CN107057349B - Laser weldable polyamide composite material - Google Patents
Laser weldable polyamide composite material Download PDFInfo
- Publication number
- CN107057349B CN107057349B CN201710348210.3A CN201710348210A CN107057349B CN 107057349 B CN107057349 B CN 107057349B CN 201710348210 A CN201710348210 A CN 201710348210A CN 107057349 B CN107057349 B CN 107057349B
- Authority
- CN
- China
- Prior art keywords
- laser
- parts
- phosphate
- compound
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
The invention discloses a polyamide composite material capable of being welded by laser, wherein, the absorption of light energy is greatly promoted by phosphate compounds of a laser absorption part or boride particles of rare earth metal elements modified by a macromolecular dispersant, while the transmission laser part adopts white mineral filler which is subjected to surface modification and contains titanium dioxide and has a specific particle size, so that the transmission of the light source is greatly ensured, the laser light energy reaches a welding part and is converted into heat energy, the heat energy is fused with the laser absorption part, and halogenated metal salts contained in the two parts can promote the improvement of the laser welding strength; but this application laser welding's polyamide composite's laser sees through part and absorption laser part, has white, the colored or transparent characteristics of light color, has solved traditional laser welding and can also absorb the not enough of visible light through adding carbon black, nigrosine as laser absorbent simultaneously, has solved promptly and need not to present laser absorptivity through adding inorganic pigment like carbon black and or organic pigment like nigrosine.
Description
Technical Field
The invention relates to a composite material for laser welding, in particular to a polyamide composite material capable of being subjected to laser welding, and belongs to the technical field of modified polymer composite materials.
Background
The concept of laser welding began in the 70's of the 20 th century and generally used diode lasers or neodymium-doped yttrium aluminum garnet synthetic crystal (Nd: YAG) lasers with wavelengths between 700-1200nm to generate a large amount of heat at the weld site, i.e., heat is generated by transmitting the laser light partially to the laser light absorbing portion, thereby melting the element contact region to form the weld site.
Compared with the traditional plastic welding process, the laser welding can be applied to various flexible structures, the welding strength is high, the rapid heating and cooling rate can reduce the heat influence on materials, and no external force is generated on the weldment, so that the stress and the deformation of the weldment are very small; in addition, the welding process of laser welding is stable, the surface and the internal quality of a welding seam are very good, the laser welding can be carried out in vacuum, air or other gas environments, the requirement on welding media is not high, and the laser welding can be carried out through glass or other materials transparent to light beams. Since laser welding has the above-mentioned unique advantages, it has been successfully applied to precision welding of micro-miniature parts.
However, the application of laser welding in the field of plastics has certain specificity, because polymers are mostly transparent in the wavelength range corresponding to laser, and therefore, additional components such as laser absorbers or laser diffusion absorbers need to be added into the polymer system to obtain the corresponding absorption performance. Currently, carbon black is generally used as a laser absorber in a laser-absorbing part of a plastic capable of laser welding, but carbon black has strong absorption not only in the near infrared region but also in the visible and infrared wavelength regions, and therefore carbon black cannot be used in a light-colored or transparent plastic product.
Nylon is widely used in various fields due to its excellent balance of mechanical properties, heat resistance, lubricity, fatigue creep resistance and organic solvent resistance, and particularly, with the large-scale popularization and application and technical innovation of nylon materials in automobiles, electronics, electrical appliances, household electrical appliances and industrial equipment, and the development trend of using laser welding instead of the conventional welding process, the nylon material available for laser welding becomes one of the favored materials. However, as mentioned above, nylon materials are also transparent at the wavelength of laser welding, although corresponding absorption properties can be achieved by adding additives, since the laser absorber which is frequently used today for nylon materials is usually carbon black, which, although exhibiting very high absorption in both the visible and IR region, is not possible in light-colored and transparent systems.
In the prior art, the additives for laser marking which generally allow coloring with a light color are antimony, antimony oxide, conductive pigments, TiO2Etc. which are added to the formulation of the laser-absorbing part and give it laser-weldable properties. Although it is possible to add the laser marking additive alone to the laser-absorbing part to impart weldability to the material, it cannot be accepted by the industry in actual processing because of the long processing time required; furthermore, the additives absorb the laser wavelength of the welding laser to a much lesser extent than carbon black, for example TiO2Are surface absorbers and therefore do not allow a high penetration depth of the laser radiation. In addition to the above requirements for finished product appearance and welding process steps, the weld strength is also plasticThe indexes of interest of the polymer welding technology. Generally, the performance of the welded polymer is attenuated compared with the performance of the resin, and particularly, after fillers (such as glass fibers, wollastonite and the like) with a certain length-diameter ratio are added, the welding strength of the welding material is obviously attenuated compared with the performance of the unwelded material, and the attenuation is mainly present in the aspects of stress concentration, defects, performance attenuation fluctuation and the like of the welding strength, so that the service life of a final welding product is greatly shortened.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a laser weldable polyamide composite material having a long service life and offering options for applications in light-colored or colorless systems.
The technical scheme of the invention is as follows:
the invention provides a laser-weldable polyamide composite material, which comprises a laser-absorbing part and a laser-transmitting part.
The laser absorption part comprises the following components in parts by weight:
80 to 100 parts of polyamide, the polyamide being the condensation product of one or more dicarboxylic acids and one or more diamines, or the polyamide being the condensation product of one or more aminocarboxylic acids, or the polyamide being the ring-opening polymerization product of one or more lactams, preferably polycaprolactam and polyhexamethylene adipamide, which may be selected from conventional products on the market.
The laser light-absorbing component is 0.5 to 10 parts, preferably 0.5 to 8.0 parts, more preferably 0.5 to 6.0 parts, and further preferably 0.5 to 4.0 parts. The laser absorbing component is a phosphate compound or a laser absorbing fine particle. Wherein the phosphate compound is one of phosphate, hypophosphite, hydrogen phosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and hydroxide phosphate, and specifically can be calcium phosphate, calcium hypophosphite, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium polymetaphosphate, potassium tripolyphosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and sodium metaphosphateAt least one of sodium tripolyphosphate, triammonium phosphate, monoammonium phosphate, iron phosphate, ferric pyrophosphate, magnesium hydrogen phosphate, magnesium phosphate, manganese hypophosphite, sodium ferric pyrophosphate, copper hydroxide phosphate and copper phosphate, preferably at least one of copper hydroxide phosphate and copper phosphate; wherein the laser absorbing particles are boride particles of rare earth metal element with particle diameter not more than 900nm, and the boride particles of rare earth metal element are LaB6、CeB6、GdB6And YB6In addition, in order to improve the dispersibility of the laser absorbing particles in the laser absorbing portion, a dispersion of the laser absorbing particles may be prepared, and a dispersant, which is a polymeric dispersant containing a hydrophilic functional group, preferably at least one of a polyamide dispersant, a polyester dispersant, an acrylic dispersant and a polyurethane dispersant, is added in advance to coat the surface of the laser absorbing particles for pre-dispersion, wherein the hydrophilic functional group contained in the polymeric dispersant provides affinity for the laser absorbing particles and the polyamide resin, and the laser absorbing particles may be uniformly dispersed in the laser absorbing portion together with the dispersant and a solvent by any feasible dispersing means, for example, a bead mill, a ball mill, a sand mill, ultrasonic dispersion, or the like, specifically, a small molecular weight polyamide may be blended with the laser absorbing particles in an organic solvent, the organic solvent was removed by vacuum drying and a solid powder with a loose appearance was formed by high temperature baking.
0.05-2.0 parts of copper halide metal compound, wherein halide ions in the copper halide metal compound are at least one of chloride ions, bromide ions and iodide ions, and the copper ions are Cu+And Cu2+At least one of (1).
0.1-10 parts of halogenated metal salt compound, wherein the metal element in the halogenated metal salt compound is at least one of alkali metal element and alkaline earth metal element, and preferably at least one of lithium chloride, calcium chloride, potassium iodide and potassium bromide; the addition of the metal halide salt compound is beneficial to improving the crystalline structure of the polyamide composite material, and is more beneficial to improving the strength of laser welding, especially when the metal halide salt compound is applied to a laser transmission part.
5-80 parts of glass fiber.
The transmission laser part comprises the following components in parts by weight:
80 to 100 parts of polyamide, the polyamide being the condensation product of one or more dicarboxylic acids and one or more diamines, or the polyamide being the condensation product of one or more aminocarboxylic acids, or the polyamide being the ring-opening polymerization product of one or more lactams, preferably polycaprolactam and polyhexamethylene adipamide, which may be selected from conventional products on the market.
0.01-5.0 parts of laser scattering agent, wherein the laser scattering agent is white mineral filler with 30-400nm particle size and modified titanium dioxide, the white mineral filler with modified titanium dioxide is titanium dioxide with organic surface treatment or titanium dioxide with hydrated inorganic surface treatment, and the organic or hydrated inorganic is 1-5% of the white mineral filler with modified titanium dioxide.
The titanium dioxide for organic surface treatment is formed by coating an organic coupling agent on the surface of titanium dioxide through chemical bonding, and then connecting and coating an organic surface modifier with the organic coupling agent through chemical acting force. Wherein the organic coupling agent is an organosiloxane compound and a titanate compound, and the organic surface modifier is C1-8Olefinic unsaturated monomer, higher aliphatic metal salt and amide compound, C1-8The olefinically unsaturated monomer is C1-8The higher aliphatic metal salt is one of aluminum stearate, calcium stearate, magnesium stearate, zinc stearate, aluminum laurate, calcium laurate, magnesium laurate and zinc laurate. Generally, the functional group of the organic coupling agent is bonded with the functional group (generally hydroxyl) on the surface of the titanium dioxide particles, the titanium dioxide pretreated by the organic coupling agent generates a plurality of reactive active centers under the action of a catalyst (or an initiator), and further reacts with the organic surface modifier, for example, the titanium dioxide reacts with C under the action of the initiator1-8Polymerization of olefinically unsaturated monomers, the above-mentioned initiators beingSelecting an initiator acting on an unsaturated monomer; or the wettability of the titanium dioxide in the polymer composite material is improved by the action of other chemical acting forces and higher aliphatic metal salts or amide compounds under the action of a catalyst, wherein the other chemical acting forces are chemical bond bonding force, hydrogen bond, van der Waals force and the like. The dispersibility and stability of the titanium dioxide subjected to the organic surface treatment are greatly improved in the polymer. The organic matter surface-treated titanium dioxide is not limited to the above-mentioned method, and can be used for titanium dioxide particles having the above-mentioned similar structure or use obtained by a process well known in the art.
The hydrous inorganic substance surface-treated titanium dioxide is formed by coating a hydrous inorganic substance on the surface of titanium dioxide by using a grinding method, a coprecipitation method or a co-oxidation method, wherein the hydrous inorganic substance is one of sodium silicate hydrate, aluminum hydrate, zirconium hydrate and zinc hydrate, and the hydrous inorganic substance is preferably one of sodium silicate pentahydrate, sodium silicate nonahydrate, aluminum sulfate octadecahydrate, aluminum sulfate hexadecahydrate, ammonium aluminum sulfate dodecahydrate, potassium aluminum sulfate dodecahydrate and aluminum chloride hexahydrate. The method is characterized in that a grinding method is preferably adopted to coat the hydrated inorganic substance on the surface of the titanium dioxide, specifically, the hydrated inorganic substance containing crystal water is ground to separate the crystal water to form a solid-liquid reaction micro-pool, form sol to coat the surface of the titanium dioxide, and further grind the sol to form oxide to coat the surface of the titanium dioxide. Taking hydrated sodium silicate as an example, a sodium silicate solid-liquid micro-pool is formed by grinding, further grinding is carried out to form a silicic acid sol to cover the surface of titanium dioxide, the silicic acid sol is further gelatinized to form gel, and then silicon dioxide is further formed to cover the surface of titanium dioxide. In addition, the particle size of the laser scattering agent is limited, and when the average particle size is larger than the limited range, the absorption or reflection degree of the titanium dioxide to the laser is increased, the laser cannot be transmitted, and the titanium dioxide is particularly not suitable for being applied to a laser transmission part, so that the laser welding is not firm.
0.05-2.0 parts of copper halide metal compound, wherein the halide ions in the copper halide metal compound are at least one of chloride ions, bromide ions and iodide ions, andthe copper ions are Cu+And Cu2+At least one of (1).
0.1-10 parts of halogenated metal salt compound, wherein the metal element in the halogenated metal salt compound is at least one of alkali metal element and alkaline earth metal element, and preferably at least one of lithium chloride, calcium chloride, potassium iodide and potassium bromide; the addition of the metal halide salt compound is beneficial to improving the crystalline structure of the polyamide composite material, and is more beneficial to improving the strength of laser welding, especially when the metal halide salt compound is applied to a laser transmission part.
5-80 parts of glass fiber.
The laser absorbing part and the laser transmitting part respectively comprise other auxiliary agents, and the other auxiliary agents are at least one of impact modifier, plasticizer, ultraviolet light stabilizer, heat stabilizer, antioxidant, antistatic agent, nucleating agent, flow enhancer, lubricant and colorant.
The beneficial technical effects of the invention are as follows: but this application laser welding's polyamide composite's laser sees through part and absorption laser part, has white, the colored or transparent characteristics of light color, has solved traditional laser welding and can also absorb the not enough of visible light through adding carbon black, nigrosine as laser absorbent simultaneously, has solved promptly and need not to present laser absorptivity through adding inorganic pigment like carbon black and or organic pigment like nigrosine. The laser transmission part adopts the surface-modified white mineral filler which is surface-modified and contains titanium dioxide and has a specific particle size, the crystal nucleus size of semi-crystalline polyamide can be effectively controlled, the refractive index ratio of resin and the filler is adjusted, the absorption, reflection, scattering and transmission of laser or visible light can be influenced by the size of the filler, the transmission of the light source is ensured to a great extent by the specific size, and the laser light can reach the welding part and be converted into heat energy to be fused with the laser absorption part; the laser absorption component contained in the laser absorption part promotes the absorption of light energy to a great extent, when laser is incident on the laser absorption component, the laser in the wavelength range excites free electrons of the laser absorption component to generate electron resonance, so that energy is absorbed, and the laser absorption component has the characteristic of small absorption of 380nm-780nm in the visible wavelength range; moreover, the two parts both contain halogenated metal salt capable of promoting the improvement of the laser welding strength, and purposefully adjust the crystallization speed, the crystallization temperature and the crystallinity of the polyamide, so that the welding strength of the polyamide composite material disclosed by the invention is further improved. In addition, the light-colored transparent polyester composite material for improving the laser weldability, which is prepared by the method, has higher visible light transmittance (more than 30 percent), and the laser absorption part of the light-colored transparent polyester composite material has the maximum value of absorption at the position of 800-1100 nm; the laser transmission part has relatively high transmission rate to semiconductor or YAG or carbon dioxide laser source laser, and the laser transmission part has transmission rate to laser higher than 30%; and compared with the tensile strength of the body material, the performance obtained under the same test condition has the performance retention rate of more than 65%, even more than 90%, even more than 96%. Articles made from the composite material are well suited for laser welding and have a long service life, so that they are particularly suitable for the production of covers, housings, add-on components and sensors, for example in the automotive, electronics, telecommunications, information technology, computer, home, sports, medical, or entertainment fields.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
The raw materials and the respective models used in the following specific examples and comparative examples are as follows:
polyamide: polyamide 6(PA6) is Volgamid24 from the Russian Gubichev nitrogen company; the polyamide 66(PA66) is EPR24 produced by the Marma group of China.
Laser absorption component:
phosphate-based compound: copper hydroxide phosphate (CAS No.:10103-48-7) is selected from Guangdong Wengjiang chemical Co., Ltd; copper phosphate (CAS No. 7798-23-4) is selected from Afahesar (China) chemical Co., Ltd.; the sodium phosphate is selected from Shanghai Michelin Biochemical technology limited and is anhydrous sodium phosphate; the iron phosphate is selected from sigma aldrich trade ltd.
Laser absorbing particles: lanthanum hexaboride (LaB)6) Gadolinium hexaboride (GdB)6) And yttrium hexaboride (YB)6) Are all selected from sumitomo metal mining companies.
Copper metal halide compound: cuprous iodide is TH-V of Qingdao Tuohai iodine products, Inc.; the cupric bromide is selected from Shanghai Aladdin Biotechnology Ltd.
Halogenated metal salt compound: the sodium bromide is selected from Zhengzhou Yiyang chemical product limited company, and the specification is industrial grade; the potassium iodide is selected from Shanghai Xicheng Chemicals, Inc.; the potassium bromide is selected from chemical reagents of national drug group.
Laser light scattering agent: sb2O3Selected from the group consisting of Hunan Yiyang flash antimony industries, Inc.; organosiloxane processing of TiO2(200nm) FRC5 from Hensman, USA; alumina treatment of TiO2(180nm) Tronox CR834 from Cormex; metal oxide surface treated TiO2(250nm) Tipaque R93 from Nippon stone industry; metal oxide surface treated TiO2(50nm) TipaqueTTO-55D from the Nippon stone industry is selected; the talcum powder is 1250-mesh talcum powder from Shanghai Qipo chemical industry Co., Ltd.
Glass fiber: the common chopped glass fiber is ECS508 of China megalithic corporation.
Detailed description of the preferred embodiment 1
A laser-absorbing part: 90 parts of PA66, 5 parts of copper hydroxide phosphate, 0.05 part of cuprous iodide and 1 part of sodium bromide;
a laser-transmitting section: 90 parts of PA66 and 2 parts of Sb2O30.5 part of titanium dioxide FRC5, 0.05 part of cuprous iodide and 1 part of sodium bromide.
Specific example 2
A laser-absorbing part: 70 parts of PA66, 2 parts of copper phosphate, 0.5 part of copper bromide, 2 parts of potassium iodide and 20 parts of glass fiber;
a laser-transmitting section: 70 parts of PA66, 1.0 part of titanium dioxide R930, 0.5 part of copper bromide, 2 parts of potassium iodide and 20 parts of glass fiber.
Specific example 3
A laser-absorbing part: 60 parts of PA66, 1 part of sodium phosphate, 2 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber;
a laser-transmitting section: 60 parts of PA66, 0.01 part of titanium dioxide CR834, 2 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber.
Specific example 4
A laser-absorbing part: 50 parts of PA6, 0.5 part of ferric phosphate, 0.5 part of cuprous iodide, 1 part of potassium bromide and 40 parts of glass fiber;
a laser-transmitting section: 50 parts of PA6 and 2 parts of Sb2O30.5 part of titanium dioxide TTO-55D, 0.5 part of cuprous iodide, 1 part of potassium bromide and 40 parts of glass fiber.
Specific example 5
A laser-absorbing part: 90 parts of PA66 and 2 parts of LaB60.05 part of cuprous iodide and 1 part of sodium bromide;
a laser-transmitting section: 90 parts of PA66 and 2 parts of Sb2O30.5 part of titanium dioxide FRC5, 0.05 part of cuprous iodide and 1 part of sodium bromide.
Specific example 6
A laser-absorbing part: 70 parts of PA66 and 2 parts of GdB60.5 part of copper bromide, 2 parts of potassium iodide and 20 parts of glass fiber;
a laser-transmitting section: 70 parts of PA66, 1.0 part of titanium dioxide R930, 0.5 part of copper bromide, 2 parts of potassium iodide and 20 parts of glass fiber.
Specific example 7
A laser-absorbing part: 60 parts of PA66 and 1 part of GdB62 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber;
a laser-transmitting section: 60 parts of PA66, 0.01 part of titanium dioxide CR834, 2 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber.
Specific example 8
A laser-absorbing part: 50 parts of PA6 and 0.5 part of LaB60.5 part of cuprous iodide, 1 part of potassium bromide and 40 parts of glass fiber;
a laser-transmitting section: 50 parts of PA6 and 2 parts of Sb2O30.5 part of titanium dioxide TTO-55D, 0.5 part of cuprous iodide, 1 part of potassium bromide and 40 parts of glass fiber.
Comparative example 1
A laser-absorbing part: 90 parts of PA66 and 5 parts of copper hydroxide phosphate;
a laser-transmitting section: 90 parts of PA66 and 2 parts of Sb2O3。
Comparative example 2
A laser-absorbing part: 70 parts of PA66, 2 parts of copper phosphate and 20 parts of glass fiber;
a laser-transmitting section: 70 parts of PA66 and 20 parts of glass fiber.
Comparative example 3
A laser-absorbing part: 60 parts of PA66, 1 part of sodium phosphate, 2 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber;
a laser-transmitting section: 60 parts of PA66, 2 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber.
Comparative example 4
A laser-absorbing part: 50 parts of PA6, 0.5 part of ferric phosphate, 0.5 part of cuprous iodide and 40 parts of glass fiber;
a laser-transmitting section: 50 parts of PA6, 0.5 part of titanium dioxide TTO-55D and 2 parts of Sb2O30.5 part of cuprous iodide and 40 parts of glass fiber.
Comparative example 5
A laser-absorbing part: 50 parts of PA6, 0.5 part of cuprous iodide, 1 part of potassium bromide and 40 parts of glass fiber;
a laser-transmitting section: 50 parts of PA6, 0.5 part of titanium dioxide TTO-55D, 0.5 part of cuprous iodide, 1 part of potassium bromide and 40 parts of glass fiber.
Comparative example 6
A laser-absorbing part: 70 parts of PA66 and 2 parts of GdB620 parts of glass fiber;
a laser-transmitting section: 70 parts of PA66 and 20 parts of glass fiber.
Comparative example 7
A laser-absorbing part: 60 parts of PA66 and 1 part of GdB62 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber;
a laser-transmitting section: 60 parts of PA66, 2 parts of cuprous iodide, 5 parts of sodium bromide and 30 parts of glass fiber.
Comparative example 8
A laser-absorbing part: 50 parts of PA6 and 0.5 part of LaB60.5 part of cuprous iodide and 40 parts of glass fiber;
a laser-transmitting section: 50 parts of PA6, 0.5 part of titanium dioxide TTO-55D and 2 parts of Sb2O30.5 part of cuprous iodide and 40 parts of glass fiber.
The polyamide composite materials of the laser-absorbing portion and the laser-transmitting portion in the above-described embodiments and comparative examples can be formed into various plastic articles by injection molding, extrusion, die pressing, foaming, etc. according to a general molding method determined by those skilled in the art as needed, and the various plastic articles can be prepared for laser welding with the laser irradiation time, radiation power, etc. according to the respective practical applications. In the following specific examples and comparative examples, the above-mentioned composite materials were produced respectively as a plate material using a laser wavelength of 150nm to 15 μm, preferably 808nm to 1100nm, and in the following examples, a laser light source of Nd: YAG or various diode lasers having desired wavelengths was used.
The following tests were carried out on the bars prepared according to the formulations of the specific examples and comparative examples, the test methods being as follows.
Tensile strength retention of welded sample bar: the laser-absorbing part and laser-transmitting part of the plate materials prepared by the formulation amounts in the above-described specific examples and comparative examples were placed in a continuous wavelength laser, welded at a speed of 40mm/s using a Nd: YAG laser, the welded plate materials were cut into dumbbell-shaped tensile specimens according to ISO 527 standard with the weld faces located at the middle positions of the span of the specimens, and tensile strength tests were conducted in a dry state at 23 ℃ with a relative humidity of 50% and a water content of not higher than 0.2%. Then, the laser absorption part and the laser transmission part are blended according to the mass ratio of 1:1 and directly molded according to ISO 527 standard to prepare test bars, the test is carried out under the same conditions as the above, at least 5 test bars with the same composition are respectively tested, and the mean value of the tensile strength of the test bars is taken as the final test result. And finally, recording the ratio of the tensile strength of the welded sample strip formed by laser welding to the tensile strength of the injection-molded sample strip formed by direct injection molding, and recording the ratio as the retention rate of the tensile strength of the welded sample strip, wherein the unit is "%".
And (3) fatigue testing: and (3) carrying out fatigue test on the cut tensile sample of the welding sample strip and the test rod by using a fatigue tester, wherein the test frequency is 10HZ, the stress ratio R is 0.1, the load of 80MPa is selected, the test temperature is 80 ℃, and the service life of the simulation material in the environment of high-frequency stress or vibration is evaluated according to the cycle number required in the fracture process.
The test results of the specific examples and comparative examples are described in the following table.
TABLE 1 results of the weld strength and fatigue resistance test of the specific examples and comparative examples
As can be seen from the above table, the polyamide composite material capable of laser welding has high visible light transmittance (more than 30 percent), and the laser absorption part of the polyamide composite material has the maximum absorption value at the position of 800-1100 nm; the laser transmission part has higher transmission rate to semiconductor or YAG or carbon dioxide laser source laser; compared with the strength of a body material of a non-welding joint surface, the strength retention rate of the material is higher, and the performance retention rate of the material is basically as high as more than 65%, mostly can reach more than 75%, and even can reach more than 98%; in addition, the fatigue resistance is greatly improved due to the improvement of the welding strength.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A laser-weldable polyamide composite comprising a laser-absorbing part and a laser-transmitting part, characterized in that:
the laser absorption part comprises the following components in parts by weight: 80-100 parts of polyamide, 0.5-10 parts of laser absorption component, 0.05-2.0 parts of copper halide metal compound, 0.1-10 parts of metal halide salt compound and 5-80 parts of glass fiber;
the transmission laser part comprises the following components in parts by weight: 80-100 parts of polyamide, 0.01-5.0 parts of laser scattering agent, 0.05-2.0 parts of copper halide metal compound, 0.1-10 parts of metal halide salt compound and 5-80 parts of glass fiber;
the laser absorption component is a phosphate compound or a laser absorption particle, the phosphate compound is one of phosphate, hypophosphite, hydrogen phosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and hydroxide phosphate, the laser absorption particle is a boride particle of a rare earth metal element with the particle size not more than 900nm, and the surface of the laser absorption particle is coated with a polymer dispersant containing hydrophilic functional groups;
the halide ion in the copper halide metal compound is at least one of chloride ion, bromide ion and iodide ion, and the copper ion is Cu+And Cu2+At least one of;
the metal element in the halogenated metal salt compound is at least one of alkali metal element and alkaline earth metal element;
the laser scattering agent is a surface-modified white mineral filler containing titanium dioxide with the particle size of 30-400nm, the surface-modified white mineral filler containing titanium dioxide is titanium dioxide subjected to surface treatment by organic matters or titanium dioxide subjected to surface treatment by hydrated inorganic matters, and the organic matters or the hydrated inorganic matters account for 1-5% of the weight of the surface-modified white mineral filler containing titanium dioxide; wherein the titanium dioxide for surface treatment of the organic matter is prepared by coating an organic coupling agent by chemical bondingCoating the titanium dioxide on the surface, and then connecting and coating an organic surface modifier with an organic coupling agent under the action of chemical action, wherein the organic coupling agent is an organic siloxane compound and a titanate compound, and the organic surface modifier is C1-8Olefin unsaturated monomers, higher aliphatic metal salts and amide compounds; wherein the hydrous inorganic surface-treated titanium dioxide is formed by coating a hydrous inorganic on the surface of titanium dioxide by using a milling method, a coprecipitation method or a co-oxidation method, and the hydrous inorganic is one of hydrous sodium silicate, hydrous aluminum compound, hydrous zirconium compound and hydrous zinc compound.
2. The laser-weldable polyamide composite according to claim 1, wherein: the phosphate compound is at least one of calcium phosphate, calcium hypophosphite, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium polymetaphosphate, potassium tripolyphosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium metaphosphate, sodium tripolyphosphate, triammonium phosphate, ammonium dihydrogen phosphate, iron phosphate, ferric pyrophosphate, magnesium hydrogen phosphate, magnesium phosphate, manganese hypophosphite, sodium iron pyrophosphate, copper hydroxide phosphate and copper phosphate.
3. The laser-weldable polyamide composite according to claim 2, wherein: the phosphate compound is at least one of copper hydroxide phosphate and copper phosphate, and the amount of the phosphate compound in the laser absorption part is 0.5-4.0 parts.
4. The laser-weldable polyamide composite according to claim 1, wherein: the boride particles of the rare earth metal elements are LaB6、CeB6、GdB6And YB6And the hydrophilic functional group-containing polymer dispersant is one of a polyamide dispersant, a polyester dispersant, an acrylic dispersant and a polyurethane dispersantOne of them is less.
5. The laser-weldable polyamide composite according to claim 1, wherein: the halogenated metal salt compound is at least one of lithium chloride, calcium chloride, potassium iodide and potassium bromide.
6. The laser-weldable polyamide composite according to claim 1, wherein: said C is1-8The olefinically unsaturated monomer is C1-8One of alkyl acrylate, and the higher aliphatic metal salt is one of aluminum stearate, calcium stearate, magnesium stearate, zinc stearate, aluminum laurate, calcium laurate, magnesium laurate and zinc laurate.
7. The laser-weldable polyamide composite according to claim 1, wherein: the hydrated inorganic matter is one of sodium silicate pentahydrate, sodium silicate nonahydrate, aluminum sulfate octadecahydrate, aluminum sulfate hexadecahydrate, ammonium aluminum sulfate dodecahydrate, potassium aluminum sulfate dodecahydrate and aluminum chloride hexahydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710348210.3A CN107057349B (en) | 2017-05-17 | 2017-05-17 | Laser weldable polyamide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710348210.3A CN107057349B (en) | 2017-05-17 | 2017-05-17 | Laser weldable polyamide composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107057349A CN107057349A (en) | 2017-08-18 |
| CN107057349B true CN107057349B (en) | 2020-01-14 |
Family
ID=59610021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710348210.3A Active CN107057349B (en) | 2017-05-17 | 2017-05-17 | Laser weldable polyamide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107057349B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111730209A (en) * | 2019-03-24 | 2020-10-02 | 张翔 | Method for making colored mark on object surface by using laser and application |
| CN111138849A (en) * | 2019-12-31 | 2020-05-12 | 浙江普利特新材料有限公司 | Color-selectable nylon composite material for laser welding and preparation method thereof |
| CN111849152B (en) * | 2020-06-29 | 2022-02-18 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
| CN115785654A (en) * | 2022-12-07 | 2023-03-14 | 苏州旭光聚合物有限公司 | High-penetration glass fiber reinforced nylon material for laser welding |
| CN115819967B (en) * | 2022-12-12 | 2024-05-03 | 苏州旭光聚合物有限公司 | Polyamide composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041748A (en) * | 2007-04-23 | 2007-09-26 | 恩施州瀑源化工有限责任公司 | TiO2 complex ore powder and preparation method thereof |
| CN101043970A (en) * | 2004-10-20 | 2007-09-26 | 默克专利股份有限公司 | Laser-weldable polymers |
| JP2009040808A (en) * | 2007-08-06 | 2009-02-26 | Mitsubishi Engineering Plastics Corp | Thermoplastic resin composition for laser welding, molded article and method for producing molded article |
| CN103435949A (en) * | 2007-01-11 | 2013-12-11 | 住友金属矿山株式会社 | Light-absorbing resin composition for use in laser welding, light-absorbing resin molded article, and method for manufacturing light-absorbing resin molded article |
-
2017
- 2017-05-17 CN CN201710348210.3A patent/CN107057349B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101043970A (en) * | 2004-10-20 | 2007-09-26 | 默克专利股份有限公司 | Laser-weldable polymers |
| CN103435949A (en) * | 2007-01-11 | 2013-12-11 | 住友金属矿山株式会社 | Light-absorbing resin composition for use in laser welding, light-absorbing resin molded article, and method for manufacturing light-absorbing resin molded article |
| CN101041748A (en) * | 2007-04-23 | 2007-09-26 | 恩施州瀑源化工有限责任公司 | TiO2 complex ore powder and preparation method thereof |
| JP2009040808A (en) * | 2007-08-06 | 2009-02-26 | Mitsubishi Engineering Plastics Corp | Thermoplastic resin composition for laser welding, molded article and method for producing molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107057349A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107057349B (en) | Laser weldable polyamide composite material | |
| JP6803855B2 (en) | Polyamide resin composition, kit, manufacturing method of molded product and molded product | |
| US20100068330A1 (en) | Powder Compositions and Methods of Manufacturing Articles Therefrom | |
| WO2007046536A1 (en) | Material for laser fusion bonding | |
| ES2627780T3 (en) | Nanodispersion of thermosetting inorganic clay and its use | |
| US20200032010A1 (en) | Fiber reinforced polymer composition | |
| KR20180023838A (en) | Polyester compositions | |
| JP4610238B2 (en) | Bonding method of resin moldings | |
| JPWO2019160117A1 (en) | Method for manufacturing polyamide resin composition, molded product thereof, and laser welded product | |
| CN107163571B (en) | Laser welding long-life flat fiber modified polyamide composite material | |
| CN107033588A (en) | Laser welding is modified light-coloured polyamide composite with flat fiber | |
| JP6872986B2 (en) | Molded products, kits and manufacturing methods for molded products | |
| CN107163515B (en) | Improve the solderable of laser-light transparent and uses polyester composite | |
| US20230383188A1 (en) | Liquid crystal polymer composition, liquid crystal polymer molded body, and electrical and electronic equipment | |
| JP2020012093A (en) | Polyamide resin composition, kit, method for producing molding and molding | |
| JP6998889B2 (en) | Molded products and manufacturing methods for molded products | |
| CN107418158B (en) | Flat fiber modified polyester composite material for welding with improved laser transparency | |
| CN107083056A (en) | Light or colourless polyamide compoiste material for laser welding | |
| JP2020070419A (en) | Polyamide resin composition, molding, kit and method for manufacturing molding | |
| CN109957176B (en) | Resin composition for vehicle exterior material and molded product for vehicle comprising the same | |
| CN112457591B (en) | Long glass fiber reinforced polypropylene composite material with good air tightness and capable of being welded by laser and preparation method thereof | |
| CN111363250A (en) | Modified plastic for laser welding and preparation method thereof | |
| CN106893266A (en) | A kind of resin combination and preparation method thereof, metal-resin composite | |
| CN111057343A (en) | Absorbent layer composite material for high-strength laser transmission welding | |
| JP2007204683A (en) | Member for use in welding and molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |