Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology, adopt a kind of new ultraviolet light polymerization rapid shaping technique, with synthetic photosensitive resin is matrix material, with the silicon carbide whisker is reinforcing agent, synthetic polymer matrix composites with photosensitive property, use monitor, video camera, ultraviolet source, grating mirror, the double transmission mirror, X-Y-Z is to workbench, positive and negative electrode forming parts mould, come finished parts with computer programme-control ultraviolet light polymerization path, reach the raising part strength, rigidity, improve laser curing velocity, efficient, reduce and pollute, reach the purpose of rapid shaping.
Technical scheme
The raw chemical material that the present invention uses is epoxy resin E-51, acrylic acid, catalyst n, accelerine, polymerization inhibitor MEHQ, light trigger isopropyl thioxanthone ITX, diluting monomer trimethylolpropane triacrylate TMPTA, cleaning agent deionized water, wiping agent absolute ethyl alcohol, reinforcing agent silicon carbide whisker, modification coupling agent silane KH-560, solvent methanol, its combination matching is: the Rectangular Parts with 60.141 * 27.187 * 1.936mm is an example, is measurement unit with gram, milliliter
Epoxy resin E-51:30.81g ± 0.01g
Acrylic acid: 16.41g ± 0.01g
N, accelerine: 0.47452g ± 0.00001g
MEHQ: 0.23486g ± 0.00001g
Isopropyl thioxanthone ITX:0.56692g ± 0.00001g
Trimethylolpropane triacrylate TMPTA:5.21g ± 0.01g
Deionized water: 450ml ± 5ml
Absolute ethyl alcohol: 100ml ± 5ml
Silicon carbide whisker: 0.0511g ± 0.00001g
Silane coupler KH-560:0.9021g ± 0.00001g
Methyl alcohol: 15.43g ± 0.01g
The preparation forming method is as follows:
(1) selected raw chemical material
To carry out selectedly to the raw chemical material that uses, and carry out purity, fineness control:
Epoxy resin E-51:99.8%
Acrylic acid: 99.99%
N, accelerine: 99.9%
MEHQ: 99.9%
Isopropyl thioxanthone ITX:99.1%
Trimethylolpropane triacrylate TMPTA:98%
Deionized water: 99.999%
Absolute ethyl alcohol: 99.99%
Silicon carbide whisker: 98.9%
Silane coupler KH-560:99.9%
Methyl alcohol: 99.99%
(2) synthesizing epoxy acrylate
1., in four-hole boiling flask, add epoxy resin E-51 30.81g ± 0.01g;
2., in four-hole boiling flask, add polymerization inhibitor MEHQ 0.23486g ± 0.00001g, and stir with agitator;
3., in isobaric dropping funel, add acrylic acid 16.41g ± 0.01g, catalyst n, accelerine 0.47452g ± 0.00001g also stirs, and makes to mix, and becomes mixed liquor;
4., place electrical heating to put four-hole boiling flask, when making four-hole boiling flask be warming up to 60 ℃, begin even dropwise addition of acrylic acid and N, the accelerine mixed liquor dropwises in 75 ℃ ± 1 ℃ of reaction temperature, continues to be warming up to 110 ℃ ± 1 ℃, reaction 240min ± 5min is kept in insulation, and 30min assaying reaction thing acidity value P at interval, when acidity value P≤5mg/gKOH, finish reaction;
Close the electrical heating cover, make it naturally cool to 20 ± 3 ℃, be epoxy acrylate after the cooling;
(3) dilution epoxy acrylate
1., take by weighing epoxy acrylate 10.42g ± 0.01g, diluting monomer trimethylolpropane triacrylate TMPTA5.21g ± 0.01g, its ratio is 2: 1;
2., epoxy acrylate, trimethylolpropane triacrylate are placed container, stir, promptly get the epoxy acrylate dilution;
(4) synthetic photosensitive resin
Take by weighing epoxy acrylate dilution 15.63g ± 0.01g, measure light trigger isopropyl thioxanthone ITX0.56692g ± 0.00001g, place beaker, place electrical heating to put in beaker and heat, heating-up temperature is 40 ℃ ± 1 ℃, and stir on limit heating, limit, make it become liquid gluey, time is 30min ± 0.5min, then solution is poured in the container, and the colloidal solution in the container is liquid photosensitive resin;
(5) modification of reinforcing agent silicon carbide whisker is handled
1., take by weighing silicon carbide whisker 0.0511g ± 0.00001g, silane coupler KH-5600.9021g ± 0.00001g, liquid photosensitive resin 3.73g ± 0.01g, deionized water 1.71g ± 0.01g, methyl alcohol 15.43g ± 0.01g;
2., with modification coupling agent silane KH-560 and methyl alcohol, deionized water is mixed into mixed solution;
3., with silicon carbide whisker, place the container that fills deionized water, then container is placed the ultrasonic cleaner vibration to clean, time is 10min ± 1min, removes the whisker surface impurity, then whisker is taken out, place in the vacuum drying chamber, the oven dry of heating, temperature is 120 ℃ ± 3 ℃, the time is 1440min ± 5min;
4., whisker is poured in the coupling agent silane KH-560 mixed solution that has been equipped with, gentle agitation is even, promptly gets the silicon carbide whisker of modification, is compatibility with liquid photosensitive resin after the modification;
(6) cleaning electrode groove
With cleaning agent deionized water 150ml ± 1ml, place in the slot electrode, then slot electrode is placed ultrasonic cleaner, to clean, the time is 5min ± 0.5min, airing;
(7) clean lens, speculum, grating
With absolute ethyl alcohol 100ml ± 5ml, white soft material to lens, speculum, grating clean one by one respectively, wiping, make it clean;
(8) mixed solution:
With the reinforcing agent silicon carbide whisker after the adding of the liquid photosensitive resin in the container modification;
Carry out at the uniform velocity gentle agitation with agitator, make it become carborundum/photosensitive resin solution;
(9) put mixed solution
In carborundum/photosensitive resin mixed solution injecting electrode groove, make it become horizontal liquid level;
(10) put slot electrode
Place X-Y-Z to the workbench upper middle position slot electrode integral body that fills mixed solution, and fixing;
(11) preparation resin-based composite material part
The preparation resin-based composite material part carries out on the ultraviolet light polymerization rapid forming equipment:
The slot electrode that fills carborundum/photosensitive resin mixed solution is placed the centre position of X-Y-Z to workbench;
Open the slot electrode power supply, make its intensification, be warming up to 40 ℃ ± 1 ℃ from 20 ℃ ± 3 ℃ of normal temperature, programming rate is 1 ℃/min, constant temperature, temperature retention time 10min ± 0.5min;
Open video camera, monitor, and perpendicular alignmnet condenser lens, observation lens and slot electrode center;
Open ultraviolet source, ultraviolet light passes through the grating alignment speculum, after the speculum refraction, and ultraviolet light perpendicular alignmnet condenser lens, condenser lens perpendicular alignmnet slot electrode;
The ultraviolet light that speculum reflects focuses on by condenser lens, and focus point is aimed at the mixed resin solution in the slot electrode;
Open X-Y-Z to workbench, by computer program control uniform rotation, carry out pointwise and successively scan, carry out ultraviolet lighting and solidify, curing rate press product parts thickness, the setting of external form overall size, the average out to 0.25 second hardening time of each focus point;
After ultraviolet light polymerization was finished, carborundum/photosensitive resin mixed solution was converted into the solid product part;
(12) cooling
Close ultraviolet source, slot electrode power supply, video camera, computer, X-Y-Z to workbench;
Take off the slot electrode of X-Y-Z on workbench, place cool place, clean environment to cool off naturally, to 20 ℃ ± 3 ℃ of normal temperature, cool time 120min;
(13) product stripping
Cooled photosensitive resin product parts, by the pin-lift arrangement demoulding, the product parts after the demoulding places clean container from slot electrode;
(14) finishing external form profile, removing profile burr, dirt make it bright and clean;
(15) detection, assay, sign
Photosensitive resin product parts to preparation carries out shape, size, color and luster, intensity, rigidity, hardness, chemical composition, mechanical and physical performance detection, analyzes, chemically examines, characterizes;
Carrying out infrared spectrum with infrared spectrometer detects;
Carry out hardness test with the microhardness instrument;
Carry out the analysis of product internal organizational structure with field emission scanning electron microscope;
(16) packing, storage
The photosensitive resin part of photocureable rapid shaping preparation is stored in cool place, drying, the clean environment, and storage temperature is 20 ℃ ± 3 ℃, and relative humidity≤40% will be prevented fires, moistureproof, sun-proof, anti-soda acid erosion.
The chemical substance that the ultraviolet light polymerization of described resin-based composite material part, rapid shaping use is: with epoxy resin E-51, acrylic acid as raw material, with N, accelerine is catalyst, be polymerization inhibitor with the MEHQ, be diluting monomer with the trimethylolpropane triacrylate, be light trigger, be reinforcing agent with the silicon carbide whisker, be the modification coupling agent, be solvent, be cleaning agent, be wiping agent with the absolute ethyl alcohol with isopropyl thioxanthone ITX with the deionized water with methyl alcohol with silane KH-560.
The ultraviolet light polymerization of described resin-based composite material part, rapid shaping slot electrode by just-negative pole forms, circle, arc, hole shape part, slot electrode side are for anodal in the middle of negative pole, the slot electrode; Square, rectangle, no hole shape part, corresponding of slot electrode are anodal, negative pole.
It is with deionized water immersion, ultrasonic oscillation, coupling agent silane KH-560 modification, vacuum drying chamber oven dry that the modification of described reinforcing agent silicon carbide whisker is handled, and is compatibility with liquid photosensitive resin after the silicon carbide whisker modification.
Described ultraviolet source preparation transmission, conversion refraction, condenser lens focus on and carry out continuously, and its focusing distance is 400mm.
Beneficial effect
The present invention compares with background technology has tangible advance, adopted brand-new preparation technology's flow process, it is with epoxy resin E-51, acrylic acid is raw material, with N, accelerine is a catalyst, with the MEHQ is polymerization inhibitor, with isopropyl thioxanthone ITX is light trigger, with the silicon carbide whisker is reinforcing agent, with silane KH-560 is coupling modifier, with the deionized water is cleaning agent, with the absolute ethyl alcohol is wiping agent, with methyl alcohol is solvent, synthesizing epoxy acrylic ester prepolymer at first, synthetic again photosensitive resin, the synthetic polymer matrix composites of reinforcing agent silicon carbide whisker after photosensitive resin and the modification with photosensitive property, in photocuring moulding equipment, carry out the rapid shaping of product parts then, carborundum/photosensitive resin mixed solution in X-Y-Z workbench and slot electrode by ultraviolet source, lens focus on, control by computer program, carrying out rapid shaping scanning by layer, point and line solidifies, the focusing scanning curing rate is fast, time is short, be 0.25 second every some hardening time, ultraviolet source, lens focus on easily and realize, it is the preparation injection molding, disc wheel, the method the most efficiently of ultra-thin part and special shape part, energy resource consumption is few, preparation cost is low, the compact internal structure of part, adhesivity is good, compactness is strong, the intensity height, quality is good, mechanical performance, stable physical property, this preparation method can prepare multiple product part and special shape part, is the quick preparation forming method of the very good resin-based composite material part with photosensitive property.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Fig. 1,2, for photosensitive resin prepares the moulding process chart fast, each preparation parameter is wanted strict control, operation according to the order of sequence.
To required raw chemical material epoxy resin E-51, acrylic acid, the N of preparation moulding, accelerine, MEHQ, isopropyl thioxanthone ITX, trimethylolpropane tris acrylic acid ester TMPTA, silicon carbide whisker, silane coupler KH-560, absolute ethyl alcohol, methyl alcohol, that deionized water wants strictness to carry out is selected, and carry out purity and control, must not there be impurity to get involved the mechanical and physical performance that prevents to generate accessory substance He influence product parts.
Required chemical substance is wanted strict with the proportioning weighing, and each value must not exceed the minimax scope, in order to avoid influence the ultraviolet light polymerization performance.
The middle part is a slot electrode 2 on the X-Y-Z workbench 1, and slot electrode 2 is formed electric field by positive pole 13, negative pole 14, and the centre is a photosensitive resin mixed liquor 12, and X-Y-Z workbench 1 connects computers 4, power supply 3 by lead 23; Display 11 connects video camera 10 by lead 24, video camera 10 perpendicular alignmnets are observed lens 6, observe lens 6 and aim at speculum 7, condenser lens 5, ultraviolet source 9 parallel alignment gratings 8, grating 8 is aimed at speculum 7, speculum 7 is aimed at condenser lens 5, and condenser lens 5 central vertical are aimed at slot electrode 2.
Slot electrode is the shaping carrier of resin-based composite material part, be crucial, can make of the alloy tool steel that conducting electricity very well or stainless steel material, the groove inner surface is smooth, be beneficial to be convenient to the demoulding after the product parts cooling is shunk, take out part, shape in the groove, size, the degree of depth can design according to the product parts shape need, can be circle, square, rectangle, triangle, pentagon, hexagon, camber line shape and special profile, the electrode of slot electrode is by positive pole, negative pole is formed, the visual part shape in its position is located at middle or peripheral, controlled by power supply, and by the electric-field intensity in the power supply control electrode groove.
X-Y-Z is to workbench, be coordinate in length and breadth and the vertical lift workbench of putting slot electrode, controlled by computer program, but equidistantly move the front, back, left, right, up, down, when making circle, arc surfaced or special shape curve product, can carry out simulation curve by computer program and move, X-Y-Z to the translational speed of workbench, apart from visual purple outside photocuring need and the thickness of product parts, area, volume and be provided with.
Ultraviolet source is the luminous energy source of photocuring, ultraviolet source can be given speculum the ultraviolet light parallel transmission by grating, it is oblique that speculum is 45 angle lappings, after speculum receives the ultraviolet light of parallel transmission, reflect through angle, ultraviolet light vertical transition direction, ultraviolet light is presented sagging direct transferring and is defeated by condenser lens, ultraviolet light line focus lens focus on the back and form the ultraviolet light focus point, the ultraviolet light focus point is aimed at the photosensitive resin mixed liquor in the slot electrode, ultraviolet source and grating, speculum, condenser lens, the distance of focus point is wanted strict calculating and setting, otherwise will influence the luminous energy and the photocuring effect of ultraviolet light focus point.
Observation lens, gamma camera, display are the supervising device of photocuring, the observation lens are magnifying glass, can be transferred to gamma camera to the function situation information of ultraviolet light polymerization, gamma camera can be transferred to monitor to photocuring information, operating personnel can be in the complete monitoring photocuring process according to photocuring information, operation, adjustment computer data, program.
To preparing required equipment: slot electrode, beaker, agitator, electric jacket, container, ultrasonic cleaning machine, detecting instrument etc. will keep clean, and pollution must not be arranged.
To the required chemical substance proportioning of ultraviolet light polymerization rapid shaping preparing product part, be what in a number range that sets in advance, to determine, be measurement unit with gram, milliliter, when carrying out preparation of industrialization, with kilogram, be upgraded to measurement unit.
Shown in Figure 3, it is ultraviolet light polymerization temperature and time coordinate graph of a relation in the slot electrode, after injecting the photosensitive resin mixed liquor by the part requirement in the slot electrode, power-on, positive and negative electrode is connected, slot electrode begins to heat up, rise to 40 ℃ ± 1 ℃ from 20 ℃ ± 3 ℃, programming rate is 1 ℃/min, intersects at the E point, and in part photocuring process constant temperature, the insulation 10min ± 0.5min, be the E-F section, after preparation is finished, powered-down, make slot electrode and product parts naturally cool to 20 ℃ ± 3 ℃, the time is 120min.
Shown in Fig. 4,5, be radially state of a control figure of circular pieces ultraviolet light polymerization, in the middle of the slot electrode 2 is the positive pole 13 rotation electrode rods of electrode, slot electrode 2 outsides are the negative pole 14 of electrode, positive pole 13, negative pole 14 are formed electrode loops, in the slot electrode 2 is the mixed liquor 12 of photosensitive resin and silicon carbide whisker, condenser lens 5, ultraviolet light focus point are aimed at slot electrode 2 and are solidified by layer, point and line, ecto-entad is cured moulding fast by circular trace, positive pole 13 and negative pole 14 form and solidify electric fields, and the conduct of going forward side by side is to control.
Shown in Figure 6, it is the state diagram of Rectangular Parts ultraviolet light polymerization, slot electrode 2 is the positive and negative power supply electric field of corresponding surface composition slot electrode in length and breadth, in the slot electrode 2 is the mixed liquor 12 of photosensitive resin and silicon carbide whisker, the focus point of condenser lens 5, ultraviolet light beam is aimed at mixed liquor 12 pointwises and is successively solidified fast, and carry out to the another side by a side by X-Y-Z axial coordinate direction, and by the program of computer installation in length and breadth Grid Track carry out.
Shown in Figure 7, be circular pieces and arc part ultraviolet light polymerization focusing scanning curve map, with slot electrode 2 outside negative poles 14, be that the parts profile outside is a starting point 16, circular trace curve 15, slot electrode 2 inner for anodal 13, be that endoporus portion is a final on trajectory 17.
Shown in Figure 8, be A-A profile behind circle, the arc part ultraviolet light polymerization, the part internal structure is parallel lamination 21.
Shown in Figure 9, be Rectangular Parts ultraviolet light polymerization focusing scanning curve map, it is to be starting point 18 with slot electrode 2 exterior lateral sides negative poles 13, carries out pointwise by round cyclic curve and successively scans curing, with slot electrode 2 another corresponding positive poles 14 is terminal point 19, and track is a rectangular path curve 20.
Shown in Figure 10, be B-B profile behind the Rectangular Parts ultraviolet light polymerization, the part internal structure is parallel lamination 22.
Shown in Figure 11, be photosensitive resin part ultraviolet light polymerization rapid shaping after, ESEM amplifies 200 times of images, the cured layer bonding state is good, gluing closely, compactness is good.
Shown in Figure 12, behind the part ultraviolet light polymerization, ESEM amplifies 55000 times of images, and internal structure is an ickiness, and bridging property and compactness are good.