel & Sumitomo Metal Corporation produces SUS 304 optical apparatus parts; and decoration parts or ornaments. In the
H-SR (hereinafter “304 H-SR”), SUS 304 H-SR2 (“304 H-SR2”) and photo-etching process, desired product figures are obtained by print-
NSSMC-NAR-301L SE1 (“301L SE1”). 304 H-SR is a stainless steel ing the product figure pattern on the subject metallic material sur-
developed for precision cutting, including photo-etching and laser face with a photo-sensitive resin (Photoresist), and then by making
processing. It is based on an austenitic stainless steel used as a thin the exposed metallic portion dissolve selectively into a corrosive
sheet spring material of 0.6 mm or below in thickness. The develop- chemical solution such as ferric chlorides. This process results in a
ment of 304 H-SR2 and 301L SE1 was based on the production tech- product that is free from burrs, strains, material deformation and
nology for 304 H-SR; precision-cutting performance of them was en- work hardening, enabling precision cutting where dimensional ac-
hanced by refining the crystal grains of the mother material. This ar- curacy in the micro-millimeter order is required. Also, since costly
ticle introduces the characteristics of austenitic stainless steel for pre- dies are unnecessary, the process is capable of meeting various pro-
cision cutting and the technical background guiding the development duction requirements, from small-lot trials to extensive mass pro-
of the steel, focusing mainly on crystal grain refining technology. duction. It is also capable of etching both surfaces (perforating holes,
as well as holes having different diameters on the two surfaces), and
2. Precision Cutting Technology processing products that have complicated sectional shapes (by
2.1 Photo-etching and laser process combining half etching of either surface with stepped etching).
The photo-etching process and laser process discussed in this ar- Laser processing is a fusion-melting method used to remove un-

* Researcher, Titanium & Specialty Stainless Steel Research Lab., Steel Research Laboratories
1-8 Fuso-cho, Amagasaki City, Hyogo Pref. 660-0891

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 NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No. 106 JULY 2014

necessary portions by radiating a laser beam directly onto the sur- laser occasionally becomes problematic. Accordingly, precise flat-
face of metallic materials that are to be processed in accordance ness, low residual stress, and high smoothness of processed surfaces
with a CAD design drawing. Laser processing is capable of process- are required for laser processing. These material criteria are similar
ing products having a density higher than those processed by photo- for the photo-etching process.
etching, and has a readiness to comply with the small lot production
of many products. One example where laser processing is applied is 3. Stainless Steel Sheets for Precision Cutting
the metal mask (“Stencil”) for printing solder paste on a print circuit Naoetsu Works, a division of Nippon Steel & Sumitomo Metal,
board. 3) The metal mask is made from a stainless sheet of is working on the improvement of processing technologies and en-
0.1 - 0.2 mm in thickness on which a circuit pattern has been printed hancing the quality of stainless steel material appropriate for above-
and cut off. Conventionally, the photo-etching process is used for mentioned precision cutting, such as the photo-etching and laser
cutting; however, laser-processed metal masks are increasing in processes. Table 1 shows an outline of 304 H-SR, 304 H-SR2 and
number to meet the requirements of printed circuit boards growing 301L SE1, which have been commercialized as materials for preci-
higher in density. Metal masks having more sophisticated functions sion cutting such as the etching and laser processes.4-6) 304 H-SR is
have also been developed for practical use. They have sectional fig- used for overall precision cutting purposes, while 304 H-SR2 and
ures processed by a controlled combined application of the etching 301L SE1 are applied particularly to uses where high precision cut-
and laser processes, and vertical laser-processed sections. Small, ting (such as for high-density metal masks) are required.
thin electronic devices like smartphones and tablet PCs are rapidly 304 H-SR2 is a fine grain steel whose development was based
become common in recent years, and to meet the demand for higher on 304 H-SR to meet the requirements of etching process users. Its
circuit density, processing that provides even higher precision is be- grains are refined to an average grain size of about 5 µm without
ing sought. Also in demand are materials that offer higher perfor- changing the chemical composition, by optimizing production con-
mance, and further developments in the processing technology. ditions. 301L SE1 has crystal grains refined to an average grain size
2.2 Characteristics required for material using in precision cutting of 2 µm or less, by integrating a special alloy composition design
High sheet thickness accuracy and flatness are required for pho- and through cold rolling and annealing technologies. Furthermore,
to-etching, in order to secure stabilized line threading behavior and since the carbon content is made low in 301L SE1, its ability to sup-
accuracy of luminous pattern exposure. Residual stress minimiza- press the occurrence of smut (which creates problems in etching
tion inside the material is also necessary to suppress twisting, cam- processing) has been confirmed.7)
ber and dimension change from expansion or contraction, and defor- Figure 1 gives an outline of the stainless steel production proc­
mation after etching processing. Furthermore, to secure good adhe- ess for precision cutting. 304 H-SR, 304 H-SR2 and 301L SE1 are
sion for the photoresist, the material is also required to have excel- all processed to their respective specified sheet thicknesses and ma-
lent wettability. Product density is tending to increase considerably, terial strengths through hot rolling, cold rolling, annealing and sub-
and now greater attention is being paid to the sharpness of etching- sequent temper rolling. High flatness is obtained with a tension lev-
processed edge surfaces and the smoothness of etching-processed eler (T/L), with the material being submitted to tension and repeat-
surfaces. edly bent and bent in the adverse direction through contact with cir-
For laser processing, the material is installed on a frame and set cumferential roller surfaces. However, although the resulting sheet
in a laser processing system. Therefore, if the material has poor flat- looks flat to the eye, the material in such a state is not appropriate
ness the distance between the laser head and the material surface for precision cutting, since a high degree of residual stress has accu-
will be uneven, and the desired finishing accuracy cannot be ob- mulated within the material.
tained. Also, deformation due to local heat during fusion-melting by Residual stress inside the material is alleviated by applying heat

Table 1 Chemical compositions, microstructures, average grain sizes, thickness and applications of SUS 304 H-SR, SUS 304 H-SR2 and NSSMC-NAR-
301L SE1

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NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No. 106 JULY 2014

treatment at a relatively low temperature (“stress relief (S/R) treat- tween the photo-resistant barrier and the material takes place and
ment”). Figure 2 shows the appearance of strip form specimens occasionally produces a faulty product. As Fig. 3 (b) shows, wetta-
(0.2 mm × 12 mm × 100 mm) that have been etched to half their bility improvement suppresses etchant percolation. In some cases,
thickness on one side (”half etching”) in a solution of ferric chlo- product yield has been enhanced greatly.
rides. In Fig. 2 (a), the temper rolled specimen exhibits a camber As mentioned above, for stainless steel sheets destined for preci-
convex with respect to the etched surface, while the T/L-treated sion cutting, a highly balanced equilibrium is now one of the re-
specimen exhibits a large camber in the direction opposite to the di- quirements for materials destined for etching processes, along with,
rection of the camber of the specimen after temper rolling. The tem- for example, excellent flatness, low residual stress, and high surface
per-rolled material is provided with tensional residual stress in the wettability. This equilibrium can be realized through integrated
neighborhood of the surface by rolling, and flatness is maintained proc­ess control, from the alloy composition stage to the production
by a state of equilibrium between the tensional residual stress and process stage.
the compressive residual stress that exists in the center area in the
thickness direction of the material. 4. Grain Refining Technology
As etching reduces surface layer thickness, the stress equilibrium 4.1 Basic information on crystal grain refining technology
in the thickness direction is broken, and a camber develops. In the The crystal grain size of conventional stainless steel is about
case of the T/L-treated material, compressive residual stress is pro- 20 - 30 µm. When finishing accuracy in the order of single digit mi-
vided close to the surface layer through repeated bending and bend- crometers is required, crystal grain size occasionally influences the
ing in the adverse direction. Although flatness is maintained by the finish of processed products. The finer the crystal grain, the more
equilibrium of the compressive residual stress and the tensional re- improved is the straightness (sharpness) of the etching-processed
sidual stress in the thickness center area, when a surface layer is re- product edge and the smoothness of the etching-processed surface.
moved by etching, compressive stress near the surface is released so In laser processing, too, the lower the melting point at crystal grain
that a camber in the direction adverse to the temper rolled material
direction is produced. On the other hand, as a result of alleviation of
the entire residual stress in the plate thickness direction of the S/R
treated material, the camber after half etching is remarkably sup-
pressed. Furthermore, as shown by 304 H-SR2 in Fig. 2 (b) and
301L SE1 in Fig. 2 (c), it has been confirmed that the camber after
half etching is reduced not only through S/R treatment but also fur-
ther reduced by incorporating a device in the previous stage of the
process.
In the production process for stainless steel sheets destined for
precision cutting, wettability is improved by applying a special sur-
face treatment after the S/R treatment, to reform the surface layer.
Poor wettability deteriorates the adhesion of photoresistant material
to steel sheets, and as Fig. 3 (a) shows, percolation of an etchant be-

Fig. 1 Schematic illustration of manufacturing process for developed

Steel Fig. 2 Appearance of the half etched specimens

Fig. 3 Appearance of specimens after stripping photo resist

(a) With percolation of etchant between resist and materials and (b) Without percolation of etchant

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 NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No. 106 JULY 2014

boundaries, compared with within crystal grains (with crystal grains martensite (α') formed in cold rolling to γ by heat treatment.11) How-
melting earlier at their boundaries),8) the finer is the crystal grain, ever, if the heat-treatment temperature is lower than required, the
and the smaller is the roughness of etching-processed surfaces. This structure becomes uneven and large amounts of untransformed crys-
means that, in both etching processing and laser processing, refining tal structure remain. On the other hand, if the heat-treatment tem-
the crystal grains of a material is very effective in improving the perature is higher than warranted, the crystal grains become coarse.
smoothness of processed surfaces. Furthermore, refining crystal Therefore, stainless steel with refined crystal grains had never previ-
grains is also effective in improving smoothness at the bent portion ously been produced on a large scale at an actual production line.
of the material, and improving the strength-elongation relationship. Nippon Steel & Sumitomo Metal now consistently mass-produces
Therefore, crystal grain size is the most important factor to be stud- fine grain material, using a process that suppresses crystal grain
ied in the development of stainless steel for precision cutting. growth through the use of minute carbides and nitrides which pre-
Prior to the development of 301L SE1 for precision cutting uses, cipitate during heat treatment,12) in addition to the reverse transfor-
the austenitic stainless steel NSSMC-NAR-301L HS1, which was mation of work-induced α' to γ.
crystal-grain-refined to improve fatigue strength, was developed.9, 10) Upon utilizing minute carbides and nitrides, a thermo dynamic
This grade has been employed by a number of car manufacturers as calculation was carried out. Figure 5 shows the phase diagram of
engine cylinder head gasket material, and has obtained an excellent SUS  301L calculated with the thermo dynamic software Thermo-
reputation. 301L SE1 provides high straightness for etching-proc­ Calc.13) It is found from the diagram that in the case of SUS 301L
essed edges, high smoothness for etching-processed surfaces, a high added with 0.05mass% Nb, for example, Nb is solid-soluted to γ
degree of flatness, and low residual stress. The material was realized phase at a high temperature above 1,100˚C, and precipitates as
through integrated controlling. As Fig. 4 shows, the entire process, Nb(C, N) at a lower temperature. Accordingly, after solid-solution
from alloy design to optimization of production conditions for cold heat treatment, minute Nb(C, N) precipitates in finishing annealing
rolling and hot rolling (covering and combining crystal-grain-refin- at a temperature lower than in solid-solution heat treatment, and the
ing techniques developed for 301L HS1, with specific production precipitate hinders the movement of crystal grain boundaries (“pin-
technologies developed for precision-cutting), is used for 304 H-SR, ning effect”), thereby suppressing crystal grain growth.
including T/L treatment, S/R treatment, and special surface treat- Figs. 6 and 7 are TEM images of thin films and extraction repli-
ment. Examples of research done on crystal-grain-refining and ef- cas of conventional SUS 301L and SUS 301L containing 0.1mass%
fects of refined crystal grains on precision cutting performance are Nb.
given hereunder. These samples were taken from sheets cold-rolled with a cold
4.2 Crystal grain refining mechanism reduction ratio of 67% from sheets made from small ingots for trial
It is known that in metastable austenitic (γ) stainless steels, such purposes, then heat-treated at 1,150˚C for solid-solution. The cold-
as SUS 304 and SUS 301L, fine crystal grains can be obtained
through the use of reverse transformation from deformation-induced

Fig. 4 Schematic illustration showing our philosophy for producing

fine-grained stainless steels Fig. 5 Calculated phase diagram of SUS 301L containing Nb

Fig. 6 TEM images of thin film prepared from annealed specimen

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NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No. 106 JULY 2014

Fig. 7 TEM images of the extraction replica prepared from annealed specimen

Fig. 9 Appearance of stainless steel sheets perforated by photoetching

(a) 301L SE1, (b) Conventional stainless steel
Fig. 8 Relationship between calculated average roughness Ra of etched
surface and average crystal grain size

rolled sheets were annealed at 1,000˚C (a) or at 850˚C (b, c). The
average crystal grain size of SUS 301L without Nb annealed at
1,000˚C is about 10 µm, and about 4 µm when annealed at 850˚C.
However, grain-refining in this case is due to the weak grain grow-
ing force because of the low annealing temperature. If the annealing
temperature is lowered excessively, the structure becomes uneven,
retaining great quantities of untransformed grains that had previous-
ly developed under the influence of cold working, and resulting in a
variation in characteristics. On the other hand, when Nb is added in
small amounts, the added Nb precipitates as minute Nb(C, N) of
about 20 nm when annealed. As a result of the pinning effect of the
Nb(C, N), and as a result also of the resulting suppression of crystal
grain growth, a structure with very fine crystal grain size around
1 µm on average can be obtained after annealing.
4.3 Effect of crystal grain refining on precision cutting perfor-
mance Fig. 10 Appearance of stainless steel sheets perforated by laser proc­
This section introduces the effect of crystal grain refining on essing, (a) 301L SE1, (b) Conventional stainless steel
smoothness of the photo-etching-, - laser- and other processed sur-
faces. Figure 8 shows the relationship between the roughness of the on general-use material (SUS 304) for comparison. As is obvious
etched surface of the material and the average crystal grain size that from the image, the smoothness of the finish of the processed wall
is varied by controlled changes in the compositions and heat-treat- of 301L SE1 is superior to that of the general-use material. En-
ment conditions of SUS 304, which was used as the base for the hanced smoothness of the etching-processed surface, or sharpness at
study. The etchant used was a ferric chloride solution of 42˚ Be’ at the cut edge, greatly contributes to cutting accuracy. Furthermore,
50˚C. The finer the crystal grains of the mother materials, the more the use of 301L SE1 could in certain cases eliminate the need for
enhanced is the smoothness of the etched surface. This is presumed electrolytic grinding, which is conventionally performed after the
to be due to the fact that, since the etching rate depends on crystal etching process.
orientation,14) as the crystal grains become finer, the rate of etching Refining crystal grains contributes to the enhancement of surface
becomes more level. smoothness after laser processing. Figure 10 shows the appearance
Figure 9 is an electron microscope image of the walls of holes of 301L SE1 sheets and a conventional material after laser process-
conically perforated by the etching method used on 301L SE1, and ing. It is found that, similar to the case of the etching-processed sur-

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 NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No. 106 JULY 2014

Fig. 11 Appearance of specimens after V-block bend tests with 90˚ bending angle and 0 mm inside radius

increases along with an increase in the reduction ratio, and elonga-

tion decreases. On the other hand, if the crystal grains of the base
steel are refined by low temperature annealing, or by the addition of
a very small amount of Nb, 0.2% yield strength increases, although
elongation decreases slightly. However, the extent of the decrease in
elongation is smaller than the increase in strength. Accordingly,
when compared at a same strength level, it is found that the grain-
refined material exhibits a greater elongation than the material high-
strengthened by cold rolling, and is superior with respect to the
strength vs. ductility relationship. These characteristics, smoothness
of the bent portion and excellent strength vs. ductility relationship,
are very effective in the application of the material where post-etch-
ing press forming and bending forming are applied, and the im-
provement in squeegee durability, in the case of metal mask use.

Fig. 12 Effect of cold rolling and grain refinement on balance of 5. Conclusion

strength and elongation Austenitic stainless steel sheets 304 H-SR, 304 H-SR2 and 301L
SE1 produced by Nippon Steel & Sumitomo Metal are suitable for
face, the roughness of the laser-processed surface is reduced by re- precision cutting processes, such as the photo-etching process and
fining the crystal grains of the subject material. Along with enhance- the laser process. They are used by a number of domestic and for-
ment of the smoothness of the processed surface, the refinement of eign customers as materials for precision parts and metal masks, and
crystal grains contributes to the suppression of foreign substance ad- are high regarded. Nippon Steel & Sumitomo Metal is now able to
hesion on processed surfaces, and to the improvement of dimen- consistently produce these stainless steels for precision cutting uses,
sional accuracy, thereby contributing to the enhancement of stability through integrated control of the entire process from alloy composi-
in operations when the material is used as a metal mask. It also con- tion to the application of production conditions such as cold rolling
tributes to eliminating subsequent processes involving chemical and heat treatment. The company plans to apply its proprietary crys-
grinding or electrolytic grinding, due to the reduction of burrs made tal grain refining technology for 301L SE1 to other steel materials as
from molten metal during laser processing. In certain cases, such well.
elimination has contributed to overall cost reduction.
With regard to the effect of refining crystal grains on bending References
work, the photos in Fig. 11 show the ridge lines on specimens of the 1) Hosoi, Y.: Stainless Steel no Kagaku to Saishin Gijutsu. First Edition.
Tokyo, Japan Stainless Steel Association, 2011, 217p (in Japanese)
three types of austenitic stainless steel sheets when bent by 90 deg.
2) Japan Stainless Steel Association: Stainless Steel Handbook. Third Edi-
Surface roughness before bending is almost the same. It is con- tion. Tokyo, Nikkan Kogyo Shinbun-sha , 1995, 1173p
firmed that when the smoothness of the ridges is compared, a re- 3) Shibuya, M.: Materia. 34 (9), 1068 (1995)
markable improvement in smoothness is recognized in both 304 4) Shibuya, M.: Convertech. 40 (7), 75 (2012)
H-SR2 and 301L SE1 (both having fine crystal grains), in compari- 5) Fujisawa, K.: Sokeizai. 53 (1), 33 (2012)
6) Hirahara, K.: Sokeizai. 49 (1), 19 (2008)
son with 304 H-SR which has conventional crystal grain size and 7) Allen, D.M. et al.: CIRP Annals - Manufacturing Technology. 54 (1),
which exhibits a rough skin with the appearance of protruded crystal 187 (2005)
grains. 8) Heish, T.R. et al.: Acta Metall. 37 (6), 1637 (1989)
Furthermore, since refining crystal grains is the method among 9) Adachi, K. et al.: Materia. 47 (1), 36 (2008)
10) Katsurai, T.: Honda R&D Technical Review. 12, 151 (2000)
steel-strengthening methods that realizes the least deterioration in
11) Takaki, S. et al.: Tetsu-to-Hagané. 74 (6), 1052 (1988)
ductility, it is effective in improving the strength vs. ductility rela- 12) Sawada, M. et al.: ISIJ Inter. 51 (6), 991 (2011)
tionship. Figure 12 shows the effects of the cold rolling reduction 13) Thermo-Calc Software: http://www.thermocalc.com
ratio and crystal grain size on 0.2% yield strength vs. the elongation 14) Sato, A. et al.: The Japan Society of Mechanical Engineers, Tohoku
relationship, in SUS 301L. When the annealed base SUS 301L hav- Branch Autumn Lecture Meeting, Proceedings. 2007 (43), 1213 (2007)
ing an average grain size of 10 µm is cold rolled, 0.2% yield strength

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NIPPON STEEL & SUMITOMO METAL TECHNICAL REPORT No. 106 JULY 2014
Masayoshi SAWADA Masayuki SHIBUYA
Researcher Senior Manager, Head of Dept.
Titanium & Specialty Stainless Steel Research Lab. Specialty Stainless Steel Technical Service &
Steel Research Laboratories Solution Dept.
1-8 Fuso-cho, Amagasaki City, Hyogo Pref. 660-0891 Titanium & Specialty Stainless Steel Unit

Hayato KITA Kazuyoshi FUJISAWA

Senior Manager Manager
Specialty Stainless Steel Technical Service & Production & Technical Control Dept.
Solution Dept. Production Div., Naoetsu Works
Titanium & Specialty Stainless Steel Unit Titanium & Specialty Stainless Steel Unit

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