17th World Conference on Nondestructive Testing, 25-28 Oct 2008, Shanghai, China

The Fluorescence Penetrant Agent Manufacture and Its Wastewater Treatment

Zhenwang LIN 1 Zhenlu CHEN 1 Dongsheng LI 2 Jiangpai LI 3 Zhonglin CHEN 1 1 Xiamen Jimei Xincheng NDT Manage Department Rm.103,No.13,Fangzhi Road,Xinglin,Jimei District,Xiamen 361022, China Tel:86-592-5287678.Fax:86-592-6259989 E-Mail : warder@public.xm.fj.cn; E-Mail :warder@188.com 2 Honeywell TAECO Aerospace (Xiamen) Co.,Ltd , Xiamen, China E-Mail :dongsheng.li@honeywell.com 3 Xiamen Airline Company Limited, Xiamen, China

Abstract The author had spent decades in theoretical research and experiments in manufacturing water washable types and post emulsifiable fluorescence penetration agentemulsifiersdevelopers of various types etc. Thus the performance of this product complied with the specification and requirements of People Republic of China aerospace industry standard HB7681-2000 and US aerospace material specification AMS 2644E standard. The Index performance of some product peers excelled and achieved international standards compared with similar product types. The author researched and explored the product in wastewater treatment with fluorescence penetration test process. By separation of oil from water and emulsion breakage and then finally achieving transparency and clear of the water. The wastewater of C O DCr value ranged from 10000 to 20000. After primary treatment, the clear water of C O DCr value reduced between 50 to 300. Whereby achieving an environmental protection level 3 effluent standards. The waste oil can be further reused optimized by further treatment. Key word: fluorescence penetrant agent; performance; wastewater treatment; resource recovery 1. Introduction
The author had written several thesis related to penetrate topics 1 2 3 and

conducted laboratory experiments and theoretical researches for decades and had researched and manufactured water washable types and post emulsifiable types fluorescence penetrate agentemulsifiersdevelopers etc. product series. The product performance complied with the specification and requirements of People Republic of China aerospace industry standard HB7681-2000 and US aerospace material specification AMS 2644E standard. The Index performance of some product peers

excelled and achieved international standards compared with similar product types. The author researched and explored the product in wastewater treatment with fluorescence penetration test process. By separation of oil from water and emulsion breakage and oil removal, oxidation mixed coagulant adsorption and filtration process and then finally achieving transparency and clear of water. Through separation of oil and water then emulsion breaking to removing oil ,oxidation degration, and filtration so as to achieve clear and transparency in the water. Whereby achieving an environmental protection level 3 effluent standards. 2. Fluorescence Penetrant agent research and manufacture: 2.1. Fluorescence Penetrant agent manufacture reference materials and test block US Magnaflux Company :ZL-60D(fluorescence water washable type level 2) ZL-67(fluorescence water washable type level 3) ZL-56(fluorescence water washable type level 4).Germany Ardrox : 985-P13 (fluorescence post emulsifiable type level 3)ZL-27A(fluorescence post emulsifiable type level 3) and US Met-L-Chek: FP-92B(fluorescence water washable type level 2) FP-923B(fluorescence water washable type level 3) FP-95A(fluorescence post emulsifiable type level 3) FP-97A(fluorescence post emulsifiable type level 4) . E-58D emulsifier D-72A developer which optimized the five spots type (twin block test) from US Sherwin Company and engaged into similar experiments for contrasting purposes. 2.2. Contents of experiments and results Having conducting researches and manufacturing samples of water washable type and post emulsifiable type fluorescence Penetrant agent and the results reflected similar effects regardless in speedy removal, background removal, crack spots fluorescence brightness were almost equivalent in contrasted with other US samples as well as experiment in working conditions. The products were odour-free, close cup flash point 93. Penetrant agent would not solidified in freezing temperature of below 0. Corrosion test, water tolerance(method A only), emulsifier test, developer test etc. too complied with specifications and requirements. Detailed contents as shown in table 1-5: Table.1 Fluorescence water washable type level 2 DesignSpecific Freezing No Character tion Gravity point 1
FA-2-1 Yellow-green liquid

Viscosity 12cst

Flash Point 93

Water Tolerance

0.925

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FA-2-2

Yellow-green liquid

0.937

12.9cst

93

Removability and Sensitivity Contrast Test No . 1 2

Reference Material Mag.ZL60D Mag.ZL60D Reference Block Sher.Dt.ww Sher.Dt.ww Wash Speed Remove Background Crack spot Fluorescent Brightness

Corrosion Test
Al Alloy Acc Acc Mg Alloy Acc Acc Steel Acc Acc

Equal Equal

Equal Equal

Equal Equal

Table 2 Fluorescence water washable type level 3

No Designtion FA-3-1 FA-3-2 Character Yellow-green liquid Yellow-green liquid Specific Gravity 0.956 0.97 Freezing point 0 0 Viscosity 13cst 16.2cst Flash Point 93 93 Water Tolerance 5 5

1 2

Removability and Sensitivity Contrast Test No . 1 2

Reference Material Met-L.923B Met-L.923B Reference Block Sher.Dt.ww Sher.Dt.ww Wash Spee d Equal Equal Remove Background Equal Equal Crack spot Fluorescent Brightness Equal Equal

Corrosion Test
Al Alloy Acc Acc Mg Alloy Acc Acc Steel Acc Acc

Table 3. Fluorescence water washable type level 4 No 1 2

Designtion FA-4-1 FA-4-2 Character Yellow-green liquid Yellow-green liquid Specific Gravity 0.94 0.99 Freezing point 0 0 Viscosity 14cst 16.2cst Flash Point 93 93 Water Tolerance 5 5

Removability and Sensitivity Contrast Test No 1 2

Reference Material Mag.ZL56 Mag.ZL56 Reference Block Sher.Dt.ww Sher.Dt.ww Wash Speed Equal Equal Remove Background Equal Equal Crack spot Fluorescent Brightness Equal Equal

Corrosion Test
Al Alloy Acc Acc Mg Alloy Acc Acc Steel Acc Acc

Table 4. Fluorescence post emulsifiable type level 3 (hydrophilic) Specific Freezing Viscosity Flash No DesignCharacter
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Emulsi-

tion 1 2 FD-3-1 FA-3-2 Yellow-green liquid Yellow-green liquid

Gravity 0.94 0.98

point 0 0 6.8cst 9.7cst

Point
93 93

fier E1 E1

Removability and Sensitivity Contrast Test No

1 2 Reference Material Ard.985-P13 Ard.985-P13 Reference Block Sher.Dt.PE Sher.Dt.PE Wash Speed Equal Equal Remove Background Equal Equal Crack spot Fluorescent Brightness 985-P13 985-P13

Corrosion Test
Al Alloy Acc Acc Mg Alloy Acc Acc Steel Acc Acc

Table 5. Fluorescence post emulsifiable type level 4 (hydrophilic) No 1 2

Designtion FD-4-1 Character Yellow-green liq. Yellow-green liq. Specific Gravity 0.955 0.98 Freezing point 0 0 Viscosity 7.6cst 9.8cst Flash Point 93 93 Emulsifier E1 E1

FA-4-2

Removability and Sensitivity Contrast Test No 1 2

Reference Material Met.-L.97A Met.-L.97A Reference Block Sher.Dt.PE Sher.Dt.PE Wash Speed Equal Equal Remove Background Equal Equal Crack spot Fluorescent Brightness 97A 97A

Corrosion Test
Al Alloy Acc Acc Mg Alloy Acc Acc Steel Acc Acc

2.3. Compare Picture: A comparison between the researched product and US AFRL qualfied product of similar types in Penetrant agent removability and sensitivity (twin block test). Referred to Picture 1~4. 2.4. Emulsifier E1: hydrophilic type. Rose red aqueous solution. Concentration level of 20. 2.5. Developer D1: Dry powder. Accumulation density 0.15. Developer did not contain asbestos.
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Picture 1: ZL-67 & FA-3-1

Picture 2: FA-4-1 & ZL-56

Picture 3: FD-3-1 &ARD.985-P13

Picture 4: FD-4-1 & FP-97A

2.6. Conclusion
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The manufactured fluorescent Penetrant agent performance complied with AMS 2644E specifications and requirements. In comparison with the US AFRL qualified products, by optimizing twin block test had shown that the performance was fundamentally equivalent. However the manufactured fluorescence water washable of type level 34 water- proof had achieved equivalent or higher sensitivity level in comparison with its peer products of international standards. The manufactured fluorescence post emulsifiable of type level 34 crack spot fluorescent brightness also achieved equivalent or higher contrasting levels in comparison with its peer products of international standards. 3. Fluorescent Penetrant agent wastewater treatment 3.1.: Necessity and method of fluorescence penetrant agent wastewater treatment: astewater As you know that application of water washable types and post emulsifiable types fluorescence Penetrant agent onto work piece or spare-parts to conduct PT check and large volume of organic waste water will be produced during the removal process in PT check (included water washprewashpost emulsifiable water wash and other removal treatment). Hence the organic waste water contained oil, organic solvent, surfactants, organic dye and etc which resulted aqueous emulsion, fluorescence pollution, oil pollution, poison and other hazards in the water. C O DCr value ranged between 10000 to 20000 do not comply with the environmental protection effluent standards and requirements. The method for the modernized organic waste water treatment mainly (4) degraded active dirt particles: Activated sludge microbiological degration treat method; Chemical oxidation degration treatment method. The author also conducted researches and adopted a swift, simplified Fenton Reagent (H2O2 FeSO47 H2O ) chemical oxidation degration method to degrade fluorescence wastewater and washable types of waste water and post emulsifiable types of waste water were to be treated separately. Therefore it provided referencing of experimentations for conducting a large scale treatment of fluorescence wastewater. 3.2. Procedures for Wastewater treatment: Waste waterseparating oil from waterheating & breaking emulsion and remove oillow dose Fenton Reagent oxidation degrationcoagulate adsorptionfilterclear water The clarity and transparency of water after treatment. Originally, the C O D Cr value for wastewater is ranged from 10000 to 20000.After primary treatment, the C O D Cr value for clear water was reduced between 50 to 300 which attained an environmental
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protection level 3 effluent standard.

3.3. Wastewater treatment method and results 3.3.1.Low dose Fenton Reagent(H2O2FeSO47H2O) oxidation degration method: Sampled 100 ml of wastewater, applied heat temperature till 70~80 then stirred and add small amount of breaking emulsifiers. Then remove the upper layer of the floated oil and filtered the precipitate at the bottom layer. Add 0.25ml 1:4 H2SO4 solution to liquid. Adjust PH level for liquid 3. Add 0.08g FeSO47 H2O , continue heating and stirred, maintained temperature at 70~80. Slowly dripped about 30% of H2O2.. Hydrogen peroxide consumption at 0.8ml~1.8ml, treatment of solution in accordance of high/low in the C O D . Cr value. Reaction: Continue heating, stirred for 15 min. The treated solution

changed to transparent from corrosive liquid which resulted termination of reaction. Then add coagulant 0.1g FeSO47 H2O [or Al2(SO4)3] and 0.2g CaO. Stirred for 1 min and it resulted precipitation of brown flocculation. Then leave it for precipitate. Proceed to filtration while in hot temperature .So as to attain clear and transparent water Remark: Wastewater of C O D Cr value which were higher, exceeded content of surfactant, achieved stability, C O D Cr value may not achieved effluent standard requirement during the first degration but repeated application of oxidation degration and coagulate adsorption treatment until it complied to the environmental protection effluent standards and requirement. 3.3.2. C O D Cr value sheet for Fluorescent pentrant wastewater treatment

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CODCr Waste water type Charcters Stability

Original waste water Separate oil from water Fenton Reagent 1st degration ~190-170 Clear water 2nd degration

Water wash type

Level 1,2

Yellow-green Turbid liquid Yellow-green Turbid liquid Yellow-green Turbid liquid Rose-red liquid

Motionless 24 hour lamination No lamination Easy lamination No lamination Easy lamination

~10000

~2500

Level 3,4

~10000

~2000
Clear Water

100-200 Clear Water

Post emulsifiable type

prewash

~20000

~50-190 190~600
Clear Water

Post emul. water wash Prewash & Post emul. water wash

~10000

~3000
Clear Water

~1000
Clear Water

Yellow-red Turbid liquid

~20000

~7000

~2000
Clear Water

~300
Clear Water

3.3.3. Before and after treatment of wastewater: See Picture 5, 6

Picture 5: Treatment of Yellow-green color wastewater

Picture 6: Treatment of Rose-red color wastewater

3.4. Conclusion and existing problem: (1) Compare with Activated sludge microbiological degration treatment method, the low dose Fenton reagent oxidation degration and coagulate adsorption treated the fluorescent Penetrant wastewater, advantages for chemical reaction which processed
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the wastewater: speedy reaction, short process flow, equipment easy to operate and etc. (2) Some post emulsifiable which cleansed wastewater that adopted separation of oil from water which were not required to undergo further treatment. CODCr value lower than 300 which were not required for treatment and can be directly effluent. If a number of fluorescent wastewater presented content of surfactant and CODCr value was higher showed that greater stability, one-time degration of CODCr value will not meet the effluent specification and requirements. So repeatedly degrading of oxidation process will consume greater amount of oxidizing agent. The technology must be further upgraded and researched in addition of adaptation of other degration method for assistance. (3) Wastewater for washable type and post emulsifiable fluorescence type shall be treated separately, separate oil from water, further by emulsion breaking shall be beneficial as it reduce the consumption of oxidation agent and related treatment cost. (4) Separated the waste oil shall be further do resource recovery or usage for fuel burning.

Reference: (1)Lin Zhenwang Metallic Penetrant testing mechanism and Penetrant agent molecular structure. 7th Asian-Pacific Conference on NDT. 1993 Shanghai China. p.728 (2)Lin Zhenwang Surfactants as Applied to Penetrant Test.US Materials Evaluation. Oct.2001 p.1205 (3)Lin Zhenwang Micro emulsion Penetrant agent manufacture 8th China NDT Conference. 2003 Suzhou China (4)Li Yafong Practical Waste Water Treat Technique. China Chemical industrial publishing house 2007

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