JP4923968B2 - Steel material with excellent fatigue crack propagation resistance - Google Patents

Description

  The present invention relates to a steel material excellent in fatigue crack propagation resistance, and relates to a steel material suitable for a thick steel plate used for materials such as a hull, an offshore structure, a bridge, a building structure, a construction machine, and an industrial machine.

  Generally, a steel structure is assembled into a desired structure by welding. When steel structures are subjected to repeated stresses in the usage environment, the stress concentrates on large shape discontinuities such as weld toes, causing fatigue cracks to develop and eventually penetrate and break. Can lead to major accidents.

  In many cases, the life of a welded structure is determined by the progress of fatigue, and from the viewpoint of reducing the life cycle cost, suppression of fatigue fracture is desired. In addition, the destruction of welded structures such as hulls, offshore structures, bridges, etc., exposes human lives to danger, and from the viewpoint of safety, it is required to suppress the occurrence and progression of fatigue cracks.

  Conventionally, as a means to suppress the occurrence of fatigue cracks, the welding toe has a smooth shape with no discontinuities, and a welding method has been devised to avoid stress concentration. Therefore, it takes a lot of time, which causes problems such as reduced construction efficiency and increased manufacturing costs.

  In addition, when the design of a structure is complicated, stress concentration is unavoidable only by construction measures, and it is not always possible to take effective measures to suppress the occurrence of fatigue cracks.

  For such problems, when fatigue cracks occur in steel, it is effective to suppress the growth of fatigue cracks by reducing the propagation speed of fatigue cracks. If the fatigue crack propagation speed is slow, even if a fatigue crack occurs, the crack can be found and repaired by periodic inspections before the structure breaks down.

If the fatigue crack propagation rate of steel can be slowed, the frequency of periodic inspections, that is, the frequency of repairs can be reduced, which is advantageous in terms of the life cycle cost of the steel.
In response to such a demand, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5 propose a steel plate and a manufacturing method for reducing the fatigue crack propagation rate.

  The technique described in Patent Document 1 and Patent Document 2 is a method of dispersing a hard second phase such as bainite and martensite in a ferrite matrix.

The technique described in Patent Document 3 shows a method for reducing the crack propagation speed in the plate thickness direction by controlling the crystal orientation of ferrite.
The technique described in Patent Document 4 shows a technique for improving fatigue characteristics by reducing the ferrite grain size to 1 to 3 μm.

  In this method, the toughness can be improved at the same time by refining the crystal grains, but rolling with a large rolling reduction of 50% or more in the austenite / ferrite two-phase region at a lower temperature than the normal hot rolling temperature. Need to do.

Patent Document 5 discloses a technique for improving fatigue crack propagation characteristics by increasing the content of Si or Al so that retained austenite is contained in the steel.
Japanese Patent Laid-Open No. 10-60575 JP-A-11-310846 JP-A-8-199286 JP 2002-363644 A JP 2004-76156 A

  However, the techniques described in Patent Document 1 and Patent Document 2 may not be able to sufficiently suppress the propagation of fatigue cracks, and there is a concern that toughness may be deteriorated.

  There is a concern that the technique described in Patent Document 3 cannot improve the fatigue crack propagation characteristics that develop in directions other than the plate thickness direction.

  The technique described in Patent Document 4 has a concern that the load on the rolling mill is increased, the occupation time of the rolling mill is increased, and the rolling efficiency is reduced. Since the technique described in Patent Document 5 increases the content of Si and Al, there is a concern that the toughness of the base material and the weld heat affected zone deteriorates.

  Accordingly, an object of the present invention is to provide a steel plate having excellent fatigue crack propagation characteristics and a method for manufacturing the same, which solve the above-described problems of the prior art.

In order to achieve the above-described problems, the present inventors diligently studied various factors affecting fatigue crack propagation characteristics and mechanical characteristics, and obtained the following knowledge.
(1) To improve fatigue crack propagation resistance, the steel sheet is composed of a ferrite phase that defines the upper limit of hardness as the soft phase and a tempered martensite phase that defines the lower limit of hardness as the hard phase. Furthermore, it is important to control the area fraction of the mixed tissue.
(2) In order to maximize the fatigue crack propagation characteristics by this mixed structure control, strict component adjustment is indispensable, and it does not increase the hardness of the ferrite phase. It is important to add Cr that promotes site formation.
(3) Furthermore, when it is combined with the addition of at least one of Mo or V having a high tempering and softening resistance, even better results can be obtained.
(4) In addition, after subjecting the steel material whose components are adjusted as described above to hot rolling, the above microstructure is obtained by performing reheating treatment and tempering treatment with optimized heating temperature and cooling rate. It can achieve the requirements and combine excellent fatigue crack propagation properties and mechanical properties.

The present invention has been completed based on the above findings and further studies, that is, the present invention,
1. Steel composition is mass%,
C: 0.05-0.30%,
Si: 0.03 to 0.35%,
Cr: 0.05 to 2.0%,
P: 0.03% or less S: 0.003% or less Al: 0.1% or less, with the balance being Fe and inevitable impurities, the metal structure being 8 Vickers hardness
340 with 5 to 130 ferrite phase and Vickers hardness of 15 to 85% area fraction
A steel material excellent in fatigue crack propagation resistance, which is a mixed structure of tempered martensite phase of 440 or less.
2. In addition to the steel composition,
Mo: 0.05-1.0%,
V: 0.01 to 0.3%
The steel material which was excellent in the fatigue crack propagation characteristics described in 1 containing 1 type or 2 types.
3. In addition to the steel composition,
Mn: 1.2% or less Cu: 0.8% or less Ni: 1.0% or less Nb: 0.1% or less Ti: 0.03% or less B: 0.005% or less Ca: 0.005% or less REM : 0.02% or less Mg: Steel material excellent in fatigue crack propagation characteristics according to 1 or 2 containing one or more of 0.005% or less.

  According to the present invention, it is possible to stably produce a thick steel plate having excellent fatigue crack propagation resistance, greatly contributing to the improvement of the reliability of the steel structure and the reduction of the life cycle cost, and a remarkable industrial effect. Play.

In the present invention, the metal structure, component composition and production conditions are defined. The reasons for these limitations will be explained in detail below.
[Metal structure]
In the present invention, not only the hardness and dispersion amount of the hard phase but also the hardness of the soft phase is specified. In order to stably achieve excellent fatigue crack propagation characteristics and mechanical properties, the hard phase in the metal structure is made into a tempered martensite phase with an area fraction of 15 to 85% and a Vickers hardness of HV340 or more, and The mixed structure is a ferrite phase in which the Vickers hardness of the soft phase is limited to HV130 or less.

  Reducing the hardness of the ferrite phase decreases the fatigue crack growth rate by expanding the strain region at the tip of the fatigue crack and suppressing work hardening during repeated load strain. In addition, when the main crack that has propagated through the ferrite phase is tempered and reaches very close to the martensite phase, a microcrack is generated from the main crack, and the main crack is bent and branched to reduce the fatigue crack growth rate.

  In order to obtain this effect, the Vickers hardness of the ferrite phase is limited to the range of HV85 to 130. In addition, Preferably, it is set as HV95 or more and 120 or less.

  Further, the Vickers hardness HV of the tempered martensite phase is limited to 340 or more and 440 or less. In addition, Preferably, it is set as HV350-420.

  If the area fraction of the tempered martensite phase is less than 15% or more than 85%, the effect of delaying fatigue crack propagation as described above cannot be obtained, so the area fraction of the tempered martensite phase is It is limited to a range of 15 to 85%. In addition, Preferably, it is 20 to 80%.

  The hardness is specified by determining the Vickers hardness of the ferrite phase and tempered martensite phase of the hardness test piece using a micro Vickers hardness tester. The load is 0.49N (50 gf), but any error may be used because the error due to the test condition can be ignored as long as it is in the range of 0.098N (10 gf) to 0.98N (100 gf).

  For each of the ferrite phase and the tempered martensite phase, the hardness is measured for at least 10 grains, and the average value is taken as the hardness.

  As the third phase excluding the ferrite phase and tempered martensite phase, when the structure such as bainite and pearlite coexists, the fatigue crack propagation characteristics deteriorate, so the area fraction of the third phase is smaller. Is good.

  However, when the structure of bainite and pearlite is less than 5% in volume fraction, the influence can be ignored. In addition, when the hard phase is an as-quenched martensite phase, tempering is essential because the ductility and toughness of the base metal deteriorate.

Next, the reason for limiting the composition of the steel material used in the present invention will be specifically described.
[Ingredient composition]
Unless otherwise specified, the “%” label for ingredients means mass%.
C: 0.05-0.30%
C is an element useful for increasing the strength of steel and ensuring the strength necessary for structural steel. Further, in order to obtain the second phase structure of the tempered martensite phase having a Vickers hardness of 340 or more, the content of 0.05% or more is required.

  On the other hand, if the content exceeds 0.30%, the HAZ toughness and weld crack resistance deteriorate, and the toughness of the base material deteriorates. For this reason, C is limited to a range of 0.05 to 0.30%. In addition, Preferably, it is 0.08 to 0.25%.

Si: 0.03-0.35%
Si acts as a deoxidizer and suppresses the formation of cementite, thereby concentrating C into austenite and promoting martensite formation during quenching. Furthermore, during tempering, it has the effect of increasing the temper softening resistance of the martensite phase. This requires at least 0.03%.

  On the other hand, if the content exceeds 0.35%, the hardness of the ferrite phase is increased, and the fatigue crack propagation resistance is decreased. In addition, the toughness of the base material deteriorates, and the weldability and HAZ toughness deteriorate significantly. For this reason, Si is limited to the range of 0.03 to 0.35%. In addition, Preferably, it is 0.05 to 0.25%.

Cr: 0.05-2.0%
Cr is an important alloying element in the present invention. Even if it is added in a large amount, the effect on the Ar ₃ transformation point is small, and the same body-centered cubic structure as α-Fe has an atomic radius close to that of Fe. Very small and does not increase the hardness of the ferrite phase. On the other hand, at the time of quenching from the austenite region, the hardenability of austenite is increased and the formation of a martensite phase as a second phase structure is promoted.

  Furthermore, during tempering, it has the effect of increasing the temper softening resistance of the martensite phase and is effective in reducing the fatigue crack propagation rate. In this invention, in order to acquire this effect, 0.05% or more of containing is required. On the other hand, if the content exceeds 2.0%, the weld crack resistance and the HAZ toughness deteriorate significantly. For this reason, Cr is limited to a range of 0.05 to 2.0%. In addition, Preferably, it is 0.1 to 1.5%.

P: 0.03% or less P is an element that increases the strength of steel and deteriorates toughness, and particularly deteriorates the toughness of welds. Therefore, it is desirable to reduce it as much as possible. If P is contained in excess of 0.03%, this tendency becomes remarkable, so the upper limit is set. In addition, excessive P reduction raises the refining cost and is economically disadvantageous, so 0.003% or more is desirable.

S: 0.0050% or less S is an element that deteriorates the toughness of the base metal and the welded portion, and is desirably reduced as much as possible. If S is contained in excess of 0.0050%, this tendency becomes remarkable, so the upper limit is set.

Al: 0.1% or less Al acts as a deoxidizer and is most commonly used in the molten steel deoxidation process of high-strength steel. Also, N in the steel is fixed as AlN, which contributes to improvement of the toughness of the base metal. On the other hand, if the content exceeds 0.1%, the toughness of the base metal decreases, and it is mixed into the weld metal during welding to deteriorate the toughness. For this reason, Al was limited to 0.1% or less. In addition, Preferably it is 0.01 to 0.07%.

    In the present invention, in addition to the basic component system described above, Mo: 0.05 to 1.0%, V: 0.01 to 0.3%, Mn: 1.2% or less, Cu: 0 if necessary. 0.8% or less, Ni: 1.0% or less, Nb: 0.1% or less, Ti: 0.03% or less, B: 0.005% or less, Ca: 0.005% or less, REM: 0.02 % Or less and Mg: One or more selected from 0.005% or less can be contained.

Mo: 0.05-1.0%
Mo enhances the hardenability of austenite during quenching, promotes the formation of martensite phase as a second phase structure, and significantly reduces temper softening of the martensite phase by generating carbides during tempering. It is effective in reducing the fatigue crack propagation rate. In order to exhibit this effect, addition of 0.05% or more is necessary. On the other hand, if added over 1.0%, the toughness is adversely affected. For this reason, Mo is limited to the range of 0.05 to 1.0%.

V: 0.01 to 0.3%
V increases the hardenability of austenite during quenching, promotes the formation of martensite phase as a second phase structure, and significantly reduces temper softening of the martensite phase by generating carbides during tempering. It is effective in reducing the fatigue crack propagation rate.

  In order to obtain this effect, addition of 0.01% or more is necessary. On the other hand, if added over 0.3%, the toughness is adversely affected. For this reason, V is limited to the range of 0.01 to 0.3%.

Mn: 1.2% or less Mn has the effect of increasing the strength of steel. On the other hand, if the content exceeds 1.2%, the ferrite phase hardness increases and the fatigue crack propagation delay effect deteriorates. For this reason, Mn is limited to 1.2% or less.

Cu: 0.8% or less Cu is an element that can increase strength while maintaining high toughness, has little influence on HAZ toughness, is useful for increasing strength, and can be selected as necessary. Can be contained.

  On the other hand, when the content exceeds 0.8%, hot brittleness is caused to deteriorate the surface properties of the steel sheet, the hardness of the ferrite phase is increased, and the fatigue crack propagation delay effect is deteriorated. For this reason, Cu is limited to 0.8% or less.

Ni: 1.0% or less Ni is an element that can increase strength while maintaining high toughness, has little effect on HAZ toughness, is useful for increasing strength, and can be selected as necessary. Can be contained. However, even if the content exceeds 1.0%, the effect is saturated, the effect commensurate with the content cannot be expected, and it becomes economically disadvantageous, the hardness of the ferrite phase increases, and fatigue crack propagation Delay effect deteriorates. For this reason, Ni is limited to 1.0% or less.

Nb: 0.1% or less Nb is an element that contributes to strength improvement, but inclusion exceeding 0.1% degrades the base metal toughness and the HAZ toughness. For this reason, Nb is limited to 0.1% or less.

Ti: 0.03% or less Ti contributes to strength improvement, and also has a strong affinity with N, precipitates as TiN during solidification, and suppresses coarsening of austenite grains in HAZ, thereby contributing to toughening of HAZ. . On the other hand, if it exceeds 0.03%, the toughness of the base metal is deteriorated. For this reason, it is desirable to limit Ti to 0.03% or less.

B: 0.0050% or less B has an effect of increasing the strength of steel through improving hardenability. On the other hand, if the content exceeds 0.0050%, the hardenability is remarkably increased and the toughness and ductility of the base metal are deteriorated. For this reason, B is limited to 0.0050% or less.

Ca: 0.005% or less Ca is a useful element that improves toughness through refinement of crystal grains, but the effect is saturated even if contained over 0.005%, so 0.005% Is the upper limit.

REM: 0.02% or less REM is an element that contributes to improvement of toughness, but even if contained over 0.02%, the effect is saturated, so 0.02% is made the upper limit.

Mg
Mg is a useful element that improves toughness through refinement of crystal grains, but even if contained over 0.005%, the effect is saturated, so 0.005% is made the upper limit.

The balance other than the components described above is Fe and inevitable impurities. Next, the manufacturing method of the thick steel plate in this invention is demonstrated.
[Production conditions]
In the description, “° C.” related to the temperature means a temperature of 1/2 t part thickness unless otherwise specified.
Reheating temperature The steel material used in the present invention is prepared by melting molten steel having the above composition by a generally known method such as a converter, an electric furnace, a vacuum melting furnace or the like, and bringing these steel materials to 1000 ° C to 1300 ° C. Reheat.

  If the reheating temperature is less than 1000 ° C, the deformation resistance in hot rolling becomes high and the amount of rolling reduction per pass cannot be made large. Therefore, the number of rolling passes increases and the rolling efficiency decreases, and the steel material The casting defect in (slab) may not be crimped.

On the other hand, when the reheating temperature exceeds 1300 ° C., surface flaws are likely to occur due to the scale during heating, and the maintenance load after rolling increases. For this reason, it is preferable to make the reheating temperature of a steel raw material into the range of 1000-1300 degreeC.
Hot Rolling Conditions The reheated steel material is hot rolled so that the rolling end temperature is equal to or higher than the Ar3 transformation point. The hot rolling conditions are not particularly limited as long as a predetermined plate thickness and shape can be satisfied except that the rolling end temperature is not less than the Ar3 transformation point.

  In the case of an extremely thick steel plate having a plate thickness of more than 80 mm, it is desirable to secure at least one rolling pass with a reduction rate of 15% or more per pass for zaku pressure bonding. If the rolling end temperature is less than the Ar3 transformation point, the deformation resistance becomes too high, the rolling load increases, and the burden on the rolling mill increases.

  In addition, in order to reduce the rolling temperature of thick materials to below the Ar3 transformation point, it is necessary to wait in the middle of rolling, which greatly hinders productivity. For this reason, the rolling end temperature is set to the Ar3 transformation point or higher. The cooling after hot rolling may be air cooling or accelerated cooling.

The correlation with the chemical composition of the Ar3 point can be roughly organized by the following equation (1).
Ar3 = 868-396C + 25Si-68Mn-21Cu-36Ni-25Cr-30Mo (1)
(However, C, Si, Mn, Cu, Ni, Cr, Mo: Content of each alloy element (mass%))
Heat treatment After hot rolling and cooling, heat treatment, which is an important process of the present invention, is performed. In the heat treatment, after reheating and holding in a two-phase temperature range of Ac1 transformation point + 10 ° C. to Ac3 transformation point−10 ° C., quenching is performed at an average cooling rate of 5 ° C./s or more.

  Although the holding time is not specified, the holding in this temperature range is intended to equalize the temperature in the steel sheet and to suppress the characteristic variation, and for 5 min. The above is preferable.

  Further, if the holding time is 1 hr or longer, the toughness of the base material deteriorates due to the coarsening of austenite grains, so that it is preferably within 1 hr. On the other hand, when the average cooling rate is 5 ° C./s or less, the hardenability of the steel sheet is reduced, so that a pearlite or bainite phase is generated as a hard phase, and the target martensite structure cannot be achieved.

  The upper limit of the average cooling rate is not particularly specified, but is preferably 80 ° C./s or less from the viewpoint of reducing the cut strain.

  In addition, the reason why the temperature range of this heat treatment is defined as Ac1 transformation point + 10 ° C. to Ac3 transformation point−10 ° C. is by efficiently promoting the concentration of C to austenite and the dilution softening of ferrite. This is because the structure after quenching becomes a mixed structure of hard martensite and soft ferrite, which effectively acts on fatigue crack propagation resistance.

  If held at a temperature of Ac1 transformation point + 10 ° C or lower, the austenite phase fraction is low, so the martensite fraction in the structure after quenching is small, and if held at a temperature of Ac3 transformation point -30 ° C or higher Not only does the ferrite phase fraction decrease, it does not promote the concentration of alloy elements such as C in the austenite phase, the hardness of the martensite structure after quenching decreases, and fatigue crack propagation resistance deteriorates. To do. For this reason, the temperature range of two-phase region heating is limited to Ac1 transformation point + 10 ° C. to Ac3 transformation point−10 ° C.

Incidentally, the points Ac1 and Ac3 can be roughly correlated with the chemical composition by the following equations (2) and (3).
Ac1 = 723-14Mn + 22Si-14.4Ni + 23.3Cr (2)
Ac3 = 854-180C + 44Si-14Mn-17.8Ni-1.7Cr (3)
(However, C, Si, Mn, Ni, Cr: Content of each alloy element (mass%))
In the present invention, the steel sheet is subjected to tempering treatment after two-phase region heating and quenching. The toughness and ductility of the base material are improved by tempering at a reheating temperature of 400 ° C. or higher and an Ac1 point or lower. In order to obtain such an effect, the tempering temperature needs to be 400 ° C. or higher. However, if the Ac1 point is exceeded, the hardness of the tempered martensite phase decreases, and the fatigue crack propagation delay effect deteriorates. .

  For this reason, it is desirable to perform the tempering process at 400 ° C. to Ac1 point. Although the holding time is not specified, if it becomes 1 hr or more, the hardness of the tempered martensite phase decreases and the delay effect of fatigue crack propagation deteriorates. It can be held for a short time.

  In the present invention, reheating, normalizing, or quenching may be performed between the hot rolling and the two-phase region heat treatment. By reheating the steel plate to a temperature range above the Ac3 transformation point and maintaining it, a uniform austenite phase is formed to the inside of the steel plate, and then air cooling or accelerated cooling is performed to further homogenize the structure in the steel plate. And refined.

  Although the upper limit of the heating temperature is not specified, the surface property of the steel sheet deteriorates when it is 1100 ° C. or higher. Also, the holding time is not specified, but if it exceeds 1 hr, the toughness of the base material deteriorates due to the coarsening of the austenite grains. Therefore, it is preferably within 1 hr. But it ’s okay.

  Using the steel material having the above composition, the ferrite structure having a Vickers hardness of 130 or less as the metal structure of the steel sheet according to the two-phase region heat treatment and tempering treatment conditions after hot rolling under the above-described conditions, A mixed structure of tempered martensite phase of 340 or more with a Vickers hardness of 15 to 85% can be obtained, and a steel plate having excellent fatigue crack propagation resistance can be produced.

  Thickness of the plate thickness shown in Table 2 by hot rolling-reheating quenching-tempering of steel materials prepared in the composition shown in Table 1 by the converter-ladle refining-continuous casting method. A steel plate was used.

  For the investigation of the texture fraction, a sample for microstructural observation was taken on the cross section parallel to the rolling direction of each steel plate obtained, and after taking Nital corrosion, the optical microstructure was photographed, and the texture fraction was analyzed using an image analyzer. The rate was determined.

  The scope of the present invention is a steel material having a tensile strength of 440 N / mm 2 or more and a total elongation of 22% or more, and the toughness is measured at −20 ° C. by a Charpy impact test using a 2 mm V notch specimen in accordance with JIS Z2242 (2006). The steel material has an absorption energy of 100 J or more.

  JIS No. 4 tensile test piece or JIS No. 5 full thickness tensile test piece is taken from the position of 1/2 thickness of each obtained steel plate, and tensile test is carried out according to the standard of JIS Z 2241 (2006). The characteristics were investigated.

In addition, V-notch test specimens were collected from the obtained steel plate thickness 1/2 position in accordance with the provisions of JIS Z 2202 (2006), and Charpy impacts were obtained in accordance with the provisions of JIS Z 2242 (2006). A test was conducted to determine the absorbed energy (vE- ₂₀ ) at -20 ° C, and the base material toughness was evaluated.

  To investigate the fatigue crack propagation characteristics, CT specimens based on ASTM E 647 were collected from each steel plate so that the load direction was parallel to the rolling direction, and fatigue crack propagation tests were conducted using the crack gauge method. Asked.

The steel material having excellent fatigue crack propagation characteristics in the present invention is a steel material having a fatigue crack propagation rate (da / dN) of 8 × 10 ⁻⁹ (m / cycle) or less at a stress intensity factor ΔK: 15 MPa / √m. .

The obtained results are shown in Table 3. In all of the examples of the present invention, the fatigue crack propagation rate (da / dN) at a stress intensity factor ΔK: 15 MPa / √m is extremely slow as 8 × 10 ⁻⁹ (m / cycle) or less, and excellent fatigue crack resistance characteristics. Have

  Furthermore, it has a base material property of tensile strength of 440 MPa or more, total elongation of 22% or more, and high strength, high ductility, and high toughness of absorbed energy vE-20> 100 J at −20 ° C.

  On the other hand, in the comparative example outside the scope of the present invention, one or more of the fatigue crack propagation characteristics and mechanical characteristics do not satisfy the target value.

Claims (3)

Steel composition is mass%,
C: 0.05-0.30%,
Si: 0.03 to 0.35%,
Cr: 0.05 to 2.0%,
P: 0.03% or less S: 0.003% or less Al: 0.1% or less, with the balance being Fe and inevitable impurities, the metal structure being 8 Vickers hardness
340 with 5 to 130 ferrite phase and Vickers hardness of 15 to 85% area fraction
A steel material excellent in fatigue crack propagation resistance, which is a mixed structure of tempered martensite phase of 440 or less. In addition to the steel composition,
Mo: 0.05-1.0%,
V: 0.01 to 0.3%
A steel material excellent in fatigue crack propagation resistance according to claim 1, comprising one or two of the following. In addition to the steel composition,
Mn: 1.2% or less Cu: 0.8% or less Ni: 1.0% or less Nb: 0.1% or less Ti: 0.03% or less B: 0.005% or less Ca: 0.005% or less REM : 0.02% or less Mg: The steel material excellent in the fatigue crack propagation characteristic of Claim 1 or Claim 2 containing 1 type or 2 types or less of 0.005% or less .