1、 MIL-DTL-98B 25 February 2013 SUPERSEDING MIL-D-98A 14 May 1962 DETAIL SPECIFICATION DIPHENYLAMINE, TECHNICAL This specification is approved for use by all Departments and Agencies of the Department of Defense 1. SCOPE 1.1 Scope. This specification covers technical diphenylamine (DPA) for use in the
2、 manufacture of smokeless powder. 2. APPLICABLE DOCUMENTS 2.1 General. The documents listed in this section are specified in sections 3 and 4 of this specification. This section does not include documents in other sections of this specification or recommended for additional information or as example
3、s. While every effort has been made to ensure the completeness of this list, document users are cautioned that they must meet all requirements cited in sections 3 and 4 of this specification, whether or not they are listed. AMSC N/A FSC 6810 DISTRIBUTION STATEMENT A. Approved for public release; dis
4、tribution is unlimited. Comments, suggestions, or questions on this document should be addressed to the Commander, U.S. Army ARDEC, ATTN: RDAR-QES-E, Picatinny, NJ 07806-5000 or emailed to usarmy.picatinny.ardec.list.ardec-stdzn-branchmail.mil. Since contact information can change, you may want to v
5、erify the currency of this address information using the ASSIST Online database at https:/assist.dla.mil. INCH-POUND PkkPOUNDPOUND Reactivated after 12 February 2013 and may be used for new and existing designs and acquisitions. Provided by IHSNot for ResaleNo reproduction or networking permitted wi
6、thout license from IHS-,-,-MIL-DTL-98B 2 2.2 Government documents. 2.2.1 Specifications, standards and handbooks. The following specifications, standards and handbooks form a part of this document to the extent specified herein. Unless otherwise specified, the issues of these documents are those lis
7、ted in the solicitation or contract. DEPARTMENT OF DEFENSE STANDARDS MIL-STD-1916 - DOD Preferred Methods for Acceptance of Product (Copies of these documents are available online at https:/assist.dla.mil from the Standardization Documents Order Desk, 700 Robbins Avenue, Bldg. 4D, Philadelphia, PA 1
8、9111-5094.) 2.3 Order of precedence. Unless otherwise noted herein or in the contract, in the event of a conflict between the text of this document and the references cited herein, the text of this document takes precedence. Nothing in this document, however, supersedes applicable laws and regulatio
9、ns unless a specific exemption has been obtained. 3. REQUIREMENTS 3.1 Conformance. A sample shall be subjected to conformance inspection in accordance with 4.1.2. 3.2 Properties of diphenylamine. The properties of diphenylamine shall be in accordance with the following: a. Setting point shall have d
10、egree centigrade not less than 51.70C and not greater than 53.00 C. b. Purity (alternate for setting point) shall have percent minimum of 99.5%. c. Insoluble material (residue) shall have percent maximum of 0.02%. d. Moisture shall have percent maximum of 0.2%. e. Acidity (as hydrochloric acid) shal
11、l have percent maximum of 0.005% f. Alkalinity (as sodium hydroxide) shall have percent maximum of 0.005%. g. Oxidizable material (as aniline) shall have percent maximum of 0.1%. 3.3 Workmanship. The diphenylamine shall be free of extraneous material, such as iron rust, wood particles, dirt, colored
12、 salts and other visible impurities. The color of diphenylamine shall be no darker than a light brown. Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-MIL-DTL-98B 3 4. VERIFICATION TABLE I. Requirements/verification cross reference. Method of Verific
13、ation Classes of Verification 1- Analysis 2- Demonstration 3- Examination 4- Test A First article B - Conformance Section 3 Requirements Description Verification Method Verification Class Section 4 1 2 3 4 A B 3.1 Conformance X X X 4.1 3.2.a Setting point X X 4.2.1 3.2.b Purity (alternate for settin
14、g point) X X 4.2.2 3.2.c Insoluble material (residue) X X 4.2.3 3.2.d Moisture X X 4.2.4 3.2.e Acidity (as hydrochloric acid) X X 4.2.5 3.2.f Alkalinity (as sodium hydroxide) X X 4.2.5 3.2.g Oxidizable material (as aniline) X X 4.2.6 3.3 Workmanship X X 4.2.7 4.1 Conformance inspection. 4.1.1 Lot fo
15、rmation. Lot formation shall be in accordance with the lot formation requirements of MIL-STD-1916, paragraph “Formation and identification of lots and batches” In addition, a lot shall consist of one or more batches of diphenylamine produced by one manufacturer, in accordance with the same specifica
16、tion, or same specification revision, under one continuous set of operating conditions. Each batch shall consist of the quantity of diphenylamine that has been subjected to the same unit chemical or physical process intended to make the final product homogeneous. 4.1.2. Sampling. 4.1.2.1 Packed by l
17、ot. A random sample of 8 containers shall be selected from each lot. When lots comprise 8 containers or less, each container shall be selected. Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-MIL-DTL-98B 4 4.1.2.1.1 Preparation of composite sample (a
18、fter packing). A primary sample of approximately 2 ounces of diphenylamine shall be removed from each of the 8 containers in order to equal 16 ounces. If there are less than 8 containers, a primary sample in sufficient quantity to equal 16 ounces shall be removed from each container. The individual
19、primary samples shall then be combined in order to form a homogeneous sample of 16 ounces. The determination shall be performed as specified in 4.2. If the composite sample fails to comply with any of the requirements specified the lot shall be rejected. 4.1.2.1.2 Prior to packing. Equal primary sam
20、ples shall be taken from different places and depths so as to form a representative sample of the lot. The individual primary samples shall then be combined in order to form a homogeneous composite sample of 16 ounces. The determination shall be performed as specified in 4.2. If the composite sample
21、 fails to comply with any of the requirements specified, the lot shall be rejected. 4.1.2.2 Molten DPA in bulk storage container. A sample of 2 ounces shall be taken in duplicate from a closed-out bulk storage tank. The closed-out bulk storage tank shall be circulated for one hour minimum prior to s
22、ampling to assure a representative sample. The bulk storage tank shall be assigned a lot number. No new molten DPA shall be transferred into the closed-out bulk storage tank. If the sample fails to comply with any of the requirements specified, the lot shall be rejected. 4.2 Methods of inspection. T
23、est methods and procedures shall be performed as specified in paragraph 4.2.1 to 4.2.6. 4.2.1 Determination of setting point. 4.2.1.1 Drying the sample. Grind 80 to 100 grams (gm) of the sample fine enough to pass through 1680 micron screen in American Standard Testing and Material E11 and dry for f
24、our hours at 40 degrees C., or melt the sample then add 20 gm. of anhydrous calcium chloride or sodium sulfate, and stir the mixture for 15 minutes at a temperature of 80 degrees C., allow the mineral salts to settle and pour off the molten diphenylamine. 4.2.1.2 Apparatus. A solidification point ap
25、paratus shown in Figure 1 shall be used with a 76 millimeter partial immersion number American Standard Testing and Material E1 type 92 C or equivalent thermometer with a range of 40 to 70 degrees C. Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-MI
26、L-DTL-98B 5 FIGURE 1. Solidification point apparatus. 4.2.1.3 Procedure. Transfer the dried sample to the inner test tube and melt it. Place the tube in the apparatus and adjust the thermometer so that the bulb is in the center of the diphenylamine. Stir the molten material vigorously by means of a
27、hand stirrer and carefully note the point where the temperature begins to rise when solidification begins. Observe the temperature every 15 seconds until the maximum reading is obtained. Observe the maximum reading as the setting point of the diphenylamine. 4.2.2 Purity by gas chromatography (altern
28、ate for setting point). A DPA control standard is analyzed every day by gas chromatography fitted with a split/splitless capillary inlet, flame ionization detector, and a non-polar capillary column. The % Purity analysis for the DPA control standard is plotted on an individuals/range statistical pro
29、cess control chart. The standard analysis must be in control prior to evaluating production samples. Out-of-control conditions are indicated by any one analysis exceeding the upper or lower control limits or a sequence of eight consecutive analyses on one side of the mean. An out of control data poi
30、nt would invoke a corrective action plan according to established trouble shooting guidelines. Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-MIL-DTL-98B 6 4.2.2.1 Procedure for making the DPA purity control standard. To a 25 ml volumetric flask add
31、 0.250 grams each of reagent grade indole, acridine and quinoline. These components are used to determine detection capability of the “lights” and “heavies” used in the % Purity determination and calculation. Dilute to mark with acetonitrile (ACN) such that the stock standard is equal to approximate
32、ly 10,000 ppm of each impurity. Place a 4 oz bottle on a 2-place balance and tare the balance. Add 5.00 grams of the DPA control (99.8%). Tare the balance. Add 70.00 grams of reagent grade acetonitrile. Add 50 l of stock standard. Shake to mix well. This standard contains approximately 0.01% of each
33、 impurity. Pour into five oz. bottles. Seal and label each bottle. 4.2.2.2 Method for determination of DPA % purity. Run a control standard by injecting 0.5 l of the control and integrating. The DPA analysis must be in statistical control prior to proceeding. Place a solid sample of the test materia
34、l in an 116o C convection oven to melt. Dilute 1.0 gram of the molten sample with 14.0 grams of reagent grade ACN. Inject 0.5 L of the diluted sample into a gas chromatograph fitted with a split/spitless capillary inlet and a flame ionization detector. Start the integrator. Report %Purity, %Lights,
35、and %Heavies. DPA purity input parameters shall be in accordance with Figure 2. % Purity = % Total area-(% Lights + % Heavies) Where: %Lights = total area% between solvent and DPA peak or A r e aS o l v e n tA r e aT o t a l 100D P Aa n dS o l v e n tb e t w e e nc o u n t sA r e a % Heavies = total
36、 area% after DPA peak or A r e aS o l v e n tA r e aT o t a l 100p e a kD P A a f t e rc o u n t sA r e a Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-MIL-DTL-98B 7 Figure 2. DPA purity analysis. 4.2.3 Insoluble material. Dissolve 25 gm. of the sa
37、mple in 100 milliliters (mL.) of benzene (specific gravity of 0.878 at 20 degrees/20 decrees C.) or ethyl ether (specific gravity 0.717 to 0.723 at 20 degrees/20 degrees C.). Filter through a tared filtering crucible and wash thoroughly with the solvent. Dry the crucible for one hour at 100 degrees
38、C., cool in a desiccator and weigh. Calculate the insoluble matter to percent of the weight of sample. 4.2.4 Moisture. Dry 4 to 6 gm. of the powdered material in a weighing bottle about 4 centimeters diameter. Heat for 4 hours at 40 degrees C. uncorked, and calculate the loss in weight to percent of
39、 the sample taken and observe as moisture. 4.2.4.1 Alternate moisture method by gas chromatography. Water in DPA is determined using a gas chromatograph fitted with a polymer-packed column and a thermal conductivity detector (or equivalent). The internal standard used in the analysis is 1000 ppm of
40、methanol (MeOH) in reagent grade acetonitrile (ACN). Approximately 500 ppm of water is added to the internal standard. The water addition increases the sensitivity of the analysis. The actual DPA Purity Analysis Gas Chromatograph Parameters HP 6890 Series Gas Chromatograph or equivalent Oven Setting
41、s: Oven Temperature Program: Temp 140 deg C # Rate(deg C/min) Final Temp (deg C) Final Time (min) Initial Time 2.00 min 1 20.00 240 2.00 Maximum Temp 320 deg C 2 25.00 260 4.00 Equib Time 0.50 min 3 0.00 Off Inlet parameters: Column Parameters Mode Split Restek RTX-5 30 M x 320 m X 0.25 Temp 250 deg
42、 C m (or equiv.) Pressure 15.6 psi Flow 2.7 ml/min Split ratio 75.0 Velocity 49 cm/sec Split flow 201 ml/min Mode Constant Flow Total flow 206 ml/min Gas Type He Detector parameters (Flame Ionization) Temp 275 deg C H2 Flow 40.0 ml/min Air Flow 400 ml/min Mode Constant Makeup Makeup flow 30.0 ml/min
43、 Makeup gas N2 Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-MIL-DTL-98B 8 concentration of MeOH in the ACN is determined by measuring the weight of the MeOH and the weight of the total internal standard solution. The actual water content of the in
44、ternal standard is determined by coulometric Karl Fischer (KF) analysis using a Brinkman 756 (KF) coulometric titroprocessor. The response factor between water and MeOH is calculated at the beginning of each shift and is determined by analyzing the internal standard solution with KF coulometric anal
45、ysis and by gas chromatography. The DPA sample is solvated in the internal standard solution, analyzed by gas chromatography and total water content of solvent and sample is determined. The water content of the DPA sample is calculated by subtracting the water content of the internal standard soluti
46、on from the total water content. 4.2.4.1.1 Procedure for making the methanol/water internal standard. Weigh 650.0 grams of dried acetonitrile (ACN) into a 16 oz. amber bottle using a 2-place balance. Using a- 4-place balance and appropriate weight of water to the bottle to make an approximate 500 pp
47、m water in ACN solution(weight of water = 0.0005 * weight of ACN) Using a 4-place balance and appropriate weight of methanol (MeOH) to the bottle to make an approximate 1000 ppm MeOH in ACN solution (weight of MeOH = 0.001 * weight of ACN). Record the exact weight of MeOH in the bottle. Determine the actual concentration of MeOH in the solvent as follows: Actual MeOH concentration ppm = g r a m sinw a t e rM e O HA C NofW t . ( 1 0*g r a m sinM e O HofW t .6 4.2.4.1.2 Method for determination of moisture by gas chromatography. Place oz. bottles and
