1、MIL-H-85477 68 W 7774706 0223650 L MILITARY SPECIFICATION HYDROXYL-TERMINATED POLYBUTADIENE MIL-H-85497(AS) 6 October 1981 IV- 59- 13- This specification is approved for use by the Naval Air Systems Command, Department of the Navy, and is available for use by all Departments and Agencies of the Depa
2、rtment of Defense. 1. SCOPE. 1.1 Scope. This specification establishes the requirements for two types of hydroxyl-terminated polybutadiene (HTPB). 1.2 Classification. The HTPB shall be of the following types: Type I Without Antioxidant. Type II With Antioxidant, Class 1 . With Antioxidant, 2,2-Methy
3、lenebs (4-Methyl-6-T-Butylphenol). Class 2 With Antioxidants, N-Phenyl-NI-Cyclohexyl- P-Phenylene Diamine and 2,5-Di-T-Butyl Hydroquinone. 2. APPLICABLE DOCUMENTS. 2.1 Issues of documents. The following documents of the issue in effect on date of invitation for bids or request for proposal form a pa
4、rt of this specification to the extent specified herein. Beneficial comments (recommendations, additions, deletions) and any pertinent data which may be of use in improving this document should be addressed to: Commanding Officer, Naval Air Engineering Center, Engineering Specifications and Standard
5、s Department (ESSD), Code 93, Lakehurst, NJ 08733, by using the self-addressed Standardization Docu- ment Improvement Proposal (DD Form 1426) appearing at the end of this document or by letter. IFSC 6810 I Q . : Licensed by Information Handling ServicesProvided by IHSNot for ResaleNo reproduction or
6、 networking permitted without license from IHS-,-,-MIL-H-85477 68 W 7797706 OL23b51 3 W MIL-H-85497 (AS) SPECIFICATIONS MILITARY MIL-A-85495 MIL-A-85501 STANDARDS MIL I TARY MIL-STD-129 MIL-STD-1218 Antioxidant, 2, 2I-Methylenebis (4-Methyl-6-t-Butylphenol). Antioxidant, N-Phenyl-NI-Cyclohexyl- P-Ph
7、enylene Diamine. Marking for Shipment and Storage. ACS Chemicals. DRAWINGS Naval Air Systems Command (Code Ident 30003) 639AS4608 Antioxidant, Hydroquinone Type. (Copies of specifications, standards, drawings, and publications re- quired by suppliers in connection with specified procurement function
8、s should be obtained from the procuring activity or as directed by the contracting officer.) 3. REQUIREMENTS. 3.1 Formulation. The formulation of Type II HTPB shall consist of a blend of Type I HTPB and antioxidants. Type II, Class 1 polymer con- tains the antioxidant specified in MIL-A-85495. Type
9、II, Class 2 polymer contains a 50:50 mixture (by weight) of the antioxidants specified in MIL-A-85501 and Drawing 639AS4608, respectively. 3.2 Chemical and physical properties. Chemical and physical prop- erties of the polymers shall conform to Table I. 2 f . Provided by IHSNot for ResaleNo reproduc
10、tion or networking permitted without license from IHS-,-,-MIL-H-85477 68 m 7977706 0323652 5 W MIL-H-85497(AS) 0.070 . . 40 2,500 . TABLE I. Chemical and physical properties. 0.080 o. 10 o. 10 70 3,600 . I* Property Hydroxyl, eq/100 grams Moisture, percent Peroxide, as H O , percent 22 Viscosity, po
11、ise at 25OC Molecular weight (GPC) Antioxidant, percent by weight Ty Min O. 075 . . 40 . 0.9 II - Max O. 085 o. 10 . 80 . 1.1 3.3 Stability. When packaged in accordance with 5.1 and stored at temperatures less than 38 degrees Celsius (OC), the Type I and Type II HTPB shall meet the requirements of t
12、his specification for a minimum of 12 months after acceptance. The shelf life may be extended for 6-month intervals after reacceptance testing for conformance to requirements of hydroxyl, moisture, and viscosity (Type I and Type 11) and antioxidant (Type II only) of Table I. 3.4 Type II HTPB. Type I
13、I, Class 1 and Class 2 HTPB shall be made from Type I HTPB which conforms to all the requirements of this speci- fica-tion and shall meet the hydroxyl, moisture, viscosity, and anti- oxidant limits of Table I after blending. 3.5 Toxic products and safety. Safety regulations and guidelines applicable
14、 to the use of HTPB should be complied with to preclude per- sonal injury and damage to equipment and facilities. 3.6 Workmanship. Workmanship shall be such that HTPB is uniform, of consistent high quality and free from visible contamination. 4. QUALITY ASSURANCE PROVISIONS. 4.1 Responsibility for i
15、nspection. Unless otherwise specified in the contract or purchase order (see 6.2.1), the contractor shall be responsible for the performance of all inspection requirements as specified herein. Except as otherwise specified, the contractor may utilize his own facili- ties or any commercial laboratory
16、 acceptable to the Government. The Government reserves the right to perform any of the inspections set forth in this specification where such inspections are deemed necessary to assure that supplies and services conform to prescribed requirements. 3 . Provided by IHSNot for ResaleNo reproduction or
17、networking permitted without license from IHS-,-,-I flIL-H-S477 68 = 9997706 0123653 7 MIL-H-85497(AS) 4.2 Sampling. The lot shall be sampled in accordance with Table II. TABLE II. Sampling plan, I I Number of composite samples Number of containers sampled (primary sample) Number of containers in lo
18、t 100 or more 51 - 99 11 - 50 1 - 10 10% (nearest whole number) 10 10 All 4.2.1 Primary samples. Physical properties tests shall be run on each primary sample (see Table 11). The material container may be sampled by use of a clean glass tube, rod, or pipet. If the container is small enough to be han
19、dled safely, the sample may be obtained by pouring. The smallest sample size possible that is consistent with test requirements shall be taken. The minimum sample size shall be two ounces. Glass containers shall be used for all liquid samples. Each sample shall be labeled with date, lot number, and
20、manufacturers container identification number. Failure of any primary sample to pass all of the physical-properties tests herein shall result in rejection of the lot represented. 4.2.2 Composite samples. Chemical properties tests shall be run on each composite sample. Divide the primary samples equa
21、lly into the number of composites shown in Table II. Blend each composite throughly by manipulation of the container. Label each composite with Roman numerals, also include date, lot numbers, and manufacturers container . identification numbers. The remainder of the primary samples shall be retained
22、 pending acceptance or rejection of the lot. Failure of any composite sample to pass all of the chemical-properties tests herein shall result in rejection of the lot represented. 4.3 Quality conformance inspections and tests. Quality conformance inspections and tests shall consist of the following:
23、a. Tests of Table I properties (see 4.4). b. Inspection of filled containers (see 4.6.1). c. Visual inspection (see 4.6.2). 4 Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,- MIL-H-5977 68 m 7797706 0123659 7 m 4.4 Tests methods. Tests shall be perfo
24、rmed using apparatus, re- agents, and procedures specified herein. The use of alternate apparatus, reagents, or procedures shall require prior written approval of the pro- curing activity. All American Chemical Society (ACS) reagents shall conform to MIL-STD-1218. 4.4.1 Hydroxyl equivalents/100 gram
25、s. 4.4.1.1 Apparatus. a. Iodine flask, 125-milliliter (mi). b. Micro buret, 10-ml. c. Steam bath. 4.4.1.2 Reagents. a. Acetic anhydride, ACS. b. Pyridine, ACS. c. Standardized alcoholic sodium hydroxide, 0.2 normal (N), pre- pared by diluting 15 ml of 50 percent NaOH (aqueous) with ethanol to 1 lite
26、r. Standardize against potassium acid phtha 1 a te d. Phenolphthalein, 1 percent in ethanol. 4.4.1.3 Determination of hydroxyl equivalents/100 grams (gm). Weigh accurately 1.0 gm of sample into a 125-ml iodine flask. Weigh 1.0 gm of sample into another similar flask for acid value. Pipet accurately
27、5 ml of acetic anhydride-pyridine mixture. NOTE: Acetic anhydride-pyridine mixture deteriorates on standing. Prepare fresh mixture, 1 part acetic anhydride to 31 parts pyridine, of sufficient quantity for daily needs) into each of two flasks, the sample flask and another similar flask for the blank.
28、 Swirl to dissolve the sample (flask may be warmed if necessary), moisten the stopper with pyridine and insert loosely into the flask. the acid value flask. Place all flasks onto a steam bath and heat for 2 hours. flask and continue heating for 10 minutes. Remove flasks from the bath and allow to co
29、ol to room temperature. Add 50 ml of pyridine to each flask, making sure that the walls of the flasks are washed down. Swirl Pipet 8 ml of pyridine into At the end of this period, add 2 ml of distilled water to each 5 Provided by IHSNot for ResaleNo reproduction or networking permitted without licen
30、se from IHS-,-,-MIL-H-85q77 68 7777706 0323655 O W -I to dissolve the sample (flask may be warmed if necessary). Add 1 ml of phenolphthalein indicator to each flask and titrate to a persistent pink with standardized alcoholic sodium hydroxide solution. Calculation: E) N BxC D 10 x B (A+- Hydroxyl eq
31、uivalents/100 gm = where A = volume of sodium hydroxide for blank, ml B = weight of sample, gm C = volume of sodium hydroxide for acid value, m1 D = weight of sample for acid value, gm E = volume of sodium hydroxide for sample, ml N = normality of sodium hydroxide Report the hydroxyl equivalents/100
32、 gm to the nearest 0.0001 unit. 4.4.2 Moisture. 4.4.2.1 Apparatus. Beckman “Aquameter,“ Model KF-4, or equal. 4.4.2.2 Reagents. a. Pyridine, ACS reagent. b. Chloroform, ACS reagent. c. Karl Fischer (I) reagent, stabilized, water equivalent of 2.0 to 3.0 milligrams/milliliter (mg/ml). . 4.4.2.3 Deter
33、mination of moisture. To the reaction beaker containing 60 ml of 1:l neutralized pyridine-chloroform solution, add from a dis- posable syringe 5 to 8 gm of sample which is weighed by difference to the nearest 0.01 gm. The stirrer should be off while adding the sample. 6 Provided by IHSNot for Resale
34、No reproduction or networking permitted without license from IHS-,-,-MIL-H-85q97 68 W 7999906 0323656 2 W MIL-H-85497 (AS) Turn on the stirrer to the same position used in the neutralization. Titrate automatically by pressing the titrate button to a 30-second end point. Calculation: VxE 10 x w Perce
35、nt moisture = where V = volume of KF reagent, ml E = water equivalent of KF reagent, mg/ml W = weight of sample, gm Report the moisture to the nearest 0.01 percent. 4.4.3 Peroxide. 4.4.3.1 Apparatus. a. Buret, 25-ml. b. Reflux condenser, 300-millimeter (nun), with 24/40 tapered stopper joints. c. He
36、ating mantle, 250 ml, Glas Col, or equal. d. Flat bottom flask, 250-ml with 24/40 tapered stopper joint, or equivalent. e. Magnetic stirrer, variable speed, with Teflon coated, stirring bars, or equal. f. Ice or cold water bath. 4.4.3.2 Reagents. a. Glacial acetic acid, ACS reagent. b. Chloroform, A
37、CS reagent. c. d. Standardized sodium thiosulfate solution, 0.01 N. Potassium iodide solution (20 gm KI/100 ml of water-methanol 1:3). e. Indicator, (Thyodene, Magnus Chemical Company), or equal. 7 Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-4.4.
38、3.3 Determination of peroxide. Weigh accurately 5.0 gm of sample into a 250-ml flask. Add 25 ml of chloroform, 5 ml of glacial acetic acid, and 10 ml of potassium iodide solution. Add a stirring bar and attach the flask to the reflux condenser. Boil the contents of the flask for 3 minutes while stir
39、ring. Cool immediately in an ice bath or cold water bath. Wash down the condenser and sides of the flask with 25 ml of distilled water. ardized sodium thiosulfate solution until one drop makes the solution clear. Add 0.4 gm of thyodene and titrate with stand- Calculation: V x N x 3.4 W Peroxide, as
40、H202, percent = where V = volume of sodium thiosulfate, ml N = normality of sodium thiosulfate W = weight of sample, gm Report the peroxide to the nearest 0.01 percent. 4.4.4 Viscosity. 4.4.4.1 Apparatus. a. Viscometer, Brookfield, Model HBF, multispeed, with spindle number 2, or equal. b. Water bat
41、h with thermostatic control to kO.lC in the range from 20 to 5OOC. 4.4.4.2 Reagent. Standard viscosity oil, OB type, National Bureau of Standards or equal for viscometer calibration at 25OC. 4.4.4.3 Standardization of viscometer. Using the standard viscosity oil as sample, and following the procedur
42、e for determination of viscosity (4.4.4.4), determine the average scale reading. Multiply this reading by 6.4 to obtain value in poises. 4.4.4.4 Determination of viscosity. Slowly pour approximately 550 ml Carefully place the spindle of sample into a 600-ml Griffin beaker or other suitable container
43、. Take care to keep trapped air at a minimum. in the sample, again attempting to avoid air entrapment. Immerse the beaker in the constant temperature water bath to about level with the 8 Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-L MIL-H-85Ll77
44、68 9 777770b 0123658 b MIL-H-85497(AS) surface of the sample, and bring the temperature of the bath to 25 fO.lC. Stir the sample slowly at intervals to aid in reaching the temperature equilibrium. When the temperature of the sample remains within the equilibrium range for 5 minutes, set the spindle
45、speed of the viscometer to 5 rpm, attach the spindle to the viscometer, attach the viscometer to a support post, and center the spindle in the beaker. Adjust the spindle index mark to the surface of the sample, and take five readings of the instrument at 1-minute intervals. Calculation: Viscosity, 2
46、5OC, poises = f x R where f = ratio of stated oil viscosity (poises) to measured oil viscosity (poises) R = average scale reading at 25OC for sample Report the viscosity at 25OC to the nearest poise. 4.4.5 Molecular weight by gel permeation chromatography (GPC). 4.4.5.1 Apparatus. a. Liquid chromato
47、graph (LC), Perkin-Elmer Model 601, or equal, equipped with dual 3,000-pound force per square inch pumps, gel permeation columns, micro styragel, 1-500, 2-1,000, 1-10,000 Angstrom unit porosities, or their equal. b. Refractometer, Perkin-Elmer Model 1107, or equal. c. Recorder, Perkin-Elmer Model 56
48、, with variable millivolt range, or equal. d. Stainless pressure filter holder, Millipore Catalog Num- ber XX30-012-00, or equal. e. Filters, Millipore Catalog Number LSWP01300, or equal. f. Volumetric flasks, 100-ml. g. Syringe, 10-cubic centimeter (cm ). 3 4.4.5.2 Reagents. a. Chloroform, ACS anhy
49、drous. 9 Provided by IHSNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-I MIL-H-85477 b m 777770b Ol123b57 8 m MIL-H-85497(AS) b. Standard HTPB polymer of known molecular weight distribution. The standard is established as follows: (1) Preparatively fraction a lot of HTPB into 8 to 10 fractions. (2) Determine the molecular weight of each fraction by vapor
