CN108956261B - Preparation method of asphalt film - Google Patents
Preparation method of asphalt film Download PDFInfo
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- CN108956261B CN108956261B CN201811044864.8A CN201811044864A CN108956261B CN 108956261 B CN108956261 B CN 108956261B CN 201811044864 A CN201811044864 A CN 201811044864A CN 108956261 B CN108956261 B CN 108956261B
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- asphalt
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Abstract
The invention provides a preparation method of an asphalt film, which comprises the following steps: A) and adding asphalt to the surface of the heavy water, and heating to obtain the asphalt film. Compared with the prior art, the invention places the asphalt on the surface of the heavy water and leads the asphalt to naturally diffuse under the heating condition, thereby obtaining the uniform asphalt film without a substrate.
Description
Technical Field
The invention belongs to the technical field of material detection, and particularly relates to a preparation method of an asphalt film.
Background
Bitumen is a material that is widely used in a variety of engineering applications, particularly in the construction of roads, airport runways and roofs. In addition to pure asphalt, various modifiers such as SBS polymers, nanoparticles, etc. are often incorporated into asphalt to improve its engineering properties; sometimes, to improve quality and save costs, different sources of bitumen can be mixed together. The engineering properties of both virgin and modified asphalts have generated a great deal of interest to material producers, contractors, and project owners.
The engineering properties of modified or unmodified asphalt are controlled by the basic physicochemical properties at the microscopic level. At present, the physicochemical properties of asphalt can be studied in a microscopic level by adopting the following methods: 1) fourier transform infrared spectroscopy (FTIR); 2) gel Permeation Chromatography (GPC); 3) atomic Force Microscopy (AFM); 4) transmission electron microscopic analysis (TEM). Wherein methods 1), 3) and 4) all involve the use of bitumen membranes for the detection of their microscopic properties.
The first method, which can be used to reveal chemical bonds in pitch, mainly uses two modes, the Attenuated Total Reflectance (ATR) mode of FTIR is used, and does not require the use of thin films; when the Transmission mode of FTIR is used, a thin film of asphalt is used to transmit light through an opaque sample. Wherein the thin film of asphalt is produced by depositing an asphalt solution on a special substrate and heating to evaporate the solvent. However, the fabrication of special substrates and films is time consuming and labor intensive. In addition, infrared spectroscopy can only reveal chemical bonds in the asphalt, and the microstructure of the asphalt cannot be observed, and according to the colloid theory, the morphology and the dispersibility of the microstructure are key factors influencing the performance of the asphalt.
The second method can reveal the molecular weight distribution of the bituminous solution, but likewise its microstructure is not observable.
The third method can show the surface appearance and the micro-mechanical property of the asphalt. The thin film for AFM detection is mainly prepared by the following two methods: solvent casting; spread (spread) or drip down in a heated dish. However, the images taken by AFM are limited to the surface of the asphalt sample, and the thin film used for AFM needs to be supported by a substrate such as a glass slide.
The fourth method can potentially reveal the microstructure of the entire bituminous sample, but one of the very important steps is to prepare an ultra-thin bituminous film so that electrons can pass through the sample, and the film sample should not be supported by any substrate, and furthermore, the film must be uniform in order to be able to quantitatively analyze the microstructure of different areas of the bituminous film. At present, no technology exists for preparing ultrathin asphalt films suitable for TEM detection. The thin films used for FTIR and AFM analysis cannot be used for TEM inspection due to deposition on the substrate, and the solvent casting rule may affect the microstructure of the original pitch. The microstructure of the pitch sample in its original state is of great interest.
The Lorentzivermore national laboratory developed a process that could be used to fabricate Large area ultra-thin Polymer films without deposition substrates (Stadermann, M., Baxamusa, S.H., Arane-Ruddle, C., Chema, M., Li, S., Youngblod, K., Surawala, T.Fabrication of Large-area Freesenting Ultrathin Polymer films.J.Vis.Exp. (100), e52832, doi:10.3791/52832 (2015)). The method modifies the surface with polyelectrolytes to alter the degree of adhesion between the polymer and the deposition substrate, but it is currently unclear whether the method is equally applicable to bituminous membranes and the process is complicated.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing an ultrathin, uniform and substrate-free asphalt film.
The invention provides a preparation method of an asphalt film, which comprises the following steps:
A) and adding asphalt to the surface of the heavy water, and heating to obtain the asphalt film.
Preferably, the density of the asphalt is less than 1.1g/cm3。
Preferably, the asphalt has a softening point of 80 ℃ or less.
Preferably, the mass of the asphalt is 0.0001-0.005 g; the heavy water is placed in a container, and the inner diameter of the container is 10-100 mm.
Preferably, the thickness of the thin asphalt film is 1 μm or less.
Preferably, the heating temperature is 80-100 ℃; the heating time is 20-60 min.
Preferably, the heating is performed in a drying furnace or a nitrogen purging furnace.
Preferably, the bitumen is added to the middle of the surface of the heavy water.
Preferably, the step a) is specifically:
transferring the heavy water into a container, adding asphalt to the surface of the heavy water, and heating for 20-60 min to obtain an asphalt film;
if no asphalt film is formed after 60min, the heating is stopped, the asphalt quality is reduced or the heating temperature is increased, and the above steps are repeated until an asphalt film is obtained.
The invention provides a preparation method of an asphalt film, which comprises the following steps: A) and adding asphalt to the surface of the heavy water, and heating to obtain the asphalt film. Compared with the prior art, the invention places the asphalt on the surface of the heavy water and leads the asphalt to naturally diffuse under the heating condition, thereby obtaining the uniform asphalt film without a substrate.
Drawings
FIG. 1 is a photograph of a thin asphalt film prepared in example 1 of the present invention;
FIG. 2 is a 3D graph showing the thickness of the thin asphalt film prepared in example 1 of the present invention;
FIG. 3 is a histogram of the thickness of the asphalt film prepared in example 1 of the present invention;
FIG. 4 is a surface height diagram of the asphalt film prepared in example 1 of the present invention;
FIG. 5 is a photograph of a thin asphalt film prepared in example 2 of the present invention;
FIG. 6 is a 3D graph showing the thickness of the thin asphalt film prepared in example 2 of the present invention;
FIG. 7 is a histogram of the thickness of the asphalt film prepared in example 2 of the present invention;
FIG. 8 is a photograph of a thin asphalt film prepared in example 3 of the present invention;
FIG. 9 is a 3D graph of the thickness of the thin asphalt film prepared in example 3 of the present invention;
FIG. 10 is a histogram of the thickness of the asphalt film prepared in example 3 of the present invention;
FIG. 11 is a TEM image of the asphalt film prepared in example 3 of the present invention;
FIG. 12 is a transmission electron micrograph of a thin asphalt film prepared in comparative example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an asphalt film, which comprises the following steps: A) and adding asphalt to the surface of the heavy water, and heating to obtain the asphalt film.
The invention puts the asphalt on the surface of the heavy water and makes the asphalt naturally diffuse under the heating condition, thereby obtaining the uniform asphalt film without a substrate.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
The asphalt is not particularly limited as long as it is known to those skilled in the art, and the density of the asphalt in the present invention is preferably less than 1.1g/cm3(ii) a The softening point of the asphalt is preferably 80 ℃ or lower. Therefore, the invention is suitable for almost all road asphalt and construction asphalt (matrix asphalt and partial modified asphalt) which are commonly used at home and abroad, and for the modified asphalt and hard matrix asphalt with higher softening point (such as No. 10 domestic solid asphalt), if the density is less than 1.1g/cm3The film can be prepared by adopting a method of increasing the film forming temperature and increasing the film forming time.
Adding asphalt to the surface of the heavy water; the heavy water is well known to those skilled in the art, and is not particularly limited, and the present invention is preferably 99.9 atomic% heavy water; the density of the heavy water is preferably 1.107g/cm3(ii) a The boiling point of the heavy water at 25 ℃ is preferably 101.4 ℃; what is needed isThe heavy water is preferably placed in a container; the inner diameter of the container is preferably 10-100 mm, more preferably 10-80 mm, still more preferably 20-60 mm, still more preferably 20-50 mm, still more preferably 25-40 mm, and most preferably 32-35 mm; the container is preferably a beaker, more preferably a glass beaker; the weight of the added bitumen determines the thickness of the bitumen film produced, for the same internal diameter of the container, theoretically the thickness H of the bitumen film is the mass of bitumen per base area of the container, in other words, in the case of a determined target bitumen film thickness, the amount of bitumen added should be directly proportional to the base area of the container; the amount of the asphalt added is preferably 0.0001-0.005 g, more preferably 0.0001-0.003 g, still more preferably 0.0005-0.002 g, and most preferably 0.0005-0.001 g; to reduce errors, the inside diameter of the container is preferably measured with a digital vernier caliper to the nearest 0.01mm, more preferably four measurements are made at about one fourth of the inside wall of the container, and the average value is recorded as the inside diameter D of the container; preferably, the weight of the container and the weight of the heavy water before the asphalt is added are recorded as M1Recording the weight of the asphalt, the heavy water and the container after the asphalt is added as M2The weight of the added asphalt is M2-M1(ii) a Theoretically, the thickness H ═ M of the asphalt film2-M1)/(πD24); in order to make the resulting thin film of asphalt uniform, it is preferable to add asphalt to the middle of the surface of the heavy water.
After adding the asphalt, heating, preferably putting the heavy water added with the asphalt into a preheated device for heating; the heating temperature is preferably more than 80 ℃, and more preferably 80-100 ℃; the temperature of heating depends on the kind of asphalt; the heating is preferably performed by a drying furnace or a nitrogen purification furnace; when a nitrogen purge oven is used, the oven is purged with nitrogen; the heating time is preferably 20-60 min, more preferably 25-50 min, and further preferably 25-45 min; the heating time depends on the temperature and the type of asphalt, and in order to reduce the time required for the asphalt softening-film forming process, it is preferable to use a vessel with a smaller inner diameter, thereby reducing the potential impact (e.g., aging) of the asphalt from the high temperature.
The bitumen film can be obtained by observing whether a uniform bitumen film is obtained, and if so, preferably cooling; the thickness of the asphalt film is preferably 1 μm or less.
If no asphalt film is formed after 60min, the heating is terminated, the asphalt quality is reduced or the heating temperature is increased, and the above steps are repeated until an asphalt film is obtained.
The invention adopts heavy water (deuterium oxide) to prepare the asphalt film, other solvents can not be replaced, and solutes in the solution can be adhered or adsorbed on the surface of the asphalt if an inorganic solution is used, so that the solutes are remained on the prepared asphalt film; on the other hand, if an organic solution/solvent is used, the organic solution/solvent can generate a chemical action of partial dissolution or complete dissolution on the asphalt, so that the surface and internal microstructure of the asphalt are influenced or even destroyed, and meanwhile, the organic solvent has high toxicity, so that the problem of experimental safety is introduced, and the operation difficulty is increased. In conclusion, heavy water is the most suitable agent for the present invention, which is residue-free, non-toxic and does not affect the properties of the bitumen.
And the density of the heavy water is greater than that of the bitumen so that the bitumen can float on the surface of the heavy water, become liquid upon heating and spread evenly over the surface, and after the solution cools, the bitumen will become solid again, resulting in a thin film of bitumen, which can be easily removed from the surface of the heavy water for subsequent study.
In order to further illustrate the present invention, the following will describe the preparation method of an asphalt film provided by the present invention in detail with reference to the examples.
The reagents used in the following examples are all commercially available.
Instruments and materials:
a drying furnace or a nitrogen purification furnace;
glass beaker, 20 ml;
a precision analytical balance, 0.0001 g-200 g +/-0.0001 g;
a digital vernier caliper, 0-150 mm +/-0.0003 mm;
heavy water, 99.9 atom% D, density 1.107g/cm3The boiling point at 25 ℃ is preferably 101.4 ℃.
The preparation method comprises the following steps:
1. the inside diameter of the glass beaker was measured to the nearest 0.01mm with a digital vernier caliper, four times at about one quarter of the inside wall of the beaker, and the average of the measurements was recorded as the inside diameter D of the glass beaker.
2. 10 ml. + -. 0.1ml of heavy water was transferred to the beaker.
3. Weighing the beaker filled with heavy water to the accuracy of 0.0001g, and recording the mass as M1Holding the beaker on an analytical balance, ensure M1Remain unchanged.
4. A sample of 0.0005-0.001 g of bitumen is weighed on another analytical balance and then carefully transferred to the surface of the heavy water, ensuring that the bitumen sample floats in the middle of the heavy water.
5. Quickly record the weight of the beaker after adding the asphalt as M2To the nearest 0.0001g by subtracting M1The weight of the sample of added bitumen was obtained.
6. The beaker is placed in a drying oven or nitrogen purge oven (temperature depends on the type of bitumen sample) preheated to 80-100 ℃. If a nitrogen purge furnace is used, a nitrogen purge is required.
7. Heating the asphalt sample for 20-60 min (depending on the temperature and the type of asphalt), or observing until an asphalt film is obtained; if a uniform thin film of pitch is not formed even after heating for 60min, the heating is terminated. Repeating steps 1-6 with a new pitch sample and using a lower mass pitch sample in step 4 or a higher heating temperature in step 6 until a pitch film is obtained.
8. For the purposes of subsequent studies, the bitumen film is quickly transferred to the desired sample holder or test substrate. The obtained asphalt film can be used for Fourier transform infrared spectroscopy detection (FTIR), Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM).
Theoretically, the thickness H ═ M (M) of the asphalt film was calculated2-M1)/(πD2/4)。
Example 1
The asphalt types are as follows: hongkong shell ShellPen 60/70 matrix asphalt with density of 1.015g/cm3The softening point is 46-47 ℃.
Sample quality: 0.0003 g.
The experimental conditions are as follows: inner diameter Φ of beaker equal to 32.04mm, temperature: film formation time at 100 ℃: for 40 minutes.
Theoretical thickness: 372.1 nm.
Actually measuring the thickness: about 387 nm.
The measuring instrument: bruker SPM8 atomic force microscope.
FIG. 1 is a photograph of the asphalt film prepared in example 1 of the present invention.
The asphalt film obtained in example 1 was examined by atomic force microscopy to obtain a 3D map of its thickness and a corresponding histogram, as shown in fig. 2 and 3.
The invention can obtain the asphalt with uniform thickness and truly reflect the surface appearance thereof, as shown in figure 4. FIG. 4 is a surface height diagram of the asphalt film obtained in example 1. The difference of the surface flatness of the asphalt film is less than 3nm, and the regular surface relief in the graph is a typical Bee Structure of the asphalt surface. (Pauli, A.T., Grimes, R.W., Beemer, A.G., Turner, T.F., & Branthaver, J.F. (2011.) Morphology of aphtalts, aphtalt fractions and model wax-jointed aphtalts fractions by atomic force microprocessor international Journal of patent Engineering,12 (4); 291-
Example 2
The asphalt types are as follows: hongkong Shell Pen 60/70 matrix asphalt with the density of 1.015g/cm3 and the softening point of 46-47 ℃.
Sample quality: 0.0008 g.
The experimental conditions are as follows: beaker internal diameter Φ 32.46mm, temperature: film formation time at 100 ℃: for 45 minutes.
Theoretical thickness: 966.7 nm.
Actually measuring the thickness: about 914 nm.
FIG. 5 is a photograph of the asphalt film prepared in example 2 of the present invention.
The asphalt film obtained in example 2 was examined by atomic force microscopy to obtain a 3D map of its thickness and a corresponding histogram, as shown in fig. 6 and 7.
Example 3
The asphalt types are as follows: asphalt (RAP) is extracted from the recovered pavement of hong Kong Tu Lu Kong,the density is 1.049-1.063 g/cm3The softening point is more than 50 ℃.
Sample quality: 0.0005 g.
The experimental conditions are as follows: calibre of beaker Φ 32.04mm, temperature: film formation time at 100 ℃: for 25 minutes.
Theoretical thickness: 620.1 nm.
Actually measuring the thickness: about 680 nm.
FIG. 8 is a photograph of the asphalt film prepared in example 3 of the present invention.
The asphalt film obtained in example 3 was examined by atomic force microscopy to obtain a 3D map of its thickness and a corresponding histogram, as shown in fig. 9 and 10.
The thin asphalt film obtained in example 3 was analyzed by a transmission electron microscope to obtain a transmission electron micrograph, which is shown in FIG. 11. The microstructure in the bitumen film can be clearly observed from figure 11.
Comparative example 1
An asphalt film (Wang, y., & Zhao, K. (2016). differential for a of aliphatic microstructures in transmission electronics, 28(11),04016137.) was prepared from the asphalt of example 3 by a solvent casting method, and analyzed by a transmission electron microscope, and a microstructure photograph thereof was shown in fig. 12.
From fig. 12, a microstructure of the asphalt similar to that of fig. 11 (example 3) can be observed, demonstrating that the present method does not affect or destroy the internal microstructure of the asphalt. And the concentration and distribution of the asphalt microstructure obtained in fig. 12 are not real, because the solvent may cause aggregation on the asphalt microstructure by using a solvent pouring method. As shown in FIG. 11, the thickness of the asphalt prepared by the method of the present invention can truly reflect the distribution of the asphalt microstructure in the film.
Claims (5)
1. A method for preparing an asphalt film, comprising:
A) adding asphalt to the surface of heavy water, and heating to obtain an asphalt film;
the asphaltHas a density of less than 1.1g/cm3；
The softening point of the asphalt is less than or equal to 80 ℃;
the heating temperature is 80-100 ℃; the heating time is 20-60 min;
the thickness of the asphalt film is less than or equal to 1 μm.
2. The method according to claim 1, wherein the amount of the pitch is 0.0001 to 0.005 g; the heavy water is placed in a container, and the inner diameter of the container is 10-100 mm.
3. The method according to claim 1, wherein the heating is performed by a drying furnace or a nitrogen purging furnace.
4. The method of claim 1, wherein the asphalt is added to the middle of the surface of the heavy water.
5. The preparation method according to claim 1, wherein A) is specifically:
transferring the heavy water into a container, adding asphalt to the surface of the heavy water, and heating for 20-60 min to obtain an asphalt film;
if no asphalt film is formed after 60min, the heating is stopped, the asphalt quality is reduced or the heating temperature is increased, and the above steps are repeated until an asphalt film is obtained.
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| CN105372274B (en) * | 2015-10-30 | 2018-10-09 | 长安大学 | A kind of evaluation method of the dispersity of nano-ZnO in pitch |
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| CN107037239A (en) * | 2016-11-28 | 2017-08-11 | 内蒙古工业大学 | The essence control thermoforming preparation method of bitumen samples is observed suitable for AFM |
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