TW200918469A - A process for an optical mold - Google Patents

Abstract

A process for an optical mold and the following processing steps of the present invention are: Blending of power of tungsten carbide, titanium carbide and titanium nitride, grinding power with a tungsten steel ball for 72 hours, cleaning the tungsten steel ball with a volatility solution, drying power, adding 2%wt paraffin, forming the optical mold with 200 DEG C and 130Mpa, degreasing the optical mold with 3 DEG C /min to 300 DEG C for 60 minutes, sintering the optical mold with 3 DEG C /min to 1600 DEG C for 30 minutes and furnace cooling to the room temperature. The process of present invention can provide an optical mold with high density, high hardness, high toughness and low brittleness.

Description

200918469 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an optical mold, a denier _ A 4 , a gas path, and more particularly to an optical mold material which is also added with a ri-man phase, The field of force technology _. 〆 概 概 概 概 概 概 概 概 概 概 概 概 概 概 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来In the future, you must use aspherical mirrors: The industry has been able to manufacture aspherical lenses with plastic materials. However, if the slaves are so ΐ = there are 3 coffee glass lenses, there is a big technical bottleneck, in order to make a breakthrough. , you must have a molded glass postal tempering glass technology, basically first, "so-called. 疋 把 先 先 学 学 学 学 学 学 研磨 研磨 研磨 研磨 研磨 先 先 研磨 先 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨The machine is pressurized to achieve the arc of the required aspherical lens. However, at present, the domestic production capacity of the plate material used for the molded glass is not available in China, and most of the technology is in the hands of foreign companies. The optical mold core material is made of a material such as carbonized crane or carbonized stone as the main component' and sintered at a high temperature. In the industry, several carbide elements in transition metal elements are widely used, such as tungsten carbide (WC), titanium carbide (T1C) and niobium carbide (10). These carbides have high melting point, south hardness and high resistance. Abrasive, high thermal and electrical conductivity and chemical stability. Among them, tungsten carbide is the most widely used, and it has a high melting point (2785 ° C) and a high hardness (16-22 GPa). Carbonized crane materials are often made by mixing (C〇) as a dry phase and carbonized crane. Because of the low melting point and melting point characteristics of the drill, the body is sintered. After the 200918469, there is a souther compactness and toughness. If there is no cobalt or other lower melting point metal as the binder phase in the end of the T-tungsten, it is more difficult for the other party, &,, and the mouth to open. Relatively speaking, if the excess is added, the old station is added. Oh. The phase also causes a decrease in the anti-corrosion and antioxidant properties of the embryo body. Therefore, the amount of the binder phase added to the telluride powder affects the sintering, /, σ, and σ, for example, carbonized —-titanium carbide-carbonized composite, because of its high Abrasion resistance and stagnation resistance, so it can be used in a large number of mechanical sliding parts and mechanical mattresses. Although during the sintering process, titanium carbide forms a solid solution with the cracked town, which promotes the strengthening of the body after sintering, but after the sintering of the tantalum carbide-titanium carbide-carbonium carbide, the carbon is distributed in the tungsten carbide and carbonization. On the grain boundary of titanium, the abrasion resistance and the drawability of the embryo body are lowered. Therefore, when the carbon content in the sintered body is too large, a free graphite phase is generated, and excessive free graphite will cause the sintered body to form pores, so the carbon content in the cemented carbide affects the mechanical properties of the alloy, and the specific gravity of the alloy And the hardness will decrease as the carbon content increases. In addition, the carbon content also affects the size of the carbonized crane. The change in carbon content in the invention can change the grain shape of tungsten carbide in the tungsten carbide-cobalt sintered body. When the tungsten carbide-cobalt alloy has saturated carbon The content of tungsten carbide grains is triangular. Furthermore, the particle size of the sintered powder affects the sintering temperature and the mechanical properties after sintering; due to the smaller nano-powder, the surface energy effect reduces the activation energy in the sintered crucible, helps to lower the sintering temperature and can be improved. Physical and mechanical properties after sintering. Therefore, in the sintering process, in order to control the growth of tungsten carbide particles, a small amount of other metal carbides such as tantalum carbide (VC), chromium carbide (Cr3c2), niobium carbide (Nbc), carbonized buttons or 6 200918469 He mixes carbides, this g-sound: Duo Tian Tian Shi ~ Shan Er Er is widely used in the grain growth inhibitors of tungsten-cobalt sintering, and the vertical towel 7 A & Z &" The use of vanadium vanadium is most common, but excessive addition of vanadium carbide can lead to a decrease in toughness and high temperature oxidation resistance. In view of this, there are many documents discussing the sintering of tungsten carbide-cobalt. However, for a small number of dry phase sintering processes, few scholars have suggested that the invention takes carbonized town as the main phase and adds a small amount. The carbonization and stone anatomic nitrogen as the secondary phase, the relevant parameters of the 私 私 私 私 私 私 私 私 。 。 。 。 。 。 。 。 。 。. SUMMARY OF THE INVENTION The main object of the present invention is to provide an optical molding material process for adding a trace amount of a secondary phase. Based on the above purposes, the main technical means of X is to provide an optical molding material process, which includes: (1) mixed powder: the male will be etched, ^, will be tungsten, titanium carbide And the powder of titanium nitride is mixed 5' and the specific gravity of the annealed tungsten in the mixed powder is far more than the specific gravity of the titanium carbide and the chaotic chemical, that is, the carbon is the secondary phase; the humanized crane is the main phase' Carbonization and titanium nitride, (:) Grinding: Fill the above-mentioned mixed powder with - tungsten steel ball into a ball mill jar and then place the ball mill jar in a lying 纟., 纟g τ+, ρ to Rolling On the ball mill, the powder of the mixture of ± is mixed by means of a tungsten steel ball rolling in a ball mill. Xianhe Steel Ball: The volatile solution is used to make a clearing of the pseudo-steel ball with the mixed powder, so as to borrow the action of the eight umbrellas and the filter; "and the solution is separated from the tungsten steel ball."

Month 1J (4) Dry powder: For action; Step dry moisture mixed powder 7 200918469 In the dry powder, the paraffin wax and the dry powder are uniformly mixed by water heating method; (6) Hot pressing: take appropriate amount of mixing The stone mouth is placed in the 敎 模 mold, whereby the powder is pressed by temperature and pressure..., /, fly unloading & clothing to increase the density of the embryo body in the subsequent process; (7) Degreasing : The pressed raw soil is double-introduced - the temperature of the graphite is degreased for the above-mentioned raw embryo; (8) Sintering: sintering the above-mentioned degreased green embryo; and, Tiancheng/mouth: sintering the above The process of the optical molding material for adding the primary phase of the present invention is completed by cooling the embryo body furnace to room temperature. Preferably, 3 gram of the tertiary end is placed in the hot press mold during hot pressing. Preferably, at the time of grinding, 72 small, preferably nt, rocky soil is added to the rm ι. In the hot material system, the temperature inside the mold was set to 2 〇〇t and the pressure was 130 MPa for pressing. Preferably, it is obtained during the hot pressing process - a green embryo having a size of about 30 Å. It is better to be a party; The opening/dish rate was 3 ° C / min, the degreasing temperature was 300 C, and the holding; the main 0 pq eight temples, and the degreasing was carried out for 6 minutes. Preferably, the sintering is carried out at a heating rate of 3 t/min, a sintering temperature of 1600 C, and a holding time of 3 Torr. Preferably, when the powder is first 麻麻|^木亘虹小杰 ιοομηι, the temperature required for sintering is lower than 1600 ° C. The cosmetic bottle of 200918469 has at least the advantages and effects of the present invention by the above molding method: 1. Good density: the optical molding material produced by the invention has a density close to the theoretical value. The existing optical molding material provides a high density optical molding material. 1. Hardness and hardness: Ji Shishi π πη _^ Also wrong is the optical molding material made by the invention, its hardness and toughness are calculated..,, ^ / ( 1 t and after the measurement The hardness and toughness after sintering with pure tungsten carbide are quite close, and the hardness and the edge of the sintered body with cobalt added are also better than that of the sintered body with cobalt added. s 古Λ k Optical hardness molding and toughness optical molding material. 3. Low brittleness: The optical molding material produced by the present invention shows that no free graphite phase is formed after sintering by x-ray analysis.

Graphlte) or a brittle phase such as η-phase due to lack of carbon can reduce the brittleness of the optical molding material. [Embodiment] In order to understand the technical features and practical effects of the present invention in detail, and in accordance with the contents of the specification, the present invention will be further described with reference to the preferred embodiments as illustrated in the accompanying drawings. The secondary phase optical molding material processing system is as shown in the first figure, and comprises: a mixed powder: a mixture of tungsten carbide, titanium carbide and titanium nitride powders and a proportion of tungsten carbide (wc) in the mixed powder. The system is much more than carbon:: (dioxide and titanium nitride (TiN) ❾ specific gravity, that is, carbonized crane as the main phase, stone reversal titanium and titanium nitride as the secondary phase, by adding a smaller amount of carbonization Titanium and titanium nitride' to control the growth of tungsten carbide grains; 9 200918469 Grinding: Mix the above materials with - and then place the ball mill on a one-bedroom drum ball mill and set 72 small ==: Tungsten steel ball in the ball mill tank, ¥ grinding hope -, _::::==:: at the end of the clear mixed powder for the work; 'liquid in the sub-tungsten tungsten steel ball to complete the filtration of the moving dry powder 1 before - the action of step-by-step money;

』力石圣. Add 2% wt of stone bad to the dry powder, and mix the paraffin and the dry powder evenly by heating; w K minus. Take «mixed money powder placed - heat dragon towel temperature is 2. ...and the pressure is - thereby for the powder; = the method of cutting, in order to increase the density of the body body density in the subsequent process can obtain a diameter of about 30 Congsheng embryo, preferably, take 3 〇 g ^; At the end of the hot pressing mold; \ Degreasing: put the pressed green embryo into the high temperature graphite furnace, and set its heating rate to 3 〇 C / _, degreasing temperature for the assignment and holding temperature for 60 minutes The action of degreasing the above-mentioned raw embryos is carried out; sintering: the above-mentioned degreased green embryos are heated at a rate of 16 Torr. (: and the holding time is 3Q, sintering is performed, wherein the smaller the diameter of the powder is, the better the temperature required for sintering is. When the end diameter is less than (10) μηι, the temperature required for sintering is low. At 1600 ° C; and the finished product · The above-mentioned sintered embryo body furnace is cooled to room temperature to complete the process of adding 30 200918469 \ micro secondary phase optical molding material of the invention. Among them, the above-mentioned 'sinter' sintering and furnace cooling to the room "The temperature and time curve of the set is difficult to show, and the spear is shown in a circle. ^, in order to prove that the tantalum carbide produced by the process of the present invention has the relevant instrument for testing and verification, it includes: Mouth. Quality, (a) Density measurement: Sintering density is measured by the electric basis of the precision of 10_4 g. The formula is: ^, =, according to A - where P is the density of the sintered specimen (g/cm3) Wa is the dry weight of the test piece in the air. ^ is the dry weight of the dry work (g); S is the float weight of the test water (4) is the density of water (g/em3). Large pieces. Carbonization can be known from the literature. The theoretical density of KM is fine 3; while the body of the privately sintered body is in the L The density of 9丞g/cm is close to the theoretical density. Therefore, it can be understood that the compactness of the embryo body has reached a certain level. &(b) fracture toughness and hardness Measurement: The fracture toughness of the test piece by the indentation cracking technique is κ.++_>-„ /, -------\ 1/2 V d is defined as Kle : 0.0889 HV*PΊΓ where Li =^ai This a is a form of pa]mqvist according to the crack, wherein the crack is a radial radial pattern from the four corners of the notch as shown in the second figure, because the length of the crack is inversely proportional to the toughness of the material, so The fracture toughness of the substrate can be estimated by measuring the crack length P. After comparing the indentation of the present invention, it is found that the substrate cracks are both + g _ η 1 - I Wang _ palmqvist form, as shown in the fourth figure The microscopic τ can be found that the notch indentation of the embryo body exhibits a radial radial crack, and the length of the crack is evaluated by I to evaluate the toughness of the embryo after sintering. The rupture of the embryo body obtained by the invention according to the results of 200918469 The toughness is about 6.56 Mpa. m 1/2 In addition, the hardness measurement of the test piece is applied with a four-pointed diamond cone indenter to apply the load surface. Health cracks, and then the optical length 'amount of each of three test pieces, s ten different ways as follows: HV = 1 8544 -

U2J was calculated by U.S. Vickers hardness tester (Hv), which was subjected to 98.1 Torr and held for 15 seconds, and the cracks generated by the microscopic measurement of the notch on the substrate were calculated on average; wherein the Vickers hardness was 'the load was the load ( Ν), d is

Indentation average diagonal length (m). After the sintered embryo body was subjected to a Vickers hardness test, its hardness was 23.142 GPa. Furthermore, the following list provides a comparison between the hardness and fracture toughness values obtained by the present invention and previous scholars in the invention of carbonization. The hardness and toughness of the process sintering can be found from the table, and the hardness after sintering of pure tungsten carbide. It is quite close to the toughness and higher than the hardness and toughness of the sintered body with cobalt added. Table 1 Sintering component density (g/cm3) Hardness (GPa) Fracture toughness (MPa·ml/2) 90WC-10CO - 17.658 6 WC-2.9Co - 19.757 6.5 WC 15.5 24.328 6.6 The present invention (WC-small amount 15.4 23.142 6.56 Tic-small amount of TiN) (c) Surface observation after sintering: In order to understand the microstructure of the surface of the embryo body after sintering, the test piece is first set. After burying, it is polished by a diamond grinder from 45 nanometers (μΐΓι) to 〇5 nm (μιη) and then polished. After polishing, the test piece is first used - optical microscope (Optical MiCroscope; ΟΜ) and a scanning electron microscope (

Scanning Electron Microscope; SEM) observation of surface porosity, which was observed by optical microscopy in 12 200918469. It can be found that there are localized pores on the sintered body as shown in the fifth figure; in fact, the grain boundary and the pores interact during sintering. The pores remaining on the grain boundary will move along with the grain boundary. If the moving speed of the grain boundary is greater than the moving speed of the pore, the last pore will remain in the grain. If no stress acts on the pore, the pore will form a spherical shape; The sixth picture is a microscopic surface image of the process after sintering by scanning electron microscopy. It can also be found that the pores have a spherical morphology, so it can be indirectly inferred that the driving force of the grain boundary energy in the sintering process of the present invention may be more than that of the pores. The drive energy is still low. Then use a Murakamrs (i〇g K3Fe(CN)6+1〇g Na0H+(10) ml AO) to etch the test piece, observe the grain distribution after sintering, and use a T〇pC〇n-SM200 at 20KV operating voltage. Next, from the seventh figure, it can be seen that the corrosion test piece has local abnormal grain growth after sintering, and the abnormal grain growth rate is usually very fast, so that it is difficult to control the microstructure of the sintered body. Due to the solid phase sintering reaction of the present invention, the grain formation caused by the uneven liquid phase distribution is not considered, and the grain orientation may be due to the particle size distribution of the powder, and the ball is in the ball milling process due to the ball milling time. If it is too long, the powder will spread to the area of small particles', which makes it easy to produce powder agglomeration: it causes abnormal grain growth during the sintering process. Another example is the eighth figure: No, after observing the ball mill by scanning electron microscope The powder also found that some of the powder exhibited partial agglomeration. (c) X-ray analysis: Qualitative analysis using X-ray diffraction with a copper target at a voltage of 4 〇κν, a current of 100 ΜΑ, and a diffraction angle of 2 〇. ~8〇. , in the q increments per minute 13 200918469 pieces of analysis. Then perform JCPDS card comparison to confirm the change in peak value. The diffraction analysis of the embryo body after sintering is shown in the ninth figure. It can be seen from the figure that there is no free carbon produced in the sintered body, but the formation of the tungsten carbide (W2C) phase is found. The existence may be due to the fact that the carbon-to-oxygen reaction causes a decrease in carbon during the sintering process, so that part of the carbon reacts with the tungsten carbide to form tungsten carbide, wherein the reaction temperature of the tungsten carbide is 125 〇. 〇 At the same time, the amount of tungsten carbide produced is related to the particle size of tungsten carbide. When the particle size is small, the surface energy of the powder is higher, so in the sintering process: the easier it is to react with oxygen molecules. . In terms of mechanical properties, a large amount of ditungsten carbide will cause the hardness of the body after sintering to decrease. Through analysis, the results show that there is no free rock after sintering, free phase (Free Graphlte) or brittle phase such as eta phase (eta_phase) due to carbon deficiency. Through the above various tests (4), the optical molding material obtained by the process of the present invention has a density of 15.429 Q g/em3 after sintering, a Vickers hardness value of 23.142 GPa, and a bursting property of 6 56 Mpa. Moreover, the results of the transmission of = W analysis showed that no free graphite phase (4) was generated after sintering or a brittle phase such as η phase (four) ring (10) was generated due to lack of. After observing the sintering by scanning electron microscopy, it was found that some of the pores remained in the spheroidal morphology of the sputum in the sputum. Therefore, it can be indirectly inferred that the driving force of the grain boundary energy in the sintered private phase may be driven more than that of the stomata. Can still be low. In addition, the mixed powder of the enamel and the diamond powder is sintered in the above-described manufacturing process to form a diamond having a polycrystalline form. The above description is merely a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention in any way, and the work can be carried out in the technical field of the present invention. Equivalent embodiments of the local modification or modification made by the technical contents disclosed in the present invention within the scope of the technical solutions are as follows: all of the technical solutions of the present invention are still within the scope of the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The first drawing is a flow chart of an optical molding material in which a micro secondary phase is added in the present invention. The second step is a graph showing the temperature versus time of the δ and 疋 of the finished product obtained by degreasing, sintering and furnace cooling to room temperature. The second figure is a schematic diagram of the Vickers indentation of the present invention. The four figures are schematic diagrams of the indentation after the hardness test of the present invention (magnification: 100 Χ). The fifth figure is a map of the sintered body of the present invention (magnification 2 〇〇χ). The sixth figure is the SEm diagram of the post-sintered embryo body of the present invention (magnification 1〇〇〇χ). The seventh figure is the metallographic structure diagram of the post-corrosion embryo body of the present invention (magnification 8(9)X. The eighth figure is the powder SEM of the present invention after ball milling. Fig. (magnification 丨〇〇〇χ) The ninth diagram is a diffraction analysis diagram of the sintered body body of the present invention. [Description of main components] 15

Claims (1)

200918469 X. Patent application scope: 1. The process of optical molding materials, including "··": powder: the proportion of carbonized tungsten, tungsten carbide and titanium nitride powder % ^ ° private + carbonized crane The system is far more than titanium carbide and: = specific gravity 'that is, tungsten carbide as the main phase, titanium carbide and titanium nitride cans (2 honing: the above mixed powder and - shaft ball filled into a ball mill == one On the bedroom roller ball mill, the above-mentioned mixed wire is ground by the method of rolling the Hegang steel ball in the ball mill tank; = cleaning the tungsten steel ball: using a volatile solution for the tungsten steel impregnated with the mixed powder; ; 'Read the mixed powder and the wet mixed powder in the solution and separated from the tungsten steel ball to complete the dry (four) dry powder: for the previous step; (5) Add money: add stone to the dry In the powder, the paraffin is uniformly mixed with the dry powder by water-heating method; (6) Heat Μ · · Appropriate amount of powder mixed with stone soil is placed in the - mold and medium, thereby pressing the powder under temperature and pressure Luo, one, sore. Increase the density of the embryo in the subsequent process (7) Degreasing: Put the "good embryos into the high-temperature graphite furnace, and degrease the above-mentioned raw embryos; (8) Burning and knotting: the above-mentioned non-fat good The embryo is subjected to an I-junction; and (the illusion of the sintered embryo is cooled to the chamber to complete the optical molding material process of the present invention plus a micro-secondary phase. 16 200918469 2 • If the patent application scope ^ ^ Le 1 2 items The optical molding material manufacturing process, wherein in the hot pressing, 3 〇庀 is not q, and the zhizhi is placed in the hot pressing mold. 3 If the patent application system is π 甘 * + into the 1 or 2 The optical molding material is made privately, wherein a grinding time of 2 k is set during the grinding. 4 · The optical molding material process described in the third paragraph of the patent application is added to the dry powder. 5 · The optical molding material manufacturing process as described in the patent application scope 4, wherein in the hot pressing, the temperature inside the 兮tn haier is 200 ° C and the pressure is 130 Mpa. 6 · Apply for a patent Optical molding as described in item 5 The material process 'in which the 压 丨 丨 士 士 直 直 直 直 直 直 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 The temperature rise rate A 3 . /min, the degreasing temperature is 30 (TC and the temperature holding time is 6 () minutes for degreasing. 8 The optical molding material process described in claim 7 of the patent application' Sintering is carried out at a heating rate of rc/mm, a sintering temperature of 1 600 C, and a holding time of 3 G. 9 The optical molding material process as described in claim 8 of the patent application, wherein the diameter of the field is less than 1 〇〇. When μη is used, the temperature required for sintering is lower than 1600 °C. The optical molding material process of claim 1, wherein 2% by weight of paraffin wax is added to the dry powder. 17 1 1 · The optical molding material according to the first aspect of the patent application, wherein the towel is pressed in a heat (four) system, the temperature inside the mold is set to 200 ^, and the pressure 200918469 is 130 Mpa. 1 2 . If the scope of the patent application, the process, in which the optical molding material can be made during the hot pressing process, 1 3 . If the patent application J is straight, the size is about 3. The embryo of the coffee. Process, wherein when degreasing is set:: The optical molding material described in item 1 is made by % ^00 ° Γ ~ opening rate is Γ (: / min, degreasing temperature is 300 C and holding time is 1 4 ^ 〇 1 Degreasing is carried out. : Please make the optical molding materials mentioned in the patent scope _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is rc/min, magic, and 'sinter with 1600 C and holding the temperature for 3 〇. Η"一,图: 如次页18