晶间腐蚀标准

Standard practices for

Detecting susceptibility to intergranular attack in austenitic stainless steels

奧氏體不銹鋼晶間腐蝕敏感性標準實驗

1.scope

1.應用範圍

these practices cover the following five tests:

1.2 這些實驗包括下列五類：

1.1.1 parctics A- oxalic acid etch test for classification of etch structures of austenitic stainless steels(section 3 to 7, inclusive)

1.1.1實驗A——奧氏體不銹鋼草酸浸蝕試驗後的浸蝕組織分類（包括3－7部分

1.2 the following factors govern the application of these practices:

1.2以下因素主導著這類實驗：

1.2.1 susceptibility to intergranular attack associated with the precipitation of chromium carbides is readily detected in all six tests.

1.2.1晶間腐蝕敏感性同碳鉻化合物的快速析出

1.2.2 sigma phase in wrought chromium-nickel-molybdenum steels. Which may or may not be visible in the microstructure, can

result in high corrosion rates only in nitric acid.

1.2.2在鉻鎳鉬鋼中可見的和不可見的sigma相，只有在硝酸中才會快速腐蝕。

1.2.3 sigma phase in titanium or columbium stabilized alloys and cast molybdenum-bearing stainless alloys, which may or may not be visible in the microstructure, can result in high corrosion rates in both the nitric acid and ferric sulfate-sulfuric acid solutions.

1.2.3在鈦合金或穩定化合金和鑄造鉬柱狀晶中的sigma相，不管在其顯微組織中可見不可見都會在硝酸和硫化鐵溶液中引起嚴重腐蝕。

1.3 the oxalic acid etch test is a rapid method of identifying, by simple etching, those specimens of certain stainless steel grades that are essentially free of susceptibility to intergranular attack associated with chromium carbide precipitates. These specimens will have low corrosion rates in certain corrosion tests and therefore can be eliminated (screened) from testing as ―acceptable.‖

1.3草酸浸蝕試驗是一個快速方法用來使這些本質上晶間腐蝕不敏感的不銹鋼試樣快速析出碳鉻化合物。

1.7 only these stainless steel grades are listed in table one for which data on the application of the oxalic acid etch test

and on their performance in various quantitative evaluation tests are available.

1.7在表一中列出哪些適合用草酸進行浸蝕試驗及各種數量測試下的性能是有效的。

Practice A oxalic acid etch test for classification of etch structures of austenitic stainless steels 2

實驗A——奧氏體不銹鋼草酸浸蝕試驗後的浸蝕組織分類

3.1 the oxalic acid etch test is used for acceptance of material but not for rejection of material. This may be used in connection with other evaluation tests to provide a rapid method for identifying those specimens that are certain to be free of susceptibility to rapid intergranular attack in these other tests. Such specimens have low corrosion rates in the various hot acid tests, requiring from 4 to 20 h of exposure. These specimens are identified by means of their etch structures, which are classified according to the following criteria：

3.1草酸浸蝕法晶間腐蝕試驗一般用來作為材料的評價，不作為材料的判廢標準。这方法一般为其它评价方法提供一个快速途径来鉴定实验试样在各种测试中是否具有晶间腐蚀敏感性。这些在各种热酸试验中腐蚀率都很低的试样，需要承受4至20小时的试验。通过对这些

腐蚀试样的腐蚀结构来进行评判。相应的定级根据下列标准：

3.2 the oxalic acid etch test may be used to screen speciments intended for testing in practice B--Ferric Sulfate-Sulfuric Acid Test, practice C—nitric acid test, practice E—copper-copper sulfate-16% sulfuric acid test, and practice F—copper-copper sulfate-50% sulfuric acid test.

3.2 草酸浸蚀试验是代替试验程序B——硫化铁和硫酸溶液试验，程序C——硝酸试验，程序F——铜和硫化铜及16%硫酸铜溶液试验，用来甄别试样。

3.2.1 each practice contains a table showing which classifications of etch structures on a given stainless steel grade are equivalent to acceptable, or possibly nonacceptable performance in that particular test. Specimens having acceptable etch structures need not be subjected to the hot acid test. specimens having nonacceptable etch structures must be tested in the specified hot acid solution.

3.2.1 每个试验程序都包括一个表格，这个表格显示给定试验不锈钢的浸蚀组织中哪类同等级别下可以被接受，或者在这特殊的实验后哪些性能可能不被接受。试样拥有可以被接爱的显微组织不必服从热酸试验。试样拥有不接爱的显微组织必须得在批定热酸溶液下进行试验。

3.3 the grades of stainless steels and the hot acid tests for

which the oxalic acid etch test is applicable are listed in table 2.

3.3 不锈钢等级和哪类钢需要进行热草酸酸测试见表2。

3.4 extra-low-carbon grades, and stabilized grades, such as 304L,316L,317L,321, and 347, are tested after sensitizing heat treatments at 650 ℃to 675℃,which is the range of maximum carbide precipitation. These sensitizing treatments must be applied before the specimens are submitted to the oxalic acid etch test. The most commonly used sensitizing treatment is 1

h at 675℃.

3.4 对于超低碳级的和稳定化级的不锈钢，如304L,316L,317L,321和347这些材料应该在其最大碳化物析出温度650 ℃到675℃区域进行敏化处理后再进行晶间腐蚀试验。敏化处理应该在草酸浸蚀试验前进行，一般用675℃保温一小时的处理方法。

4. apparatus

4．仪器装置

4.1 source of direct current-battery, generator, or rectifier capable of supplying about 15 V and 20 A.

4.1 直流电源——同时可以有能力提供15伏和20安的电池、发电机或者变压器。

4.2 ammeter-range 0 to 30 A (note 1)

4.2 电流表（安培计）——范围是0至30安培（注1）

4.3 variable resistance (note 1)

4.3 可变电阻（注1）

4.4 cathode-A cylindrical piece of stainless steel or, preferably, a 1-qt (0.946-L) stainless steel beaker.

4.4 阴极——一个圆柱形的不锈钢棒，最好是一个一加仑的不锈钢烧杯。

4.5 large electric clamp- to hold specimen to be etched. 4.5 大带电夹具——用来支撑浸蚀试样。

4.6 metallurgical microscope-for examination of etched microstructures at 250 to 500 diameters.

4.6 金相显微镜——在250至500倍直径内检查腐蚀样的显微结构。

4.7 electrodes of the etching cell- the specimen to be etched is made the anode, and a stainless steel beaker or a piece of stainless steel as large as the specimen to be etched is made the cathode.

4.7 腐蚀容器的电极——试样用来作为阳极，同时一个不锈钢烧杯或者和试样一样大小的一个圆棒作为阴极。

4.8 electrolyte- oxalic acid,(H2C2O4.2H2O), reagent grade, 10 weight% solution.

4.8 电解液——草酸，(H2C2O4.2H2O),分析纯级，重量百分比10%。Note 1- the variable resistance and the ammeter are placed in the circuit to measure and control the current on the specimen

to be etched.

注1——各种可变电阻和安培计都安装在回路里以用来测量和控制试样腐蚀时的电流。

5. preparation of the test specimens

5. 试样制备

5.1 cutting- sawing is preferred to shearing, especially on the extra-low-carbon grades. Shearing cold works adjacent metal and affects the response to subsequent sensitization. Micro scopical examination of an etch made on a specimen containing sheared edges, should be made on metal unaffected by shearing.

A convenient specimen size is 25 by 25 mm(1 by 1 in.)

5.1 切割——用锯子同切割相比一般情况下总是优先选择，特别是对于超低碳不等级的不锈钢。切割使相鄰材料變形，影響著下一步的材料敏感性。浸蝕試樣的微觀檢查包括有切邊的微觀檢查，以確保試樣剪切邊沒有對材料的敏感性產生影響。一般试样尺寸为25×25mm（1英吋×1英吋）。

5.2 the intent is to test a specimen representing as nearly as possible the surface of the material as it will be used in service. Therefore the preferred sample is a cross section including the surface to be exposed in service. Only such surface finishing should be performed as is required to remove foreign material and obtain a standard, uniform finish as

described in 5.3. for very heavy sections, specimens should be machined to represent the appropriate surface while maintaining reasonable specimen size for convenient testing.

5.3 抛光——对所有材料而言，交叉部位应当进行抛光而进行浸蚀和金相检查。有焊缝试样应当包括母材、热影响区和焊缝熔合线。

5.4 etching solution- the solution used for etching is prepared by adding 100g of reagent grade oxalic acid crystals (H2C2O4.2H2O)to 900ml of distilled water and stirring until all crystals are dissolved.

5.4 浸蚀溶液——在900毫升蒸溜水中加入100克草酸晶体(H2C2O4.2H2O)，并且充分搅拌使所有晶体充分溶解于水中。

5.5 etching conditions- the polished specimen should be etched at 1 A/cm2 for 1.5min. To obtain the correct current density.

5.5 浸蚀条件——抛光后的试样应当在1 A/cm2电流强度下浸蚀1.5分钟。为获得准确的电流密度，需：

5.5.1 the total immersed area of the specimen to be etched should be measured in square centimeters, and

5.5.1 试样所有的浸蚀面积以平方厘米为单位进行测定，而且

5.5.2 the variable resistance should be adjusted until the ammeter reading in amperes is equal to the total immersed area of the specimen in square centimeters.

5.5.2 各种电阻必须进行调整到安培计读数（单位：安培）等于试样

总的浸蚀面积（单位：平方厘米）。

5.6 etching precautions

5.6 浸蚀注意事项

5.6.1 caution- etching should be carried out under a ventilated hood. Gas, which is rapidly evolved at the electrodes with some entrainment of oxalic acid, is poisonous and irritating to mucous membranes.

5.6.1 注意——浸蚀试验须在通风柜内进行，因为腐蚀过程中会产生很多表毒有害的气体，会使人体受到伤害刺激黏膜。

5.6.2 a yellow-green film is gradually formed on the cathode. This increases the resistance of the etching cell. When this occurs, the film should be removed by rinsing the inside of the stainless steel beaker (or the steel used as the cathode) with an acid such as 30% HNO3.

5.6.2 在阴极表面逐渐形成一黄绿色薄膜。这将增加腐蚀容器的电阻。当发生这样的情况时，必须用酸，如30%硝酸清洗不锈钢容器内壁来清洗掉这层黄绿薄膜（或者将这作为阳极）。

5.6.3 The temperature of the etching solution gradually increases during etching. The temperature should be kept below 50℃ by alternating two beakers. One may be cooled in tap water while the other is used for etching. The rate of heating depends on the total current (ammeter reading) passing through the cell.

Therefore, the area etched should be kept as small as possible while at the same time meeting the requirements of desirable minimum area to be etched.

5.6.3 在浸蚀过程中浸蚀液的温度会逐渐升高，但这必须用两个腐蚀槽来交替使用以使温度控制在50℃以下。当一个在使用时，另一个用自来水冷却。这个温度升高的速度取决于通过浸蚀槽的总电流（从安培计可以读出）。因此在固定时间内获得理想浸蚀结果那浸蚀面积得尽可能地小。

5.6.4 immersion of the clamp holding the specimen in the etching solution should be avoided.

5.6.4 在腐蚀试验过程中要避免将试样支撑架子浸没于腐蚀溶液中。

5.7 rinsing- following etching, the specimen should be thoroughly rinsed in hot water and in acetone or alcohol to avoid crystallization of oxalic acid on the etched surface during drying.

5.7 清洗——试样浸蚀后，必须用自来水和丙酮或者酒精彻底清洗，以防止在干燥过程中草酸在浸蚀表面形成结晶体。

5.8 on some specimens containing molybdenum (AISI 316,316L,317,317L),which are free of chromium carbide sensitization, it may be difficult to reveal the presence of step structures by electrolytic etching with oxalic acid. In such cases, an electrolyte of a 10% solution of ammonium

persulfate,(NH4)2S2O8, may be used in place of oxalic acid. An etch of 5 or 10 min at 1A/CM2 in a solution at room temperature readily develops step structures on such specimens.

5.8 一些含钼材料（AISI 316,316L,317,317L），其对碳铬化合物不敏感，用草酸来浸蚀很难对其晶界进行浸蚀，在这种情况下，一种称为过硫酸铵盐的10%电解质（(NH4)2S2O8）可以用来代替草酸。在室温下，用1A/CM2 5到10分钟就可以在试样上很容易地显示晶界浸蚀状况了。

6. classification of etch structures

6.浸蚀组织的分类

6.1 the etched surface is examined on a metallurgical microscope at 250* to 500* for wrought steels and at about 250* for cast steel.

6.1 金相顯微鏡下的浸蝕組織檢驗，對熟鋼一般用250到500倍下觀察，而鑄鋼一般用250倍觀察。

6.2 the etched cross-sectional areas should be thoroughly examined by complete traverse from inside to outside diameters of rods and tubes, from face to face on plates, and across all zones such as weld metal, weld-affected zones, and base plates on specimens containing welds.

6.2

6.3the etch structures are classified into the following types

(note 2)

6.3 浸蝕組織一般分為以下幾類：

6.3.1 step structure (figure 1)—steps only between grains ,no ditches at grain boundaries.

6.3.1

6.3.2 dual structure (figure 2)_some ditches at grain boundaries in addition to steps, but no single grain completely surrounded by diktches.

6.3.3 ditch structure (figure 3)-one or more grains completely surrounded by ditches.

6.3.4 isolated ferrite (figure 4)-observed in castings and welds. Steps between austenite matrix and ferrite pools. 6.3.5 interdendritic ditches (figure 5)-observed in castings and welds. Deep interconnected ditches.

6.3.6 (figure 6)-structure contains a few deep end-grain pits along with some shallow etch pits at 500*.(of importance only when nitric acid test is used.)

6.3.7 end-grain pitting 2 (figure 7)-structure contains numerous, deep end-grain pits at 500*.( of importance only when nitric acid test is used.)

Note 2: all photomicrographs were made with specimens that were

etched under standard conditions: 10% oxalic acid, room temperature, 1.5 min at 1 A/cm2.

6.4 the evaluation of etch structures containing steps only and of those showing grains completely surrounded by ditches in every field can be carried out relatively rapidly. In cases that appear to be dual structures, more extensive examination is required to determine if there are any grains completely encircled. If an encircled grain is found, the steel should be evaluated as a ditch structure. Areas near surfaces should be examined for evidence of surface carburization.

6.4.1 on stainless steel castings (also on weld metal,) the steps between grains formed by electrolytic oxalic acid etching tend to be less prominent than those on wrought materials or are entirely absent. However, any susceptibility to intergranular attack is readily detected by pronounced ditches.

6.5 some wrought specimens, especially from bar stock, may contain a random pattern of pits. If these pits are sharp and so deep that they appear black(fig.7) it is possible that the specimen may be susceptible to end grain attack in nitric acid only. Therefore, even though the grain boundaries all have step

structures, specimens having as much or more end grain pitting than that shown in fig.7 cannot be safely assumed to have low nitric acid rates and should be subjected to the nitric acid test whenever it is specified. Such sharp, deep pits should not be confused with the shallow pits shown in fig 1 and fig.6.

7. use of etch structure classifications

7.1 the use of these classifications depends on the hot acid corrosion test for which stainless steel specimens are being screened by etching in oxalic acid and is described in each of the practices. Important characteristics of each of these tests are described below.

7.2 practice B-ferric sulfate-sulfuric acid test is a 120 h test in boiling 50% solution that detects susceptibility to intergranular attack associated primarily with chromium carbide precipitate. It does not detect susceptibility associated with sigma phase in wrought chromium-nickel-molybdenum stainless steels (316, 316L, 317, 317L),which is known to lead to rapid intergranular attack only in certain nitric acid environments. It does not detect susceptibility to end grain attack, which is also found only in certain nitric acid environments. The ferric

sulfate-sulfuric acid test does reveal susceptibility associated with a sigma-like phaseconstituent in stabilized stainless steels, AISI 321 and 347, and in cast chromium-nickel-molybdenum stainless steels(CF-8M, CF-3M, C6-8M, and CG-3M).

7.3 practice C- nitric acid test is a 240 h test in boiling, 65% nitric acid that detects susceptibility to rapid intergranular attack associated with chromium carbide precipitate and with sigma-like phase precipitate. The latter may be formed in molybdenum-bearing and in stabilized grades of austenitic stainless steels and may or may not be visible in the microstructure. This test also reveals susceptibility to end grain attack in all grades of stainless steels.

7.4 practice E- copper-copper sulfate-16% sulfuric acid test is a 24 h test in a boiling solution containing 16% sulfuric acid and 6% copper sulfate with the test specimen embedded in metallic copper shot or grindings, which detects susceptibility to intergranular attack associated with the precipitation of chromium-rich carbides. It does not detect susceptibility to intergranular attack associated with sigma phase or end-grain corrosion, both of which have been observed

to date only in certain nitric acid environments.

7.5 practice F – copper-copper sulfate-50% sulfuric acid test is a 120 h test in a boiling solution that contains 50% sulfuric acid, copper sulfate, and metallic copper and that detects susceptibility to intergranular attack associated with the precipitation of chromium-rich carbides. It does not detect susceptibility to attack associated with sigma phase.