Radiation detectable and protective articles
Abstract
Compositions and methods for forming radiation opaque polymer articles are disclosed. In one embodiment, radiological inspection equipment and methods are used to determine the presence and attributes of such radiopaque polymer articles. The radiation opaque polymer article of the present invention mixes radiation opaque materials such as barium, bismuth, tungsten or compounds thereof with powdered polymers, pelletized polymers or solvents or polymer solutions, emulsions or suspensions in water. Can be created by doing. In addition to creating radiation-detectable objects, the radiation-impermeable polymer materials of the present invention can also be used to create radiation protection articles such as radiation protection clothing and containment vessels. Also, enhanced radiation protection can be achieved by the use of nanomaterials. The principles of the invention can be used to provide protection against other types of hazards, including flame, chemical, biological and projectile hazards.

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Projected expiry passed 16 December 2025, 0.8 years ago.
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81 claims: 11 independent, 70 dependent
- 1ポリマーを放射線不透過性材料と混合することによって放射線不透過性ポリマー混合物を作成するステップと、 該放射線不透過性ポリマー混合物を使用して放射線不透過性ポリマー物品を形成するステップと、 該放射線不透過性ポリマー物品を放射線源に暴露するステップと、 どれほど多くの該放射線が該放射線不透過性ポリマー物品を透過するのかを検出するステップと、 該検出された放射線を使用して該放射線不透過性ポリマー物品の存在および/または属性を決定するステップとを含む、放射線不透過性ポリマー物品を検出する方法。
- 2ポリマーが、ポリウレタン、ポリアミド、ポリ塩化ビニル、ポリビニルアルコール、天然ラテックス、ポリエチレン、ポリプロピレン、ポリイソプレン、ポリスチレン、ポリスルホン、エチレン酢酸ビニル、ポリエステル、アクリロニトリル-ブタジエン-スチレン、アクリル、ポリカーボネート、ポリオキシメチレン、アセタール、ポリテトラフルオロエチレン、イオノマー、セルロース、ポリエーテルケトン、シリコーン、エポキシ、エラストマーおよびポリマーフォームからなる群より選択される、請求項1記載の検出方法。
- 3放射線不透過性材料が、バリウム、硫酸バリウム、塩化バリウム、他のバリウム化合物、タングステン、炭化タングステン、酸化タングステン、他のタングステン化合物、ビスマス、ビスマス化合物、タンタル、タンタル化合物、チタン、チタン化合物、ジアトリゾエートメグルミン(Diatrizoate Meglumine)(注射用)USP、アセトリゾエートナトリウム(Acetrizoate Sodium)、ホウ素、ホウ酸、酸化ホウ素、ホウ素塩類、他のホウ素化合物、ベリリウム、ベリリウム化合物、ブナミオジルナトリウム、ジアトリゾエートナトリウム、エチオダイズド油、イオベンザム酸、イオカルム酸、イオセタム酸、ヨージジパミド(Iodipamide)、イオジキサノール、ヨード油(Iodized Oil)、ヨードアルフィオン酸(Iodoalphionic Acid)、o-ヨウ化ヒプル酸ナトリウム、ヨードフタレインナトリウム、ヨードピラセット、イオグリク酸、イオヘキソール、イオメグラム酸、イオパミドール、イオパノ酸、イオペントール、ヨーフェンジラート(Iophendylate)、ヨーフェノキシ酸(Iophenoxic Acid)、イオプロミド、イオプロン酸、イオピドール、イオピドン、イオタラム酸、イオトロラン、イオベルソル、イオキサグル酸、イオキシラン、イポデート、メグルミンアセトリゾエート、メグルミンジトリゾエートメチオダールナトリウム(Meglumine Ditrizoate Methiodal Sodium)、メトリザミド、メトリゾ酸、フェノブチオジル、フェンテチオタレイン(Phentetiothalein)ナトリウム、プロピリオドン、ヨードメタム酸ナトリウム(Sodium Iodomethamate)、ソゾヨード酸(Sozoiodolic Acid)、酸化トリウムおよびトリパノエートナトリウム(Trypanoate Sodium)からなる群より選択される、請求項1記載の検出方法。
- 4ポリマー混合物が、可塑剤、乳化剤、界面活性剤、沈殿防止剤、均染剤、乾燥促進剤、接着剤および流れ改善剤からなる群より選択される一つまたは複数の添加物をさらに含む、請求項1記載の検出方法。
- 5ポリマー混合物が難燃剤をさらに含む、請求項1記載の検出方法。
- 6難燃剤が、アルミニウム三水和物、水酸化マグネシウム、有機臭素化化合物および有機塩素化化合物からなる群より選択される、請求項5記載の検出方法。
- 7ポリマー混合物がナノ材料をさらに含む、請求項1記載の検出方法。
- 8ナノ材料が、ナノ粒子、ナノチューブおよびナノプレートレットからなる群より選択される、請求項7記載の検出方法。
- 9放射線不透過性材料が鉛を含む、請求項1記載の検出方法。
- 10放射線不透過性材料がスズを含む、請求項1記載の検出方法。
- 11放射線不透過性ポリマー物品が押出しおよび射出成形によって形成される、請求項1記載の検出方法。
- 12放射線不透過性ポリマー物品が押出しおよび真空成形によって形成される、請求項1記載の検出方法。
- 13放射線不透過性ポリマー物品が、既存の物品に放射線不透過性コーティングを塗布することによって形成される、請求項1記載の検出方法。
- 14放射線源がX線を発生させる、請求項1記載の検出方法。
- 15遮断された放射線のレベルを計測することによって放射線不透過性ポリマー物品の存在を確認する、請求項1記載の検出方法。
- 16画素のパターンに配列された複数の放射線検出器をさらに含む、請求項1記載の検出方法。
- 17各画素によって検出された放射線の量を評価することによって放射線不透過性ポリマー物品の輪郭を決定する、請求項16記載の検出方法。
- 18汚染物質の存在または非存在をさらに検出する、請求項1記載の検出方法。
- 19各画素によって検出された放射線の量を評価することによって放射線不透過性ポリマー物品中の切れ目、亀裂または他の欠陥を特定する、請求項16記載の検出方法。
- 20放射線不透過性ポリマー物品が景品である、請求項1記載の検出方法。
- 21放射線不透過性ポリマー物品が武器または爆発物である、請求項1記載の検出方法。
- 22放射線不透過性ポリマー物品がストローまたは他の食器類である、請求項1記載の検出方法。
- 23放射線不透過性ポリマー物品が医療装置である、請求項1記載の検出方法。
- 24医療装置がカテーテルである、請求項23記載の検出方法。
- 25放射線不透過性ポリマー物品が箱または他の容器に収容されている、請求項1記載の検出方法。
- 26ポリマーを放射線不透過性材料と混合することによって放射線不透過性ポリマー混合物を作成するステップと、 該放射線不透過性ポリマー混合物を使用してポリマー物品を形成するステップと、 該物品を箱に入れるステップと、 該箱を放射線源に暴露するステップと、 どれほど多くの該放射線が該箱に透過するのかを検出するステップと、 該検出された放射線を使用して該放射線不透過性物品が該箱に収容されているかどうかを決定するステップとを含む、箱に収容されたポリマー物品の存在を検出する方法。
- 27ポリマーが、ポリウレタン、ポリアミド、ポリ塩化ビニル、ポリビニルアルコール、天然ラテックス、ポリエチレン、ポリプロピレン、エチレン酢酸ビニル、ポリエステル、アクリロニトリル-ブタジエン-スチレン、アクリル、ポリカーボネート、ポリイソプレン、ポリスチレン、ポリスルホン、ポリオキシメチレン、アセタール、ポリテトラフルオロエチレン、イオノマー、セルロース、ポリエーテルケトン、シリコーン、エポキシ、エラストマーおよびポリマーフォームからなる群より選択される、請求項26記載の検出方法。
- 28放射線不透過性材料が、バリウム、硫酸バリウム、塩化バリウム、他のバリウム化合物、タングステン、炭化タングステン、酸化タングステン、他のタングステン化合物、ビスマス、ビスマス化合物、タンタル、タンタル化合物、チタン、チタン化合物、ジアトリゾエートメグルミン(注射用)USP、アセトリゾエートナトリウム、ホウ素、ホウ酸、酸化ホウ素、ホウ素塩類、他のホウ素化合物、ベリリウム、ベリリウム化合物、ブナミオジルナトリウム、ジアトリゾエートナトリウム、エチオダイズド油、イオベンザム酸、イオカルム酸、イオセタム酸、ヨージパミド、イオジキサノール、ヨード油、ヨードアルフィオン酸、o-ヨウ化ヒプル酸ナトリウム、ヨードフタレインナトリウム、ヨードピラセット、イオグリク酸、イオヘキソール、イオメグラム酸、イオパミドール、イオパノ酸、イオペントール、ヨーフェンジラート、ヨーフェノキシ酸、イオプロミド、イオプロン酸、イオピドール、イオピドン、イオタラム酸、イオトロラン、イオベルソル、イオキサグル酸、イオキシラン、イポデート、メグルミンアセトリゾエート、メグルミンジトリゾエートメチオダールナトリウム、メトリザミド、メトリゾ酸、フェノブチオジル、フェンテチオタレインナトリウム、プロピリオドン、ヨードメタム酸ナトリウム、ソゾヨード酸、酸化トリウムおよびトリパノエートナトリウムからなる群より選択される、請求項26記載の検出方法。
- 29ポリマー混合物が、可塑剤、乳化剤、界面活性剤、沈殿防止剤、均染剤、乾燥促進剤、接着剤および流れ改善剤からなる群より選択される一つまたは複数の添加物をさらに含む、請求項26記載の検出方法。
- 30ポリマー混合物が難燃剤をさらに含む、請求項26記載の検出方法。
- 31難燃剤が、アルミナ三水和物、水酸化マグネシウム、有機臭素化化合物および有機塩素化化合物からなる群より選択される、請求項26記載の検出方法。
- 32ポリマー混合物がナノ材料をさらに含む、請求項26記載の検出方法。
- 33ナノ材料が、ナノ粒子、ナノチューブおよびナノプレートレットからなる群より選択される、請求項26記載の検出方法。
- 34中空の防爆性容器と、 爆弾を該容器に挿入し、爆弾挿入ののち該容器を封止することを可能にするための、該容器上のハッチと、 ポリマーおよび放射線不透過性材料を含む、該容器上の放射線不透過性ポリマー層とを含む、放射線防護爆弾格納容器。
- 35ポリマーが、ポリウレタン、ポリアミド、ポリ塩化ビニル、ポリビニルアルコール、天然ラテックス、ポリエチレン、ポリプロピレン、エチレン酢酸ビニル、ポリエステル、アクリロニトリル-ブタジエン-スチレン、アクリル、ポリカーボネート、ポリイソプレン、ポリスチレン、ポリスルホン、ポリオキシメチレン、アセタール、ポリテトラフルオロエチレン、イオノマー、セルロース、ポリエーテルケトン、シリコーン、エポキシ、エラストマーおよびポリマーフォームからなる群より選択される、請求項34記載の格納容器。
- 36放射線不透過性材料が、バリウム、硫酸バリウム、塩化バリウム、他のバリウム化合物、タングステン、炭化タングステン、酸化タングステン、他のタングステン化合物、ビスマス、ビスマス化合物、タンタル、タンタル化合物、チタン、チタン化合物、ジアトリゾエートメグルミン(注射用)USP、アセトリゾエートナトリウム、ホウ素、ホウ酸、酸化ホウ素、ホウ素塩類、他のホウ素化合物、ベリリウム、ベリリウム化合物、ブナミオジルナトリウム、ジアトリゾエートナトリウム、エチオダイズド油、イオベンザム酸、イオカルム酸、イオセタム酸、ヨージパミド、イオジキサノール、ヨード油、ヨードアルフィオン酸、o-ヨウ化ヒプル酸ナトリウム、ヨードフタレインナトリウム、ヨードピラセット、イオグリク酸、イオヘキソール、イオメグラム酸、イオパミドール、イオパノ酸、イオペントール、ヨーフェンジラート、ヨーフェノキシ酸、イオプロミド、イオプロン酸、イオピドール、イオピドン、イオタラム酸、イオトロラン、イオベルソル、イオキサグル酸、イオキシラン、イポデート、メグルミンアセトリゾエート、メグルミンジトリゾエートメチオダールナトリウム、メトリザミド、メトリゾ酸、フェノブチオジル、フェンテチオタレインナトリウム、プロピリオドン、ヨードメタム酸ナトリウム、ソゾヨード酸、酸化トリウムおよびトリパノエートナトリウムからなる群より選択される、請求項34記載の格納容器。
- 37ポリマー層が、可塑剤、乳化剤、界面活性剤、沈殿防止剤、均染剤、乾燥促進剤、接着剤および流れ改善剤からなる群より選択される一つまたは複数の添加物をさらに含む、請求項34記載の格納容器。
- 38ポリマー層が難燃剤をさらに含む、請求項34記載の格納容器。
- 39難燃剤が、アルミナ三水和物、水酸化マグネシウム、有機臭素化化合物および有機塩素化化合物からなる群より選択される、請求項38記載の格納容器。
- 40ポリマー層がナノ材料をさらに含む、請求項34記載の格納容器。
- 41ナノ材料が、ナノ粒子、ナノチューブおよびナノプレートレットからなる群より選択される、請求項40記載の格納容器。
- 42ポリマーおよび放射線不透過性ナノ材料を含む放射線不透過性ポリマー混合物。
- 43ナノ材料が、ナノ粒子、ナノチューブおよびナノプレートレットからなる群より選択される、請求項42記載の放射線不透過性ポリマー混合物。
- 44放射線不透過性ナノ材料が、タングステン、バリウム、ホウ素、タンタル、ビスマス、劣化ウラン、酸化セリウム(CeO 2 )、酸化イットリウム(Y 2 O 3 )、酸化ランタン(La 2 O 3 )および酸化ネオジム(Nd 2 O 3 )の群より選択される物質から形成されている、請求項42記載の放射線不透過性ポリマー混合物。
- 45放射線不透過性ナノ材料が、鉛またはスズを含む物質から形成されている、請求項42記載の放射線不透過性ポリマー混合物。
- 46放射線不透過性ナノ材料が、遷移金属ジカルコゲニドを含む物質から形成されている、請求項42記載の放射線不透過性ポリマー混合物。
- 47ナノ材料が、ナノ球体、ナノ半球体およびナノパラボラからなる群より選択される、請求項42記載の放射線不透過性ポリマー混合物。
- 48ポリマーが、ポリウレタン、ポリアミド、ポリ塩化ビニル、ポリビニルアルコール、天然ラテックス、ポリエチレン、ポリプロピレン、エチレン酢酸ビニル、ポリエステル、アクリロニトリル-ブタジエン-スチレン、アクリル、ポリイソプレン、ポリスチレン、ポリスルホン、ポリカーボネート、ポリオキシメチレン、アセタール、ポリテトラフルオロエチレン、イオノマー、セルロース、ポリエーテルケトン、シリコーン、エポキシ、エラストマーおよびポリマーフォームからなる群より選択される、請求項42記載の放射線不透過性ポリマー混合物。
- 49難燃剤をさらに含む、請求項42記載の放射線不透過性ポリマー混合物。
- 50難燃剤が、酸化アンチモン、アンチモンペントキサイト(antimony pentoxite)、モリブデン化合物、チタン、ジルコニウム、亜鉛、炭化シリコン、シリコンニトレート(silicon nitrate)、窒化アルミニウム、アルミナ三水和物、水酸化マグネシウム、有機臭素化化合物、有機塩素化化合物、天然および合成のナノ粘土、パイロフィライト、緑泥石、スメクタイト、モンモリロナイト、パリゴルスカイト、滑石、バーミキュライト、ソーコナイト、サポナイト、ノントロナイトおよび雲母からなる群より選択される、請求項49記載の放射線不透過性ポリマー混合物。
- 51高められた化学的、生物学的または投射物防護を付与するための添加物をさらに含む、請求項42記載の放射線不透過性ポリマー混合物。
- 52添加物が、アルミナ酸化物、エアオニア(aironia)酸化物、フェライト酸化物、チアネート(tianate)酸化物、混合複合酸化物、炭化物粉末、窒化物粉末およびホウ化物粉末からなる群より選択される、請求項51記載の放射線不透過性ポリマー混合物。
- 53ナノ材料が、天然ナノ粘土、合成ナノ粘土、層状ケイ酸およびナノチューブからなる群より選択される、請求項42記載の放射線不透過性ポリマー混合物。
- 54ナノ材料がポリマー混合物中に広く分散している、請求項42記載の放射線不透過性ポリマー混合物。
- 55ポリマーと、 耐火性材料と、 放射線不透過性材料とを含む、放射線および火炎の危険の両方に対して防護することができるポリマー混合物。
- 56放射線不透過性材料が、バリウム、硫酸バリウム、塩化バリウム、他のバリウム化合物、鉛、タングステン、炭化タングステン、酸化タングステン、他のタングステン化合物、ビスマス、ビスマス化合物、タンタル、タンタル化合物、チタン、チタン化合物、ジアトリゾエートメグルミン(注射用)USP、アセトリゾエートナトリウム、ホウ素、ホウ酸、酸化ホウ素、ホウ素塩類、他のホウ素化合物、ベリリウム、ベリリウム化合物、ブナミオジルナトリウム、ジアトリゾエートナトリウム、エチオダイズド油、イオベンザム酸、イオカルム酸、イオセタム酸、ヨージパミド、イオジキサノール、ヨード油、ヨードアルフィオン酸、o-ヨウ化ヒプル酸ナトリウム、ヨードフタレインナトリウム、ヨードピラセット、イオグリク酸、イオヘキソール、イオメグラム酸、イオパミドール、イオパノ酸、イオペントール、ヨーフェンジラート、ヨーフェノキシ酸、イオプロミド、イオプロン酸、イオピドール、イオピドン、イオタラム酸、イオトロラン、イオベルソル、イオキサグル酸、イオキシラン、イポデート、メグルミンアセトリゾエート、メグルミンジトリゾエートメチオダールナトリウム、メトリザミド、メトリゾ酸、フェノブチオジル、フェンテチオタレインナトリウム、プロピリオドン、ヨードメタム酸ナトリウム、ソゾヨード酸、酸化トリウムおよびトリパノエートナトリウムからなる群より選択される、請求項55記載のポリマー混合物。
- 57放射線不透過性材料が、鉛、スズ、タングステン、バリウム、ホウ素、タンタル、ビスマス、劣化ウラン、バリウム、酸化セリウム(CeO 2 )、酸化イットリウム(Y 2 O 3 )、酸化ランタン(La 2 O 3 )および酸化ネオジム(Nd 2 O 3 )からなる群より選択されるナノ材料を含む、請求項55記載のポリマー混合物。
- 58放射線不透過性材料が、ナノ球体、ナノ半球体、ナノチューブまたはナノパラボラの形状に形成されたナノ材料を含む、請求項55記載のポリマー混合物。
- 59難燃剤が、ナノ粘土、ナノゼオライト、ゾル・ゲル誘導金属酸化物、炭化シリコン(SiC)、シリコンニトレート(SiN)、シリコンナノチューブ、フルオロポリマー、アルミナ三水和物、水酸化マグネシウム、臭素化化合物、酸化アンチモン、アンチモンペントキサイト、モリブデン化合物、チタン、ジルコニウム、亜鉛、炭化シリコン、シリコンニトレート、塩素化化合物、パイロフィライト、緑泥石、スメクタイト、モンモリロナイト、パリゴルスカイト、滑石、バーミキュライト、ソーコナイト、サポナイト、ノントロナイトおよび雲母からなる群より選択されるナノ材料を含む、請求項55記載のポリマー混合物。
- 60請求項42記載のポリマー混合物から形成された物品。
- 61衣類である、請求項60記載の物品。
- 62衣類が下着、ベスト、帽子、グローブ、全身スーツ、エプロン、シャツ、ズボン、ポケットまたは股間プロテクタである、請求項61記載の物品。
- 63爆弾抑制ブランケットである、請求項60記載の物品。
- 64乗り物、壁、船舶、航空機、宇宙航空機または容器のライナまたはコーティングである、請求項60記載の物品。
- 65請求項55記載のポリマー混合物から形成された物品。
- 66衣類である、請求項65記載の物品。
- 67衣類が下着、ベスト、帽子、グローブ、全身スーツ、エプロン、シャツ、ズボン、ポケットまたは股間プロテクタである、請求項66記載の物品。
- 68爆弾抑制ブランケットである、請求項65記載の物品。
- 69乗り物、壁、船舶、航空機、宇宙航空機または容器のライナまたはコーティングである、請求項65記載の物品。
- 70放射線不透過性ナノ材料の組成物を人体に注入するステップと、 放射線を使用して該人体中の細胞の形態を検出するステップとを含む、放射線学的検出に対するヒト細胞のコントラストを高める方法。
- 71ポリマーと、 化学的または生物学的抵抗性材料と、 放射線不透過性材料とを含む、放射線および化学的または生物学的危険の両方に対して防護することができるポリマー混合物。
- 72放射線不透過性材料が、鉛、スズ、バリウム、硫酸バリウム、塩化バリウム、他のバリウム化合物、タングステン、炭化タングステン、酸化タングステン、他のタングステン化合物、ビスマス、ビスマス化合物、タンタル、タンタル化合物、チタン、チタン化合物、ジアトリゾエートメグルミン(注射用)USP、アセトリゾエートナトリウム、ホウ素、ホウ酸、酸化ホウ素、ホウ素塩類、他のホウ素化合物、ベリリウム、ベリリウム化合物、ブナミオジルナトリウム、ジアトリゾエートナトリウム、エチオダイズド油、イオベンザム酸、イオカルム酸、イオセタム酸、ヨージパミド、イオジキサノール、ヨード油、ヨードアルフィオン酸、o-ヨウ化ヒプル酸ナトリウム、ヨードフタレインナトリウム、ヨードピラセット、イオグリク酸、イオヘキソール、イオメグラム酸、イオパミドール、イオパノ酸、イオペントール、ヨーフェンジラート、ヨーフェノキシ酸、イオプロミド、イオプロン酸、イオピドール、イオピドン、イオタラム酸、イオトロラン、イオベルソル、イオキサグル酸、イオキシラン、イポデート、メグルミンアセトリゾエート、メグルミンジトリゾエートメチオダールナトリウム、メトリザミド、メトリゾ酸、フェノブチオジル、フェンテチオタレインナトリウム、プロピリオドン、ヨードメタム酸ナトリウム、ソゾヨード酸、酸化トリウムおよびトリパノエートナトリウムからなる群より選択される、請求項71記載のポリマー混合物。
- 73放射線不透過性材料が、鉛、スズ、タングステン、バリウム、ホウ素、タンタル、ビスマス、劣化ウラン、バリウム、酸化セリウム(CeO 2 )、酸化イットリウム(Y 2 O 3 )、酸化ランタン(La 2 O 3 )および酸化ネオジム(Nd 2 O 3 )からなる群より選択されるナノ材料を含む、請求項71記載のポリマー混合物。
- 74化学的または生物学的抵抗性材料が、ナノセラミックス、天然ナノ粘土、合成ナノ粘土、ナノチューブおよび層状ケイ酸からなる群より選択されるナノ材料を含む、請求項71記載のポリマー混合物。
- 75天然ナノ粘土が、モンモリロナイト、カオリン、スメクタイト、パリゴルスカイト、雲母、滑石、緑泥石およびバーミキュライトからなる群より選択される、請求項74記載のポリマー混合物。
- 76ポリマーが、ポリウレタン、ポリアミド、ポリ塩化ビニル、ポリビニルアルコール、天然ラテックス、ポリエチレン、ポリプロピレン、エチレン酢酸ビニル、ポリイソプレン、ポリスチレン、ポリスルホン、ポリエステル、アクリロニトリル-ブタジエン-スチレン、アクリル、ポリカーボネート、ポリオキシメチレン、アセタール、ポリテトラフルオロエチレン、イオノマー、セルロース、ポリエーテルケトン、シリコーン、エポキシ、エラストマーおよびポリマーフォームからなる群より選択される、請求項71記載のポリマー混合物。
- 77請求項71記載のポリマー混合物から形成された物品。
- 78衣類である、請求項77記載の物品。
- 79衣類が下着、ベスト、帽子、グローブ、全身スーツ、エプロン、シャツ、ズボン、ポケットまたは股間プロテクタである、請求項78記載の物品。
- 80爆弾抑制ブランケットである、請求項77記載の物品。
- 81乗り物、壁、船舶、航空機、宇宙航空機または容器のライナまたはコーティングである、請求項77記載の物品。
Independent claims81
92 paragraphs, as filed
Field of Invention The present invention relates to radiation-detectable protective articles. The radioactive articles of the present invention can be easily detected by the use of X-rays and other radioactive emissions. The methods and compositions for producing such radiation-detectable articles also apply to the creation of articles that protect against radiation and other types of hazards such as flame, chemical, biological and projectile hazards. be able to.
Mutual Reference to Related Applications This application claims the priority of US Patent Application No. 11 / 019,952 filed December 20, 2004 (the content of this application is incorporated herein by reference for all purposes). This application was filed on July 16, 2003, and is a partial continuation of application No. 10 / 620,954 issued as US Pat. No. 6,841,791 entitled "Multiple Hazard Protection Articles And Methods For Making Them." This application was filed on September 9, 2002 and was issued as US Pat. No. 6,828,578 entitled "Lightweight Radiation Protective Articles And Methods For Making Them" and was issued on December 7, 2004 as US Pat. No. 6,828,578. This is a partial continuation of application No. 10 / 238,160 issued as B2, which was filed on August 27, 2001 and issued as US Pat. No. 6,459,091 B1 on October 1, 2002. "Lightweight" This is a partial continuation of Application No. 09 / 940,681 entitled "Radiation Protective Garments", which was filed on December 7, 1998 and issued as US Pat. No. 6,281,515 on August 28, 2001. This is a partial continuation of application No. 09 / 206,671 entitled "Lightweight Radiation Protective Garments". The disclosures in each of these prior applications are incorporated herein by reference.
Background of the Invention Radiation has been used by humans in many ways. The most well-known destructive use of radiation is the atomic bomb. The electromagnetic radiation emitted by the atomic bomb penetrates deeply into human tissues and damages human cells. In recent years, the threat posed by nuclear bombs has increased, with increasing terrorism and the very realistic possibility that terrorists can produce "dirty bombs" using easily accessible nuclear waste. There is no doubt that it is. The devastating threat of such nuclear bombs to humankind has created a need for cost-effective radiation protection, including the need for lightweight radiation protection suits. Ideally, such lightweight radiation protective clothing would also provide protection against other types of hazards such as flame, chemical, biological, projectile hazards and other forms of electromagnetic radiation. There will be. In this way, first responders, such as firefighters, paramedics, police officers or military personnel, can use a single piece of clothing to provide themselves with protection against all types of dangers they may face. it can. Such "universal" protective clothing is a "Multiple Hazard" whose disclosure is incorporated herein by reference. It is taken up in the applicant's co-pending application No. 10 / 620,954 (Patent Document 1), which was filed on July 16, 2003, entitled "Protection Articles And Methods For Making Them".
Also, many constructive uses have been developed to utilize radiation. These constructive uses include medical x-rays and nuclear power plants. However, other constructive uses of radiation have not yet been discovered. For example, many industries use automated high-speed machines to manufacture products quickly and inexpensively. The food industry is one such industry. For example, many popular brands of breakfast cereals are mostly manufactured and packaged by machines. To market this mass-produced breakfast cereal, breakfast cereal makers often include extras or "prize", such as models of popular superheroes, in the cereal box. This giveaway is usually mechanically inserted and sealed during the packaging process.
When high-speed automated manufacturing methods are used, there is a need for quality control procedures. Returning to the boxed cereal example, if the boxed cereal assembly machine runs out of prizes or its prize insertion device is clogged, many cereal boxes may be sealed, shipped and sold without prizes. unknown. In the case of children's cereals, boxed cereals are often bought for the prizes in them, and if the manufacturer cannot pack the prizes in the cereal box, it can lead to customer anger and disappointment.
As such, whether the manufactured product is made in full compliance with the company's manufacturing standards (eg, including any free gift), especially in high speed manufacturing technology, and whether the product is foreign material. It is necessary to be able to promptly inspect that it is not included. For boxed cereals, this ensures that all of the cereal boxes that are considered to contain the giveaway actually contain the giveaway and are free of foreign matter, such as stones or metal, that could accidentally get into the final assembly. Including.
Human visual inspections are often performed to maintain quality control, but visual inspections are difficult to perform effectively on products manufactured on high speed assembly lines. One challenge associated with visual inspection is to give the inspector sufficient time to perform an appropriate inspection without slowing down the manufacturing process. When trying to detect a free gift in a cereal box, the challenge is the fact that the serial box is visually opaque and therefore not suitable for visual inspection of items such as free gifts inside the cereal box. Complicated by.
<patcit num="1"><text>U.S. Patent Application No. 10 / 620,954</text></patcit>
INDUSTRIAL APPLICABILITY The present invention includes compositions and methods for forming radiation-impermeable polymer articles. When these radioactive opaque polymer articles are used in high speed automated manufacturing methods, their attributes and presence can be easily confirmed by the use of radiological inspection equipment.
The radiation opaque polymer article of the present invention mixes radiation opaque materials such as barium, bismuth, tungsten or compounds thereof with powdered polymers, palpated polymers or solvents or polymer solutions, emulsions or suspensions in water. Can be created by doing. Polymers are advantageously non-limiting polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, acrylonitrile-butadiene-styrene, acrylic, polycarbonate, polyoxymethylene, acetal. You can choose from a wide range of plastics, including Polytetrafluoroethylene (TEFLON ), ionomers, celluloses, polyether ketones, silicones, epoxys, elastomers, polymer foams and other polymeric compounds.
The radiation opaque polymer mixture can then be used to form radiation opaque polymer articles by a number of existing industrial methods such as injection molding, extrusion and thermoforming. For example, in the case of injection molding, the radiation opaque polymer mixture can be heated in an extruder and then injected into a mold until it takes on the shape of the mold. After the radiation opaque polymer mixture has cured to a suitable molding shape, it is removed from the mold. In the case of a superhero model, the molded model can be wrapped in cellophane and inserted into a cereal box as a free gift.
The radiation opaque article can also be advantageously formed by spraying, adhering or coating an existing article with a radiation opaque adhesive mixture. For example, a lightweight, radiation-impermeable material can be mixed with an adhesive, such as a gum adhesive or a liquid polymer, to form a radiation-impermeable adhesive mixture. Then, the radiation-impermeable adhesive mixture is applied to the existing article by spraying the radiation-impermeable adhesive mixture onto the article or immersing the article in the radiation-impermeable adhesive mixture. You can do either.
During the manufacturing process, radiation inspection equipment can be used to detect the presence and attributes of radiation opaque polymer articles. In one embodiment, X-rays are passed through the radiation opaque polymer article itself or a radiation permeable package containing the radiation opaque polymer article. Then, an X-ray detector is placed on the opposite side of the radiation opaque polymer article to detect where the radiation is attenuated and where the radiation has passed. This X-ray detector can confirm the presence of a radiation opaque polymer article and, if desired, the attributes of the radiation opaque polymer article (eg, correct dimensions, quantity, presence of defects, etc.). Can be done. The X-detector can also make sure that unwanted foreign matter, such as stones and scrap metal, is not in the finished product.
Numerous methods and compositions used to create radiation-impermeable detectable objects can also be used to provide protection against a wide range of ionizing radiation, such as neutrons, ultraviolet light, gamma rays and high frequencies. it can. In our ongoing prior application No. 10 / 620,954, the disclosure of which is incorporated herein by reference, the radiopaque polymer compounds of the invention may have other hazards (eg, flames). , Chemically, biologically, projectiles, etc.) are also used to create radiation protective clothing that can also provide protection. Similarly, the same type of mixture can be sprayed onto clothing to attenuate radiation in the same way that an adhesive mixture of radioprotective materials can be sprayed onto an existing article to make it radiation detectable.
As another part of the invention, recent advances in nanotechnology can be used to create better radiation-detectable and radiation-attenuating articles. In certain embodiments, these radiation-attenuating articles can also provide protection against other types of hazards such as flame, chemical, biological, projectile hazards and a wide range of electromagnetic radiation energies. These nanomaterials exhibit unique electrical, mechanical and optical properties due to their small size and high surface area to volume ratio. In the present invention, various nanomaterials can be used to enhance the mechanical, thermal, damping and barrier protection of the product.
In the present invention, nanomaterials are used in at least three different ways. In one embodiment, nanomaterials have previously been disclosed either to enhance radiation protection or to provide additional protection, such as protection against flames, chemicals, biology and / or projectiles. Added to radiation protection polymer materials. In the second aspect, nanoparticles formed from a radiation opaque material (eg barium, bismuth, tungsten, etc.) are in the radiation protection mixture instead of the bulkier form of the same or similar radiation opaque material. Used in. The use of such radiation opaque nanomaterials allows for a more uniform dispersion of the radiation opaque material in the polymer mixture, and accordingly higher levels of the radiation opaque material before the polymer becomes fragile. Can be concentrated. In the third aspect, the nanomaterials are formed as separate nanomaterial layers. Such separate nanomaterial layers can either be added to the product or formed as a separate product.
Nanomaterials for use in the present invention include nanoparticles, nanotubes and nanoplatelets. Nanoparticles are formed primarily as solid particles, but can also consist of hollow nanoparticles, nanoshells, hemispheres, parabolas, and the like. Nanoparticles can be formed from a variety of metallic / non-metallic powders, including oxides, sulfides and ceramic powders. Nanoplatelets are layered nanomaterials containing natural and synthetic nanoclays such as silicic acid and transition metal dicalcogenides (ie, tantalum dicalcogenides that have interacted with lithium). Nanotubes are tube-like nanomaterials that have a diameter of a few nanometers and can still be a few microns long.
When attenuating electromagnetic radiation such as radio waves, ultraviolet light and ionizing radiation, nanoparticles are conventional radiation opaque materials such as tungsten, tantalum, barium or compounds thereof, shell structures such as metal coated magnetic particles. For example, Fe<sub>2</sub>O<sub>3</sub>/ Au, SiO<sub>2</sub>It can be formed with / Au or other coated semiconductor particles, such as PbS / CdS. Hollow metal, metal oxide / sulfide nanospheres or nanospheres of other compounds; nanoparticles with parabolic, hemispherical and shell structures can also be used in the present invention. Shaped nanoparticles (eg, nanoparabolas, nanohemispheres, nanospheres, etc.) are thought to deflect, reflect, and capture radiation in a manner similar to how mirrors deflect, reflect, and capture light waves. These shaped nanoparticles do not need to be formed from a radiation opaque material, as these shaped nanoparticles are thought to attenuate radiation differently than powdered radiation opaque nanoparticles. , Alternatively, it may be formed from a material such as metal / semiconductor hybrid particles. For example, hybrid CdS-coated Ag nanoparticles exhibit red-shifted plasmon resonance absorption. This resonant absorption band of metal nanoparticles is a function of particle size. As the particle size decreases, the theoretical wavelength of maximum absorption intensity can be approached. By creating these nanospheres, nanohemispheres and nanoparabolic structures with specific shapes and curvatures, the optical properties are used for the smaller wavelengths of the spectrum of light, of radio, ultraviolet and ionizing radiation frequencies. Electromagnetic radiation can be attenuated. Electromagnetic radiation is not absorbed as in the case of heavy metals, but is effectively redirected, shifted or reflected so that its energy is reduced to lower levels or converted to heat.
In order to enhance the chemistry and flame retardancy of the polymer mixture, nanomaterials of appropriate composition can be uniformly dispersed in the polymer mixture. For example, nanoclay, when properly dispersed in a polymer, forms a tortuous pathway in the polymer matrix, making it difficult for harmful chemicals, biological agents and other gases, such as oxygen, to penetrate the polymer. By increasing its chemical properties. To increase the flame retardancy of polymers, use small proportions of nanoclay or other nanoplatelets in the range of 2-10% with conventional flame retardants in the nanoscale or micron range, such as alumina trihydrate, water. It can be added with magnesium oxide or other organobromine and organochlorinated compounds. Nanotubes can be used to increase the mechanical properties of the polymer mixture, such as tensile strength, flexibility, modulus of elasticity and electrical conductivity.
There are three common methods for dispersing nanomaterials in a polymer mixture. The first method is direct mixing of the polymer and nanomaterials, either as separate phases or in solution. The second method is in-situ polymerization in the presence of nanomaterials, and the third method is in-situ particle processing involving in-situ formation and in-situ polymerization of nanomaterials. Nanomaterials also include several such as evaporation, sputtering (glow discharge, ion beam, laser), ion plating, chemical vapor deposition (CVD), plasma enhanced CVD, thermal spraying, immersion coating, fluidized bed and spray spray. It is also possible to coat a large number of substrates by technology.
It should also be noted that nanomaterials tend to aggregate and reduce their surface area, and therefore the desired properties of the resulting nanocomposite cannot be achieved without proper dispersion and distribution in the polymer matrix. thing. In order to disperse the nanomaterials in the polymer and process the resulting mixture by standard manufacturing techniques, it is preferable to surface modify the nanomaterials. For example, in the case of nanoclay, the clay surface is modified by a method known as compatibilization so that the nanoclay is attracted to the resin matrix and thus thoroughly dispersed. The two most common known compatibilization methods are onium ion modification and ion dipole interactions.
By blending the nanomaterial into the polymer mixture of the present invention or by creating a high-purity nanolayer, a radiation protection shield is created to make the article radiation-detectable, radiation-protective (ultraviolet, high-frequency, electromagnetic radiation, X-ray). Or gamma rays) or "universal" protection (ie, protection against one or more hazards, such as neutron radiation, flames, chemical, biological or projectile hazards) it can. The resulting radiation-impermeable polymer mixture, with or without nanomaterials, further contains the chemical films, anti-ballistic fabrics (woven or non-woven) or flame retardant described in the patent application cited above. It can be laminated on the material.
Detailed Description of the Invention First, with reference to FIG. 1, an example of the radiation-impermeable polymer article 10 of the present invention is shown. In this case, the radiation opaque polymer article 10 is a free gift that can be inserted into a cereal box in the form of a plastic toy model. The radiation opaque polymer article 10 is preferably formed from a polymer mixture comprising one or more radiation opaque materials and one or more polymers. The formulation of one or more radiation opaque materials is important for this polymer mixture. The reason is that the polymer itself is permeable to many forms of radiation, such as X-rays, and as such it is not possible to produce a radiation opaque polymer article that is effective using the polymer alone. Because it cannot be done.
As radiation opaque materials, barium sulphate, tungsten and bismuth are preferred choices for the present invention as they have less known health hazards than, for example, lead. Barium, other barium compounds (eg barium chloride), tungsten compounds (eg tungsten carbide and tungsten oxide), bismuth compounds, tantalum, tantalum compounds, tin, titanium, titanium compounds, Diatrizoate Meglumine (for injection) ) USP (sold by Nycomed under the trade name HYPAQUE ), Acetrizoate Sodium, boron, boric acid, boron oxide, boron salts, other boron compounds, berylium, beryllium compounds, bunamiodyl sodium, Diatrizoate sodium, etiodized oil, iobenzamic acid, iocarbic acid, iosetamic acid, iodipamide, iodixanol, iodized oil, iodoalphionic Acid), o-sodium hyplate iodide, sodium iodophthalene, iodopyraset, iogric acid, iohexol, iomegramic acid, iopamidel, iopanoic acid, iopentor, iophendylate, iophenoxic acid, Iopromide, Iopronic acid, Iopidol, Iopidone, Iotaramic acid, Iotrolan, Ioversol, Ioxagluic acid, Ioxylan, Ipodate, Meglumine ditrizoate Methiodal Sodium, Meglumine Ditrizoate Methiodal Sodium Phentetiothalein Sodium, Propyriodone, Sodium Iodomethamate, Sozoiodolic Acid, Thorium Oxide and Trypanoate Other radiation-impermeable materials such as Sodium) can also be used, but are not limited to these. These radiation-impermeable materials are available from a variety of chemical suppliers such as Fisher Scientific, PO Box 4829, Norcross, Georgia 30091 (telephone (not listed for public order and morals violations)), Aldrich Chemical Company, PO Box 2060, Milwaukee, It can be purchased from Wisconsin (telephone (not listed for public order and morals violations)) and Sigma, PO Box 14508, St. Louis, Missouri 63178 (telephone (not listed for public order and morals violations)). Those skilled in the art will readily recognize that other radiation opaque materials containing the same metal can be used interchangeably with those described above.
The polymers used in the polymer mixtures of the present invention are preferably polyurethane, polyamide, polyvinyl chloride, polyvinyl alcohol, natural latex, polyethylene, polypropylene, ethylene vinyl acetate, polyester, polyisoprene, polystyrene, polysulfone, acrylonitrile-butadiene-. A wide range of products including styrene, acrylic, polycarbonate, polyoxymethylene, acetal, polytetrafluoroethylene (TEFLON ), ionomers, cellulose, polyether ketones, silicones, epoxys, elastomers, polymer foams and other polymer compounds. You can choose from, but are not limited to, plastics.
Incorporating conventional additives into the polymer mixture to improve the flexibility, strength, durability or other properties of the final product, and / or ensuring that the polymer mixture has adequate uniformity and consistency. It may help to guarantee. These additives, where appropriate, are plasticizers (eg epoxy soybean oil, ethylene glycol, propylene glycol, etc.), emulsifiers, surfactants, retardants, leveling agents, drying accelerators, adhesives, streams. May be improver and flame retardant.
The proportions of these various polymer mixture components can vary. With a larger proportion of conventional size radiation opaque material, radiation detection techniques can generally more easily identify the presence and attributes of a radiation opaque polymer article. Nevertheless, if the proportion of radiation opaque material of conventional size is too high compared to the polymer, the polymer mixture will weaken and easily disintegrate when dried or cooled. From our own research, we found that over 50% by weight of the polymer mixture can be barium sulphate, tungsten, bismuth or other conventional size radioprotective material, and the majority of the mixture consists of polymer. I found that I could do it.
In one preferred embodiment, the polymer mixture contains about 85% by weight of a conventional size radiation opaque material and about 15% by weight of the polymer. In this preferred embodiment, the radiation opaque materials used in the polymer mixture are tungsten (75%), barium sulphate (20%) and bismuth (5%). Currently the preferred polymer for this preferred embodiment is a mixture of ethylene vinyl acetate (EVA) and polyethylene.
It may be appropriate to consider the use of lead as one of the radiation opaque materials for polymer mixtures. Due to its potential health hazard, lead may not be as preferred as many of the other radiation-impermeable materials listed above, but it still has a role in some radiation-impermeable polymer mixtures. Maybe.
A number of known production methods can be advantageously used to form the radiation impermeable polymer articles of the present invention. For example, the radiation opaque polymer mixture of the present invention can first be melted in an extruder and then pushed into the mold of an injection molding machine in melted form by a piston. FIG. 2 shows such an injection molding machine 20. In the aspect of FIG. 2, the radiation opaque polymer mixture 24 is charged into the hopper 26. The hopper 26 then feeds the radiation opaque polymer material 24 to the extruder 30, which melts the polymer mixture 24 to a dough-like consistency by use of the extruder 32. The extrusion screw 34 moves the molten polymer mixture towards the mold 40. The molten polymer mixture is ejected into the mold 40 through the extrusion nozzle 36 under pressure as soon as it leaves the extruder 30. Once the polymer mixture has cooled in the mold 40, it can be removed from the mold 40 in its finished form. Further examples of injection molding equipment and methods are described in Walter's US Pat. No. 6,572,801 B1, whose disclosure is incorporated herein by reference.
Thermoplastic resins, thermosetting resins and elastomers can all be injection molded. By using multiple inlets (not shown) to the mold 40, simultaneous injection molding allows the molding of parts with different materials, colors and / or features. Moreover, other types of molding techniques can be used depending on the shape, thickness, weight range, tolerances, surface roughness and economical batch size of the injection part. These other types of molding techniques include rotary molding, blow molding, foam molding, compression molding, resin transfer molding, die casting, sand casting, for large hollow sealed or semi-sealed structures. Investment casting method, polymer casting method, molded article rolling method, mold forging method, extrusion method, press molding method, roll molding method, spinning method, thermal molding method, lay-up method, powder method, laser prototype preparation method and adhesion method. However, it is not limited to these.
Many other known plastic molding techniques can be used to form the radiation impermeable polymer articles of the present invention. For example, the polymer mixture of the same invention can be put back into the hopper of the extruder and heated, in which case it can be adhered to the conveyor belt as a thin film in molten form. Then, a reduced pressure is applied to the thin film to attract the molten film so as to be in close contact with the mold cavity, and the thin film is formed into its desired shape. Such vacuum forming techniques are described in more detail in Gilbert's US Pat. No. 6,319,456 B1, whose disclosure is incorporated herein by reference. Alternatively, instead of drawing the thin film into a vacuum mold, the thin film sheet can simply be cut into a desired planar shape.
As a further alternative, articles such as superheroes can also be preformed and then made radiation opaque by the deposition of a thin radiation opaque layer. In such cases, mixing a lightweight, radiation-impermeable material with an adhesive, such as a gum adhesive or liquid polymer, can advantageously form a radiation-impermeable layer. The preformed article is then adhered either by spraying the radiation opaque adhesive mixture onto the outer surface of the article or by immersing the article in a solution of the radiation opaque adhesive mixture. be able to.
The mold used in the injection molding method shown in FIG. 2 may be, for example, the shape of the superhero model 10 shown in FIG. Injection molding is used today to produce, in addition to giveaways, many other types of plastic articles that can benefit from being the radiation-impermeable polymer articles of the present invention. For example, plastic straws are often attached to children's juice cartons so that children can drink without spilling the juice. Similarly, plastic tableware, such as spoons and forks, may be attached to a serving of food, embedded in a plastic container. If a straw or other tableware is missing from the food container, the user must either throw away the product or try to eat it by hand from the container and thereby manage to get rid of the associated stains. Either. If the straw or other tableware in this example is made of the radiation opaque polymer of the invention, then using a radiation inspection device, all containers leaving the assembly line will come with a radiation opaque straw or other. It can be confirmed that it has the tableware of.
Because the straws or other tableware in this example touch the user's mouth, for polymer mixtures, non-toxic radiation-impermeable materials such as barium sulphate, iodine, rather than toxic materials such as lead, It will be important to choose bismuth or a combination of them or their compounds. An additional factor to consider when choosing a suitable radiation opaque material is the degree of radiation attenuation provided by the material. For example, in the case of straws and juice boxes, cardboard juice boxes allow radiation to pass through freely. Therefore, a radiation opaque compound with strong attenuation is not required to produce sufficient radiation contrast between the straw and the box. More specifically, in the example of straw and juice box, a radiation opaque compound having a relatively weak damping property, for example, an iodine compound can be used, and a radiation permeable compound having a strong damping property, for example, The bismuth compound can be used at a lower concentration.
Other packaging industries will also benefit from the principles of the invention. In disposable medical products, the majority of the device is made of plastic, and if the contents are missing, the entire device is likely to fail. Using the radiation opaque plastics of the present invention, it is possible to ensure that all the contents of the medical device are present by X-ray examination of the sealed medical package in the factory. Also in the medical field, catheters can be made of radiation-impermeable materials that use the principles of the invention, which allows careful monitoring of catheter insertion into the human body using X-ray machines. Will do. By so monitoring the catheter insertion, the physician will be able to ensure that the catheter reaches the correct position within the patient's body.
As a further application, guns, knives and explosives are now made of plastic, which cannot be detected by the X-ray scanners used at airports. If such plastic guns, knives and / or explosives fall into the hands of terrorists, they can be misused to threaten flight attendants and passengers. Using the principles of the invention, the government mandates that all plastic guns, knives and explosives contain one or more radiation-impermeable materials of the invention, and X-rays used at airports. It could be easily detected by a scan machine. Given the importance of detecting guns, knives and explosives at airports, the government is likely to want to require the use of highly dampening radiation opaque compounds, such as bismuth compounds, for these applications. ..
Next, with reference to FIG. 3, a radiation detector 50 and a method for detecting the radiation opaque polymer article 10 of the present invention are shown. In the method shown in FIG. 3, the box or other container 52 containing the radiation opaque polymer article 10 moves along the conveyor belt 60 in the high speed manufacturing process. In this preferred embodiment, the X-ray tube 70 is used to generate radiation to detect the presence or absence of the radiation opaque polymer article 10 in the box or other container 52. The X-ray tube 70 is controlled by an X-ray control device 72 that transmits a control signal to the high voltage generator 74. The high voltage generator 74 applies a high voltage between the anode and the cathode of the X-ray tube 70 to generate X-ray 76. A lead plate 78 with slits 79 is placed between the X-ray tube 70 and the box or other container 52. The lead plate 79 acts to focus X-rays in a box or other container 52 to be inspected and prevent external X-rays from harming manufacturing workers.
X-rays are detected by the X-ray detector 80 after passing through the box or other container 52 to be inspected. The X-ray detector 80 can include a scintillator and one or more MOS image sensors. In such an arrangement, the incident X-rays are converted into visible light by a scintillator, and the visible light is detected by a MOS image sensor. The MOS image sensor, on the other hand, outputs a detection signal 82 having characteristics corresponding to the amount of incident X-rays detected.
A data processor 84 is used to analyze the detection signal 82 received from the X-ray detector 80. Since the box 52 itself transmits X-rays uniformly, a detection signal without discontinuities would indicate that the radiation opaque polymer article 10 is missing from the box 52. In contrast, the radiation opaque polymer article 10 blocks some of the radiation, so a detection signal with sharp discontinuities would usually indicate the presence of the radiation opaque polymer article 10 in the box. Let's go.
Further confirmation that the radiation opaque polymer article 10 is actually in the box 52 can be made by measuring the level or pattern of X-rays detected by the X-ray detector 80. For example, the amount of radiation detected by the X-ray detector 80 for a box 52 with a radiation-detectable article 10 can be measured and loaded into the memory of the data processor 84 as a template. The data processor 84 then compares the level for each subsequent box 52 on the conveyor 60 with the stored template value, and if the two values match within a predetermined tolerance, the box 52 is actually radiation-free. The data processor 84 can conclude that it contains the permeable polymer article 10. In contrast, if the data processor 84 concludes that the box 52 lacks the radiation opaque polymer article 10, it signals alarm 86 to warn the person in charge of the missing box 12. be able to. Alternatively, the data processor 84 may instruct the operation unit 88 to either stop the assembly line or push the missing box out of the assembly line.
For more accurate detection, the X-ray detector 80 can also have a pattern of detection pixels, each of which detects the transmission of X-rays in a small defined area. To establish a template, a box 52 containing a radiation-impermeable polymer article 10 is irradiated with X-rays and the X-rays are detected by a pixel pattern. Then, the X-ray level detected for each pixel is stored in the memory of the data processor 84 as a template for future inspection. The data processor 84 then compares, pixel by pixel, the level of radiation detected in each box 52 inspected during the manufacturing process to a stored template, first in which the inspected box 52 is a radiation opaque polymer. It is determined whether or not the article 10 is included within a predetermined tolerance. The data received from the detailed detection pixels can then be used to determine the shape (eg, outer contour) of the radiation opaque polymer article. Moreover, the use of detection pixels also allows analysis of cracks, cuts or other defects in the radiation opaque polymer article 10. The use of pixel data in radiological inspection equipment to detect the presence of cracks or cuts in an article is described in more detail in Sawada's US Pat. No. 6,574,303 B2, the disclosure of which is incorporated herein by reference. ..
In addition to detecting the presence and attributes of the desired object in the box, the radiological inspection device 50 shown in FIG. 3 simultaneously or in lieu of unwanted contaminants such as stone, mud or scrap metal. It can also be detected. Data Processor 84 uses a suspicious difference in the detected radiation attenuation to alarm because such contaminants are likely to attenuate radiation differently than both boxes and radiation permeable polymer articles. Either the 86 can be sounded or the operation unit 88 can be used to stop the conveyor 60.
So far, the methods and compositions for forming radiation-impermeable detectable articles have been focused on. Nevertheless, many of the same principles are applied to the harmful effects of radiation, including UV, electromagnetic, high frequency, neutrons, X-rays and gamma rays and other hazards (eg flames, chemicals, biological and projectiles) It can be applied to the manufacture of articles to be protected. For example, in the co-pending prior application No. 10 / 620,954 of the inventors, the disclosure of which is incorporated herein by reference, the ray-impermeable polymer compounds of the invention are resistant to radiation and other hazards. Used to create protective clothing. Similarly, in the same manner as in the previous example, an adhesive mixture of lightweight radioprotective materials could be sprayed, adhered or coated onto a preformed object to make it radiation detectable, that same type of mixture. Can be sprayed, glued or coated on clothing to make it radiation protected.
FIG. 4 shows a full-body suit 100 constructed from a radioprotective polymer mixture of the present invention. To provide complete surface protection, the full body suit 100 is preferably a one-piece jumpsuit that covers every part of the human body. Elastic bands 112, 114 can be used around the hand and foot areas to help ensure a tight fit. Alternatively, the gloves 116, boots 118 and hood 120 can be separate pieces so that they overlap the rest of the jumpsuit and leave no exposed skin surface. The full body suit 110 can also include a velcro fastener or zipper flap 119 to make it easier for the user to enter the full body suit 110. Preferably, a transparent eyeshield 124 is included in the full body suit 110 to provide facial protection. For convenience, the eyeshield 124 can also be winged, for example, with corner rivets 126 to allow the user to swivel the shield 124 up and down. Alternatively, eye protection may be an independent device, such as safety glasses (not shown). To provide radiation protection, the eyeshield 124 is preferably formulated with lead or other radiation opaque compounds capable of attenuating radiation.
With reference to Figure 6, in addition to the hazards posed by radiation when formed into articles, there are numerous life-threatening hazards, including the hazards of toxic chemicals, infectious biological agents, flames and metal projectiles. A composite cross section 200 is shown that can provide protection against it. As part of this multiple hazard protection composite, two fabric layers 204, 208 having a radiation protection polymer mixture 206 sandwiched between them can be provided. To these three layers 204, 206, 208, additional layers 210, 220, 230 can be added to protect against various hazards. For example, a non-porous chemical protective layer 210 and / or 220 can be added to the three radiation protective layers 204, 206, 208. This non-porous chemical layer can be a polymer film 210 laminated on three radiation protection layers 204, 206, 208 and / or sewn or otherwise adhered to the three radiation protection layers. It can also be one of the chemical protective cloth 220.
The chemical protective layers 210, 220 can be constructed of known chemical protective polymers and / or fabrics. For example, one known class of chemical protective fabrics is non-woven fabrics, such as flush spun polyethylene fabrics, polypropylene fabrics sold by DuPont under the trade name Tyvek®, such as Kimberly-Clark's Kleenguard®, Kappler's Proshield 1 , Lakeland's Safeguard 76 , polyethylene and polypropylene blends and cellulose-based fabrics such as DuPont's Sontara and Kimberly Clark's Prevail . Similar types of non-woven fabrics are made by laminating a class of plastic films on one or both sides of the non-woven fabric, such as DuPont's TyChem® series fabrics, Kimberly Clark's Hazard Gard I, It would be II fabrics, Kappler's CPF and Responder series fabrics, and ILC Dover's Ready 1 fabrics . These non-woven fabrics are typically combined with the three radiation protection layers 204, 206, 208 by stitching or otherwise adhering the fabrics together.
Chemical protection can also be provided by using polyvinyl chloride and / or chlorinated polyethylene film, such as Chemturion from ILC Dover. These films can also be laminated or extruded on three radiation protection layers 204, 206, 208.
Another class of chemical protective layer is a laminate of a polymer film with microscopic pores on a cloth, such as Gore-tax® or polypropylene-based cloth, such as DuPont's NexGen , Kimberly Clark's Kleenguard. Ultra , Lakeland's Micro-Max and Kappler's Proshield 2 . Chemical protection can also be provided by materials incorporating an absorbent layer, such as carbon / fabric combinations sold by Blucher GmbH and Lanx. Another class of chemical protective fabric is a woven fabric coated on one or both sides with rubber or plastic. These coated chemical protective fabrics include polyvinyl chloride / nylon composites, polyurethane / nylon composites, neoprene / aramid composites, butyl / nylon composites, chlorinated polyethylene / nylon composites, polytetrafluoroethylene ( That is, there are Teflon®) / glass fiber composites and chlorobutyl / aramid composites.
Since the chemical protective layers 210, 220 are preferably non-porous, they also provide protection against infectious biological agents.
The fabric shown in FIG. 6 can provide a wide range of protection by simply adding one or more chemical protective layers 210, 220 to the three radiation protective layers 204, 206, 208, but nevertheless. Additional or alternative layers 210, 220, 230 may also be selected to protect against additional hazards or promote heat dissipation. For example, if the chemical protective layer 210 is a plastic laminate, the layer 220 in FIG. 6 may be another woven or non-woven layer, and the layer 230 may be a flame protective layer, such as a DuPont Nomex (registered). Trademark) The layer may be made from fire resistant aramid cloth. Other types of refractory materials include combinations of Nomex® aramid fabrics and Kevlar® aramid fabrics, such as Southern. Sold by Mills, melamine resin and aramid fiber combination, polytetrafluoroethylene (ie Teflon®) and aramid fiber combination, rayon and aramid fiber combination, polybenzimidazole and aramid fiber There are combinations with, polyphenylene benzobisoxazole and aramid fibers, polyimide and aramid fibers, and Mylar plastic films. Moreover, traditional flame-retardant additives include aluminum trihydrate (ATH), magnesium hydroxide or organobromine or chlorinated compounds. Alternatively, layer 230 can be a bulletproof or shrapnel layer made from aramid and / or polyethylene fibers that do not allow bullets to penetrate.
Alternatively, it may be wise to form layer 230 of the heat dissipating material. One method of forming such a heat dissipation layer is the same method as mixing a radiation protection material with a polymer to form a radiation protection layer 206, such as compounds with high thermal conductivity, such as silver, copper, gold. , Aluminum, beryllium, calcium, tungsten, magnesium, zinc, iron, nickel, molybdenum, carbon and / or tin mixed with the polymer.
Although Figure 6 shows the 6-layer hazard fabric 200, those skilled in the art will readily recognize that multiple hazard fabrics can be made with more or less layers than 6 layers. Let's do it. For example, the woven or non-woven layers 204, 208 shown in FIG. 6 can be omitted. It is also possible to combine various hazard protection or heat dissipation layers into a single layer. For example, the radiation protection layer 206 of the present invention has been found to provide excellent heat dissipation by itself, but strong heat conductors such as silver, copper and / or aluminum are radiation-free for the radiation protection layer 206. These heat dissipation can be enhanced by adding to the mixture of permeable materials.
Then, with reference to FIG. 7, the bulletproof vest 300 with additional hazard protection is shown. Most of the Bulletproof Vest 300 is a conventional design similar to that disclosed in US Pat. No. 4,989,266 of Borgese, the disclosure of which is incorporated herein by reference. Bulletproofing is provided primarily by layers of polyethylene fibers 314 and / or aramid fibers 316. Commercially available polyethylene fabrics used in bulletproof vests include Honeywell's Spectra series ultra-high molecular weight polyethylene fabrics and Honeywell's Spectraguard ultra-high molecular weight polyethylene fabrics further containing fiberglass. Commercially available aramid fabrics used in bulletproof vests include DuPont's Kevlar® series aramid fabrics and Akzo's Twaron series aramid fabrics. In this preferred example, the bulletproof vest has one or more aramid fibers 316 sandwiched between layers of polyethylene fibers 314. To obtain a higher level of protection against bullets and shrapnel, typically create more layers of aramid fiber 314 and / or polyethylene fiber 316. Further strength can be created by laying bulletproof material plies at 90 ° orientation with each other and encapsulating them between layers of thermoplastic resin. The addition of ceramics and plates can provide an even higher level of protection. The bulletproof vest 300 shown in FIG. 7 is preferably held integrally by the cloth insert casing 312.
An additional layer 320 can be inserted to add additional hazard protection to the bulletproof vest 300 shown in FIG. This additional layer 320 can, in one aspect, be a radiation protection layer. By adding such a radiation protection layer to the bulletproof vest, the bulletproof vest will provide protection against radiation as well as bullets and shrapnel. Similarly, flame, chemical and / or biological protection could be imparted by using the types of multi-layer materials described in connection with FIG. For radiation protection alone, it would usually be desirable to place an additional layer 320 close to the user's body in order to take advantage of the excellent heat dissipation of the radiation protection layer. In contrast, in the case of fabrics that impart flame, chemical and / or biological protection, typically a layer of bulletproof vest to prevent such contaminants from penetrating the bulletproof vest 300. It would be desirable to add it near the outside.
Next, with reference to FIG. 8, a multi-piece protective suit 400 that can be used as underwear is shown. For certain purposes, it's best to hide the fact that you're wearing protective clothing. For example, police officers or other first-hand responders may wish to be protected against radiation and other hazards but not warn others that such hazards may exist. .. Similarly, personnel operating an X-ray inspection machine at an airport may panic about accidental contact with the same X-ray inspection machine while being protected from constant radiation exposure throughout the day. May not want.
In the aspect of FIG. 8, the multi-piece protective garment includes a vest 410, two shoulder flaps 420, a posterior crotch flap 430, an anterior crotch flap 440 and two thigh flaps 450. The vest section 410 is mounted through the headhole 412 through the user's head so that the front vest panel 414 covers the user's chest and the rear vest panel 415 covers the user's back. For snug fit, use strap 416 to attach the front vest panel 414 to the rear vest panel 415. Strap 416 can be tightened in a number of well-known methods, including snap buttons, VELCRO fasteners, tie straps, buckles and more. The posterior crotch flap 430 and the anterior crotch flap 440 are used to protect the user's hip and crotch areas. The posterior crotch flap 430 is attached to the user's buttocks and the anterior crotch flap 440 is attached to the user's crotch. Upper straps 434 and 444 are provided so that the rear crotch flap 430 and the front crotch flap 440 can be attached to the lower part of the vest portion 410 and hung from the vest. Lower straps 432 and 442 are provided on both crotch flaps 430 and 440 for snug fit and pull them under the crotch to connect to the corresponding lower straps 432 and 442 from the crotch flaps 430 and 440. can do. Two thigh flaps 450 are provided to protect the user's thighs. These thigh flaps 450 are curved so that they can be wrapped around the user's left and right thighs. Four straps 452 and 454 are provided on each of these thigh flaps. The thigh flap lower strap 452 wraps around the user's upper leg and attaches to the corresponding thigh flap lower strap 452. In contrast, the thigh flap upper strap 454 can also be secured to the bottom of the anterior crotch flap 440, or, like the thigh flap lower strap 452, wraps around the user's upper leg, Either it can be secured to the corresponding thigh flap strap 454. The user's shoulders are protected by the shoulder flap 420. These shoulder flaps 420 are used to cover the user's left and right shoulders while attached to the upper 418 of the vest section 410. By leaving the sides of the vest 410 open and using the shoulder flap 420 attachment, the multi-piece protective garment 400 of the present invention provides freedom of arm movement while providing protection for vital organs. I am considering it. Similarly, by separating the vest 410 from the crotch flaps 430, 440 and thigh flaps 450, the user is free to move his legs and torso while also gaining protection for life-supporting organs. ..
The multi-piece protective clothing 400 is constructed from the same types of radiation and hazardous protective materials as described above. In the case of radiation protection only, the radiation protection polymer film can be adhered to the cloth as described in the simultaneous pending application No. 10 / 620,954, and then cut into a shape as shown in FIG. .. Alternatively, a number of multilayer materials of the type shown in FIG. 6 or multilayer composites of the type shown in FIG. 7 can be cut into the shapes shown in FIG. 8 to include radiation, chemical, biological, flame and projectile hazards. It can also provide protection against danger. These same principles apply to the manufacture of hazard protection blankets, "dirty" or nuclear bomb suppression blankets, jackets, trousers, shirts, drapes, x-ray aprons, vests, hats, gloves and similar protective items, as well as underwear. It can also be applied. These same principles can also be applied to the manufacture of liners or coatings for vehicles, walls, ships, aircraft, spacecraft, residential foundations and containers to block a wide range of electromagnetic and ionizing radiation.
FIG. 9 shows an alternative mode for constructing parts for multi-piece protective clothing 400. In this aspect, the posterior crotch flap 530 is constructed from standard fabric in the form of pockets. The protective layer is then made in the form of an insert 540 that can be fitted into the top of the pocket. The strap 536 is sewn to the bottom of the cloth pocket 530 to prevent the insert 540 from falling out of the pocket 530 after insertion. This pocket 530 and insert 540 approach allows the use of different types of inserts depending on the expected risk. For example, if the user is likely to encounter a radiation-only hazard, an insert that protects against the radiation-only hazard can be used. On the other hand, if projectiles, chemical or biological hazards are also considered, thicker inserts can be used that will provide protection against those additional hazards. This type of pocket 530 and insert 540 also pockets on the back of the vest 410 (see Figure 8), for example to provide additional protection for the spinal column or as a belt loop to receive a belt or lumbar support brace. Can also be used to form.
Moreover, recent advances in nanotechnology can be used to create better radiation-detectable protective articles. In certain embodiments, these radiation-attenuating articles can also provide protection against other types of hazards such as flame, chemical, biological, projectile hazards and a wide range of electromagnetic radiation energies.
Nanomaterials are materials that have structural features (eg, particle size or particle size) in the range of 1-100 nanometers in at least one dimension. Due to their small size and high specific surface area to volume ratio, these materials exhibit unique mechanical, electrical, electronic and optical properties. In addition, nanomaterials, unlike traditional micron-sized materials, are less likely to generate large stress concentrations, which, on the other hand, increase their yield strength, tensile strength and Young's modulus.
In the present invention, nanomaterials are used in at least three different ways. In one embodiment, the nanomaterial is the radiation previously disclosed, either to enhance radiation protection or to provide additional protection, such as flame, chemical, biological and / or projectile protection. Added to protective polymer materials. In the second aspect, nanoparticles formed from a radiation impermeable material (eg barium, bismuth, tungsten, etc.) or other hazardous protective material are polymer instead of the bulkier form of the same or similar protective material. Used in a mixture. The use of radiation opaque nanomaterials allows for a more uniform dispersion of the radiation opaque material in the polymer mixture, resulting in a higher concentration of the radiation opaque material before the polymer becomes fragile. It will be possible. In the third aspect, the nanomaterials are formed as separate nanomaterial layers. Such separate nanomaterial layers can either be added to the product or formed as a separate product.
Nanomaterials used in the present invention include nanoparticles, nanotubes and nanoplatelets.
The first type of nanomaterial used in the present invention is nanoparticles. Suitable nanoparticles include nanoparticles of conventional radiation opaque materials, nanoceramics, nanoshells, nanoparticles and other nanoparticles in the form of hemispheres and parabolas. By substituting radiation-impermeable nanopowder for bulky radiation-impermeable materials, or by blending a mixture of both nano-sized radiation-impermeable powder and micron-sized radiation-impermeable powder. The relative proportion of radiation opaque material in the polymer mixture can be increased. By blending a larger proportion of radiation opaque nanopowder into the polymer mixture, the resulting product can have enhanced electromagnetic radiation attenuation capabilities.
Nanopowder of radiation opaque material is commercially available and can be blended into polymers using standard blending techniques. Types of radiation opaque nanopowder that can be used include: tungsten, barium, boron, lead, tin, bismuth, depleted uranium, cerium, yttrium, tantalum, lanthanum, neodymium and their compounds. Tungsten (APS: 100 nm) and tantalum (APS: 100 nm) nanopowder can be purchased, for example, from Argonide Nanomaterial Technologies, Sanford, Florida. Rare earth radiation-impermeable nanomaterials of cerium oxide, yttrium oxide or neodymium oxide can be purchased from NanoProducts Corporation, Longmont, CO.
Moreover, nanoparticles formed in the form of hollow nanospheres, nanohemispheres, nanoparabolas and nanoshells can also be used in the present invention to achieve radiation impermeability and attenuation of a wide range of electromagnetic radiation. These shaped nanoparticles are believed to deflect, reflect, and capture radiation in the same way that mirrors deflect, reflect, and capture light waves. These shaped nanoparticles are thought to attenuate radiation differently than powdered radiation-impermeable nanoparticles, so they do not need to be formed from radiation-impermeable materials and instead are metal / semiconductor hybrids. It can also be formed from materials such as particles. For example, hybrid CdS-coated gold nanoparticles have been shown to exhibit red-shifted plasmon resonance absorption. This resonant absorption band of metal nanoparticles is a function of particle size. As the particle size decreases, the theoretical wavelength of maximum absorption intensity can be approached. By creating these metal nanospheres, hemispheres and parabolic structures with specific shapes and curvatures, the optical-like properties are transformed into smaller wavelengths in the electromagnetic spectrum, including radio waves, ultraviolet and ionizing radiation, such as X-rays and gamma rays. On the other hand, it can be used to attenuate. These nanoparticles effectively redirect, shift or reflect electromagnetic radiation, unlike traditional heavy metals that absorb or scatter electromagnetic radiation, and then convert it to lower energy or heat.
Referring to FIG. 5A, the deflection of radiation 132 by the concave inner surface 134 of the nanohemisphere is shown. In FIG. 5B, radiation 142 passes through the concave outer surface 144 of the nanosphere 140, but is internally reflected and thereby captured by the concave inner surface 146 of the same nanosphere 140.
As is known in the art, parabolic or hemispherical resonant antennas have very sharp directivity. Similarly, when producing similar resonant properties for nano-level radiation, it is preferable to direct the nanomaterials in space to create a layer that blocks radiation coming from a particular direction (eg, outside the garment). Would be desired. Nevertheless, omnidirectional shielding can be effectively achieved by applying a coating of randomly placed particles in hundreds of layers. For better performance, such coatings of nanomaterials should have minimal voids. As such, when making a mixture of nanomaterials and binders, it is preferred that the nanomaterials are the majority of the coating, eg, greater than 70% by weight, more preferably 85% to 95% by weight.
Ceramic nanoparticles can also be added to the radiation opaque polymer mixture to increase mechanical strength, such as tensile strength and creep resistance, as well as heat resistance, ballistic resistance, electromagnetic wave attenuation and neutron emission attenuation. it can. Advantageously, oxides of aluminum, zirconium, silicon, titanium, murite and spinel and carbides / nitrides such as boron carbide, silicon carbide, titanium carbide, tungsten carbide, boron nitride, silicon nitride, titanium diboride, diboride. Ceramic nanoparticles can also be incorporated into the polymer mixture to provide radiation attenuation, including, but not limited to, zirconium diboride and other intermetallic compounds such as nickel aluminide, titanium aluminide and molybdenum diboride. These ceramic nanomaterials include chemical vapor deposition, pulsed laser deposition, conventional powder treatment (ie, sol-gel treatment), plasma synthesis, thermal decomposition, carbon thermal reduction, hydrothermal, emulsion, combustion synthesis, NIST, It can be prepared by a number of methods, including precipitation methods, electric arcs and ball milling. It is also possible to add metal second phase particles to ceramics to enhance mechanical, thermal and electromagnetic wave attenuation properties. Metals such as tungsten, molybdenum, nickel, copper, cobalt and iron can be added to the ceramics using conventional metallurgy and solution chemistry methods such as sol gel and coprecipitation.
Alternatively, the nanoparticles can be synthesized by some additional techniques. One such technique allows the inner removable template particles, such as silica or polymer beads, to be coated on a multistage colloid or vapor phase assembly with a metallic material and then removed to create an empty metal shell. It is a colloid template method. Creating a uniform coating on a particle template by colloidal self-assembly is based on the concept of self-assembled organic molecular species. The two ends of the molecule to be joined have specific functional groups (ie, thiols, amines, carboxyl groups) that can be targeted for specific interactions with the clusters used to make the templates and coatings. Have. The uniform and dense packing of molecules around the template leads to dense packing of clusters that form a porous but space-filled shell around the template. SiO<sub>2</sub>/ Au, Fe<sub>3</sub>O<sub>4</sub>Non-interactive metal-coated magnetic particles, including / Au, NiO / Co, silver, platinum, tantalum, tungsten, aluminum and copper or coated semiconductor particles, such as PbS / CdS, are such composite particle structures. This is an example. Alternatively, PbS-coated CdS nanocomposites having a diameter of several nanometers can be synthesized by ion substitution in an inverse microemulsion. The refraction non-linearity in these nanocomposites can be attributed to the optical Stark effect and strong interfacial and nanoparticle interactions.
Hollow nanospheres can also be synthesized by utilizing the nanoscale Kirkendall effect. When nanocrystals such as cobalt are exposed to sulfur, there is a difference in diffusion, causing cobalt atoms to move outward faster than sulfur atoms, thereby creating hollow nanospheres of cobalt sulfide. Cobalt oxide and cobalt selenate can also be synthesized by this technique. Similarly, it may be possible to use this technique to synthesize other metals such as silver, gold, platinum, aluminum, copper and tungsten.
Nanoparticles can also be made by in-situ particle formation / in-situ polymerization. In this method, a stable suspension of metal particles is prepared in the presence of the polymer. Once in solution, the composite can be cast or added with additional monomers of the same or different polymer types to form the nanocomposite. The reaction takes place in the presence of a protective polymer, limiting the size of the nanocomposite from which it is obtained. The particle size is also controlled by the selection of metal precursors and metal / polymer interactions. For example, PdCl<sub>2</sub>(NH<sub>4</sub>)<sub>2</sub>PdCl<sub>4</sub>In comparison with, the former tends to form halogen-bridged complexes and therefore tends to form agglomerates of nanoparticles, while the latter does not. The interaction of the metal precursor with the polymer is also important in controlling the particle size. If the polymer has a stronger interaction with the precursor, the metal precursor is blocked from phase separation and the particle size tends to decrease. The technique can also be used to form nanoparticles by the use of micelles formed from amphipathic block polymers or crosslinked gelation matrices. While using the copolymer to form micelles, introduce any metal salt that can penetrate the micelles or is stable in the micelle corona. When a reducing agent is added, metal particles form in the micelles or in the corona, giving rise to some morphology.
In general, nanoparticle size is controlled in several ways depending on the synthesis technique used. For example, in the gas phase, the synthetic particle size is controlled by varying system parameters such as temperature, gas flow rate and system pressure. In other methods, such as the sol gel technique, the particle size can be changed by varying the concentration and temperature of the solution. In mechanical grinding, the particle size rather depends on the speed and grinding time of the grinding medium.
Hollow nanocrystals can be purchased from the Molecular Foundry of the Berkeley National Laboratory in Berkeley California, which specializes in the synthesis of hollow metal, metal oxide / sulfide nanocrystals.
The second type of nanomaterial used in the present invention is nanotubes. Nanotubes are typically formed from carbon. When added to a polymer mixture, nanotubes represent another way to enhance mechanical properties such as modulus of elasticity, chemical resistance, flame resistance, strength and electrical conductivity of the mixture. Carbon nanotubes have unique electrical properties because the electron conduction process in the nanotubes is confined in the radial direction, and as a result, can also be used to attenuate electromagnetic radiation. As a method for producing these nanotubes, there is a chemical vapor deposition technique for growing nanotubes using a catalyst and a hydrocarbon precursor. Nanotubes can also be made by electric arc, laser ablation, chemical vapor deposition and high pressure carbon monoxide conversion (HiPCO). HiPCO uses high-pressure disproportionation of carbon monoxide gas in the presence of iron-carbonyl-catalyzed vapors to produce large quantities of 80% pure nanotubes. Other types of nanotubes include hexagonal boron nitride nanotubes, nanotubes made of dicalcogenide (ie MoS).<sub>2</sub>, WS<sub>2</sub>), Oxide nanotubes (ie V<sub>2</sub>O, MoO<sub>3</sub>), Gold nanotubes and organic nanotubes. Nanotubes can be purchased from Materials and Electrochemical Research Corporation, Tucson, Arizona.
Once produced, the nanotubes should undergo a purification process before being incorporated into the radiation opaque polymer mixture of the present invention. Purification and processing methods include prefiltration, dissolution, microfiltration, sedimentation and chromatography. The obtained nanotube product is then preferably dispersed in the polymer mixture together with a surfactant such as sodium dodecyl sulfate.
A third type of nanomaterial that can be added to a radiation opaque polymer mixture is nanoplatelets (ie, plate-like nanofillers). Nanoplatelets are typically layered materials with a high aspect ratio and a thickness of about 1 nm.
Nanoplatelets will increase the chemical, ballistic, flame, electromagnetic radiation and neutron resistance of the mixture when added in large amounts to the polymer mixture. Nanoplatelets include nanoclays, such as montmorillonite clay. Montmorillonite clay belongs to the smectite tribe, and the smectite tribe also belongs to clays such as bentonite, hectorite, pyrophyllite, talc, vermuquilite, saponite, saponite and nontronite, layered silicic acid (ie kanemite and macatite). ) And layered double hydroxides. Clays of other groups such as kaolinite and chlorite and other phyllosilicates such as mica can also be used. Not only do transition metal dicalcogenides (ie, tantalum dicalcogenides intercalated with lithium) are dispersed in the polymer mixture to provide a mixture with nanoclay-like properties (thanks to its similar layered structure). It is also possible to increase the electromagnetic radiation attenuation.
Natural nanoclays such as smectite clay are substances with high stratification and weak bonds. Each layer consists of two silica tetrahedral sheets and an edge-sharing octahedral sheet of either alumina or magnesia. Due to the isomorphic substitution of aluminum with alumina or magnesium on the silicate layer, each unit cell has a negative charge. The natural nanoclay layer is held together by layers of charge compensating cations such as lithium (Li +), sodium (Na +), potassium (K +) and calcium (Ca +). These charge-compensating cations provide the abundant intercalation chemistry and surface modification pathways required to disperse the nanoclay in the polymer. Synthetic clays such as hydrotalcite carry a positive charge to the platelet. In order for these layered nanoclays to be useful in a radiation opaque polymer mixture, the layers should separate and be properly dispersed in the mixture. In the case of nanoclays such as silicate clay, they are hydrophilic in nature, but polymers tend to be hydrophobic. In order to obtain intercalation and exfoliation of these clays, the passages or layers of these clays must be opened so that the polarity of the resulting clay matches the polarity of the polymer and the polymer intercalates between the layers. You have to do it. This is done by exchanging inorganic cations with organic cations. Larger organic cations swell the layer and increase the hydrophobicity of the clay. The organically modified clay can then intercalate with the polymer by several routes. For positively charged clays, such as hydrotalcite, anionic surfactants can be used. Other types of clay modifications can be used depending on the choice of polymer. Such include the interaction between ionic dipoles, the use of silane coupling agents and the use of block polymers. An example of an ionic dipole interaction is the intercalation of small molecules, such as dodecylpyrrolidone, into clay. Clay edge and polymer Undesirable interactions with can be eliminated by modifying the edges with a silane coupling agent. Alternatively, the use of copolymers can also be used to carry out compatibility between clay and the polymer, where one component of the copolymer is compatible with the clay and the other component of the copolymer is compatible with the polymer.
Incorporating a small amount (about 2-5% by weight) of nanoclay into the polymer mixture can also substantially improve the resistance of the polymer mixture to harmful chemicals. However, the level of chemical resistance improvement depends on many factors such as the degree of exfoliation of the nanoplatelets in the polymer mixture, the proportion of nanomaterial filler, its aspect ratio and the arrangement of the platelets. By blending the nanoclay within the polymer mixture, oxygen permeation in the mixture is particularly reduced, which reduces polymer degradation by reducing the oxidation of the resin and thus its flame retardancy. In addition, the inorganic phase can act as a sink to prevent the polymer chains from decomposing.
To increase the flame retardancy of the polymer mixtures of the invention, traditional flame retardant additives such as alumina trihydrate (ATH), magnesium hydroxide or organobromine and chlorinated compounds are often added. Be done. Nevertheless, in order to achieve acceptable levels of flame retardancy (eg in the case of cables or wires), these flame retardant additives are usually required at very high levels. These high additive levels make the manufacturing process more difficult and thus weaken the polymer end products.
In the present invention, nanomaterials can be used in polymer mixtures to eliminate this flame retardant fragility problem. More specifically, the addition of low weight% (eg 2-10%) of nanoclay with traditional bulky refractory additives such as ATH or magnesium hydroxide will result in the same or improved levels in the polymer mixture. The amount of additives required to achieve the fire resistance of the clay can be significantly reduced. Other nano-sized flame-retardant additives that can be added to the polymer mixture are nano / micron-sized compounds of nano / micron-sized oxides such as antimony oxide, molybdenum, titanium, zirconium and zinc. Also, silicon carbide, silicon nitrate (silicon) Nitrate), aluminum nitride, silicon nanotubes, carbon nanotubes, and boron nitride nanotubes may be used to increase the fire resistance of the polymer. Moreover, conventional refractory additives such as ATH or magnesium hydroxide can be added in the nanosize range to more effectively achieve refractory in the polymer mixture. The use of these nanomaterials will make the resulting polymer mixture stronger, lighter and more flexible.
One of the major limitations in the use of nanomaterials in polymer compositions is processing. More specifically, nanomaterials tend to aggregate and reduce their surface area, and therefore the desired properties of the resulting nanocomposite cannot be achieved without proper dispersion and distribution in the polymer matrix. .. In order to effectively disperse the nanomaterials in the polymer and process the resulting mixture by standard manufacturing techniques, the nanomaterials should be surface modified. For example, in the case of nanoclays, the clay surface can be modified by a method known as compatibilization so that the nanoclays are attracted to the polymer resin matrix and thus thoroughly dispersed. The two most common known compatibilization methods are onium ion modification and ion dipole interactions.
Once the nanomaterial aggregation problem is resolved, there are three common methods for dispersing nanomaterials in a polymer mixture. The first method is direct mixing of the polymer and nanomaterial, either as separate phases or in solution. The second method is in-situ polymerization in the presence of nanomaterials, and the third method is in-situ particle processing involving in-situ formation and in-situ polymerization of nanomaterials.
For example, to prepare chemical flame resistant nanocomposites, polymers such as ethylene vinyl acetate (EVA) can be mixed directly with nanoplatelets such as nanoclay, silicic acid or transition metal dicalcogenide. .. Such mixtures can be made with or without conventional flame retardants such as ATH and magnesium hydroxide. The resulting polymer mixture can then be machined with a twin-screw extruder and molded into the desired product using injection molding or injection molding. Formulations using a twin-screw extruder generate a large amount of shearing force, which helps to strip the nanomaterials in the polymer mixture. Addition of nanoclay or nanotubes will increase the viscosity of the polymer mixture. Therefore, the rheology of the mixture should be closely monitored and controlled by adding fluid additives that are compatible with the polymers and fillers used (ie, nanoclays or nanotubes).
Nanomaterials can also be coated on several different substrates, including polymeric substrates, to produce the protective products of the invention. Nanocomposites use known techniques such as evaporation, sputtering (glow discharge / ion and beam / laser), ion plating, chemical vapor deposition (CVD), plasma-enhanced CVD, thermal spraying, immersion coating, fluidized bed and spray spray. It can be used to coat several different substrates. Nanomaterials can also be applied on a variety of substrates by other technologies, such as single spraying, high voltage electric field-aided spraying, roll stocking, extrusion, coating and liquid coating with existing technologies such as simultaneous extrusion. It can also be applied as a coat.
Alternatively, the nanomaterial may be adhered to a flexible film, and then the film may be coated with a pressure-sensitive adhesive to produce an adhesive material having a shielding property. To protect human skin from the sun's UV rays, for example, nanomaterials can be mixed with a binder to form a spray or ointment that is applied directly to the skin. Furthermore, since the thickness of hundreds of rows of nanomaterials is about 1 micrometer, the nanoshielding material of the present invention is made transparent to visible light, thereby making goggles and others with excellent optical properties. Can be used in the manufacture of transparent shields.
Next, with reference to FIG. 10, a bomb containment 760 including a bomb containment 762, a front hatch 764, a wheel assembly 766 and a bomb tray 768 is shown. The sphere 762 and front hatch 764 of the containment vessel 760 are constructed of a hard, explosive resistant material, such as hardened steel. The existing containment vessel 760 is constructed to contain conventional bomb explosions, but is not designed to contain or attenuate nuclear radiation, such as γ and neutron emissions or light rays. However, using the principles of the invention, the bomb containment 760 can be reconstructed to protect against the nuclear hazards posed by, for example, "dirty bombs" or radiation bombs.
In a preferred embodiment, the radiation protection polymer layer 770 is adhered to the outside of the bomb containment 760. Similarly, the radiation protective polymer layer 770 is formed from a mixture containing one or more of the above radiation impermeable materials and one or more of the above polymers. In the preferred embodiment shown in FIG. 10, the radiation opaque polymer mixture is used to form curved radiation opaque tile 772. These radiation impervious tiles 772 can be formed by any number of known manufacturing methods including injection molding, extrusion, vacuum forming, drape molding, pressure molding and plug assist molding. Then, the radiation opaque tile 772 is adhered to the outer surface of the bomb containment vessel 760 and to each other. A smooth decorative layer (not shown) can then be applied onto the radiation opaque tile 772 to improve the appearance of the bomb containment 760. Alternatively, the radiation opaque polymer layer can be formed in one piece or bomb-contained by adhesive spraying, rotomoulding, injection molding, immersion in a liquid bath, painting or other known coating and injection molding methods. It can also be uniformly coated on the outside or inside of the vessel.
During operation, the hardening material of the bomb containment vessel 760 contains the explosive power of the bomb, and the radiation protection layer 770 of the present invention contains the radiation emitted by the bomb. The radiation protection layer of the present invention can also be adhered to the inside of the bomb containment vessel 760, but we are less effective due to the damage that the explosion causes to the radiation protection layer 770. I don't think it should be.
The present invention has been described herein with reference to specific preferred embodiments and methods. However, it will be apparent to those skilled in the art that various modifications and modifications can be made without departing from the broader nature and scope of the invention described in the claims. For example, one of ordinary skill in the art will recognize that the principles of the present invention apply to many types of articles in addition to the toys, tableware, weapons and medical devices described above. More specifically, the relatively lightweight radiation opaque material of the present invention is incorporated into virtually any type of plastic product (eg, auto parts, telephones, storage containers, etc.) and of such products. Allows the existence and / or attributes to be evaluated by X-ray. Moreover, the principles of the invention will apply to virtually any type of manufacturing process for plastic products. Although X-ray examination has been described in a preferred embodiment, other types of radiation, such as α, β or γ rays, can be used in place to detect radiation opaque polymer articles. In the case of nanomaterials, many nanomaterials have been found to have minimal toxicity, which is enhanced when nanocomposites are added intravenously or orally to the human body for use in radiography. Tissue contrast can also be provided. Therefore, the specification and drawings should be understood in an exemplary sense rather than in a limiting sense, and the present invention is limited only by the claims.
<figref num="1">It is a front view of the radiation opaque polymer article of this invention.</figref><figref num="2">It is a side view of the injection molding apparatus for producing the radiation impermeable polymer article of this invention.</figref><figref num="3">FIG. 5 is a perspective view of a device for detecting the presence and attributes of a radiation opaque polymer article on a high speed assembly line.</figref><figref num="4">It is a front view of a radiation protection whole body suit.</figref><figref num="5A">It is a side view of a nanohemisphere for attenuating radiation.</figref><figref num="5B">It is a side view of a nanosphere for attenuating radiation.</figref><figref num="6">FIG. 6 is a cross-sectional view of a composite material that can provide multiple forms of hazard protection.</figref><figref num="7">It is a figure which shows the vest formed by a large number of danger protection layers.</figref><figref num="8">It is an exploded view of the protective clothing which can be worn as underwear.</figref><figref num="9">FIG. 5 shows a pocket and a hazard protection insert for that pocket.</figref><figref num="10">It is a perspective view of a radiation-attenuating bomb containment vessel.</figref>
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Numbers
- Publication
- 2008538136
- Publication, DOCDB
- 2008538136
- Publication, EPODOC
- JP2008538136
- Application
- 2007547006
- Application, DOCDB
- 2007547006
- Application, EPODOC
- JP20070547006
Titles2
- Japanese
- 放射線検出性防護物品
- English
- Radiation-detectable protective article
Classification
- CPC, 3
- G21F1/00
- G21F3/02
- G21F5/00
- IPC, 18
- G01N23 00
- C08L101 00
- G21F1 10
- C08K3 08
- C08K3 16
- C08K3 30
- C08K3 22
- C08K3 38
- C08K5 00
- C08K3 34
- B65D81 30
- B65D25 34
- B65D79 02
- A41D13 00
- A41D31 00
- A41D31 02
- A42B1 04
- A41D19 00
Designated states4
- Regional, 4
- Zimbabwe
- Turkmenistan
- Türkiye
- Togo