CN106370689A - Detection method of change rule of plastisol moulding degree of nitro-cotton in high-solid-content propellant - Google Patents
Detection method of change rule of plastisol moulding degree of nitro-cotton in high-solid-content propellant Download PDFInfo
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Abstract
The invention discloses a detection method of change rule of plastisol moulding degree of nitro-cotton (NC) in a high-solid-content propellant. The method includes the steps of: a) firstly aging the propellant at a certain temperature for different times t to obtain a series of samples, and processing the samples into blocks being not more than 15*10*10 (mm*mm*mm) in size, and placing the sample blocks in special test tubes and performing low field nuclear magnetic detection to obtain transverse relaxation times T2 of the samples; and b) with the T2 as y-coordinate and t as x-coordinate, drawing a T2-t curve, which can reflect the change rule of the plastisol moulding degree of the NC in the samples with the t. The method, during detection, is free of change on spatial status of the NC and can actually show the plastisol moulding degree of the NC. The change rule of the plastisol moulding degree of the NC in the propellant with the t can serve as a basis of determining security service life of the propellant. The method also is a researching mean, wherein formula of the propellant can be regulated or manufacturing process can be improved by comparing the plastisol moulding degree of the NC in the propellants having similar formulas or being prepared through different technologies.
Description
Technical field
The invention belongs to gunpowder physicochemical property detection field, relate generally in high solids content propellant powder that nitrocotton is molten to mould degree
Detection method, the molten detection method moulding degree Changing Pattern of nitrocotton more particularly, in sample.
Background technology
Nitrocellulose is the product that cellulose and nitric acid occur esterification, and its molecule skeleton symbol is [c6h7o2(oh)3-x
(ono2)x]n.From the appearance, nitrocellulose and the cellulose before nitrification do not have too big difference, are a kind of white or micro- Huangs
Solid fabric shape material, tasteless.In China, because mostly nitrocellulose is prepared for raw material using purified cotton, custom
It is called nitrocotton nc.
A large amount of at present gun propellants using mainly have single-base gun propellant, double-base propellant, naked nitric acid ester propellant powder,
Three bases and nitramine gun propelllant etc. are several, and they are all with nc for skeleton and main adhesive, mould so that inertia and energetic plasticiser are molten
The system of (also referred to as plasticising, plasticizing), by add the speciality polymer material that a certain amount of high-energy solid explosive forms.
Nc molecule is linear polymeric, and its melt temperature is higher than its decomposition temperature (about 170 DEG C), so can not be with traditional
Thermoplastic method molding, but need to be processed molding in the molten state of moulding.
In propellant powder, the strand of nc is actual is in plasticizer concentrated solution, and nc is in physical crosslinking shape in propellant powder
State, is not chemically crosslinked a little.So the molten of nc moulds degree with nc self character (if nitrogen content, the degree of polymerization are to dissolving in propellant powder
The impact of property), the plasticizer dissolubility and nc spatiality (physical crosslinking state) in plasticizer concentrated solution have relation.
Ambient temperature during propellant powder storage, and the molecule knot of the solid constituent (nitroguanidine, RDX, HMX etc.) added
Structure, particle diameter etc. also can produce impact to the molten degree of moulding of nc in propellant powder.
In high solids content propellant powder system, the content of nc and plasticizer is considerably less than single-base powder and double-base powder, substantial amounts of solid
Body component (as nitroguanidine, RDX, HMX etc.) needs to be uniformly filled in nc skeleton, and therefore nc needs to be in preferably
Molten mould state, the molten degree of moulding of nc affects substantially on the physical and mechanical property of high solids content propellant powder.
Propellant powder physical and mechanical property refers to propellant powder during manufacturing, store, transport and using, by various load
The property of produced deformation and destruction during effect.Propellant powder requires there are the mechanical properties such as certain comprcssive strength, compression ratio.Due to
Propellant powder relies on that plasticizer is molten to mould nc and curing molding, and therefore in research propellant powder, the molten of nc moulds degree, for propellant powder technique
The determination of parameter is significant, is also the basis place of other performances such as research propellant powder physical mechanicses further simultaneously.
Nc has semi-rigid strand, and extremely strong intramolecular, intermolecular hydrogen bonding act on so as to high temperature rigidity is low, low
Warm poor toughness.Many organic substances to nc can limited dissolving swelling, optional one pack system plastification solvent or multicomponent plasticising
Solvent nc is carried out molten mould, improve its process industrial art performance, or improve the physical and mechanical property of nc product, thus widening its application
Field.
Say from microcosmic angle, the molten substantially plasticizer molecule of moulding of nc diffuses between nc strand so as to segment
Spacing increases, and Mobility of the chain segments forms the structural transformation process of physical cross-linked network, the speed of this process and plasticizer molecule
Diffusion rate is closely related.
From the perspective of thermodynamics, molten the moulding of nc belongs to plasticizer small molecule and diffuses between nc macromole, the two
The mutually immiscible process forming macromolecule concentrated solution, its molten compatibility moulded between speed and effect certainty and component is closely related.
Effect between nc and plasticizer is not to complete moment, but first local action, then spread to intramolecule, entirely
Nc Plasticising system reaches to balance each other and takes long enough.
Plastification solvent and nc contact, infiltration and solvent molecule in diffusion process to infiltration in the middle of nc strand and with chain on
There is solvation in functional group.In solute nc and plastification solvent system, there are three kinds of different molecular separating force, one is between solute molecule
In, two is power between solvent molecule, and three is power between solute and solvent molecule.Only mix during beginning, spread.Because nc divides than solvent
Son is big many, and movement velocity is very slow, solvent molecule very little, can will soon creep in nc, and after nc lyosoption, generation volume
Expand (swelling), thus segment is pushed open, so that intermolecular force is slackened.Solvent molecule continues to pierce, so that having least a portion of
Macromole is segregated into being dissolved in solvent.Acted on due to above, reduce flowing temperature and the glass transition temperature of nc,
It is made to have plasticity.
Nc under room temperature is in glassy state.Glass transition temperature is nc molecule segment from frozen state to movable
The transition temperature of state.Above this temperature, nc enters elastomeric state, shows the deformability more much bigger than during glassy state.
From texture, nc belongs to continuous phase in whole propellant powder compound system, and the quality of its inherent quality is right
Propellant powder physical and mechanical property has important and directly affects.Because nc is the product that natural cotton fiber and nitric acid occur esterification
Thing, so nc structure is extremely uneven, is mainly manifested in polydispersity, the inhomogeneities of itrate group distribution of the degree of polymerization
Two aspects.
The nc degree of polymerization is often in 250～1000 scopes.In nc, high polymerization degree component ratio is bigger, and the molten state of moulding more difficult to get access is entered
Row processing, will apply bigger load in spinning or extrusion process, and the material rigidity obtaining is also higher；Low polymerization degree in nc
When component ratio is larger, be easier to carry out molten mould, but the product strength obtaining is less.
The nc of nitrogen content 11%～13.5% is used for the history of the existing last 100 yearses of military field as book with discs, is weight
One of explosive wastewater raw material wanted.Nc nitrifies poor quality, itrate group skewness, can lead to many adverse consequencess, such as
Solubility property deteriorates, solution " coarse ", and poor to plasticizer absorption performance, stability is also bad, easily certainly fires during storage
Single-base powder, double-base powder or even triple base propellant fried, that manufactured with this nc, technique is difficult to specification.Gel, plasticizing, calendering and spiral shell pressure are all
Highly difficult.Particularly with highly filled propellant powder such as high nitrogen propellant powder, nitramine gun propelllants, nc nitrification quality inhomogeneities will be led
Cause poor processability, process safety is poor, and Storage period is short, powder column resists outer loading capability low, stores and serviceability and safety
All it is deteriorated.
In addition, nc degree of esterification is higher, nitrogen content is higher, and energy is higher, but the thing followed is to be more difficult to plasticized, molding
Processing is also more difficult, and powder column mechanical property is also more difficult to ensure.
In propellant powder, the molten degree of moulding of nc is except having outside the Pass with nc self character, also relevant to the dissolubility of nc with plasticizer.
From the impact mechanical performance of macromolecular material, the shock resistance improving macromolecular material should strengthen its punching
Hit toughness.Polymer Systems for plasticising, from superplastiser and can adjust plasticizer consumption strengthening its toughness.
The fifties, multiple nc energetic plasticisers, in order to change the mechanical property of m30 nitroguanidine triple-base propellant, were once studied by the U.S..
Nitroglycerine ng, diethlene glycol dinitrate, triethylene glycol dinitrate, dinitrotoluene (DNT) dnt, Ji Na are energetic plasticisers,
Dibutyl phthalate dbp is inert plasticizer, and they can be mixed with nc very well in molecular level.
Ng is the good solvent of nc, and the Pi Luomian being 12.6% for nitrogen content can be miscible with arbitrary proportion, for high nitrogen
Amount nc, its dissolubility also reaches more than 60%.Dnt is widely used as the plasticizer of nc, improves plasticity and the moisture resistance of gunpowder,
Improve the compatibility to nc for ng or Ji Na.The addition of dbp improves the solubility property of ng and nc, and it can be dissolved each other with ng arbitrary proportion.
Ji Na has preferable plasticizing capacity to nc, is particularly that ng can not be than to the plasticizing of the nc of high nitrogen quantity.Vaseline is the knot of nc
Structure plasticizer, with nc and immiscible, play the lubrication between supermolecule, so that producing larger deformation between macromolecule,
Make the easy processing and forming of nc.
Except above-mentioned described nc self character, plasticizer characteristic, in high solids content propellant powder nc molten mould degree also with
Physical crosslinking state (spatiality) in propellant powder for the nc has much relations.The external force that propellant powder is subject to aborning acts on,
And the environmental stress being subject in storage, all impact is produced on the physical crosslinking state of nc.
Molten the moulding of plasticizer and nc has carried out more research.For example plasticising can be recorded by dynamic rheological property experiment
Agent is molten to mould storage moduluss g during nc ' dynamic time spectrum, judge that the molten of nc moulds journey according to g ' versus time curve
Degree, g ' numerical value is bigger, and nc molten is described, and to mould degree bigger.
Nc and plasticizer are made after propellant powder finished product as one of raw material, no longer have mobility it is impossible to be flowed with dynamic again
The experiment such as change carries out the molten detection moulding degree of nc.There is presently no and suitably can be used for the molten nothing moulding degree of nc in propellant powder finished product
Damage detection method.
For the high single, double base propellant powder of nc content, research worker, Producer and user are all less concerned about that the molten of nc is moulded
Degree.This is because in single, double base gun propellant formulation nc content all more than 50% (quality), even as high as 98% (quality),
A small amount of solid additive, will not change the molten of nc and mould rule and molten mould effect.And cannon operating pressure typically all exists at that time
Below 300mpa, in cannon coyote hole, propellant powder loading density is less, and preferably, ignition condition is gentleer, therefore propellant powder for breathability
Grain stressing conditions are also gentleer.Based on above 2 points, usual propellant powder production unit is not checked to the mechanical property of its product,
Never there is matters of aggravation.
Three guanidine propellant powder are to add a kind of new routine energetic emission obtained from nitroguanidine nq on the basis of double-base powder
Medicine, can eliminate heavy caliber howitzer, gun produced barrel erosion, gun muzzle in using general double-base powder and single-base powder
The defects such as flame, flareback.
Nc content in three guanidine gun propellant formulations has dropped to less than 20% (quality), simultaneously because three guanidine medicine kindlings are relatively
Conventional propellant powder is poor, and therefore, the ignition intensity of the ignition system being matched with it is strengthened therewith, necessarily makes during igniting to powder
Impulsive force increases therewith.Just because of the mechanical property of three guanidine propellant powder (U.S. m15 and m17 propellant powder) is not so good as conventional single, double base
Propellant powder, particularly cryogenic mechanics performance are poor, and major accident once occurred in 76mm cannon.By adjustment formula, improve
Manufacturing process, improves the mechanical property of three guanidine propellant powder, derives mechanical property preferable m30 and m31 series emissions medicine, washes in a pan
Eliminate former m15 and m17 propellant powder, made the mechanical property of three guanidine propellant powder substantially meet the requirement of conventional weapon.But, on
The sixties in century High-pressure gun development, employ high loading density powder charge so as to reach 0.80g/cm3Above high filling
Density, powder charge poor air permeability, ignition condition is severe, easily causes the igniting of powder charge local and produces pressure wave.Can make between powder or powder
Produce powerful active force with bullet bottom or bore wall, the mechanical property of three guanidine propellant powder is at that time difficult to meet demand, the therefore U.S.
Propose development and " there is the high gun pressure weapon novel emission of double-base propellant mechanical property and three guanidine propellant powder energy responses
The requirement of medicine ".
Since occurring in that three guanidine medicines and high-performance cannon (high gun pressure, high initial speed), inner trajectory during artillery shooting is anti-
Chang Xianxiang happens occasionally, or even occurs thorax swollen and bombing bore accident.These phenomenons are subject to propellant powder circle, cannon and ammunition circle quickly
Greatly pay close attention to, and carried out substantial amounts of research, result shows that this is relevant with the pressure wave in cannon thorax.It is demonstrated experimentally that cannon exists
In actual shooting course, Propellant Bed non-momentary area ignition, in thorax, then (in coyote hole), form multiple pressure waves.Pressure wave
May result in propellant powder fragmentation, causing to make the acute liter of pressure because combustion front increases severely, affecting ballistic stability, thus result in pressure wave
Destruction.
Since the seventies in last century, the direction of low vulnerability gun propellant (lova propellant powder) Yi Shi various countries propellant powder development,
For state-of-the art, the representative formula of lova propellant powder be exactly by up to 70%～80% solid explosive (for example
Rdx, hmx) and the macromolecular material composition less than 20% for the content, or even the macromolecular material of the formula having only about 16%.Cause
This, one of development high energy, key technology of low vulnerability gun propellant formula are how to improve the mechanical property of propellant powder, otherwise
High energy, low vulnerability gun propellant formula just cannot be realized.
Mechanical property due to high solids content propellant powder is subject to higher attention, so developing corresponding method of detection.At present,
Assessment to propellant powder mechanical property and detection still rest on compressibility of materials test and shock resistance test, respectively with various
At a temperature of compressive strength, compression ratio and impact strength represent.On the basis of these tests build on conventional material test,
It can evaluate the ability that destruction resisted under external force by material, but this evaluation methodology cannot rationally and reliably be commented
Determine the mechanical property of propellant powder.Since the seventies in last century, in the particularly later stage eighties, various countries have developed a series of height that measure should
Under variable Rate, the mechanical response of propellant powder is it is intended to search out a kind of characteristic number to evaluate the sound of the mechanics under propellant powder high strain rate
Should, such as Gas Gun impact test, mechanical test of dropping hammer, servo-hydraulic test, sled test.The domestic Gas Gun that is also adopted by touches
Hit instrument, the device that drops hammer, Thelma Hopkins (hopkinson) bar and big gun and penetrate the means such as impinger and combine with closed bomb vessel, research
Propellant powder mechanical response in a dynamic condition.It has been also carried out the research of some new methods simultaneously, but still in developmental stage.
In high solids content propellant powder, nc content is greatly reduced, and in propellant powder, the molten Changing Pattern moulding degree of nc is to propellant powder
Effect on Mechanical Properties become big, set up the molten of nc in high solids content propellant powder and mould degree detecting method, obtain the molten degree of moulding of nc and become
Law, is on the one hand conducive to estimating, judges the safe operating life in terms of mechanics for the propellant powder, on the other hand can be used for developing
Novel emission medicine, by adjusting plasticizer species, quantity and processing technique, obtains physical and mechanical property preferably new large arch dam
Amount propellant powder.
Content of the invention
In high solids content propellant powder, nc adhesive is less, along with when using, mechanical environment is severe, with single, double base propellant powder
Compare, the mechanical property of high solids content propellant powder is paid special attention to.Nc is molten to mould that degree is good, and the toughness of propellant powder is strong, not fragile
Broken, nc is molten to mould that degree is poor, and the poor toughness of propellant powder is easily broken.So the molten degree of moulding of nc can speculate propellant powder in propellant powder
The quality of mechanical property.
In order to obtain the molten Changing Pattern moulding degree of nc in high solids content propellant powder, the present invention takes following technology solution party
Case:
(1) by propellant powder sample at a temperature of certain heat ageing different time t, obtain series of samples, series of samples is placed on sample
In product bottle, cover tightly lid and be stored at room temperature；
(2) series of samples is processed into respectively the bulk that size is not more than 15mm × 10mm × 10mm, is respectively put into low field
In nuclear-magnetism Special test tube；
(3) Special test tube placing sample is respectively put into the sample cell of low field nuclear-magnetism, treats set by sample and sample cell
When temperature is identical, low field nuclear-magnetism is used to detect, low field nuclear-magnetism operating condition is respectively: hydrogen spectrum, resonant frequency 21.7hmz, using certainly
Cycle wave train cpmg continuous sampling, obtains the one pack system T2 t of sample with t-invfit software2；
(4) each sample duplicate detection 3～5 times, calculate t2Meansigma methodss, with t2Meansigma methodss are made for abscissa for vertical coordinate t
Figure, obtains t2- t curve；Nc is molten mould degree preferable when, t2Numerical value is larger, nc is molten mould degree poor when, t2Numerical value is less, t2- t is bent
Line can reflect in sample that nc is molten moulds the Changing Pattern with ageing time t for the degree.
Method as defined above it is characterised in that when propellant powder sample itself present less bulk when, can special examination in the past
The sample of 2～4 pieces of aging same times is put into so that sample cumulative volume is about 15mm × 10mm × 10mm in pipe.
Method as defined above is it is characterised in that can also first become to be not more than 15mm × 10mm × 10mm's by sample treatment
Bulk, then carries out heat ageing and subsequent detection again.
Method as above, it is characterised in that described propellant powder sample, can also be the propellant powder sample of different process
Or the propellant powder sample that formula is similar, that now obtain is t2- process curve or t2- formula curve, can research and produce technique not
With or propellant powder when formula is different in the molten of nc mould situation.
Method as defined above, it is characterised in that described propellant powder sample, can be heating same time under different temperatures
Propellant powder sample, that obtain is t2- temperature curve, can study at different temperatures molten of nc in propellant powder and mould situation.
Method as defined above is it is characterised in that when detecting series of samples, described low field nuclear-magnetism sample cell temperature should keep
Unanimously, should not be higher than 55 DEG C, during sample detection, heated time should be consistent, and when sample cell is more than 45 DEG C, each sample always detects
The volatilization in case liquid plasticizer in sample in detection process is heated that time does not exceed 0.5h, in change sample, nc is molten moulds shape
State.
The inventive method, has the advantage that
(1) spatiality of nc in propellant powder can not be destroyed, obtain the molten Changing Pattern moulding degree of nc；
(2) in propellant powder, the molten Changing Pattern moulding degree of nc can react the change of propellant powder mechanical property, mechanical property
Impact ballistic performance, ballistic performance is closely related with safe operating life, so the molten degree of moulding of nc can be used for judging propellant powder
Safe operating life；
(3) it is alternatively arranged as a kind of research meanses, mould degree by nc is molten in relatively different propellant powder, adjust in propellant powder and increase
Mould the kind of solvent, composition, quantity or improve manufacturing process, obtain and there is the new high solids content of more preferable physical and mechanical property send out
Penetrate medicine product.
With reference to embodiments and accompanying drawing the present invention is described in further detail.
Brief description
Fig. 1 is the T2 t of sample a and sample b2Change curve with ageing time；
Fig. 2 is plasticizer (nitroglycerine ng) in sample a, in sample b plasticizer (nitrine nitramine dianp, ng) residue
Rate αiChange curve with ageing time；
Fig. 3 is the infrared spectrogram of insoluble solids and nitrocotton nc in sample b；
Fig. 4 is the T2 t of sample c2Change curve with ageing time；
Fig. 5 is the surplus ratio α of plasticizer (ng, diethyl phthalate dep) in sample ciChange with ageing time is bent
Line；
Fig. 6 is the T2 t of sample d and sample e2With the change curve driving the molten time.
Specific embodiment
Embodiment 1
New energetic plasticiser nitrine nitramine dianp is in a liquid state at normal temperatures, not only have high energy, high burn rate, low burn temperature,
The advantages of combustion gas relative molecular mass is little, gas production is big, impact sensitivity, friction sensitivity and heat sensitivity are respectively less than the conventional plasticising containing energy
Agent ng.
The mechanical property to propellant powder for the dianp, especially cryogenic mechanics performance improve significantly compared with ng, use
Dianp replaces part ng in standard propellant powder, makes modified double base or modified triple-base propellant, has produced in batches.
The research purpose of the present embodiment is that contrast dianp, ng mould effect to the molten of nc in high solids content propellant powder.
Using heat aging method, accelerate the decomposition of nc, ng, dianp in propellant powder sample, periodically take out sample, detection obtains
Obtain t2- t curve.Additionally, using the nc in infrared spectrum, elementary analysiss, liquid chromatographic detection propellant powder sample, ng,
Dianp, by them in the sample with the Changing Pattern of ageing time, analysis interpretation t2How-t curve reacts high solids content
In propellant powder, nc is molten moulds degree Changing Pattern.
1. preparation of samples
By certain conventional three guanidine propellant powder sample a, (in sample, the mass fraction of nc, ng is respectively 30%, 16%, remaining component
For solid) in the ng of mass fraction 6% be substituted for dianp, make three folded guanidine propellant powder sample b, be respectively prepared burning zone thickness
2mm aperture 2mm length is the single hole tubular powder of 15mm, respectively prepares 9.
2. sample heat ageing
Because propellant powder thermally decomposes under the conditions of nature or storage at normal temperature relatively slowly it is impossible to carry out so being up to decades
Test, generally each state all adopts high temperature accelerated aging test, periodic detection correlated performance, obtains experimental data, obtains related
Each component changes of contents rule and performance variation law.This test is also adopted by high temperature accelerated ageing propellant powder sample, accelerate nc,
The change of ng, dianp.
Sample a, b are individually placed in two rustless steel containers, seal respectively and put into 95 DEG C of oven ageings.Aging
Open lid during to 0,3,5,8,12,17,22,27,34d, respectively take out 1, then again cover tightly continuation aging residue medicated strip, directly
All take out to sample during 34d.
3. determine low field nuclear-magnetism operating condition, obtain the t of sample2- t curve
Low field nuclear-magnetism is mainly by relaxation behavior come the mobility of Study Polymer Melts molecule.t2Handed over by inside spin system
Transducing amount causes, and reflects the chemical environment residing for Hydrogen Proton on sample interior polymer, with the binding force suffered by Hydrogen Proton and
Its degree of freedom is relevant, and the constraint degree of Hydrogen Proton is inseparable with the internal structure of sample.Hydrogen Proton carry the baby bigger or
Degree of freedom is less, t2Shorter.Propellant powder sample is detected by low-field nuclear magnetic resonance instrument, investigate in sample molecule suffered by nc it
Between binding force, the nc bigger t of constraint that is subject to of motion2Less.
t2Also relevant with sample temperature during detection, even same sample, temperature higher t during detection2Value is bigger, and this is
Because temperature more macromolecule is more active.In high solids content propellant powder, nc high polymer content is few, and raising detection temperature can increase t2Letter
Number value.But the energetic plasticiser in high solids content propellant powder has low volatility and is heated from urging decomposability, works as heating temperature
During higher than 60 DEG C, urge loss that decomposability bring substantially increase due to volatility with certainly.If so temperature is too high during detection, meeting
Reduce plasticizer loading, in change sample, nc is molten moulds state, leads to testing result to be unable to response sample truth, and detects
During potential safety hazard larger.Therefore when detecting high solids content propellant powder sample, sample heating temperature should not be too high, i.e. low field
Nuclear-magnetism sample cell temperature should not be higher than 55 DEG C, and when sample cell temperature is more than 45 DEG C, whole detection times of each sample are unsuitable
More than 0.5h.If t2Signal value is not ideal enough, and sample noise is smaller, when figure is bad, when should adjust repeated sampling wait
Between the instrument parameter such as tw, multiple scanning frequency n s, echo number nech, and can not rashly sample cell temperature be adjusted too high.
This test employs Shanghai Niu Mai electronics scientific technology co micro-mr-cl type low-field nuclear magnetic resonance analyser: hydrogen
Spectrum, resonant frequency 21.7hmz, using cpmg continuous sampling, repeated sampling waiting time tw=2500ms, echo number nech=
5000, multiple scanning frequency n s=64 time, spectrum width sw=200khz.Sample cell temperature is 35 DEG C.Obtained with t-invfit software
One pack system T2 t to sample2.The t of sample a, b2- t curve is shown in Fig. 1.
4. plasticizer loading is with the Changing Pattern of ageing time
T for reasonable dismissal sample2- t curve is how nc is molten in response sample moulds degree Changing Pattern, have detected
Plasticizer surplus ratio in each sample.
In sample a, plasticizer is ng, and in sample b, plasticizer is dianp and ng.With in liquid chromatograph external standard method detection sample
Dianp, ng content [Agilent company of the U.S. 1120compact lc high performance liquid chromatograph: UV-detector, Detection wavelength
210nm；Mobile phase is acetonitrile solution (volume ratio is 65:35)].With dianp, ng surplus ratio αi(detection level contains with initially
The ratio of amount) map for abscissa for vertical coordinate ageing time time, obtain Fig. 2.As seen from Figure 2, sample a and sample b
In plasticizer surplus ratio all gradually decrease with the prolongation of ageing time.
5.nc content is with the Changing Pattern of ageing time
Acetone not only can dissolve the small organic molecules such as ng, dianp, or the optimum solvent of nc.Propellant powder sample is divided
Aging 0,3, the sample of 5d Yong not find after acetone soak 24h:, all dissolving is in acetone for nc, nq, ng etc.；After aging 8d
Sample, has part chip not dissolve in acetone, the longer sample of ageing time, insoluble particles are more.
Add water (volume of water is 1/3rd of acetone volume) respectively in the acetone soln of sample, due to acetone water
The solvability of nc is weakened, the nc being previously dissolved in acetone can separate out in gel state.Find through observing: unaged sample
Nc is had to separate out in solution, solution shows the distinctive polarization color of nc, but the longer sample solution of ageing time, nc separates out fewer.Say
The bright prolongation with ageing time, acetone-insoluble nc gradually decreases, the solids increase insoluble in acetone.Speculate that these are insoluble
The nc that solid mainly changes.When heating-up temperature is less than 100 DEG C, there is depolymerization, the generation of peroxide and water in nc
Three kinds of processes such as solution, therefore sample aging after acetone insoluble matter, be not singly the less nc of nitrogen content, but structure and nc phase
As more complicated analyte.
In not aged propellant powder, the molecular weight distribution of nc can be measured with gel chromatography, but propellant powder after aging certain time
Middle nc dissolubility is deteriorated, or even can not be dissolved by an organic solvent, so can not be detected with gel chromatography again.The present embodiment is with infrared
Spectrographic method and elemental analyser characterize to these insoluble matters.
Insoluble solids in aging 34d sample b are taken out from acetone water, cleans, dry in the shade, (beautiful with infrared spectrometer detection
State thermoelectricity Buddhist nun's high-tensile strength company nexus 870 Fourier transformation infrared spectrometer: kbr tabletting, scans 32 times, spectral region
4000cm-1～400cm-1, resolution 4cm-1), contrasted with nc standard spectrogram, seen Fig. 3.Insoluble solids as can be seen from Figure 3
Functional group as the functional group of nc, illustrate that insoluble solids are the residues after nc decomposes.
Detect aging 34d sample with elemental analyser (German elementar company vario el iii type elemental analyser)
Insoluble particles in product, insoluble particles nitrogen content 12.0% in insoluble particles nitrogen content 11.7% in a, b.Sample a and b makes when producing
The original nitrogen content of nc is 12.7%, and after sample a and b heat ageing are described, nc slowly decomposes, and nitrogen content declines, under nitrogen content
After dropping to a certain degree, acetone is no longer its good solvent.Nc analyte insoluble in acetone occurs after aging 8d, and with old
The prolongation of change time, the nc analyte insoluble in acetone gradually increases, and in other words, in propellant powder, the dissolubility of nc is increasingly
Difference.
6. the t of sample2In-t curve response sample, nc is molten moulds degree Changing Pattern
In propellant powder, the molten degree of moulding of nc is caused by two aspect factors: one, energy of thermal motion improvement is molten moulds degree；2nd, plasticising
Agent reduces, nc dissolubility variation can make molten degree of moulding be deteriorated.
The t of the change interpretation sample according to ng, dianp, nc2- t curve:
(1) aging initial
The propellant powder sample just produced, because production technology does not make that nc is completely molten to be moulded, so just started heat ageing
When, also there is nc and continue the molten phenomenon moulded in plasticizer, nc molecule continues to stretch after being heated in plasticizer, is formed more equal
Even physical cross-linked network.In sample, nc starts slowly to decompose, dissolubility do not have be deteriorated, although and in sample plasticizer have
Reduced, but not up to " saturation ", and viscosity is diminished after heating, the more preferable dissolving-Swelling Capacity to nc.Therefore this rank
The molten degree of moulding of section nc gradually improves, the t of sample2Increase.Figure it is seen that the t of sample b2Gathering way than sample a
Hurry up, illustrate that dianp is faster than ng to the molten speed of moulding of nc.
(2) aging mid-term
Also do not affect dissolubility in the decomposition of this stage nc, a small amount of minimizing of plasticizer does not mould product to the molten of nc
Raw negative effect, now sample nc adhesive spatial network is the most uniform.Heat ageing under the same terms, due to sample a and b plasticizer
Kind is different, and to mould degree change be different for nc molten.Figure it is seen that t2It is increased to peak, b needs aging 3d, and
A needs aging 5d.After illustrating that in propellant powder 38% ng has changed dianp into, the molten time of moulding shortens 40%.Acceptable from Fig. 2
Find out although in two samples to the molten of nc, plasticizer moulds that speed is slightly different, but be finally attained by same molten moulding degree.
(3) the aging later stage
Continue aging, the decomposition of nc gradually makes its dissolubility be deteriorated, the minimizing of plasticizer also makes it that dissolving of nc-molten is moulded
Reduced capability, the constraint that in sample, nc molecular motion is subject to becomes big, the therefore t of sample a and b2Reduce.After aging 12d, a's and b
t2Before aging, thus it is speculated that now the mechanical property of sample is than old when illustrating that the constraint that now nc is subject to has been better than unaged
Poor before change.
Embodiment 2
The safe handling of propellant powder is related to the ballistic performance of weapon use, still can not set up at present in its storage and thermally decompose
Relation and propellant powder trajectory characteristic number between, therefore, it is impossible to be estimated, can only determine it by firing test and use the longevity
Life, extremely expensive.Although by measuring propellant powder heat, in medicine, nc viscosity, mechanical property etc. decline and can determine whether to use the longevity safely
Life, but error is larger, factor is complicated.The mechanical property of high solids content propellant powder has considerable influence to ballistic performance, and home and abroad is ground
The person of studying carefully more properly characterizes the mechanical property parameters of high solids content propellant powder finding, for judging the safe handling longevity of propellant powder
Life.
Nc has semi-rigid strand, for improving its plasticity, it is increased frequently with small molecule plasticizer when using
Mould.Plasticizer reduces, nc dissolubility all can make the motion of nc molecule be subject to bigger constraint situations such as variation, macroscopically shows as sending out
Penetrate efficacy of a drug degradation, such propellant powder can cause gun pressure to rise by premature breakdown in emission process, and impact uses safety.
Some novel emission medicines are to have the characteristics such as high energy, Di Shaoshi, high intensity, on the formula basis of original propellant powder
On improve, add some new energetic materials and functional additive.The research purpose of the present embodiment is: investigation we are bright to be
No it is observed that the nitramine gun propelllant molten change moulding degree of nc under heat stress.
In certain double-base propellant increase rdx be modified, make nitramine gun propelllant sample c, make 12 a diameter of 10mm,
Length is the column medicine of 15mm.Sample is put in baking oven, 85 DEG C of difference aging 0,1,3,6,8,14,27,32,39,46,
58th, 67d, the sample of taking-up is respectively put in sample bottle, covers tightly lid room temperature and deposits.After all taking out Deng all samples, with this
The t of method detection sample2Value.Equally, in order to explain t2How nc is molten moulding degree change in response sample for t curve, uses liquid phase
Chromatography has investigated the change with ageing time for the surplus ratio of plasticizer in sample.
This test employs Shanghai Niu Mai electronics scientific technology co micro-mr-cl type low-field nuclear magnetic resonance analyser: hydrogen
Spectrum, resonant frequency 21.7hmz, using cpmg continuous sampling, repeated sampling waiting time tw=2500ms, echo number nech=
5000, multiple scanning frequency n s=64 time, spectrum width sw=200khz.Sample cell temperature is 40 DEG C.Obtained with t-invfit software
One pack system T2 t to sample2.The t of sample c2See Fig. 4 with ageing time change curve.
In sample c in addition to energetic plasticiser ng, also inert plasticizer diethyl phthalate dep.Use liquid chromatography
[Agilent company of the U.S. 1120compact lc high performance liquid chromatograph: UV-detector, Detection wavelength 210nm；Mobile phase is
Acetonitrile solution (volume ratio is 55:45)] detect ng and dep surplus ratio α in aged samplesi(detection level and initial content
Ratio).With αiAgeing time is mapped, sees Fig. 5.From fig. 5, it can be seen that with the prolongation of ageing time, ng and dep in sample
All persistently reducing.This is because not having firm bridged bond to be connected between nc and plasticizer, sample is heated post-plasticization agent because volatilization
Depart from the constraint of nc etc. reason.
From Fig. 5 it can also be seen that: in the 7d of aging beginning, the decrement very little of ng and dep and also essentially identical, this
Caused by the less loss of stage plasticizer is mainly due to volatilization of being heated；After 7d, due to tranquilizer decrement more than 50% it is impossible to inhale
Receive ng analyte and slow down the Autocatalytic decomposition of ng, now ng, in addition to volatilization of being heated, also there occurs that Autocatalytic decomposition reacts, leads
The less loss causing ng is significantly faster than that dep.
Fig. 4 can be explained in conjunction with Fig. 5: 85 DEG C of aging incipient stages, the loss of plasticizer seldom, nc be heated after molecular weight
Unfold, the constraint that nc is subject to diminishes, the t of sample2Increase, heating makes the molten degree of moulding of nc in sample improve；Continue aging by
It is deteriorated in the minimizing of plasticizer, nc dissolubility, the constraint that nc is subject to becomes big, the molten degree of moulding of nc declines, t2Reduce；Aging 14d
The t of sample afterwards2Less than unaged sample, when illustrating that the constraint that in now sample, nc is subject to has been better than unaged, the molten of nc is moulded
Degree has been not so good as the sample just produced.In propellant powder, the molten degree of moulding of nc reduces, and macroscopically shows as propellant powder product
Physical and mechanical property change that toughness reduces, rigidity increases, and increased the danger using process, uses the longevity safely
Life shortens.The mechanical toughness therefore speculating sample after aging 14d is already below numerical value when just producing.
Embodiment 3
Gun propellant property is not only relevant with formula, also closely related with technique.The raising of gun propellant property, often brings work
The innovation of skill or improvement, promote the development of technique.Equally, the development of technique meets the requirement of gun propellant property again, can economical,
Safely produce the product of uniform quality, stable performance.In development of new propellant powder, the manufacture work of consistent view propellant powder
Skill should be adapted with specific formula, with safety, economically produce superior in quality propellant powder as criterion, should not limit to
Among a certain constant technology pattern.In fact, the improvement of the concrete technology method according to caused by the difference of formula be through
Often occur.Therefore, development propellant powder technique is constantly subjected to pay attention to, and is one of problem of people's research.
The gunpowder compactness being manufactured with extrusion molding is good, and favorable reproducibility is widely used in manufacture propellant powder.With extrusion molding manufacture
Propellant powder is with nc as base, adds volatile solvent or difficult volatile solvent plasticising, adds other and dissolve each other or immiscible with nc
Solid constituent composition.The Issues of Basic Theory being related to during processing and manufacturing mainly has: dissolving each other between nc and solvent,
The dispersion of each component with mix, and the rheological behavior of spice.
Nc only can not make its extrusion molding with the method for liter high-temperature it is necessary to by solvent plasticising, gives nc with plasticity,
Can extrusion molding.Volatile solvent (as ethanol acetone) can be may also be employed using difficult volatilization solvent containing energy (as ng).Nc with molten
Agent forms the adhesive of gunpowder, all has conclusive impact to the processing performance of gunpowder, mechanical property and energy response.
Nc is under the action of the solvent, or swelling, or dissolving, so that material is become and has plastic plastic body, this
Process is frequently referred to plasticizing or molten moulds.Because in high solids content propellant powder, solid constituent content is high, nc fusion time is than single base, double-basis
Propellant powder is much longer.
Depending on the adaptability of various processes is formula and performance according to propellant powder, typically will not be fixed on a certain
Among constant technology pattern, its criterion is economically and safely to produce superior in quality propellant powder product.
In order that ng is molten moulds high nitrogen quantity nc manufacture propellant powder, it is allowed to dissolving by volatile solvent and plastifies and be uniformly dispersed,
After molding, solvent is driven away out, this technique is referred to as solvent process.The general briquetting pressure of this technique is relatively low, explosion hazard
Little.Do not contact with water due in production process, water-soluble component can be added, so regulation ballistic performance is easier.By
The arc of solvent to be driven away after molding, therefore Types of Medicine is thick unsuitable excessive.This technique is suitable to manufacture powder and small size powder column.
The work of the present embodiment is: with the inventive method compare two kinds of sample formation rear-guards molten during the molten of nc mould degree
Changing Pattern, as volatile solvent addition one of criterion so that research and production personnel can be to the production technology of propellant powder
It is adjusted.
Certain high solids content propellant powder adopts solvent process to produce, and sample d adds more volatile solvents than sample e,
After sample formation, all drive molten at 50 DEG C.
Because the volatile solvent in sample d and sample e drives away speed, therefore drive molten heat time heating time with hour as list
Position.For enabling the truth of testing result response sample, the sample taking out from 50 DEG C of baking ovens is to put in sample bottle to protect
Deposit, but direct detection t2.
This test employs Shanghai Niu Mai electronics scientific technology co micro-mr-cl type low-field nuclear magnetic resonance analyser: hydrogen
Spectrum, resonant frequency 21.7hmz, using cpmg continuous sampling, repeated sampling waiting time tw=1500ms, echo number nech=
1300, multiple scanning frequency n s=64 time, spectrum width sw=200khz.Sample cell temperature is 50 DEG C.Obtained with t-invfit software
One pack system T2 t to sample2.The sample d and t of sample e2See Fig. 6 with driving molten drying time change curve.
As can be seen from Figure 6: before driving molten beginning, the constraint being subject to containing nc in the more sample d of volatile solvent is less than
Sample e, the t of sample d2Value is significantly greater than the t of sample e2Value；Start to drive molten after, due to the less loss of volatile solvent, sample d and sample
The retard motion of nc, t in product e2Value all quickly diminishes；After driving molten 24h, in sample d and sample e, volatile solvent has been driven away substantially
Entirely, the t of two samples2Value reaches unanimity.Due to energetic plasticiser ng in sample etc. can not be made substantially in 50 DEG C of heating 24h
Less loss, so the t of now sample2Value reacted drive molten after sample in the molten of nc mould degree, that is, propellant powder product is just produced
When coming, the molten of nc moulds degree.The t of Fig. 62- time curve illustrates although volatile solvent is more than sample e in sample d, but through driving
After molten, in two samples, the molten degree of moulding of nc is identical, and in sample e, enough to make, nc is molten to be moulded preferably the content of volatile solvent.
Summarize:
Can be seen that due to the inventive method from above 3 embodiments is a kind of lossless detection method, the t obtaining2- t is bent
Line can react the molten Changing Pattern moulding degree of nc in high solids content propellant powder.In propellant powder sample, nc is molten moulds degree and sample
Physical and mechanical property and moulding processability have certain relation.Obtain the molten Changing Pattern moulding degree of nc in propellant powder, macroscopically
React the change for propellant powder physical and mechanical property, can be used as one kind foundation judging propellant powder safe operating life.The method
It is alternatively arranged as a kind of research meanses, nc is molten to mould journey by comparing in the propellant powder that the similar propellant powder of formula or different process produce
Degree, adjusts gun propellant formulation or improves manufacturing process.
Claims (6)
1. in high solids content propellant powder the molten detection method moulding degree Changing Pattern of nitrocotton nc it is characterised in that the method bag
Include following steps:
Step one, by high solids content propellant powder sample at a temperature of certain heat ageing different time t, obtain series of samples, serial sample
Product are placed in sample bottle, cover tightly lid and are stored at room temperature；
Step 2, series of samples is processed into respectively the bulk that size is not more than 15mm × 10mm × 10mm, is respectively put into low field
In nuclear-magnetism Special test tube；
Step 3, the Special test tube placing sample is respectively put into the sample cell of low field nuclear-magnetism, treats set by sample and sample cell
When temperature is identical, low field nuclear-magnetism is used to detect, low field nuclear-magnetism operating condition is respectively: hydrogen spectrum, resonant frequency 21.7hmz, using certainly
Cycle wave train cpmg continuous sampling, obtains the one pack system T2 t of sample with t-invfit software2；
Step 4, each sample duplicate detection 3～5 times, calculate t2Meansigma methodss, with t2Meansigma methodss are made for abscissa for vertical coordinate t
Figure, obtains t2- t curve；Nc is molten mould degree preferable when, t2Value is larger, nc is molten mould degree poor when, t2It is worth less, t2- t curve can
Mould the Changing Pattern with t for the degree so that nc is molten in reflection sample.
2. the method for claim 1 is it is characterised in that when propellant powder sample itself small volume, can low field in the past
Put into the sample of 2～4 pieces of aging same times in nuclear-magnetism Special test tube so that sample cumulative volume be about 15mm × 10mm ×
10mm.
3. the method for claim 1 it is characterised in that can also first by sample treatment become be not more than 15mm × 10mm ×
The bulk of 10mm, then carries out heat ageing and subsequent detection again.
4. the method for claim 1, it is characterised in that described propellant powder sample, can also be what different process produced
Propellant powder sample or the similar propellant powder sample of formula, that now obtain is t2- process curve or t2- formula curve, can study
In propellant powder when production technology difference or formula are different, the molten of nc moulds situation.
5. the method for claim 1, it is characterised in that described propellant powder sample, can also be heating under different temperatures
The propellant powder sample of same time, that obtain is t2- temperature curve, can study at different temperatures molten of nc in propellant powder and mould
Situation.
6. the method for claim 1 is it is characterised in that when detecting series of samples, described sample cell temperature should keep
Unanimously, and should not be higher than 55 DEG C, during sample detection, heated time should keep the same, and when sample cell is more than 45 DEG C, each sample is total
Detection time does not exceed 0.5h, the volatilization in case liquid plasticizer in sample in detection process is heated, and changes nc in sample
Molten mould state.
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| CN106908468A (en) * | 2017-03-03 | 2017-06-30 | 西安近代化学研究所 | Gel state cloud detonator cross-linked state Changing Pattern detecting system under high temperature |
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| CN110845914A (en) * | 2019-11-27 | 2020-02-28 | 四川北方硝化棉股份有限公司 | Nitrocellulose paint sheet plasticizing process |
| CN110861233A (en) * | 2019-11-21 | 2020-03-06 | 四川北方硝化棉股份有限公司 | Method for plasticizing nitrocellulose chip |
| CN114112584A (en) * | 2021-11-19 | 2022-03-01 | 西安近代化学研究所 | Sample preparation kit for determining curing temperature of high-solid-content propellant powder and using method |
| CN114112754A (en) * | 2021-11-19 | 2022-03-01 | 西安近代化学研究所 | Device and method for determining curing time of small columnar three-base propellant based on nitrocotton plastic dissolving effect value |
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| CN106908468A (en) * | 2017-03-03 | 2017-06-30 | 西安近代化学研究所 | Gel state cloud detonator cross-linked state Changing Pattern detecting system under high temperature |
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| CN114112584A (en) * | 2021-11-19 | 2022-03-01 | 西安近代化学研究所 | Sample preparation kit for determining curing temperature of high-solid-content propellant powder and using method |
| CN114112754A (en) * | 2021-11-19 | 2022-03-01 | 西安近代化学研究所 | Device and method for determining curing time of small columnar three-base propellant based on nitrocotton plastic dissolving effect value |
| CN114112754B (en) * | 2021-11-19 | 2023-07-18 | 西安近代化学研究所 | Device and method for determining curing time of small columnar three-base propellant based on nitrocotton plastic dissolving effect value |
| CN114112584B (en) * | 2021-11-19 | 2023-07-18 | 西安近代化学研究所 | Sample preparation kit for determining curing temperature of high-solid-content propellant powder and use method |
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